WO1993008510A1

WO1993008510A1 - Colored toner for developing electrostatic image

Info

Publication number: WO1993008510A1
Application number: PCT/JP1992/001371
Authority: WO
Inventors: Hiroshi Kamada; Hitoshi Masuda; Yukinobu Hasegawa; Hiroyoshi Shimomura; Hiroshi Serizawa; Kensuke Okuda; Masatoshi Maruyama
Original assignee: Nippon Carbide Kogyo Kabushiki Kaisha
Priority date: 1991-10-22
Filing date: 1992-10-21
Publication date: 1993-04-29
Also published as: EP0609443A4; EP0609443B1; DE69228314D1; CA2121893A1; DE69228314T2; EP0609443A1; CA2121893C

Abstract

A colored toner for developing electrostatic images which has a degree of gelation of 2.0 % or less and comprises an association of secondary particles containing polymer particles having acidic or basic polar groups and an organic pigment and/or an organic dye treated with a treatment containing a surface treatment which has the same ionic character as that of the polymer particles in such a manner that the absolute value of z-potential will be 10 to 100 mV at a pH value of 5; and a developer for electrostatic images which comprises said toner and a carrier.

Description

Description Color toner for electrostatic image development [Technical field]

The present invention relates to a color toner for forming an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like.

[Background technology]

Conventionally, a widely used toner is prepared by appropriately blending a coloring agent such as carbon black, a charge controlling agent and / or a magnetic material with a styrene Z acrylate copolymer powder obtained by a suspension polymerization method, It has been manufactured by melt-kneading with an extruder or the like, followed by pulverization and classification. (See Japanese Patent Application Laid-Open No. Sho 51-233354).

However, the toner obtained by the above-mentioned melt-kneading and pulverization method has a limitation in controlling the particle size of the toner, and it is difficult to produce a toner having a small particle size with good yield, and the dispersion is not uniform. However, when used as a developer due to the distribution of the charge amount becoming broad, there is a problem that the resolution cannot be avoided and the drawbacks such as capri and scattering can not be avoided.

When such toner is used as a full-color toner, if it is fixed by heat, its color developability will be poor, and not only will the full color image due to the superposition principle become unclear, but also its color reproducibility will deteriorate, and it will be used for OHP, etc. In this case, clear images could not be obtained because of poor transparency.

The present invention has high image density and resolution, and generates capri and scattering It is another object of the present invention to provide a toner having excellent color developability, color reproducibility, and color transparency when copied on a 0 HP sheet.

[Disclosure of the Invention]

The present invention provides a polymer particle having an acidic polar group or a basic polar group, and a treating agent containing a surface treating agent having the same ionicity as the polymer particle, so that the absolute value of the f potential at PH 5 is 10 to 1 A secondary particle comprising an organic pigment and Z or an organic dye that has been treated to have an O mV and is characterized by having a gelation degree of 2.0% or less. To provide a color toner for developing electrostatic images.

The toner of the present invention preferably has a toner particle shape factor S value of 100.5-16.0.

Also, let rm be the average of the particle diameter of the toner obtained from the distance between the circumscribed parallel lines, and rn be the average of the minimum value of the radius of curvature of the individual associated particles constituting the toner on the toner particle surface, and V = rmZrn And

1. 0 1≤V ≤S 2 0

2.5≤r m≤l 6

0. 0 5 ^ r n <r m

It is preferable that the relationship

Further, the present invention provides an electrostatic image developer containing the toner for developing an electrostatic image and a carrier.

Hereinafter, the toner for developing an electrostatic image of the present invention will be described.

The toner of the present invention comprises a polymer particle having an acidic polar group or a basic polar group (hereinafter sometimes referred to as a primary particle), an organic pigment specifically treated as described below, and Z or an organic pigment. Secondary particles composed of dyes Consists of associated particles. Here, the association means that a plurality of secondary particles aggregate to form particles having a larger particle size.

Preferred examples of the polymer having an acidic polar group or a basic polar group include styrenes, alkyl (meth) acrylates, and comonomers having an acidic polar group or a basic polar group (hereinafter, referred to as “comonomer having a polar group”). ) Is a copolymer of

Preferred specific examples of such a copolymer include:

(A) 90 to 20% by weight, preferably 88 to 30% by weight, based on the sum of (a) and (mouth),

(Mouth) alkyl (meth) acrylates based on the sum of (mouth) and (mouth) 80 to 10% by weight, preferably 70 to 12% by weight, and

(C) When the total of (a) and (mouth) is 100 parts by weight, 0.05 to 30 parts by weight, preferably 1 to 20 parts by weight, of a comonomer having a polar group is contained. Is a copolymer of

Further, in addition to the monomers (a), (mouth), and (c), the copolymer may optionally contain a comonomer that can be copolymerized to such an extent that the performance of the toner of the present invention is not impaired.

