CA1311957C - Toner for developing electrostatic images - Google Patents
Toner for developing electrostatic imagesInfo
- Publication number
- CA1311957C CA1311957C CA000522029A CA522029A CA1311957C CA 1311957 C CA1311957 C CA 1311957C CA 000522029 A CA000522029 A CA 000522029A CA 522029 A CA522029 A CA 522029A CA 1311957 C CA1311957 C CA 1311957C
- Authority
- CA
- Canada
- Prior art keywords
- toner
- resin
- weight
- group
- ion complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/001—Electric or magnetic imagery, e.g., xerography, electrography, magnetography, etc. Process, composition, or product
- Y10S430/105—Polymer in developer
Abstract
Abstract of the Disclosure:
A toner for developing an electrostatically charged image, comprising (A) an inner layer comprising a resin ion com-plex having a coloring agent and optionally a charge controlling agent and/or a magnetic material substantially dispersed therein, and (B) an outer layer containing a flowability imparting agent;
and a process for producing a toner for developing an electrostatically charged image, which comprises dis-persing a coloring agent and optionally a charge control-ling agent and/or a magnetic substance in a resin emulsion having a charge, mixing the dispersion with a resin emul-sion having an opposite charge to prepare a dispersion of a resin ion complex, adding a flowability imparting agent to the dispersion, and spray-drying the resulting disper-sion.
A toner for developing an electrostatically charged image, comprising (A) an inner layer comprising a resin ion com-plex having a coloring agent and optionally a charge controlling agent and/or a magnetic material substantially dispersed therein, and (B) an outer layer containing a flowability imparting agent;
and a process for producing a toner for developing an electrostatically charged image, which comprises dis-persing a coloring agent and optionally a charge control-ling agent and/or a magnetic substance in a resin emulsion having a charge, mixing the dispersion with a resin emul-sion having an opposite charge to prepare a dispersion of a resin ion complex, adding a flowability imparting agent to the dispersion, and spray-drying the resulting disper-sion.
Description
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This invention relates to a toner for develop-ing an electrostatic image in electrophotography, electro-static recording, electrostatic printing and the like.
It has generally been the practice to use heat transfer rollers heated at about 150 to 200C in fixing a toner image onto a receptor sheet such as paper. In recent years, attempts have been made to lower the fixing temperature and increase the fixing speed. As a result of such attempts, a toner composed of microcapsules each comprising a core portion containing a coloring substance and a shell of a resin as shown in Japanese Laid-Open Patent Publication No. 76233/1979 has attracted attention because an image developed with such a toner can be trans-ferred and fixed by a pressure-fixing method at room temperature. The microcapsular toner has the advantage that since fixing rollers need not to be heated, th wait-; ing time at the start of the operation of the copying machine, etc. can be shortened, and the energy required for heating can be saved. On the other hand, toners now in use are prepared generally by kneading a toner resin with a coloring agent and other additives under heat, and then finely pulverizing the mixture. The microcapsular toner has the great advantage of not requiring this finely pulverizing step for its preparation.
The application of the microcapsular toner requires a relatively high fixing pressure, and in spite of these advantages, this may lead to the defect that the fibers of the receptor sheet are destroyed or an excessive gloss is imparted to the surface of the receptor sheet.
If the shell wall of the microcapsule is decreased in thickness in order to remove this defect, the shell wall of the toner is partly destroyed during toner production or during stirring for charging within the developing device, blocking occurs during storage of the toner, or .: ~
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the chargeability of the toner during the development is reduced.
It is an object of this invention to solve the problems of the conventional toners produced by the melt-kneading/pulverizing process or of the microcapsulartoner, and to provide a toner which has excellent fix-ability at room temperature and lower temperatures, and good f lowability conducive to the freedom from contamina-tion of copied images or the inside of the copying machine by scattering during development, and which imparts a high resolution.
According to this invention, there is provided a toner for developing an electrostatically charged image, comprising lS (A) an inner layer comprising a resin ion com-plex having a coloring agent and optionally a charge controlling agent and/or a magnetic material substantially dispersed therein, and (B) an outer layer containing a flowability imparting agent.
