WO2007111346A1 - 混合環状フェノール硫化物、それを用いた電荷制御剤及びトナー - Google Patents
混合環状フェノール硫化物、それを用いた電荷制御剤及びトナー Download PDFInfo
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- WO2007111346A1 WO2007111346A1 PCT/JP2007/056576 JP2007056576W WO2007111346A1 WO 2007111346 A1 WO2007111346 A1 WO 2007111346A1 JP 2007056576 W JP2007056576 W JP 2007056576W WO 2007111346 A1 WO2007111346 A1 WO 2007111346A1
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- Prior art keywords
- toner
- acid
- cyclic phenol
- cyclic
- phenol sulfide
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/09—Colouring agents for toner particles
- G03G9/0902—Inorganic compounds
- G03G9/0904—Carbon black
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09758—Organic compounds comprising a heterocyclic ring
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen
Definitions
- the present invention relates to a charge control agent used in an image forming apparatus for developing an electrostatic latent image in fields such as electrophotography and electrostatic recording, and a negatively chargeable toner containing the charge control agent About.
- an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfate, and amorphous silicon, or an organic photoreceptor using a charge generator and a charge transport agent. This is developed with toner, transferred to paper or plastic film, and fixed to obtain a visible image.
- an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfate, and amorphous silicon
- the photosensitive member has positive and negative chargeability depending on its configuration.
- development is performed with a reverse sign charging toner, while the printed part is discharged.
- reversal development is performed, development is performed with a toner having the same sign.
- the toner is composed of a binder resin, a colorant and other additives, but is generally charged to provide desirable tribocharging properties (charging speed, charge level, charge stability, etc.), stability over time, and environmental stability.
- a control agent is used. This charge control agent greatly affects the properties of the toner.
- a light-colored, preferably colorless, charge control agent that does not affect the hue is required.
- These light-colored or colorless charge control agents include metal complex salts of hydroxybenzoic acid derivatives (for example, see Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, for negatively charged toners).
- Patent Document 4 metal complex salts of anthranilic acid derivatives (for example, see Patent Documents 5 to 6), organic boron compounds (for example, see Patent Documents 7 to 8), biphenol compounds (for example, Patent Document 9) ), Force lix (n) allenic compounds (see, for example, Patent Documents 10 to 15) and cyclic phenol sulfides (for example, see Patent Document 16).
- positively chargeable toners include quaternary ammonium salt compounds (see, for example, Patent Documents 17 to 19).
- Patent Document 1 Japanese Patent Publication No. 55-042752
- Patent Document 2 Japanese Patent Laid-Open No. 61-069073
- Patent Document 3 Japanese Patent Application Laid-Open No. 61-221756
- Patent Document 4 JP-A-57-111541
- Patent Document 5 Japanese Patent Laid-Open No. 61-141453
- Patent Document 6 Japanese Patent Laid-Open No. 62-094856
- Patent Document 7 US Pat. No. 4,767,688
- Patent Document 8 Japanese Patent Laid-Open No. 1-306861
- Patent Document 9 JP-A 61-003149
- Patent Document 10 Japanese Patent No. 2568675
- Patent Document 11 Japanese Patent No. 2899038
- Patent Document 12 Japanese Patent No. 3359657
- Patent Document 13 Japanese Patent No. 3313871
- Patent Document 14 Japanese Patent No. 3325730
- Patent Document 15 Japanese Unexamined Patent Publication No. 2003-162100
- Patent Document 16 Japanese Patent Application Laid-Open No. 2003-295522
- Patent Document 17 Japanese Patent Laid-Open No. 57-119364
- Patent Document 18 JP-A-58-009154
- Patent Document 19 Japanese Patent Laid-Open No. 58-098742
- Patent Document 20 Japanese Patent Laid-Open No. 10-081680
- charge control agents are complexes or salts having metal power such as chromium and zinc, which are problems concerning waste regulations and are not necessarily safe.
- the toner cannot be completely colorless, or the charge rising speed is slow, there is a problem in the environmental stability of the charge amount at high temperature and high humidity, the charge amount itself is low, and there are many reversely charged toners.
- some have defects such as poor dispersibility and stability of the compound, and none have satisfactory performance as a charge control agent.
- An object of the present invention is to provide a novel mixed cyclic phenol sulfide and a specific cyclic phenol sulfide.
- the present invention is also particularly useful for color toners, has a charge rising speed that is high, has a high charge amount, has excellent environmental stability, and is also suitable for waste regulations. It ’s a problem!
- the object is to provide a safe charge control agent.
- Another object of the present invention is to provide a negatively chargeable toner having high charging performance using the charge control agent.
- the present invention has been obtained as a result of earnest research to achieve the above object, and has the following gist.
- Cyclic phenol sulfate represented by the general formula (1), wherein m is 8, and cyclic phenol sulfate where m is an integer other than 8.
- Mixed cyclic phenol sulfide which is a mixture of products.
- R represents a linear or branched alkyl group having 1 to 6 carbon atoms, and m is an integer of 4 to 9.
- cyclic phenol sulfides in which m is 4, 6, and 8 are mixed.
- a charge control agent comprising the above-mentioned mixed cyclic phenolic sulfate or a specific cyclic phenolic sulfate as an active ingredient.
- a toner comprising the above-mentioned mixed cyclic phenolic sulfate or a specific cyclic phenolic sulfate, a colorant and a binder resin.
- the mixed cyclic phenol sulfate of the present invention is a compound excellent in environmental stability and a compound excellent in charge control effect.
- the mixed cyclic phenol sulfate of the present invention is used as a toner. As a result, it is possible to obtain a quick rise and a high charge amount, and as a result, a clear image can be obtained.
- the charge control agent of the present invention is excellent in charge control characteristics, environmental resistance, and durability, and has good image density, dot reproducibility, and fine line reproducibility that capri has when used in toners. An image can be obtained.
- the toner containing the mixed cyclic phenolic sulfate of the present invention can maintain stable development characteristics with little variation in charging characteristics even in a high or low humidity environment.
- the charge control agent which is a mixed cyclic phenol sulfide of the present invention, has a charge amount that is higher in charge rising speed than conventional charge control agents, and has charging characteristics excellent in environmental stability. is doing. In addition, it is completely colorless, so it is useful for color toners. It does not contain metals such as chromium and zinc, which are concerned about environmental problems, and it has excellent dispersibility and stability of compounds.
- the cyclic phenol sulfide of m is 8.
- the content is preferably 1 mol% or more, more preferably 1.5 mol% or more, and particularly preferably 2 mol% or more.
- the content of cyclic phenol sulfide having m of 8 is preferably 1.5 mol% to 25 mol%, and the content of cyclic phenol sulfide having m force is 75 mol% to 98.5 mol%.
- the content of the cyclic phenol sulfide content of the cyclic phenol sulfide is 2 mol% to 15 mol 0/0, m force m is 8 is 85 mole% to 98 mole 0/0 .
- a mixture of a cyclic phenol sulfide having an m of 8 and a cyclic phenol sulfate having an m force may be used, but in addition, a cyclic phenol sulfide having an m of 5, m 1 or 2 or more of cyclic phenol sulfides in which m is 7, cyclic phenol sulfides in which m is 7 and cyclic phenol sulfides in which m is 9.
- a cyclic phenol sulfate having m of 6, 7, 8, or 9 it is also preferable to use a cyclic phenol sulfate having m of 6, 7, 8, or 9 alone.
- a cyclic phenol sulfate having m of 8 is preferably used alone.
- the term “single” means that when the total amount of the cyclic phenol sulfide is 100 mol%, the content of the cyclic phenol sulfate m of 8 is 90 mol% or more, preferably 95 mol% or more, particularly Preferably, it is substantially 100 mol%.