Examples of the styrenes include styrene, n-methylstyrene, m-methylstyrene, p-methylstyrene, -methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, ρ-n-butylstyrene, p-tert-butyl Styrene, p-n-hexynolestyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p- Chlorstyrene, 3,4-dichlorostyrene, p-Chlorme And styrene.

Examples of the above alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, η-butyl acrylate, isoptyl acrylate, butyl acrylate pill, η-octyl acrylate, dodecyl acrylate, acrylyl acrylate, 2-Ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, η-butyl methacrylate, isobutyl methacrylate, methacrylate Examples include η-octyl acrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate and the like. Among them, those having 1 to 12 carbon atoms in the ester portion are preferable, those having 3 to 8 carbon atoms are more preferable, and (meth) acrylic acid esters of aliphatic alcohols having 4 carbon atoms are particularly preferably used. .

Examples of the comonomer having an acidic polar group include a β-ethylenically unsaturated compound having a carboxyl group and an a, β-ethylenically unsaturated compound having a sulfone group.

Examples of the S ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, gay cinnamate, monobutyl maleate, monooctyl maleate, And metal salts thereof such as sodium and zinc.

Examples of the a, yS ethylenically unsaturated compound having a sulfone group include sulfonated ethylene, Na salt thereof, arylsulfosuccinic acid, arylyl And octyl sulfosuccinate, and its Na salt.

Examples of the comonomer having a basic polar group include an ester group having an amine group or a quaternary ammonium group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably (meth) acryl. Acid ester, (meth) acrylic acid amide or (meth) acrylic acid amide optionally mono- or di-substituted with an alkyl group having 1 to 18 carbon atoms on N, and N as a ring member And vinyl compounds substituted with a heterocyclic group and N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, a (meth) acrylate of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferably used as a comonomer having a basic polar group.

Examples of the (meth) acrylate of the aliphatic alcohol having an amine group or a quaternary ammonium group include, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acetylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Quaternary ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt and the like.

Examples of the above (meth) acrylic acid amide or (meth) acrylic acid amide mono- or di-monosubstituted with an alkyl group having 1 to 18 carbon atoms on N include acrylamide and N-butyl. Acrylamide, N, N-dibutyl acrylamide, piperidyl acrylamide, methacryl amide, N-butyl methacryl amide, N, N-dimethyl acryl amide, N-butadecyl acryl Amides and the like can be mentioned. Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member include vinyl pyridine, vinyl pyrrolidone, vinyl N-methylpyridinium chloride, and vinyl N-ethylpyridinium chloride. And the like.

Examples of the N, N-diarylmonoalkylamine include N, N-diarylmethylammonium chloride, N, N-diarylethylammonium chloride and the like.

The polymer particles of the present invention can be obtained by polymerizing the above monomer composition by an emulsion polymerization method, a suspension polymerization method, a precipitation polymerization method, or an interfacial polymerization method (including a coacervate method). The resin particles may be mechanically pulverized into particles. If necessary, a method of associating primary particles of a polymer by using a zeta potential is also used. Preferred methods for producing polymer particles are an emulsion polymerization method, a suspension polymerization method, and a method utilizing zeta potential.

The above polymer is used in the toner in an amount of 40 to 99.9% by weight.

Further, the polymer preferably has a glass transition point of from 190 to 100 ° C, more preferably from 130 to 80 ° C, and still more preferably from 110 to 70 ° C. . When the glass transition point exceeds the upper limit, the low-temperature fixability tends to deteriorate, and when the glass transition point falls below the lower limit, the powder fluidity of the toner tends to decrease.The average particle size of the primary particles of the polymer is , Preferably from 0.11 to 10 / rrn, more preferably from 0.01 to 8 m, even more preferably from 0.01 to 5 m, particularly preferably from 0.01 to 3πι.

The zeta potential of the polymer particles is preferably set to an appropriate value when a toner is produced by an association method utilizing the zeta potential described below. Acidic polar group ^: Potential P ₅ ) at pH 5 of the containing polymer particles is -2 to 60 mV, Γ potential (Γ P ₉ ) at pH 9 is -20 to 110 OmV, and P ₅ is greater than Γ P ₉ Is preferred.

Also, the case of a basic polar group-containing particles, polymer particles ^ TP ₅ is + 20~ +10 OmV. ^ ΓΡ ₉ is the + 2 tens 6 OMV, and it Ganmaro ₅ is larger than ^ P ₉ Is desirable.

The organic pigments and organic dyes used in the present invention were treated with a surface treating agent having the same ionicity as the polymer particles used, and as a result, the absolute value of the ^ potential at pH 5 became 10 to 10 OmV. Things. By using an organic pigment and / or an organic dye treated in this manner, the reaction between the polar group in the polymer and the pigment or dye is suppressed, and as a result, the color of the gel is less than 20% of the gelation degree. It was found that a toner was obtained o

The surface treatment agent used must have the same ionicity as the polymer particles used, but may contain other types of surface treatment agents.