The term "resin ion complex" denotes a resin particle-to-particle ionically crosslinked resin complex which results when a cationic resin emulsion and an anionic resin emulsion are mixed in such proportions that ; 25 the charges of these resin are nearly neutralized.
Examples of the cationic resin constituting the resin ion complex in accordance with this invention are copolymers containing units from styrenes, alkyl ~meth)-acrylates and cationic chargeable functional comonomers.
Those free from an anionically chargeable comonomer are suitable. Especially suitable are copolymers obtained by emulsion polymerization and having an average particle diameter of O.OS to 1 micron, preferaly 0.07 to O.S
micron, especially preferably 0.1 to 0.3 micron. Pre-ferred examples are copolymers composed of ~a) 90 to 20% by weight, preferably 60 to 40~ by !:
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(b) 80 to 10~ by weight, preferably 60 to 40% byweight, of the alkyl (meth)acrylates, and (c) 0.05 to 10% by weight, preferably 0.5 to 5%
by weight, of the cationically chargeable functional comonomers.
The percentages are calculated based on the total weight of (a), (b) and ~c). The copolymers may include units from another comonomer which can be copolymerized without impairing the properties of the toner of this invention.
Examples of the styrenes (a) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, alpha-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-t-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene and 3,4-dichlorostyrene. Styrene is es-pecially preferred.
Examples of the alkyl ~meth)acrylates (b) in-clude methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, i stearyl acrylate, 2-chloroethyl acrylate, methyl alpha-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Advantageously used are (meth)-acrylates of aliphatic alcohols having 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, especially pre-ferably 4 carbon atoms.
Examples of the cationically chargeable func-tional comonomers are ~i) (meth)acrylates of aliphatic alcohols having an amino group or a quaternary ammonium ,~ group and 1 to 12 carbon atoms, preferably 2 to 8 carbon 35 atoms, especially preferably 2 carbon atoms, ~ meth)-acrylamide or ~meth)acrylamide mono- or di-substituted on .1,:; : ,"
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N with an alkyl group having 1 to 18 carbon atoms, (iii) vinyl compounds substituted by a heterocyclic group having N as a ring member, and (iv) N,N-diallyl-alkylamines or quaternary ammonium salts thereof. of these,- (meth))-acrylates of aliphatic alcohols having an amino group ora quaternary ammonium group are preferred as the cation-ically chargeable functional comonomer.
Examples of the (meth)acrylates of aliphatic alcohols having an amino or quaternary ammonium group in (i) include dimethylaminoethyl acrylate, dimethylamino-ethyl methacrylate, diethylaminoethyl acrylate, diethyl-aminoethyl methacrylate, quaternary ammonium salts of the above four compounds, 3-dimethylaminophenyl acrylate and 2-hydroxy-3-methacryloxypropyltrimethyl ammonium salt.
Examples of the ~meth)acrylamide or ~meth)-acrylamide mono- or di-alkyl substituted on N in (ii) include acrylamide, N-butylacrylamide, N,N-dibutylacryl-amide, piperidyl acrylamide, methacrylamide, N-butyl-methacrylamide, N,N-dimethylacrylamide and N-octadecyl-aCrylamide.
Examples of the vinyl compounds substituted by a heterocyclic group having N as a ring member in ~iii) include vinylpyridine, vinylpyrrolidone, vinyl-N-methyl-pyridinium chloride and vinyl-N-ethyl pyridinium chloride.
'~ 25 Examples of the N,N-diallylalkylamine or qua-~ ~ teenary ammonium salt theeeof in ~iv) are N,N-diallyl-- methyl ammonium chloride and N,N-diallylethyl ammonium chloride.
Examples of the anionic resin constituting the resin ion complex in accordance with this invention are ,~ copolymees compeising units feom styrenes, alkyl ~meth)-;~ aceylates and anionically chaegeable functional co-~;I monomees. Those feee from a cationically chargeable functional comonomer are prefereed. Copolymers obtained ; 35 by emulsion polymerization and having an aveeage paeticle ~ diametee of O.OS to 1 micron, preferaly 0.07 to 0.5 micron, .,,, ~,, . .