- linear or branched alkyl group having 1 to 6 carbon atoms represented by R in the general formula (1) include the following groups. Methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, sec butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethyl Propyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethenolevbutinore group, 2-ethinolevbutenore group, 1, 1-dimethylenobutynole group, 1,2-dimethylbutyl group, 1,3 dimethylbutyl group, 1,4 dimethylbutyl group, 2,2 dimethylbutyl group,
- the mixed cyclic phenol sulfate of the present invention can be produced by a known method (for example, see Patent Document 20).
- the charge control agent of the present invention is preferably used by adjusting the volume average particle diameter to 0.1 to 20 ⁇ m, more preferably 0.1 to LO / z m. If the volume average particle size is less than 0. m, the charge control agent that appears on the toner surface is extremely small and the desired charge control effect cannot be obtained. If the volume average particle size is greater than 20 m, the toner force is lost. This is not preferable because the charge control agent increases and adverse effects such as in-flight contamination occur.
- a method for adding a mixed cyclic phenol sulfide, which is a charge control agent used in the present invention, to a toner a method of adding a kneading agent to a binder resin together with a coloring agent, kneading, and pulverization (pulverized toner) Or a method of adding a mixed cyclic phenolic sulfate to a polymerizable monomer monomer and polymerizing it to obtain a toner (polymerized toner), which is added to the inside of toner particles in advance (internal addition); There is a method in which toner particles are produced in advance and added (externally added) to the surface of the toner particles.
- a preferable addition amount of the mixed cyclic phenol sulfate of the present invention when it is internally added to the toner particles is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 100 parts by mass of the binder resin. Used at ⁇ 5 parts by mass. Further, when externally added to the toner particles, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass. Also mechanocemi It is preferable to fix the toner particles to the surface of the toner particles.
- the charge control agent comprising the mixed cyclic phenol sulfide of the present invention as an active ingredient can be used in combination with other known negatively chargeable charge control agents.
- Preferred charge control agents to be used in combination include azo iron complexes or complex salts, azo chromium complexes or complex salts, azo manganese complexes or complex salts, azo conole complexes or complex salts, azo zirconium complexes or Complex salts, chromium complexes or complex salts of carboxylic acid derivatives, zinc complexes or complex salts of carboxylic acid derivatives, aluminum complexes or complex salts of carboxylic acid derivatives, zirconium complexes or complex salts of carboxylic acid derivatives.
- the carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-tert-butylsalicylic acid. Further, boron complexes or complex salts, negatively chargeable resin type charge control agents, and the like can be mentioned.
- the amount added is other than the charge control agent that is the mixed cyclic phenol sulfide of the present invention with respect to 100 parts by mass of the binder resin.
- the charge control agent is preferably 0.1 to: LO parts by mass.
- any known binder resin can be used.
- Polyester polymers such as vinyl polymers such as styrene monomers, acrylic acid monomers, and methacrylic acid monomers, or copolymers that have two or more of these monomers, polyol resins , Phenolic resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, etc. .
- styrene monomer acrylic acid monomer
- methacrylic acid monomer that form the vinyl polymer or copolymer are exemplified below, but are not limited thereto.
- styrenic monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylolstyrene, p-n- Aminolestyrene, p-tert-butylstyrene, p- n-hexyl styrene, p- n-octyl styrene, p- n-nonyl styrene, ⁇ - n-decyl styrene, ⁇ - n-dodecino styrene, p-methoxy Styrene such as styrene, p-chronole styrene, 3,4-dichlorostyrene, m-dinit
- acrylic monomer acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate
- acrylic acid such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and acrylic acid ester, or esters thereof.
- Methacrylic acid monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid.
- methacrylic acid such as 2-ethylhexyl, stearyl methacrylate, methanol methacrylate, dimethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate, and esters thereof.
- Examples of other monomers that form the vinyl polymer or copolymer include the following:
- Monoolefins such as ethylene, propylene, butylene and isobutylene
- Polyenes such as butadiene and isoprene
- Vinyl halides such as butyl chloride, vinylidene chloride, butyl bromide and vinyl fluoride.
- butyl esters such as vinyl acetate, propionate butyl and benzoate butyl; (5) butyl ethers such as butyl methyl ether, butyl ether and butyl isobutyl ether; (6) butyl methyl ketone; Bile ketones such as bule hexyl ketone and methyl isopropyl ketone; (7) N-bure compounds such as N-bulepyrrole, N-bullcarbazole, N-bullindole and N-bullpyrrolidone; Naphthalenes: (9) Atari Mouth-Tolyl, Metallic Mouth-Tolyl, Acrylic Acid Or (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkelluccinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride , Unsaturated dibasic acid anhydrides such as itaconic anhydride, al
- the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
- the crosslinking agent used in this case include divinylbenzene and dibutylnaphthalene as aromatic dibi-louie compounds.
- diacrylate compounds combined with an alkyl chain include ethylene glycol ditalylate, 1,3 butylene glycol ditalylate, 1,4 butanediol ditalylate, and 1,5 pentanediol ditalylate. 1,6-hexanediol ditalylate, neopentylglycol ditalylate, or a compound obtained by replacing atallate of the above compound with metatalylate.
- Diacrylate compounds combined with an alkyl chain containing an ether bond include, for example, diethylene glycol ditalylate, triethylene glycol ditalylate, tetraethylene glycol ditalylate, polyethylene glycol # 400 ditalylate, poly (ethylene glycol).
- Examples include ethylene glycol # 600 diatalate, dipropylene glycol diatalate, or those obtained by replacing the acrylate of the above-mentioned compound with meta acrylate.
- polyester type diatalylate examples include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).
- polyfunctional crosslinking agent examples include pentaerythritol triatalylate, trimethylolethane triatalylate, trimethylolpropane tritalylate, tetramethylolmethane
- crosslinking agents can be used in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of other monomer components.
- aromatic dibi-louis compounds particularly dibutylbenzene is preferred
- aromatics are also suitable for use in the toner resin for fixing and offset resistance.
- diacrylate compounds connected by a linking chain containing one group and one ether bond are preferable.
- Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2'-azobisisobutyryl-tolyl, 2,2'-azobis (4-methoxy-1,2,4). Dimethylvalero-tolyl), 2,2'-azobis (2,4 dimethylvale-tolyl), 2,2'-azobis (2-methylbutyoxy-tolyl), dimethyl-2,2'-azobisisobuty 1, 1'-azobis (1-cyclohexanecarbo-tolyl), 2- (force ruberamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4 trimethylpentane), 2 phenol 2 ' , 4'— Dimethyl-4'-methoxyvaleronitryl, 2, 2 'azobis (2 methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide and other
- the binder resin is a styrene-acrylic acid-based resin
- gel permeation chromatography hereinafter abbreviated as GP C
- THF resin component tetrahydrofuran
- the THF soluble component is also preferably a binder coagulum in which a component having a molecular weight distribution of 100,000 or less is 50 to 90%. More preferably, it has a main peak in a region having a molecular weight of 5,000 to 30,000, and most preferably in a region having a molecular weight of 5,000 to 20,000.
- the acid value of a bully polymer such as styrene-acrylic acid-based resin having a binder resin is 0.1 mgKOH / g to 100 mgKOH / g 0.1 mgKOH / g to 70 mgKOH More preferably, Zg is 0.1 mgKOHZg to 50 mgKOHZg.
- Examples of the monomer constituting the polyester polymer include the following.
- Divalent alcohol components include ethylene glycol, propylene glycol, 1,3 butanediol, 1,4 butanediol, 2,3 butanediol, diethylene glycol, triethylene glycol, 1,5 pentanediol, and 1,6 hexanediol.