As the organic dye used in the present invention, a disperse dye used in a state of being dispersed in a medium is used in order to set the absolute value of the ^ electric position at pH 5 to 10 to 10 OmV by the treatment as described above. Can be

The above-mentioned organic pigments and organic dyes are not particularly limited as long as they exhibit a color other than black, and one or more organic pigments and / or organic dyes may be combined as necessary. good. Further, a metal may be contained in these organic pigments and organic dyes.

Preferred examples of these organic pigments include the following. Wear.

(A) azo pigments:

Nonzaiello-G Benzijin Yellow, Benzidin Orange, Permanent Red 4R, Pyrazolone Red, Risole Red, Brilliant Toss Powerlet G, Bon Maroon Light, etc.

(Mouth) Acid dye pigments and basic dye pigments:

Orange I I, Acid Orange R, Jaoxin, Quinoline Yellow, Tartrazine Yellow, Acid Green, Peacock Blue, Alkali Blue, and other dyes precipitated with a precipitant. Dyes such as rhodamine, magenta, makalite green, methyl violet, and Victoria blue are precipitated with tannic acid, tartar, PTA, PMA, PTMA, etc.

(C) Mordant dye pigments:

Metal salts of hydroxylanthraquinones, alizarin mudder lake Co

(2) Phthalocyanine pigment:

Phthalocyanine blue, sulfonated copper phthalocyanine, etc.

(E) Quinacridone pigments and dioxane pigments:

Quinacridone red, quinacridone bioreed, carbazole dioxazine bioreed, etc.

Other organic fluorescent pigments, aniline black, etc.

In addition, as the organic dye, a Nig mouth dye, an aniline dye, or the like is used.

The following are specific examples of suitable pigments and dyes. ₀

(1) Red pigment

C. I. Pigment red

31, 57, 81, 84, 89, 112, 122, 123, 139, 144, 149, 166, 177,

178, 190 etc.

C. I. Pigment Violet

1, 19, 38 and so on.

(2) Yellow pigment.

C. I. Pigment Yellow

6, 12, 13, 14, 17, 83, 95 and so on.

(3) Blue pigment

C.I.Pigment Blue

2, 3, 9, 14, 15, 16, 25, 60, 66 and so on. (4) Green pigment

C.I.Pigment Green

2, 7, 12, 36, 37 and so on.

(5) Red dye

C.I.Solventred

3, 16, 19, 24, 49, 52, 83, 125,

179 etc.

C.I.Solvent Violet

1, 21 and so on.

(6) Yellow dye C.I.Solvent Yellow

2, 6, 14, 15, 16, 19, 21, 25, 60,

77 etc.

C.I.Solvent Orange

2, 7, 37 and so on.

C. I. Disverziero

242 etc.

(7) Blue dye

C.I.Solven.Toble-ichi

4, 25, 40, 49, 55, 70, 83, 86 and so on.

C.I.Disperse Blue

60 etc.

Examples of surface treatment agents for treating pigments or dyes as described above include the following.

(1) Anionic surfactant, dispersant

Mixed fatty acid sodium or potassium limestone, semi-hardened tallow fatty acid sodium or potassium stone, sodium stearate, sodium oleate, castor oil limestone, sodium lauryl sulfate, potassium, ammonium, or triethanol Amine, higher alcohol sodium sulfate, sodium dodecylbenzenesulfonate, sodium or alkyl sodium alkylnaphthalenesulfonate, sodium dialkylsulfone succinate or sodium phosphate, α-alkyl phenyl phenyl ether disulfonate, sodium alkyl phosphate diethanola Min salt or potassium salt, sodium polyoxyethylene lauryl ether sulfate or triethanol Sodium salt of aromatic sulfonic acid formalin condensate such as luminamine, polyoxyethylene alkyl phenyl ether sodium sodium sodium alkane sulfonate, sodium salt of naphthalene sulfonic acid formalin condensate, polycarboxylic acid type polymer Surfactants, silicon-based surfactants, fluorine-based surfactants, etc.

(2) Nonionic surfactants and dispersants

Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene sorbitan monolaurate or monostearate, polyoxyethylene sorbitan monolaurate or monostearate Or monostearate or tristearate or monooleate or trioleate Or sesquioleate or distearate, silicon-based surfactant, fluorine-based surfactant, etc.

(3) Cationic surfactant, dispersant

Polyoxyethylene sorbate tetraoleate, coconutamine acetate, stearylamine acetate, coconutamine hydrochloride, stearylamine hydrochloride, stearylamine oleate, lauryl methylammonium chloride, stearyltrimethyl Ammonium chloride mouth ride, distearyl dimethyl ammonium chloride, alkyl base N-dimethylammonium chloride, lauryl betaine, stearyl betaine, lauryl dimethyl amine oxide, lauryl carboxymethyl hydroxyshethyl imidazolinium betaine, silicon surfactant, fluorine surfactant, etc. In addition, a surfactant of nonionic and anionic and a surfactant of nonionic and cationic can be used in one molecule.