' ~ , ~ 3 ~ 5 3 especially preferably 0.1 to 0.3 micron, are suitable.
Preferred examples are copolymers composed of (a') 90 to 20% by weight, preferably 60 to 40%
by weight, of the styrenes, ~b') 80 to 10% by weight, preferably 60 to 40%
by weight, of the alkyl (meth)acrylates, and (c') 0.05 to 10% by weight, preferably 0.5 to 5%
by weight, of the anionically chargeable functional co-monomers. The weight percentages of these monomers (a'), (b') and (c') are calculated based on the total weight of (a'), (b') and (c'). The copolymers may further include units from another comonomer which can be copolymerized without impairing the properties of the toner.
The styrenes in (a') are the same as the styrenes (a) in the cationic resin, and the alkyl (meth)-acrylates in (b') are the same as the alkyl (meth)-acrylates ~b) of the cationic resin.
The anionically chargeable functional comonomers ~c" may, for example, ~i') alpha,beta-ethylenically unsaturated compounds having the group -COO and ~ii') alpha,beta-ethylenically unsaturated compounds having the group -SO3H.
Examples of the alpha,beta-ethylenically un-saturated compounds having the group -COO in ~i') include ; 25 acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monobutyl maleate, monooctyl maleate, and metal salts ~such as Na and Za salts) of these compounds.
Examples of the alpha,beta-ethylenically un-saturated compound having the group -SO3H in ~ii') are sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt.
Further examples of the anionic resin consti-tuting the resin ion complex in accordance with this invention include emulsifiable polyolefinic resins such as oxidlzed polypropylene and oxidized polyethylene, and .
1 31~ ~r;l copolymers of olefins and ethylenic vinyl monomers having an acidic group, such as an ethylene/acrylic acid co-polymer and an ethylene/methacrylic acid copolymer.
The resin ion complex forming the inner layer of 5 the toner of this invention preferably contains the cat-ionic resin and the anionic resin in such proportions that the charges of these resins are nearly neutralized. Those resin ion complexes in which at least 70~, preferably at least 80%, more preferably at least 90%, of the charge of 10 one of the cationic resin or the anionic resin is neu-; tralized may also be used.
The resin ionda~complex has a glass transition C temperature of -90 to- 10~C, preferably -50 to 80C, more preferably -10 to 60C and a degree of gellation, ex-15 pressed as the insoluble resin content upon extraction with a Soxhlet extractor under acetone refluxing for 30 minutes, of from 0.5 to 50% by weight, preferably 5 to 30%
by weight, preferably 10 to 30% by weight. If the glass transition point is too high beyond 100C, the fixability 20 f the toner at low temperatures tends to be reduced. If it is too low below -90C, the flowability of the toner tends to be reduced undesirably. On the other hand, if the degree of gellation is too high beyond 50% by weight, the fixability of the toner at low temperatures tends to 25 be reduced undesirably. If it is too low below 0.5% by weight, scattering of the toner tends to increase un-desirably.
The flowability imparting agent constituting the outer layec of the toner of this invention is a hydro-30 phobic substance selected from the group consisting of hydrophobic fluorine resins, urethane resins, polyamide resins, aromatic condensation resins, inorganic oxides, clay minerals, surface-active agents and colored dyes and pigments. The fluorine resins and hydrophobic inorganic 35 oxides are preferred, and the fluorine resins are es-pecially preferred.
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Examples of the fluorine resins inclu~e polymers of (meth)acrylates of perfluoroalcohols having ~ to 12 carbon atoms in the alkyl moiety, vinylidene fluoride resins, vinyl fluoride resins, vinyl trifluoride resins and vinyl tetrafluoride resins.
Examples of the urethane resins are polyconden-sates of an alcohol component such as polyethylene glycol and polyacrylate and a polyisocyanate component such as toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Examples of the polyamide resins are nylon 66, nylon 6, nylon 11, and copolymers of these.
Examples of the aromatic condensation resins are benzoguanamine-formaldehyde resins, phenol-formaldehyde resin, melamine-formaldehyde resin and xylene-formaldehyde resin.