- trihydric or higher alcohols include sorbitol, 1, 2, 3, 6 hexanetetrol, 1,4-sonolebitan, pentaerythritol, dipentaerythritol, tripentaerythritol. Thritol, 1, 2, 4 Butanetriol, 1, 2, 5 Pentatriol, Glycerol, 2 Methylpropanetriol, 2-Methyl-1, 2, 4 Butanetriol, Trimethylolethane, Trimethylolpropane, 1, 3, 5 Tri Examples thereof include hydroxybenzene.
- the acid component forming the polyester polymer includes benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid.
- Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkelluccinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkeny And unsaturated dibasic acid anhydrides such as succinic acid anhydride.
- Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 2,5,7 naphthalenetricarboxylic acid, 1,2,4 naphthalenetricarboxylic acid, 1,2,4 butanetricarboxylic acid, 1 , 2, 5 Monohexanetricarboxylic acid, 1,3 dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8 octanetetracarboxylic acid, emporic trimer acid, or these Anhydrides, partially lower alkyl esters, and the like.
- the molecular weight distribution of the THF-soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000. It is preferable in terms of adhesion and offset resistance.
- the THF soluble component is preferably a binder resin having a molecular weight of 100,000 or less and a component of 60 to 100%. More preferably, at least one peak is present in a region having a molecular weight of 5,000 to 20,000.
- the binder resin is polyester resin
- its acid value is preferably 0.1 mgKOHZg to 100 mgK OHZg, more preferably 0.1 mgKOHZg to 70 mgKOHZg, and more preferably 0.1 mgKOHZg to 50 mgKOHZg. ⁇ .
- the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent.
- the vinyl polymer component and the Z or polyester-based resin component contain a monomer component capable of reacting with both of these resin components.
- a monomer component capable of reacting with both of these resin components can also be used.
- the monomers that make up the polyester-based resin components include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof.
- the monomer constituting the bulle polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
- the total binder resin has 60% by mass or more of resin having an acid value of 0.1 to 50 mg KOHZg. Is preferred.
- the acid value of the binder resin component of the toner composition is determined by the following method and conforms to the basic operation ISK-0070.
- the sample should be used after removing additives other than the binder resin (polymer component) in advance, or the acid value and content of the components other than the binder resin and the crosslinked binder resin should be determined in advance. Seek out. Sample pulverized product 0.5-2. Weigh Og precisely and let the weight of the polymer component be Wg. For example, when measuring the acid value of the binder resin from toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is determined by calculation.
- the toner binder resin and the composition containing the binder resin have a glass transition temperature (Tg) of preferably 35 to 80 ° C., particularly preferably 40 to 75 °, from the viewpoint of toner storage stability. C. If Tg is lower than 35 ° C, the toner deteriorates in a high-temperature atmosphere, and offset occurs immediately upon fixing. On the other hand, when Tg exceeds 80 ° C, the fixability tends to decrease.
- Tg glass transition temperature
- Examples of the magnetic material that can be used in the present invention include (1) magnetic iron oxide such as magnetite, maghemite, and ferrite, and iron oxide containing other metal oxides. Or (2) iron, cobalt, Metals such as Kel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium Alloy with metal. (3) and mixtures thereof are used.
- magnetic materials include Fe 2 O, ⁇ —Fe 2 O, ZnFe 2 O, Y 2 Fe 2 O 3, Cd
- a particularly suitable magnetic substance is a fine powder of triiron tetroxide or ⁇ -iron sesquioxide.
- heterogeneous elements include lithium, beryllium, boron, magnesium, ano-remium, kaium, phosphorus, genoremanium, zirconium, tin, iodo, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt,- Examples include nickel, copper, zinc, and gallium.
- Preferred heterogeneous elements are also selected from magnesium, aluminum, silicon, phosphorus or zirconium forces.
- Heterogeneous elements may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as oxides, or may be oxidized or oxidized on the surface. It may be present as a porridge, but it is preferably contained as an oxide!
- the different elements can be incorporated into the particles by mixing the salts of the different elements at the time of magnetic substance production and adjusting the pH. Further, it can be deposited on the particle surface by adjusting the pH after the formation of the magnetic particles or adjusting the pH by adding a salt of each element.
- the amount of the magnetic substance used is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the binder resin.
- These magnetic materials preferably have a number average particle size of 0.1 to 2 / ⁇ ⁇ , more preferably 0.1 to 0.5 m. The number average diameter can be determined by measuring a photograph taken with a transmission electron microscope with a digitizer.
- magnetic characteristics of the magnetic material magnetic characteristics at 10K Oersted application are A coercive force of 20 to 150 enorested, saturated magnetic layer of 50 to 200 emu / g, residual magnetic layer of 2 to 20 emu Zg is preferable.
- the magnetic material can also be used as a colorant.
- the colorant that can be used in the present invention includes black or blue dye or pigment particles in the case of a black toner.
- black or blue pigments include carbon black, ashlin black, acetylene black, phthalocyanine blue, and indanthrene blue.
- black or blue dyes include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.
- magenta colorants include condensed azo compounds, diketopyropyronic compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds Perylene compounds are used.
- pigment-based magenta colorants CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 184, 202, 206, 207, 209, CI Pigment Neutlet 19, CI knot red, 1 2, 10, 13, 15, 23, 29, 35, methyl violet rake, eosin rake, rhodamine rake B, alizarin rake, brilliant carmine rake 3B.
- the pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
- dye-based magenta colorants include CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, CI Dino Single Thread 9, CI solvent violet 8, 13, 14, 21, 27, oil soluble dyes such as CI disperse violet 1, CI basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, CI basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 Basic dye power S
- cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone, Basic dye lake compounds can be used.
- pigment-based cyan colorants CI pigment blue 2, 3, 15, 16, 17, CI knot blue 6, CI acid blue 45, or phthalimidomethyl groups 1 to 5 on the phthalocyanine skeleton This is a single-substituted copper phthalocyanine pigment.
- CI pigment green 7, 12, 36, 37, 38 and other green colorants can be blended and used.
- Typical examples of phthalocyanine dyes include C. I. Solvent Blue 25, 55, 70, C. I. Direct Benoray 25, 86, Anole Power Rib Nole Lake, Victoria Benore Lake, etc.
- yellow colorant a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, or a arylamide compound is used.
- yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 1.
- the amount of the colorant used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
- the toner of the present invention may be mixed with a carrier and used as a two-component developer.
- a carrier such as ordinary ferrite and magnetite can be used.
- the resin-coated carrier is made of a coating material that is a resin that coats (coats) the carrier core particles and the surface of the carrier core particle.
- styrene monoacrylate is used as the resin used in the coating material.
- any resin that can be used as a coating (coating) material for a carrier such as resin or polyphenylene sulfide resin is acceptable. These of ⁇ alone or can be used more [0056]
- a Noinder type carrier core in which magnetic powder is dispersed in rosin can also be used.
- the resin core is dissolved or suspended in a solvent and adhered to the coated carrier core, or simply in a powder state.
- a mixing method can be applied.
- the proportion of the resin coating material relative to ⁇ co Tokyaria may be suitably determined, but ⁇ Kotokiya preferably to the rear is 0.01 to 5 mass 0/0, more preferably from 0.1 to 1% by weight Good.
- Examples of use in which a magnetic material is coated with a coating (coating) agent of two or more kinds of mixtures are as follows: (1) dimethyldichlorosilane and dimethylsilicone oil (mass ratio of 1 to 100 parts by mass of fine titanium oxide powder) : 2) treated with 12 parts by mass of mixture, (2) 100 parts by mass of fine silica powder treated with 20 parts by mass of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) It is done.
- styrene-methyl methacrylate copolymer a mixture of fluorine-containing resin and styrene copolymer, or silicone resin is preferably used, and silicone resin is particularly preferable.
- Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and styrene methyl methacrylate copolymer, polytetrafluoroethylene and styrene-methacrylic acid.
- silicone resin examples include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with the silicone resin.
- oxides such as ferrite, iron-rich ferrite, magnetite, and gamma iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used.
- the elements contained in these magnetic materials are iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bis. Examples include mass, calcium, manganese, selenium, titanium, tungsten, and vanadium.
- Preferable examples include copper-zinc-iron ferrites mainly composed of copper, zinc and iron components, and manganese magnesium monoiron ferrites mainly composed of manganese, magnesium and iron components.
- the resistance value of the carrier is preferably adjusted to 10 6 to 10 1 Q Q 'cm by adjusting the degree of unevenness of the surface of the carrier and the amount of the resin coated.
- a carrier having a particle size of 4 to 200 / ⁇ ⁇ can be used.
- the force is preferably 10 to 150 ⁇ m, more preferably 20 to LOO ⁇ m.
- the coconut resin carrier preferably has a 50% particle size of 20 to 70 ⁇ m.
- the two-component developer it is preferable to use 1 to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier. It is good to use at 0 parts by mass.
- the toner of the present invention may further contain a wax.
- the waxes used in the present invention are as follows.
- aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sazol wax.
- Oxides of aliphatic hydrocarbon waxes such as acid-polyethylene wax. Or a block copolymer thereof.
- Plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax.
- Animal waxes such as beeswax, lanolin and whale wax.
- Waxes mainly composed of fatty acid esters such as mineral waxes such as ozokerite, ceresin, and petrolatum, montanate ester waxes, and castor waxes. Examples include those obtained by partially deoxidizing fatty acid esters such as deoxidized carnauba wax.
- waxes further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group.
- Unsaturated fatty acids such as brannic acid, eleostearic acid, and phosphoric acid.
- Saturated alcohols such as stearyl alcohol, eicosinorenoreconole, behe-noreanoreconole, force noreupinoreanoreconole, serinolecohol, mesylalcohol, or long-chain alkyl alcohol.
- a polyhydric alcohol such as sorbitol.
- Fatty acid amides such as linoleic acid amide, olefinic acid amide, lauric acid amide.
- Methylene bis strength purinamide ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylenebisstearic acid amides.
- Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, ⁇ '-dioleyl adipic acid amide, ⁇ , N'-dioleyl sepasinic acid amide.
- m Aromatic bisamides such as xylene bisstearic acid amide and N ,, '-distearylisophthalic acid amide.
- Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate.
- a partial ester compound of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol. Examples thereof include methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.
- polyolefin obtained by radical polymerization of olefin under high pressure is used.
- Synthetic waxes using a compound having 1 carbon atom as a monomer and hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group.
- hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group.
- these waxes include waxes graft-modified with butyl monomers such as styrene, maleic acid esters, acrylates, methacrylates, and maleic anhydride.
- these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, and low molecular weights.
- Solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities are preferably used.
- the wax used in the present invention preferably has a melting point strength of S70 to 140 ° C, and more preferably 70 to 120 ° C in order to balance the fixing property and the offset resistance. 70 ° C If the temperature is lower than 140 ° C., the anti-blocking property tends to be lowered.
- the plasticizing action and the releasing action which are the actions of the wax, can be expressed simultaneously.
- Examples of the wax having a plasticizing action include a wax having a low melting point, a structure having a branch on the structure of the molecule or a structure having a polar group, and a wax having a releasing action.
- Examples of the wax and molecular structure having a high melting point include those having a linear structure and those having no functional group.
- Examples of use include a combination of two or more different waxes having a difference in melting point of 10 ° C to 100 ° C, and a combination of polyolefin and graft-modified polyolefin.
- the melting point of at least one of the waxes is preferably 70 to 120 ° C., more preferably 70 to 100 ° C., which tends to easily exert the function separation effect.
- relatively waxes having a branched structure those having a polar group such as a functional group, and those modified with a component different from the main component exhibit plasticity, and have a more linear structure.
- Nonpolar or non-denatured ones that do not have functional groups or functional groups exhibit mold release action.
- Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene; combinations of polyolefins and graft modified polyolefins; alcohol waxes, fatty acid waxes or esters A combination of wax and hydrocarbon wax; a combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax; a combination of Fischer-Tropsch wax and Porrio olefin wax; a combination of paraffin wax and microcrystalline wax; a carnauba wax; Candelilla wax, rice wax or A combination of montan wax and hydrocarbon wax can be mentioned.
- the peak top temperature of the maximum peak is in the region of 70 to 110 ° C in the endothermic peak observed in the DSC measurement of the toner. More preferably, it should have a maximum peak in the region of 70 to 110 ° C. This makes it easier to balance toner storage and fixability.
- the total content of these waxes is preferably 0.2 to 20 parts by weight, more preferably 0.5 to It is effective to be used in the LO mass part.
- the melting point of the wax is the melting point of the wax, which is the peak top temperature of the endothermic peak of the wax measured by DSC.
- the DSC curve used in the present invention is the DSC curve measured when the temperature is raised at a temperature rate of 10 ° C Zmin after the temperature is raised and lowered once and the previous history is taken.
- a fluidity improver may be added to the toner of the present invention.
- the fluidity improver improves the fluidity of the toner (becomes easier to flow) when added to the toner surface.
- carbon black fine powder of vinylidene fluoride, fluorinated resin powder such as polytetrafluoroethylene fine powder
- wet-process silica fine-process silica such as dry-process silica
- fine powder unoxidized titanium fine powder unalumina
- examples thereof include treated silica, treated titanium oxide, and treated alumina, which are surface-treated with a silane coupling agent, a titanium coupling agent, or silicone oil.
- the particle size of the fluidity improver is preferably an average primary particle size of TO. 001 to 2111, and particularly preferably 0.002 to 0.
- a preferable fine powder silica is a fine powder produced by a gas phase acid of a silicon halogen-containing material, and is so-called dry silica or fumed silica.
- Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names.
- AEROSIL -130, -300, -380,-TT600,-MOX170, -MO X80, -COK84 Ca-0-SiL (CABOT, same applies below)-M-5, -MS —7, —MS—75, —HS—5, —EH—5, Wacker HDK (manufactured by WACKER-CHEMI EGMBH Co., Ltd., the same shall apply) —N20 V15, N20E, T30, — T40: D—C FineSilica ( Dowko Jung Co., Ltd.): Fransol (Fransil Co., Ltd.).
- a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halide compound is more preferable.
- the treated silica fine powders those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80% are particularly preferred.
- Hydrophobization is provided by chemical or physical treatment with an organic silicon compound that reacts or physically adsorbs with fine silica powder.
- a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organic silicon compound is preferable.
- Examples of the organic silicon compound include hydroxypropyltrimethoxysilane, phenoltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, and vinyl.
- the flowability improver is preferably one having a number average particle diameter of 5 to LOONm, more preferably 5 to 50 nm.
- a preferable application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.
- toner of the present invention as other additives, photoconductor 'carrier protection, improvement in cleaning property, thermal property' electrical property 'physical property adjustment, resistance adjustment, softening point adjustment, fixing rate improvement
- photoconductor 'carrier protection improvement in cleaning property
- thermal property' electrical property 'physical property adjustment improvement in resistance adjustment
- softening point adjustment fixing rate improvement
- metal soaps fluorosurfactants
- dioctyl phthalate tin oxide
- zinc oxide zinc oxide
- carbon black antimony oxide, etc.
- conductivity imparting agents titanium oxide, aluminum oxide, alumina, etc.
- Inorganic fine powder can be added as necessary. These inorganic fine powders may be hydrophobized as necessary.
- lubricants such as polytetrafluoroethylene, zinc stearate and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and those having a polarity opposite to that of toner particles
- abrasives such as cesium oxide, silicon carbide, and strontium titanate
- anti-caking agents such as sodium bicarbonate
- black fine particles can also be used as a developability improver.