The organic pigment and / or organic dye is used in the toner in the range of 60 to 0.1% by weight.

The production of the toner of the present invention is performed by aggregating a mixture of the polymer particles primary particles in a water-dispersed state, a surface-treated organic pigment and / or organic dye, and an optional charge control agent, a release agent, and the like. This is accomplished by making particles and further aggregating the secondary particles to form associated particles.

The form of the secondary particles constituting the associated particles, which is the toner of the present invention, is not limited as long as the present invention is not impaired. However, it is preferable that the primary particles of the polymer and the colorant be used. Secondary particles that are agglomerated with particles due to ionic bonds, hydrogen bonds, metal bonds, weak acid-weak base bonds, etc.

In addition, the form of aggregation of the associated particles is not particularly limited as long as the polymer particles and the colorant are aggregated. In general, aggregated particles are formed by associating secondary particles.Association methods using potential, coagulation, coagulation, interfacial polymerization, etc. Any of the following methods can be used. Among them, the association method is preferably used. -The average particle diameter of the secondary particles is preferably 0.05 to 12 m, more preferably 0.2 to 8 πι, and particularly preferably 0.5 to 5 ^ m. In addition, The particle size of the bright associated particles is preferably 2.5 to 12 zm, more preferably 2.5 to llm.

An example of a preferred method for producing the toner of the present invention is as follows. Pigments and / or dyes and other compounds are added to the polymer dispersion obtained by emulsion polymerization, and the mixture is uniformly dispersed.After stirring for 0.5 to 10 hours, preferably for 1 to 5 hours, polarity is maintained. The primary particles of the polymer having a group and the surface-treated organic pigment and the like aggregate to form secondary particles of 1 to 5 zm. When this dispersion is further stirred for 0.5 to 10 hours, preferably 1 to 5 hours while heating, the secondary particles further aggregate and grow into associated particles of 1 to 20 m. The obtained dispersion of the associated particles is stabilized, and further heated to a temperature higher than the glass transition point of the polymer, preferably at a temperature higher than 20 ° C. for 1 to 12 hours, preferably 1 to 10 hours. Continue stirring for hours. Then, associated particles are formed in which at least a part of the contact portion between the secondary particles in the associated particles is film-formed and fused. The dispersion liquid of the obtained associated particles is dehydrated, washed and dried to obtain a toner as the associated particles. Since such associated particles are formed by film fusion between the secondary particles, they become toners that are hardly disintegrated during storage, transportation, production of magnetic developers, and the like.

The above manufacturing method is an example of an association method using the f potential. The Γ-potential of the polymer particles and the surface-treated pigment particles is reduced by a rise in temperature, so that the aggregation and association of the secondary particles are promoted. Other methods for lowering the electric potential include controlling the pH, adding a metal salt, and the like.

The magnetic toner of the magnetic developer of the present invention is externally and internally added with a performance-imparting agent such as a fluidizing agent, a life stabilizer, and a printing durability improver as long as its performance is not impaired. It does not matter.

Preferable examples of such performance-imparting agents include metal oxides such as silica, titanium oxide, aluminum oxide, zinc oxide, cerium oxide, and magnetite, and hydrophobized products thereof, and Cd, Mn, P of stearic acid. b, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, A1, Zn salt, Cd of oleic acid, Mn, Pb, Ba, Ni, Co, S r, Cu \ Mg, Ca ゝ Fe, A1, Zn salt, Palmitic acid Cd, MnPb, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, A 1, Zn salt, Cd, Mn, Pb, Ba of linoleic acid Ni, Co, Sr, Cu, Mg, Ca, Fe, AI, Zn salt, Zn, Cd salt of ricinoleic acid Metal salts of higher fatty acids such as Pb salt of force prillic acid, Pb salt of force bronic acid, etc., titanates such as barium titanate and strontium, ultra fine powder of acrylic resin, Polyvinylidene fluoride resin, Tet Fluorine-based resins such as hydrofluoric modified styrene resins, polyvinylidene chloride 榭脂, polyvinyl chloride resin, Mera Min resins, Fuwenoru resins, Benzoguanamin resins, and urea resins such any ultrafine powder and the like.

The toner of the present invention has a low gelation degree of 2% or less. When the gelling degree exceeds 2%, the light transmittance of the toner is lowered, and good color developability cannot be obtained. The gelation degree is preferably 1.80% or less, more preferably 1.00% or less, and particularly preferably 0.50% or less.