Examples of the hydrophobic inorganic oxides include hydrophobic silica, alumina powder, calcium carbonate, apatites, and oxides of divalent or higher metals such as zinc, tin, iron, titanium, or manganese.
Examples of the clay minerals are mixtures of naturally occurrng metal oxides such as bentonite, talc and clay.
The colored dyes and pigments may, for example, include carbon black, nigrosine dye, aniline dye, chrome yellow, ultramarine blue, methylene blue chloride, Rose Bengale, magnetite and ferrite.
Examples of the surface-active agents are silicone-type surface-active agents and fluorine-type surface-active agents.
In the toner of this invention, the outer layer of the flowability imparting agent is covered in thin layer with the outside of the inner layer composed of the resin ion complex and the coloring agent, etc. It is not necessary for the thin layer to cover the entire surface of the inner layer of the resin ion complex. It is only :, ;"
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necessary that the thin layer covers the surface of the inner layer to such an extent as is necessary for the toner to have good flowability. The thin layer of the flowability imparting agent may be in the form of a thin film, or a layer of a powder intimately adhering to the surface or the surface layer of the inner layer.
The outer layer may be formed by using a known method. According to this invention, it may be conveni-ently formed by mixing two resin emulsions having opposite charges, subjecting the mixture to an aging treatment, uniformly mixing the resulting dispersion with the flow-ability imparting agent, and then spray-drying the mix-ture.
Especially preferably, the flowability imparting agent also has the ability to control positive or negative chargeability. Such a flowability imparting agent is, for example, a polymer of a perfluoroalcohol acrylate, a fluorine-containing surface-active agent, benzoguanamine-formaldehyde resin, and hydrophobic silica. When the ` 20 charge-controlling flowability imparting agent is used, it i8 not necessary to incorporate a charge con~rolling agent in the resin ion complex in the inner layer, and the ; amount of the charge controlling agent used can be dras-tically reduced.
The toner of this invention compeises 80 to 99.9% by weight, preferably 95 to 99.5% by weight, of the inner layee composed of the eesin ion complex and the coloring agent, etc. and 20 to 0.1% by weight, preferably ,b, 5~0 to 0.5~ by weight, of the outer layer of the flow-ability imparting agent.
The toner of the invention is peefeeably sub-stantially in the foem of spherical paeticles having a paeticle diameter of 1 to 30 miceometees, peeferably 5 to 20 miceometers, and has a softening point of 60 to 200C, preferably B0 to 150C. The softening point, as used heeeln, denotes a temperature at which one half of a ~ , ::
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sample weighing 1 g flows in a test using a Koka-type flow tester ~made by Shimazu Seisakusho) under conditions involving a load of 30 kg, a die nozzle diameter of 1 mm, a die length of 10 mm and a temperature elevation rate of 3C/min.
The coloring agent used in this invention needs not to be special, and includes, for example, carbon black, nigrosine dye, aniline dye, chrome yellow, ultra-marine blue, methylene blue chloride, Rose Bengal, magnetite and ferite.
Examples of the charge controlling agent which can be optionally included into the inner layer of the toner of this invention are electron-donating dyes of the nigrosine type, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salts, alkylamides, chelates, pigments and fluorine treat-ment activating agents for controlling positive charging;
and electron-accepting organic complexes, chlorinated paraffin, chlorinated polyesters, polyesters having an excess of an acidic group, and sulfonylamine of copper phthalocyanine for controlling negative charge.
The magnetic material which may optionally be included in the inner layer of the toner of this invention may, for example, be magnetite or ferrite.
A preferred example of the process for producing the toner of this invention is as follows: The coloring agent, and optionally the charge controlling agent and/or the magnetic material are dispersed in a cationic or anionic resin emulsion, and then a resin emulsion having an opposite charge is mixed with it in an amount nearly equal to one required for neutralizing the charge of the first-mentioned resin to form a uniform dispersion of the resin ion complex. The flowability imparting agent is mixed with the dispersion. The mixture is spray-dried and as required, classified.
More preferably, after obtaining a uniform !
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optimal ~or complexing, and then the dispersion is sub-jected to an aging treatment at 60 to 90C, preferably 70 to 80C for about 0.5 to 2 hours, and then the flowability imparting agent is added.