- These additives are silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organic substances for the purpose of charge amount control and the like. It is also preferable to treat with a treatment agent such as a key compound or various treatment agents.
- the charge control agent of the present invention is sufficiently mixed together with the additives and toner as described above by a mixer such as a Henschel mixer, Bonoreminore, Nauter mixer, V-type mixer, W-type mixer, or super mixer.
- a mixer such as a Henschel mixer, Bonoreminore, Nauter mixer, V-type mixer, W-type mixer, or super mixer.
- the target toner for electrostatic charge development can also be obtained by stirring and externally treating the toner particle surface uniformly.
- the toner of the present invention is thermally stable and can maintain stable charging characteristics that are not subject to thermal changes during the electrophotographic process.
- the charge distribution of the fresh toner is very uniform. That Therefore, in the toner of the present invention, even in the untransferred and recovered toner (waste toner), almost no change is observed in the saturated triboelectric charge amount and the charge distribution as compared with the fresh toner.
- a polyester resin containing an aliphatic diol is selected as a binder resin, or a metal-crosslinked styrene / acrylic acid copolymer is used.
- the difference between the fresh toner and the waste toner can be further reduced by producing the toner by a method in which a binder resin is used and a large amount of polyolefin is added thereto.
- the toner of the present invention can be produced by a known production method.
- the above-described toner constituent materials such as binder resin, charge control agent, and colorant are sufficiently mixed by a mixer such as a ball mill.
- a method (pulverization method) obtained by kneading the mixture well with a heating kneader such as a hot roll kneader, cooling and solidifying, pulverizing and classifying is preferable.
- a toner is produced by a polymerization method in which a predetermined material is mixed with a monomer that constitutes the binder resin to form an emulsion or suspension, followed by polymerization to obtain a toner, a core material, and a shell material.
- the so-called microcapsule toner can be manufactured by a method in which a predetermined material is contained in the core material, the shell material, or both of them.
- the toner of the present invention can be produced by sufficiently mixing the desired additive and toner particles with a mixer such as a Henschel mixer.
- a binder resin, a colorant, a charge control agent, and other necessary additives are uniformly mixed.
- a known stirrer such as a Henschel mixer, a super mixer, or a ball mill can be used.
- the obtained mixture is hot-melt kneaded using a closed-type uni- der or a single-screw or twin-screw extruder.
- the kneaded product is coarsely pulverized using a crusher and a non-mill mill, and further pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill.
- an air classifier for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) class microplex, a DS separator, etc., classification is performed to a predetermined particle size.
- a high-speed agitator such as a Henschel mixer or a super mixer. Stir and mix.
- the toner of the present invention can also be produced by a suspension polymerization method or an emulsion polymerization method.
- a polymerizable monomer, a colorant, a polymerization initiator, a charge control agent, and, if necessary, a crosslinking agent and other additives are uniformly dissolved or dispersed to form a monomer.
- a suitable stirrer or disperser such as a homomixer, homogenizer, atomizer, microfluidizer, in a continuous phase containing the monomer composition and the dispersion stabilizer, such as an aqueous phase.
- Disperse using a one-component fluid nozzle, gas-liquid fluid nozzle, electric emulsifier Preferably, granulation is performed by adjusting the stirring speed, temperature, and time so that the droplets of the polymerizable monomer composition have a desired toner particle size.
- the polymerization reaction is carried out at 40 to 90 ° C. to obtain toner particles having a desired particle size.
- the resulting toner particles are washed, filtered and dried.
- the above-described method can be used for the external addition treatment after the production of the toner particles.
- the average particle diameter is 0.1 to 1.
- O / zm which is excellent in uniformity compared with the particles obtained from the suspension polymerization method described above, but depending on the case. Is to make particles grow by adding a polymerizable monomer after using emulsified particles as the core, V loose seed polymerization, or the method of coalescing and fusing the emulsified particles to an appropriate average particle size. You can also.
- the production by these polymerization methods does not require a pulverization step, so that it is not necessary to impart brittleness to the toner particles. Further, a large amount of low soft spot material that has been difficult to use by the conventional pulverization method is used. Therefore, the selection range of materials can be expanded. Since the release agent and colorant, which are water-phobic materials, are hardly exposed on the toner particle surface, contamination of the toner carrying member, the photoconductor, the transfer roller and the fixing device can be reduced.
- the toner of the present invention By producing the toner of the present invention by a polymerization method, characteristics such as image reproducibility, transferability, and color reproducibility can be further improved, and the toner particle size can be reduced to cope with minute dots. And a toner having a sharp particle size distribution can be obtained relatively easily.
- the polymerizable monomer used when the toner of the present invention is produced by the polymerization method a vinyl polymerizable monomer capable of radical polymerization is used.
- a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer may be used. it can.
- Monofunctional polymerizable monomers include styrene, a-methyl styrene, 13-methyl styrene, o-methylol styrene, m-methylol styrene, p-methylol styrene, 2, 4-dimethyl styrene, p- Styrenic polymerizable monomers such as n-butynole styrene, p-tert-butynole styrene, p-n-hexinoless styrene, p-phenol styrene; methyl acrylate, ethyl acrylate, n-propyl acrylate , Isopropyl acrylate, n-butinorea acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate
- Water-soluble initiators include ammonium persulfate, potassium persulfate, 2, 2'-azobis (N, ⁇ '-dimethyleneisobutyroamidine) hydrochloride, 2, 2'-azobis ( 2-aminodipropane) hydrochloride, azobis (isobutylamidine) hydrochloride, 2,2'-azobisisobutyric-tolylsulfonate, ferrous sulfate or hydrogen peroxide.
- 2, 2'-azobis N, ⁇ '-dimethyleneisobutyroamidine hydrochloride
- 2-aminodipropane 2-aminodipropane
- azobis isobutylamidine hydrochloride
- 2,2'-azobisisobutyric-tolylsulfonate ferrous sulfate or hydrogen peroxide.
- the polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the polymerizable monomer, and may be used alone or in combination.
- the dispersant used when producing the polymerized toner include, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate.
- Aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina I can give it.
- organic compounds examples include polybulal alcohol, gelatin, methinoresenorelose, methinorehydroxypropenoresenorelose, ethinoresenorelose, sodium salt of canoleboxymethylcellulose, and starch. These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- the inorganic compound may be produced under high-speed stirring in a dispersion medium. I'll do it.
- the toner obtained by the polymerization method tends to have less irregularities on the toner particles than the toner obtained by the pulverization method without any special treatment, and is irregular, so that the electrostatic latent image carrier and the toner As a result, the toner adhesion is increased, and as a result, a higher image density and a higher quality image can be obtained with less in-machine contamination.
- the toner particles are dispersed in water and heated, a hot water bath method in which the toner particles pass through a hot air current, or a mechanical impact method in which mechanical energy is applied and processed.
- Effective devices for reducing the degree of unevenness include a Mechano-Fusion System (made by Hosokawa Micro Corporation) using a dry mechanochemical method, an I-type jet mill, and a hybridizer that is a mixing device with a rotor and liner ( Nara Machinery Co., Ltd.), and Henschel mixer, which is a mixer having high-speed stirring blades.
- the average circularity (C) is the total number of particles obtained by calculating the circularity (Ci) according to the following equation (2) and then measuring the total circularity of all particles measured as indicated by the following equation (3). It means the value divided by (m).
- the circularity (Ci) is measured using a flow particle image analyzer (for example, FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.).
- the measurement method is to prepare a dispersion in which about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a non-ionic surfactant is dissolved, and the dispersion is irradiated with ultrasonic waves (20 kHz, 50 W) for 5 minutes.