The shape factor S value representing the shape of the toner of the present invention is preferably 100.5 to; L60, more preferably 102.0 to 155, more preferably 1 5.0 to 155, still more preferably 107.0 to 140, and particularly preferably 107.0 to 140. 1 10.0 to 135. Here, the S value is a shape factor obtained by dividing the square of the perimeter of the toner particles by the area. That is, the planar image of the toner particles is processed by an image processor or the like, the perimeter (PM) and the area (A) are calculated, and are obtained by the following equation.

S value = [(PM) ² + (4A r)] xl 00

The S value expresses the feeling of planar unevenness of the particles. The S value becomes closer to 100 as the shape of the toner particles approaches a circle (sphere), and increases as the surrounding shape becomes more complicated. Value.

When the S value is smaller than the above lower limit, the toner particles tend to be spherical, and when used as a developer, the charge amount is low, and image density is insufficient or fogging is likely to occur. Etc., and the life tends to be shortened.

In addition, if the value exceeds the above upper limit, the surface condition becomes unstable and the surface becomes stochastically non-uniform, so that when the developer is used, the charge amount is not stable and the charge amount distribution is not uniform. Thus, the above-described problems on the image are likely to occur, and the life characteristics tend to be shortened due to the generation of fine powder and the like.

Further, in the toner of the present invention, the average of the particle diameter of the toner (the average rm of 100 particles) and the average of the minimum value of the radius of curvature of the surface of each particle constituting the toner (the average of 1000 particles) rn Should have the following relationship:

1.01≤V ≤320 where V = r m / r n

2.5≤ r m≤ 16

0.05≤ r n <rm The V value is more preferably from 1.01 to 320, more preferably from 1.05 to 3 hours, and particularly preferably from 2.0 to 250. Here, the particle diameter of the toner is the distance between two circumscribed parallel lines.

The above toner preferably has a volume average particle size of 2.5 to 12 zm. The meaning of the V value here is that the aforementioned S value expresses a flat feeling of unevenness, and further expresses unevenness three-dimensionally. Such unevenness is caused by the primary particles of the polymer, the colorant particles, the charge controlling agent, and the secondary particles thereof.

Therefore, by processing the individual φ toner flat image with an image processor or the like, the unevenness of the particle surface can be quantified as a radius of curvature, and by deriving the relationship with the average particle diameter of each toner, the overall toner particles can be obtained. It is possible to express the concavo-convex feeling (especially as associated particles).

When the V value is smaller than the above lower limit, the toner particles have a substantially spherical shape with no surface irregularities and are almost spherical. As described above, when such a toner is used as a developer, the charge amount is low, and the image density is insufficient or fogging is likely to occur. Regarding the life characteristics, in the case of an electrophotographic system in which cleaning is performed with a cleaning blade, the frictional force of the toner catching the blade is extremely reduced, causing cleaning failure and the like to occur. Tend to be shorter.

When the V value is larger than the upper limit, the unevenness of the toner surface is relatively small, and when the V value is smaller than the lower limit, the behavior is very similar. Therefore, not only the above-mentioned problem is likely to occur, but also in the electrophotography of the above-described method, the frequency of catching the blade on the blade is extremely reduced, and cleaning failure is likely to occur. The color toner obtained by the present invention is a color toner excellent in color developing property due to very good transparency, excellent in color reproducibility and resolution, less fogging and scattering, and excellent in various physical properties.

A developer is produced by mixing the toner of the present invention and a magnetic carrier. For example, it is manufactured by stirring, mixing and charging 20 to 95 parts by weight of a magnetic carrier and 5 to 80 parts by weight of a toner with a V-type mixer or a ball mill.

As the magnetic carrier, iron or ferrite, which is well known, is used. Further, ferromagnetic fine particles bound with a resin can also be used.

The average particle diameter of the magnetic carrier is preferably 10 to 200, more preferably 20 to 180 m, and particularly preferably 30 to 17 Om. If the upper limit value is exceeded, clogging occurs between the doctor blade and the sleeve when restricting the spike of the developer. Therefore, it is preferable to use a particle size of 1Z2 or less, preferably 1 to 5 or less for the doctor gap.

[Example]

The following examples illustrate preferred embodiments of the present invention.

The test method used in the examples is as follows.

(A) Measurement of gel content

ASTM D2765-84 and D3351-174 were referenced. 1 g of the toner is hydraulically press-molded (press 6, 4T / 2 cmΦ, 5 min) at room temperature to form a disk-shaped tablet with a diameter of 2 cm. Wrap the tablet in a 400-mesh stainless steel wire mesh and immerse it in the acetone reflux for 7 hours. After cooling, remove the steel and air dry at room temperature for 1 hour at 50 ° C Allow to air-dry for 1 hour, weigh, and determine the acetone insoluble content as the gel content according to the following formula. w _{bb to} w _mm

Genole () x 00

^W _a a Weight of toner molded piece

W _L b: Weight of wire mesh and residue in metal steel after drying W m: Weight of wire mesh

(Mouth) Transmittance measurement method A single color toner image is printed on an OHP sheet, and the solid part with an image density I D == 1.0 or higher is manufactured by Tokyo Denshoku Co., Ltd.