The toner of this invention has excellent fix-ability at room temperature to relatively low tempera-~- tures, for example at 20 to 150C. Since it has excellent flowability, no non-uniformity occurs in triboelectric chargeability, and scattering or fogging does not occur.
It also gives an image having a high resolution.
Since the process for producing the toner of this invention does not require a melt-kneading/pul-verizing step, the toner having the excellent propertiesas stated above can be produced at low cost.
The following examples illustrate the present invention more specifically. Unless otherwise specified, all amounts and percentages in these examples are by ~ ~s ; 20 Weight.
~; Preparation of a cationic emulsion-polymeriza-tioh resin ~resin A) Styrene monomer ~ST) 60 parts ~iS 25 Butyl acrylate ~BA) 40 pats 2-Hydroxy-3-methacryloxypropyl-5 parts trimethyla onium chloride A mixture of the above monomers was added to an aqueous solution composed of the~following ingredients.
30 ~ ~ Water 150 parts Nonionic emulsifier ~Emulgen 950) 1 part Cationic emulsifier ~Sanizol B-50) 1.2 parts Potasslum~persulfate 0.5 part With stirring, the mixture was subjected to '~ 35~ polymerization at 70C for 8 houes to give a cationic ." . j j, ., emulsion~;polymerization resin having a solids content of 40S.~ ~
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Pre~aration of an anionic emulsion-polymeriza-tion resin tresin B) Styrene monolner ~ST) 60 parts Butyl acrylate ~A) 40 parts Me~h~crylic acid ~M~A) 1 part A mixture of the above monomer~ was added to an aqueous solutlon composed of the following ingredients.
Water 100 parts Nonionic emulsi~ier ~mulgen~950~ 1 part Anionic emulsiEier (Neogen~R~ 1.5 paets Potassium per~ulate 0.5 part The mixture was subjected to polymerization with stirring at 70C for 8 hours to give an anionic emulsion-poly-merization cesin having a solids content of 50~.
Preparation of a toner ~e6in A 125 parts Carbon black ~Diablack~100) 10 paets Nigrosine dye ~Bontron~N-04) 10 parts A mixture of the above ingredient~ was dispeesed 20 in a ball mill for 48 hours, and the di~peraion was ad-justed to pH 12 with aqueous ammonia. Sub~equently, 100 parts of resin 8 and 500 partR of water were added, and with stirring, the mixture was maintained at 70C for 1 hour. 8y microscopic observation, it was confirmed that 25 the resin included carbon and the nigrosene dye and grew to particles with a diameter of about 10 micrometers.
Subsequently, 4 parts of hydroxyapatite (Supertite~10 made by Nihon Chemical Co., Ltd.) wa~ added as a 1Owability imparting agent. The liquid di&persion wa~ cooled, and - 30 dried by using a spray dryer ~Mobile Mino a product of A~hizawaniro Atomizer) at an inlet temperature of 120C, an outlet temperature o~ 90C and a eed rate of 1.5 liters/min. by operating the atomizer at 3 x 10 e/m to obtain a test toner. The toner h~d a Tg of 40C, a degree of gellation of 20~, and a sotening point of 148C and as in the form o nearly true spherical particle~ with an !
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13~ 67566-1031 average particle diameter o'~ 12 microm~tec~. The toner showed excellent flowability.
Copving test Four parts of the toner obtaine~ as above was mixed with 800 parts of an iLon pow~cr ~DSP-257@9made by Dowa Iron Powder Industry Co., Ltd.) to prepare a de-veloper. The mixture was set in a commercial copying machine ~SF-75 ~made by Sharp Co.), and copying was per-formed. Copied images having a high density and reduced fogging were obtained. The test was carried out by vary-ing the temperatute o~ fixing rollers. Good fixa~ility was obtained at temperature~ o~ 100C and above.