- the average circularity value is preferably 0.955 to 0.990 force S, and more preferably, a phenomenon in which, when toner particles are adjusted to 0.960 to 0.985, the transfer residual toner increases. Tends to be difficult to cause re-transfer.
- a micron sizer is used from the viewpoint of image quality and toner productivity.
- the toner particle diameter is preferably 2 to 15 / z m in terms of volume average particle diameter. More preferably, it is 3 to 12 m.
- the average particle size exceeds 15 m, the resolution and sharpness tend to be dull, and when the average particle size is less than 2 m, the resolution is good, but due to the poor yield during toner production. There is a tendency to cause health problems such as high cost problems, toner scattering in the machine, and skin penetration.
- the particle content of 2 m or less is 10 to 90% based on the number by particle size measurement using a Coulter counter (TA- TA manufactured by Coulter Co., Ltd.). It is desirable that the content of particles of 12.7 m or more is 0-30% by volume! /.
- the specific surface area of the toner is preferably 1.2 to 5.
- the specific surface area is measured using, for example, a BET specific surface area measuring device (for example, Flo W SorbII2300, manufactured by Shimadzu Corporation), and the toner surface for 30 minutes at 50 ° C. After desorbing the adsorbed gas, it is cooled rapidly with liquid nitrogen, re-adsorbed with nitrogen gas, and heated again to 50 ° C. The degassing capacity at this time is defined as the value obtained.
- the apparent specific gravity was measured using, for example, a powder tester (for example, manufactured by Hosokawa Micron Corporation).
- a powder tester for example, manufactured by Hosokawa Micron Corporation.
- 0.2 to 0.6 g / cm 3 is preferable.
- 0.2 to 2 Og / cm 3 is preferable although it depends on the kind and content of the magnetic powder.
- the true specific gravity in the case of the non-magnetic toner is preferably 0.9 to 1.2 g / cm 3.
- the magnetic toner it depends on the kind and content of the magnetic powder. 9-4. Og / cm 3 is desirable.
- the true specific gravity of the toner is calculated as follows. Accurately weighed toner 1. OOOg, put Re this tablet molding machine of 10 mm [Phi, to compress molded under pressure of 200 kgf / cm 2 under vacuum. The height of this cylindrical molded product is measured with a micrometer, and the true specific gravity is calculated from this.
- the fluidity of the toner is defined by, for example, a flow angle of repose and a static angle of repose by a repose angle measuring device (for example, manufactured by Tsutsui Rika Co., Ltd.).
- the flow angle of repose is preferably 5 to 45 degrees in the case of the electrostatic charge developing toner using the charge control agent of the present invention.
- the rest angle of repose is preferably 10-50 degrees.
- the average value of the shape factor (SF-1) in the case of the pulverized toner is 100 to 400, and the average value of the shape factor 2 (SF-2) is preferably 100 to 350.
- SF-1 and SF-2 indicating the shape factor of the toner are 1000 times using, for example, an optical microscope (for example, BH-2 manufactured by Olinos Co., Ltd.) equipped with a CCD camera.
- the enlarged toner particle group is sampled so that there are about 30 in one field of view, and the obtained image is transferred to an image analyzer (for example, Luzettas FS manufactured by Nireco Corporation).
- the shape factor was calculated by repeating the process until it became individual.
- the shape factor (SF-1) and shape factor 2 (SF-2) are calculated using the following formula.
- SF-1 represents the strain of a particle, and the closer the particle is to a sphere, the larger the value is, the closer it is to 100.
- SF-2 represents the unevenness of the particle. The closer the particle is to a sphere, the larger the value, the closer to 100 the shape of the particle is.
- the toner of the present invention has a volume resistivity of 1 X 10 12 to 1 X in the case of a non-magnetic toner.
- the toner volume resistivity is obtained by compression-molding toner particles to prepare a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and setting this on a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.).
- a high insulation resistance meter for example, 4339A manufactured by Hewlett-Packard Co., Ltd.
- the toner of the present invention the dielectric loss tangent of the toner is, in the case of a non-magnetic toner 1.
- the volume resistivity of the toner in this case is determined by compressing and molding toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, setting this on a solid electrode, and an LCR meter (for example, Hewlett-Packard) It is defined as the dielectric loss tangent value (Tan ⁇ ) obtained when measuring at a measurement frequency of 1 ⁇ and a peak-to-peak voltage of 0.1 KV using 4284A).
- the toner of the present invention desirably has an Izod impact value of 0.1 to 30 kg 'cmZcm.
- the Izod impact value of the toner is measured in accordance with JIS standard K-7110 (hard plastic impact test method) by heat-melting the toner particles to produce a plate-shaped test piece.
- the toner of the present invention preferably has a toner melt index (Ml value) of 10 to 150 g / 10 min.
- the melt index (Ml value) of the toner is measured according to JIS standard K-7210 (Method A). In this case, the measurement temperature is 125 ° C and the load is 10 kg.
- the toner of the present invention desirably has a 4mm temperature drop of 90 to 220 ° C, which is desirable for the melting start temperature of the toner of 80 to 180 ° C.
- the toner melting start temperature is obtained by compression-molding the toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using this a thermal melting characteristic measuring device such as a flow tester (for example, Shimadzu Corporation). CFT—5 OOC) and melting starts when the load is measured at 20 kgf / cm 2.
- the temperature when the piston drops 4 mm is defined as the 4 mm drop temperature.
- the toner of the present invention preferably has a glass transition temperature (Tg) of 35-80 ° C, more preferably 40-75 ° C.
- Tg glass transition temperature
- the glass transition temperature of the toner is measured using a differential thermal analysis (hereinafter abbreviated as DSC) device, and the peak value of the phase change that appears when the temperature is raised at a constant temperature, rapidly cooled, and reheated. Define what you want more.
- DSC differential thermal analysis
- the endothermic peak observed in the DSC measurement of the toner of the present invention preferably has a maximum peak peak temperature in the region of 70 to 120 ° C.
- the melt viscosity of the toner is preferably 1000 to 50000 boise, more preferably 1500 to 38000 boise.
- the toner melt viscosity is obtained by compressing and molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, which is then measured by a thermal melting property measuring device such as a flow tester (CFT-500C manufactured by Shimadzu Corporation). ) to set, it is defined as a value measured at a load 20kgfZcm 2.
- the solvent-dissolved residue of the toner of the present invention is preferably 0 to 30% by mass as THF-insoluble, 0 to 40% by mass as insoluble in ethyl acetate, and 0 to 30% by mass as insoluble in chloroform. Good.
- the solvent-dissolved residue is obtained by uniformly dissolving Z or dispersing toner lg in 100 ml of each solvent of THF, ethyl acetate and chloroform, and filtering the solution Z or dispersion, and drying the filtrate. Quantify and use this value to calculate the percentage of insoluble matter in the organic solvent in the toner.
- the toner of the present invention can be used in a one-component developing method which is one of image forming methods.
- the one-component developing method is a method for developing a latent image by supplying a thinned toner to a latent image carrier.
- Toner thinning usually includes a toner conveying member, a toner layer thickness regulating member, and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member, and the toner layer thickness regulating member and the toner conveying member abut each other. Is done using the equipment
- the two-component development method uses a toner and a carrier (having a role as a charge imparting material and a toner conveying material), and the carrier is made of the above-mentioned magnetic material or glass bead.
- the developer toner and carrier
- the developer is agitated by the agitating member, generates a predetermined amount of charge, and is conveyed to the development site by a magnet roller or the like.
- developer is held on the roller surface by magnetic force, and a magnetic brush whose layer is regulated to an appropriate height by a developer regulating plate or the like is formed.
- the developer moves on the roller and makes contact with the electrostatic latent image holder or face it in a non-contact state at a fixed interval to develop and visualize the latent image.