Transmitted light measurement was performed with 800 MK2.

Tm is the transmission percentage at the wavelength m, and Tn is the transmission percentage at the wavelength n.If the lower value obtained by Τ = (1-1 TnZTm) x 100 is 100 to 85%,

85 for 85-70%, △ for 70-60%, x for 60-55%

The case of 55% or less was evaluated as XX. The measurement wavelength was selected as follows. M = 490 nm for cyan color n = 615 nm

For magenta color; m = 700nm

n = 540 nm

For yellow color; m = 600nm

n = 415 n m

(C) Method for evaluating color development

A solid portion image (paper) of the toner single color was taken out, and the color difference ΔΕ (in NBS unit) was measured using a color analyzer TC-1800 MK2 manufactured by Tokyo Denshoku Co., Ltd.

As the color standard, the Color Chart No. 5-1 issued by the Electrophotographic Society of Japan was used.

The color difference ΔΕ (NBS unit) between the working example and the standard product is

◎, 0 ~ 0.5

0.5 for 0.5 to 1.5

△, 1.5 to 3.0

X for 3.0 to 6.0,

X X if 6.0 or higher

Was evaluated.

(2) Copy image density evaluation method

Using a Macbeth reflection densitometer RD-914, the density of the image (solid black portion of the Electrophotographic Society Test Chart NOl-R 1975) was measured.

(E) Cover

The whiteness is measured using a color difference meter (CR-200) manufactured by Minolta Co., Ltd. Calculate color difference L, a, b and whiteness of natural paper before copying ''

KoO = l 00- [(100-L) ² + a ² + b ^ 3 1X2 Whiteness of non-image area after copying

K = l 00- [(100-L) ² + a ² + b ² ] 1 2

Calculate the fogging with the following formula

Fog (%) = KZK. xlOO

The lower the number, the better the fog. It can be judged as good at 0.5 or less, and poor at 1.0 or more.

(To) Resolution

The electrophotographic society test chart N01-R1975 was copied, and the 8.0-point resolution pattern was magnified 100 times with an optical microscope, and visually judged as follows.

5. Fine lines are reproduced, and there is almost no fogging between fine lines

4. Fine lines are reproduced, but fog is slightly recognized between thin lines. 3. Reproducibility of fine lines is somewhat poor, and fog between fine lines is somewhat large.

2. Reproduction of fine lines is poor, and there are many fogs between fine lines.

1. Thin line is not reproduced and it is a single line

The higher the number, the better the resolution. A resolution of 4 or less is considered good, and a resolution of 3 or less is bad.

(G) How to measure S and V values

The obtained toner was subjected to image processing using LUZEX 3 U manufactured by Nikon Corporation to determine the S value. At this time, the number of measured samples was 10,000, and the average value was taken as the S value. An electron micrograph (10000x) of the toner particles was applied to the same processor to determine the V value, and the average value of 1000 measured pieces was taken as the V value. Done c

(H) Particle size change

A life test (10000 sheets) was performed on the copy test of the working example and the comparative example, and the distribution of several toners in the initial developer (5% / m or less of the particle number%) and the A comparison value with the toner number distribution was taken.

At 130% or more, scattering occurs and the charge amount becomes unstable, resulting in failure.

Good at 110% or less.

(I) Visual evaluation

In the copy life test (10000 sheets), the state during life was observed and evaluated. As observation items,

(1) Poor cleaning

(2) Turn up the cleaning blade

(3) Scatter

(4) Toner accumulation point Z white point

Etc. were observed.

[Example 1]

(Preparation of acidic polar group-containing polymer resin)

Styrene monomer (ST) 82 parts

Butyl acrylate (B A) 18 parts

Acrylic acid (AA) 5 parts

The above monomer mixture

100 parts of water

Nonionic emulsifier

(Emulgen 950 manufactured by Kao Corporation) 1 copy Anion emulsifier

(Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.5 parts

The resulting mixture was polymerized at 80 ° C. for 8 hours with stirring using a persulfuric acid catalyst as a catalyst to obtain an acidic polar group-containing emulsion having a solid content of 50%.

(Preparation of surface-treated organic pigments)

Water 9 2 parts

C.I. pigment red 1 2 2 8 copies

Anion-based surface treatment agent 1

(Daiichi Kogyo Pharmaceutical Co., Ltd. Neogen R) 1 copy

Anion type surface treatment agent 2

(Formalin naphthalene sulfonate

Sodium salt of condensate, 2 parts by Demol N) manufactured by Kao Corporation

The above mixture was kept at about 25 ° C. for 2 hours while being dispersed and stirred by a disperser to obtain a mixed wave of the surface-treated organic pigment.