~XA~PLES 2-10 Example 1 wa~ repeated using the ~aterials indicated in ~able 1. The results shown in Table 1 were obtained. ~he abbreviations u~ed in ~able 1 were as follow6: ' ; 2-EHA: 2-ethylhexyl acrylate BD: butadiene DMAA: dimethylaminoethyl acrylate ~" M8M: monobutyl maleate ,,~i VP; vinylpyridine ~, ASSN: ~odiu~ allyl~ulEosuccinate LMA: lauryl ~ethacrylate ' 2S DMPC: N,N-diallylmethyl ammonium chloride ,, IA: itaconic acid BQA: benzoguanamine re6in ~made by Japan Catalytic Chemical Co., Ltd.) ' Alumina powder: aluminum oxide C made by Japan i~ ' 30 Aero~il Co., Ltd.
Nylon: X4001 made by ~oray Inc.
In 6xample 10, the nylon u6ed a6 a flowability ,~ impa~rting agent was added a6 a l~ l60propanol 601ution.
XAMYL~S 11-13 ; ~ 35Example 1 wa~ repeated except that the carbon black and the niqro~ine dye,added to the resin A in the - ~" ~, ~ ' ~; ' ~ . , i ....... . . .
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1~ 67566-1031 preparation of th~ toner were cl~anged to 65 parts of magnetite (BL-120~made by Titanium Industry Co., Ltd.) ~nd 1.5 parts of a chromium-type dye (Bontron S-34, a product of Orient Chemical Co. Ltd.~; and in the copying test, a copying machine (NP-20~made by Canon Co., Ltd.) was used instead of the copying machine described in Example 1. The results are shown in Table 1. The ab-breviations used were as ~gllows:-Silica: Aerosi ~R972 made by Japan Aerosil Co., Ltd. ~
Urethane: Bondic 1310F made by Dainippon Ink and Chemicals, Inc.
FR: resin obtained by copo~merizing a per-fluoroacrylate ~Su~fron~*SC-101 made by Asahi Glass Co., Ltd.) In Example 13, FR as the flowability imparting agent was added after it was diluted with isopropanol to a solids content of 15~
Example 11 was repeated except that the flow-ability imparting agent was not added. The resulting toner had no significant flowability, and the copying test was impo6sible.
Method of evaluatinq flowabilitv ,;
Twenty grams of the toner was pUt in a plastic bottle and left to stand in a constant-temperature chamber at 50C for 9 hours. The degree of agglomeration of the toner was then measured by a powder tester ~made by Hosokawa Micron Co., Ltd.), and used as a measure of flowability.
By using a t4Z-mesh sieve, the test was con-ducted by vibration channel 4 For 30 seconds, and then the weight of the toner remaining on the sieve was measured, and evaluated on the following scale.
A: less than 0.5 g B: 0.5 to 1 g , !
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C: l~to 5 g D: more than 5 g E: all the toner agglomerated firmly in the plastic bottle.
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This invention relates to a toner for develop-ing an electrostatic image in electrophotography, electro-static recording, electrostatic printing and the like.
It has generally been the practice to use heat transfer rollers heated at about 150 to 200C in fixing a toner image onto a receptor sheet such as paper. In recent years, attempts have been made to lower the fixing temperature and increase the fixing speed. As a result of such attempts, a toner composed of microcapsules each comprising a core portion containing a coloring substance and a shell of a resin as shown in Japanese Laid-Open Patent Publication No. 76233/1979 has attracted attention because an image developed with such a toner can be trans-ferred and fixed by a pressure-fixing method at room temperature. The microcapsular toner has the advantage that since fixing rollers need not to be heated, th wait-; ing time at the start of the operation of the copying machine, etc. can be shortened, and the energy required for heating can be saved. On the other hand, toners now in use are prepared generally by kneading a toner resin with a coloring agent and other additives under heat, and then finely pulverizing the mixture. The microcapsular toner has the great advantage of not requiring this finely pulverizing step for its preparation.
The application of the microcapsular toner requires a relatively high fixing pressure, and in spite of these advantages, this may lead to the defect that the fibers of the receptor sheet are destroyed or an excessive gloss is imparted to the surface of the receptor sheet.
If the shell wall of the microcapsule is decreased in thickness in order to remove this defect, the shell wall of the toner is partly destroyed during toner production or during stirring for charging within the developing device, blocking occurs during storage of the toner, or .: ~
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the chargeability of the toner during the development is reduced.