- a driving force for the toner it is possible to obtain a driving force for the toner to fly through a space of a constant interval by generating a direct current electric field between the developer and the latent image holding member. It can also be applied to a method of superimposing alternating current to develop an image.
- the charge control agent of the present invention is also suitable as a charge control agent (charge enhancing agent) in a coating for electrostatic powder coating.
- the coating for electrostatic coating using this charge enhancer is excellent in environmental resistance, storage stability, especially thermal stability and durability, has reached a coating efficiency of 100%, and is a thick film with no coating defects. Can be formed.
- a 1L four-necked flask equipped with a stirrer, condenser, thermometer and gas inlet tube was charged with 130.3 g of 4-tertbutylphenol, 10.9 g of elemental sulfur and 28.3 g of potassium hydroxide. Hold 40 ml of tetraethylene glycol dimethyl ether and stir in a nitrogen stream, keep at 130 ° C, react for 2 hours while removing water and hydrogen sulfide generated in the reaction, and further increase the temperature to 180 ° C for 4 hours. Then, water and hydrogen sulfide produced by the reaction were removed and the reaction was carried out forcefully.
- the reaction mixture was cooled to room temperature, to which 150 Oml of jetyl ether was added and hydrolyzed with dilute sulfuric acid of ImolZL. The organic layer was separated and concentrated to dryness to obtain 124.8 g of a reaction mixture.
- reaction mixture was cooled to room temperature, 500 ml of toluene and jetyl ether were added thereto, and hydrolyzed with dilute sulfuric acid of ImolZL.
- the mixture obtained by separating the organic layer and concentrating to dryness was purified by column chromatography (carrier: silica gel 5 kg, eluent: hexane Z chloroform) to obtain the mixed cyclic phenolic sulfate of the present invention. 46. 8g was obtained.
- the structure of the mixed cyclic phenol sulfate of the present invention was determined by LCZMS measurement.
- the measurement conditions for LC ZMS are as follows.
- (L) HPLC measurement conditions, apparatus: Waters 2695, column: Shiseido Capsule Pack C18ACR (5, inner diameter 4.6, column length 250 mm), column temperature: 40 ° C, mobile phase: tetrahydrofuran (hereafter Z acetonitrile Z water Z trifluoroacetic acid 450 ⁇ 400 ⁇ 150 ⁇ 2 ( ⁇ , ⁇ / ⁇ / ⁇ ), flow rate: 1.
- T IC total ion chromatography
- the mixture obtained by the above method was purified by recrystallization with THFZ Kuroguchi form force. It has been clarified that the mixed cyclic phenol sulfate of the present invention obtained by purification is the following mixture.
- the reaction mixture was cooled to room temperature, hydrolyzed by adding 80 ml of 3 mol ZL sulfuric acid aqueous solution, and then 200 ml of a mixed solvent of isopropyl alcohol Z water (88Z12, vZv) was added to precipitate crystals.
- the crystals are removed by filtration, and the obtained crystals are washed twice with 200 ml of a mixed solvent of isopropyl alcohol Z water (88Z12, vZv) and 240 ml of water, and further with 200 ml of a mixed solvent of isopropyl alcohol Z water (88Z12, vZv). did. After drying at 120 ° C. under reduced pressure, 113.2 g of crude crystals were obtained.
- HPLC high performance liquid chromatograph
- the crude crystal is I ⁇ 3 ⁇ 4ert butyl in the general formula (1)
- the cyclic tetramer which is m force is 96.1% in the peak area ratio
- R is tert — Cyclic octamer with butyl and m of 8 is a mixture with a peak area ratio of 3.6%. And became a force.
- molar ratio it is 97.7 mol% cyclic tetramer and 2.3 mono% cyclic octamer.
- Example 2 50 g of the crude crystals obtained in Example 2 were dispersed in THFlOOml and stirred overnight at room temperature. The crystals were removed by filtration and further washed with 45 ml of THF. The filtrate obtained by filtering the crystals and the washing solution were combined, concentrated under reduced pressure using an evaporator, and then dried to obtain 7.4 g of brown crude crystals. This brown crude crystal 7. Og was dispersed in 106 ml of toluene and stirred overnight at room temperature. The crystals were removed by filtration and further washed with 10 ml of toluene to obtain 2.6 g of yellowish white crystals.
- Fig. 7 shows the TIC chart of the obtained cyclic octamer (TC8A).
- the synthesis was carried out by the method described in JP-A 2003-295522. That is, in a 1L four-necked flask equipped with a stirrer, condenser, thermometer and gas inlet tube, 113 g of 4-tert-butylphenol, 36 g of simple sulfur and 7.5 g of sodium hydroxide, 19 g of tetraethylene glycol dimethyl ether The mixture was gradually heated to 230 ° C over 4 hours with stirring under a nitrogen atmosphere, and further stirred for 2 hours.
- Fig. 8 shows a TIC chart of the obtained cyclic phenolic sulfate.
- Comparative Compound 2 a compound described in JP-A 2003-295522 (Compound Example E: see the following figure) was synthesized. The synthesis was performed by the method described in JP-A 2003-295522. That is, to a 2 L four-necked flask equipped with a stirrer, a condenser, and a thermometer, 20 g of Comparative Compound 1, 1 L of acetone, 24 g of KCO, and 260 ml of bromoacetate were sequentially added.
- Fig. 9 and Fig. 10 show the TIC chart and MS chart of the obtained cyclic phenolic sulfate, respectively.
- styrene-acrylic acid-based copolymer resin (CPR-100 manufactured by Mitsui Chemicals, Inc.), 1 part of mixed cyclic phenolic sulfate synthesized in Example 1 or 3, carbon black (manufactured by Mitsubishi Chemical Corporation) 5 parts of MA-100) were melt-mixed by a heating and mixing apparatus at 110 ° C, and the cooled mixture was coarsely framed with a non-mer mill. Further, the fine powder frame was formed by a jet mill, followed by classification to obtain a black toner having a volume-based average particle diameter of 10 ⁇ 0.5 m.
- Example 1 For comparison, instead of the mixed cyclic phenol sulfide synthesized in Example 1 in place of the compound synthesized in Comparative Example 1 (Compound Example A), a toner was prepared under the same conditions as in Example 4 and its charge was reduced. Was measured. The results are summarized in Table 1.
- Example 1 For comparison, instead of the mixed cyclic phenol sulfide synthesized in Example 1 in place of the compound synthesized in Comparative Example 2 (Compound Example E), a toner was prepared under the same conditions as in Example 4 and its charge was Was measured. The results are summarized in Table 1.
- Example 1 For comparison, instead of the compound cyclic phenol sulfide synthesized in Example 1 in place of the compound synthesized in Comparative Example 1 (Compound Example A), a toner was prepared under the same conditions as in Example 5 and its charge amount was Was measured. The results are summarized in Table 1. The results are summarized in Table 1.
- Example E For comparison, instead of the compound cyclic phenol sulfide synthesized in Example 1 in place of the compound synthesized in Comparative Example 2 (Compound Example E), a toner was prepared under the same conditions as in Example 5 and its charge was reduced. Was measured. The results are summarized in Table 1. The results are summarized in Table 1.
- each of the mixed cyclic phenol sulfates of the present invention has a charging performance superior to that of a single cyclic phenol sulfate, and the charge control agent containing the mixed compound has an excellent charge imparting effect. Furthermore, it has been proved that the negatively chargeable toner containing the charge control agent has high charging performance.
- the mixed cyclic phenol sulfide of the present invention has excellent charging performance, and the charge control agent having the mixed compound has clearly higher charging performance than the conventional charge control agent. Further, it is completely colorless and is useful for color toners. Furthermore, it does not contain heavy metals such as chromium compounds, which are a concern for environmental problems, and can provide a very useful toner.