(Adjust toner)

The acidic polar group-containing resin emulsion 200 parts

100 parts of the organic pigment mixture

250 parts of water

The above mixture was kept at about 30 ° C for 2 hours while being dispersed and stirred by a slasher. Thereafter, the mixture was heated to 80 ° C. with further stirring and maintained for 3 hours. Observation with an optical microscope during this time revealed that the particle size of the polymer particles and the secondary particles of the organic pigment was 1.2 ^, and that the associated particles (toner particles) in which the secondary particles were associated had a particle size of about 6,5. It was confirmed to grow to jtt m. Cooled and obtained tona One was separated by a dispersion centrifuge, washed with water, and vacuum dried at 50 ° C for 10 hours. The gel content of the obtained toner was measured and found to be 0.3%. Further, as a result of image processing of this toner, the S value was 119.5 and the V value was 2.35.

To 100 parts of the obtained toner, 0.8 parts of hydrophobic silica as a fluidizing agent was added and mixed using a Henschel mixer to obtain a test toner. This toner was combined with a commercially available ferrite carrier to a toner concentration of 3% and used as a test developer. When this was subjected to a copy test using a commercially available full-color copying machine ARTAGE 800 ORE ALA manufactured by Ricoh, an image with high density and high resolution was obtained. In addition, the color development was good, and the transparency on the OHP sheet was very good. The results are shown in Tables 1 and 2.

Note the average particle diameter of the acidic polar group-containing polymer of the primary particles (particles of the resin Emarujon) is a 0.08〃M, in ^ potential ^ P ₅ gar 21 mV at pH 5, the potential P ₉ in pH9 is one 8 OMV and the average particle diameter of the organic pigments wherein the surface treatment is a 0.2 / m, was ^ photoelectric position tC ₅ gar 23mV at pH 5.

[Examples 2 and 3]

Instead of the organic pigment of Example 1, CI Pigment Yellow Y-17 is used in Example 2, CI Pigment Blue B-15: 3 is used in Example 3, and the other components are the same as in Example 1. I got When the toners of Examples 2 and 3 were put into the above-described copying machine and tested, an image having excellent color reproducibility was obtained. The results are shown in Tables 1 and 2.

[Example 4] (Basic polar group-containing polymer resin)

Styrene monomer (ST) 85 parts

Butyl acrylate (BA) 15 parts

Getylaminoethyl methacrylate (DE) 5 parts

The above monomer mixture

100 parts of water

Cationic emulsifier

(Saosol B-50 manufactured by Kao Corporation) 2 copies

Nonon emulsifier.

(Emagen 950, Kao Corporation) 1.6 copies

And mixed with an azo-based polymerization initiator (Wako Pure Chemical Industries V-50) as a catalyst at 80 ° C for 8 hours with stirring to obtain a resin emulsion containing a basic polar group with a solid content of 50%. I got

(Preparation of surface-treated organic pigments)

Water 92 parts

C. I. Pigment thread 122 8 parts

Cationic surface treatment agent

(Sanosol B50 manufactured by Kao Corporation) 1.5 parts

Nonionic surface treatment agent

(Kao Corporation Emargen 950) 0.5 parts

The above mixture was kept at about 25 ° C. for 2 hours while being dispersed and stirred by a disperser, and a dispersion liquid of a surface-treated organic pigment was obtained while being dispersed by a Gaulin homogenizer.

(Adjust toner) 200 parts of the basic polar group-containing resin emulsion

100 parts of the surface-treated organic pigment mixture

250 parts of water

The above mixture was kept at about 30 ° C for 5 hours while stirring with a slasher. Thereafter, the mixture was heated to 80 ° C. with further stirring and maintained for 3 hours. Observation with an optical microscope during this time confirmed that the associated particles of the polymer particles and the secondary particles of the organic pigment grew to about 5.2 m. After cooling, the obtained toner dispersion was separated by a centrifugal separator, washed with water, and dried in a vacuum at 50 ° C for 10 hours.

The gel content of the obtained toner was measured and found to be 0.2%. To 100 parts of the obtained toner, 1.2 parts of hydrophobic silica as a fluidizing agent was added and mixed using a pen mixer to obtain a test toner. This toner was combined with a commercially available ferrite carrier to a toner concentration of 5% and used as a test developer. When this was subjected to a copy test using a commercially available full-color copying machine ART AG E5330 manufactured by Ricoh Co., Ltd., an image with high density and high resolution was obtained. In addition, the color development was good, and the transparency was excellent when copied on an OHP sheet. The results are shown in Tables 1 and 2.

[Examples 5 and 6]

In the same manner as in Example 4, CI Pigment Yellow Y-17 was used in Example 5 instead of the organic pigment of Example 4, and CI Pigment Blue B-15: 3 was used in Example 6. To obtain a toner. When the toners of Examples 5 and 6 were put into the above-described copying machine and tested, images having excellent color reproducibility were obtained. The results are shown in Tables 1 and 2. [Examples 7, 8, 9]

Instead of the polymerized monomer of Example 1

Styrene 90 parts

2-ethylhexyl atalylate 10 parts

Methacrylic acid 8 parts

Was used to obtain a toner in the same manner as in Examples 1, 2, and 3. When this toner was put into the copying machine of Example 1 and tested, an image density having excellent color reproducibility and excellent transmittance was obtained. The results are shown in Tables 1 and 2.

[Example 10]

The organic pigment in the preparation of the surface-treated organic pigment and dye of Example 1 was used.

Organic dye C.I.

(Nippon Kayaku Co., Ltd. SRF-46)

A toner was obtained in the same manner as in Example 1 except that the organic pigment C.I. When this toner was put into the copying machine of Example 1 and tested, an image having good transparency was obtained. The results are shown in Tables 1 and 2.

[Example 11]

Organic pigment in surface preparation of organic pigment and dye of Example 1

Organic dye C.I.

(SRF-46 manufactured by Nippon Kayaku Co., Ltd.)

Further, the same stirring conditions as in Example 1 except that the stirring conditions in the toner preparation of Example 1 were maintained at about 30 ° C for 5 hours, further heated to 93 ° C, and maintained for 5 hours To obtain a toner. When this toner was put into the copying machine of Example 1 and tested, an image having good transparency was obtained. The results are shown in Tables 1 and 2.

[Comparative Example 1]

Using the same monomer composition as in Example 1, suspension polymerization was carried out using benzoyl peroxide as a catalyst to obtain a resin for toner. The organic pigment used in Example 1 was added to this resin at the same ratio without surface treatment, melt-kneaded, and pulverized with a dip mill to obtain a toner with an average particle size of 9.3 // m. Was. The gel content of this toner was 6.5%. Using this toner, a developer was prepared in the same manner as in Example 1, and a similar copy test was performed. As a result, an image having poor transparency and low resolution was obtained. The results are shown in Tables 1 and 2.

[Comparative Example 2]

An emulsion containing an acidic polar group was obtained in the same manner as in Example 1. Using an organic pigment without surface treatment, a toner was prepared in the same manner as in Example 1, and a copying test was performed. The gel content of this toner was 4.2%. The results are shown in Tables 1 and 2.

[Comparative Example 3]

The toner obtained in Comparative Example 1 was subjected to spheroidizing treatment using a high pretizer (manufactured by Nara Machinery Co., Ltd.), and a copy test was performed using this toner in exactly the same manner as in Example 1. The results are shown in Tables 1 and 2.

510

Table

Image characteristics

Tona-ichi Gel content Permeable chromogenic initial paper Resolution Life life Image density Capri degree Particle size Visual evaluation Change state "i C%) (%) (%) Husband ItE リ 0. ϋ fi 3 ◎ 〇 1.34 0.25 4 103 None

0 Δ D.4 U. ◎ ◎ 1.43 0.20 4 105 None C None ό Ό.a ◎ ◎ 1.26 0.5 5 101 Especially

4 0 Π 0 〇〇 1.44 0.40 5 104 None rr c c

0 40 ◎ ◎ 1.46 0.45 4 107 None

0 0 Π 0 ◎ ◎ 1.36 0.30 5 101 None

7 0. U U> l ◎ ◎ 1.41 0.20 5 109 Nothing in particular

8 5.8 0.35 ◎ 〇 1.35 0.40 5 108 None q 6 1 0.4 ◎ ◎ 1.29 0.20 5 102 None i 特に n J R. C 04 ◎ 〇 L32 0.25 5 102 None

11

丄丄 t ϋ · 0 Q n 45 ◎ 〇 1.36 0.45 5 101 None in particular Comparative example

1 9.3 6.5 X X Δ1.08 1.80 1 131 None

2 6.3 5 X mm 1.17 0.50 4 105 None

3 9.3 6.5 XX Δ 1.19 0.70 2 101 Tally Jung Defective Table 1 2

Claims

The scope of the claims

1. The absolute value of f potential at PH 5 is 10 to 10 by a polymer particle having an acidic polar group or a basic polar group and a treating agent containing a surface treating agent having the same ionicity as the polymer particle. The electrostatic image development is an association particle of secondary particles containing an organic pigment and Z or an organic dye treated to be OmV, and having a gelation degree of 2.0% or less. For color toner.

2. The toner according to claim 1, wherein the shape factor S value of the toner particles is 100.5 to 160.0.

3. When the average of the particle diameter of the toner obtained from the distance between the circumscribed parallel lines is rm, and the average of the minimum radii of the curvature radii on the toner particle surface of each associated particle constituting the toner is rn, and V rmZrn.

1.01≤V ≤320

2.5≤rm≤l 6

0.05 ^ r n <rm

3. The electrostatic latent image developing toner according to claim 1 or 2, wherein

4. An electrostatic image developer containing the color toner for developing an electrostatic image and a carrier.