- FIG. 1 is a TIC chart of the mixed cyclic phenolic sulfate of Example 1.
- FIG. 5 is an MS chart of TC7A.
- FIG. 7 is a TIC chart of TC8A in Example 3.
- FIG. 8 is a TIC chart of the cyclic phenol sulfate of Comparative Example 1.
- FIG. 9 is a TIC chart of the cyclic phenol sulfate of Comparative Example 2.
- FIG. 10 is an MS chart of the cyclic phenol sulfate of Comparative Example 2.
Description
Claims
Priority Applications (5)
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CN200780018971.7A CN101454307B (zh) | 2006-03-29 | 2007-03-28 | 混合环状苯酚硫化物和使用它的电荷控制剂及调色剂 |
JP2008507513A JP5256021B2 (ja) | 2006-03-29 | 2007-03-28 | 混合環状フェノール硫化物、それを用いた電荷制御剤及びトナー |
EP07740014A EP2003127B1 (en) | 2006-03-29 | 2007-03-28 | Cyclic phenol sulfide mixture, and charge controlling agent or toner using the same |
KR1020087026079A KR101360833B1 (ko) | 2006-03-29 | 2007-03-28 | 혼합 환형 페놀 황화물, 이것을 사용한 전하 제어제 및 토너 |
US12/240,520 US7901858B2 (en) | 2006-03-29 | 2008-09-29 | Mixed cyclic phenol sulfides, and charge control agents and toners using the same |
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JP2006090976 | 2006-03-29 | ||
JP2006-090976 | 2006-03-29 |
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US12/240,520 Continuation US7901858B2 (en) | 2006-03-29 | 2008-09-29 | Mixed cyclic phenol sulfides, and charge control agents and toners using the same |
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WO2007111346A1 true WO2007111346A1 (ja) | 2007-10-04 |
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US (1) | US7901858B2 (ja) |
EP (2) | EP2003127B1 (ja) |
JP (1) | JP5256021B2 (ja) |
KR (1) | KR101360833B1 (ja) |
CN (1) | CN101454307B (ja) |
WO (1) | WO2007111346A1 (ja) |
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WO2009136634A1 (ja) * | 2008-05-09 | 2009-11-12 | 保土谷化学工業株式会社 | 環状フェノール硫化物の金属化合物を用いた電荷制御剤及びトナー |
JP2010060610A (ja) * | 2008-09-01 | 2010-03-18 | Kao Corp | 電子写真用トナー |
JP2010072037A (ja) * | 2008-09-16 | 2010-04-02 | Ricoh Co Ltd | フルカラー電子写真用トナーとこれを用いたトナーキット、フルカラー画像形成方法、フルカラー画像形成装置およびプロセスカートリッジ |
JP2010117631A (ja) * | 2008-11-14 | 2010-05-27 | Konica Minolta Business Technologies Inc | トナー |
JP2010249995A (ja) * | 2009-04-14 | 2010-11-04 | Konica Minolta Business Technologies Inc | 静電荷像現像用トナーおよびその画像形成方法 |
WO2011105334A1 (ja) | 2010-02-26 | 2011-09-01 | 保土谷化学工業株式会社 | 電荷制御剤およびそれを用いたトナー |
WO2012036171A1 (ja) | 2010-09-15 | 2012-03-22 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
WO2012035996A1 (ja) | 2010-09-14 | 2012-03-22 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
CN102472988A (zh) * | 2009-08-07 | 2012-05-23 | 保土谷化学工业株式会社 | 含有环状苯酚硫化物的聚合调色剂 |
WO2012102137A1 (ja) | 2011-01-27 | 2012-08-02 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
US8790855B2 (en) | 2010-09-13 | 2014-07-29 | Hodogaya Chemical Co., Ltd | Charge control agent and toner using same |
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US9835965B2 (en) | 2013-09-24 | 2017-12-05 | Hodogaya Chemical Co., Ltd. | Charge control agent and toner using same |
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EP2065376A4 (en) * | 2006-08-29 | 2010-09-08 | Hodogaya Chemical Co Ltd | PROCESS FOR PRODUCING CYCLIC PHENOLIC SULFIDES |
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CN111077753B (zh) * | 2019-12-19 | 2022-09-16 | 苏州恒久光电科技股份有限公司 | 一种高润滑性opc鼓的加工方法 |
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Cited By (16)
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WO2009136634A1 (ja) * | 2008-05-09 | 2009-11-12 | 保土谷化学工業株式会社 | 環状フェノール硫化物の金属化合物を用いた電荷制御剤及びトナー |
JP5194322B2 (ja) * | 2008-05-09 | 2013-05-08 | 保土谷化学工業株式会社 | 環状フェノール硫化物の金属化合物を用いた電荷制御剤及びトナー |
JP2010060610A (ja) * | 2008-09-01 | 2010-03-18 | Kao Corp | 電子写真用トナー |
JP2010072037A (ja) * | 2008-09-16 | 2010-04-02 | Ricoh Co Ltd | フルカラー電子写真用トナーとこれを用いたトナーキット、フルカラー画像形成方法、フルカラー画像形成装置およびプロセスカートリッジ |
JP2010117631A (ja) * | 2008-11-14 | 2010-05-27 | Konica Minolta Business Technologies Inc | トナー |
JP2010249995A (ja) * | 2009-04-14 | 2010-11-04 | Konica Minolta Business Technologies Inc | 静電荷像現像用トナーおよびその画像形成方法 |
CN102472988A (zh) * | 2009-08-07 | 2012-05-23 | 保土谷化学工业株式会社 | 含有环状苯酚硫化物的聚合调色剂 |
WO2011105334A1 (ja) | 2010-02-26 | 2011-09-01 | 保土谷化学工業株式会社 | 電荷制御剤およびそれを用いたトナー |
US8790855B2 (en) | 2010-09-13 | 2014-07-29 | Hodogaya Chemical Co., Ltd | Charge control agent and toner using same |
WO2012035996A1 (ja) | 2010-09-14 | 2012-03-22 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
US8900785B2 (en) | 2010-09-14 | 2014-12-02 | Hodogaya Chemical Co., Ltd. | Charge control agent and toner using the same |
WO2012036171A1 (ja) | 2010-09-15 | 2012-03-22 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
WO2012102137A1 (ja) | 2011-01-27 | 2012-08-02 | 保土谷化学工業株式会社 | 電荷制御剤及びそれを用いたトナー |
US9835965B2 (en) | 2013-09-24 | 2017-12-05 | Hodogaya Chemical Co., Ltd. | Charge control agent and toner using same |
US9703223B2 (en) | 2013-09-25 | 2017-07-11 | Hodogaya Chemical Co., Ltd. | Toner, developer, and toner cartridge |
US10474050B2 (en) | 2015-09-17 | 2019-11-12 | Hodogaya Chemical Co., Ltd. | Toner and charge control agent using pyrazolone derivative or salt of derivative |
Also Published As
Publication number | Publication date |
---|---|
KR101360833B1 (ko) | 2014-02-11 |
CN101454307A (zh) | 2009-06-10 |
EP2457910B1 (en) | 2014-02-26 |
EP2003127A9 (en) | 2009-04-22 |
CN101454307B (zh) | 2014-01-15 |
EP2457910A1 (en) | 2012-05-30 |
EP2003127A2 (en) | 2008-12-17 |
EP2003127A4 (en) | 2010-05-26 |
JP5256021B2 (ja) | 2013-08-07 |
JPWO2007111346A1 (ja) | 2009-08-13 |
KR20090009211A (ko) | 2009-01-22 |
US20090035678A1 (en) | 2009-02-05 |
US7901858B2 (en) | 2011-03-08 |
EP2003127B1 (en) | 2012-08-01 |
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