It is an object of this invention to solve the problems of the conventional toners produced by the melt-kneading/pulverizing process or of the microcapsulartoner, and to provide a toner which has excellent fix-ability at room temperature and lower temperatures, and good f lowability conducive to the freedom from contamina-tion of copied images or the inside of the copying machine by scattering during development, and which imparts a high resolution.
According to this invention, there is provided a toner for developing an electrostatically charged image, comprising lS (A) an inner layer comprising a resin ion com-plex having a coloring agent and optionally a charge controlling agent and/or a magnetic material substantially dispersed therein, and (B) an outer layer containing a flowability imparting agent.
The term "resin ion complex" denotes a resin particle-to-particle ionically crosslinked resin complex which results when a cationic resin emulsion and an anionic resin emulsion are mixed in such proportions that ; 25 the charges of these resin are nearly neutralized.
Examples of the cationic resin constituting the resin ion complex in accordance with this invention are copolymers containing units from styrenes, alkyl ~meth)-acrylates and cationic chargeable functional comonomers.
Those free from an anionically chargeable comonomer are suitable. Especially suitable are copolymers obtained by emulsion polymerization and having an average particle diameter of O.OS to 1 micron, preferaly 0.07 to O.S
micron, especially preferably 0.1 to 0.3 micron. Pre-ferred examples are copolymers composed of ~a) 90 to 20% by weight, preferably 60 to 40~ by !:
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(b) 80 to 10~ by weight, preferably 60 to 40% byweight, of the alkyl (meth)acrylates, and (c) 0.05 to 10% by weight, preferably 0.5 to 5%
by weight, of the cationically chargeable functional comonomers.
The percentages are calculated based on the total weight of (a), (b) and ~c). The copolymers may include units from another comonomer which can be copolymerized without impairing the properties of the toner of this invention.
Examples of the styrenes (a) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, alpha-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-t-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene and 3,4-dichlorostyrene. Styrene is es-pecially preferred.
Examples of the alkyl ~meth)acrylates (b) in-clude methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, i stearyl acrylate, 2-chloroethyl acrylate, methyl alpha-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Advantageously used are (meth)-acrylates of aliphatic alcohols having 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, especially pre-ferably 4 carbon atoms.
Examples of the cationically chargeable func-tional comonomers are ~i) (meth)acrylates of aliphatic alcohols having an amino group or a quaternary ammonium ,~ group and 1 to 12 carbon atoms, preferably 2 to 8 carbon 35 atoms, especially preferably 2 carbon atoms, ~ meth)-acrylamide or ~meth)acrylamide mono- or di-substituted on .1,:; : ,"
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N with an alkyl group having 1 to 18 carbon atoms, (iii) vinyl compounds substituted by a heterocyclic group having N as a ring member, and (iv) N,N-diallyl-alkylamines or quaternary ammonium salts thereof. of these,- (meth))-acrylates of aliphatic alcohols having an amino group ora quaternary ammonium group are preferred as the cation-ically chargeable functional comonomer.
Examples of the (meth)acrylates of aliphatic alcohols having an amino or quaternary ammonium group in (i) include dimethylaminoethyl acrylate, dimethylamino-ethyl methacrylate, diethylaminoethyl acrylate, diethyl-aminoethyl methacrylate, quaternary ammonium salts of the above four compounds, 3-dimethylaminophenyl acrylate and 2-hydroxy-3-methacryloxypropyltrimethyl ammonium salt.
Examples of the ~meth)acrylamide or ~meth)-acrylamide mono- or di-alkyl substituted on N in (ii) include acrylamide, N-butylacrylamide, N,N-dibutylacryl-amide, piperidyl acrylamide, methacrylamide, N-butyl-methacrylamide, N,N-dimethylacrylamide and N-octadecyl-aCrylamide.
Examples of the vinyl compounds substituted by a heterocyclic group having N as a ring member in ~iii) include vinylpyridine, vinylpyrrolidone, vinyl-N-methyl-pyridinium chloride and vinyl-N-ethyl pyridinium chloride.
'~ 25 Examples of the N,N-diallylalkylamine or qua-~ ~ teenary ammonium salt theeeof in ~iv) are N,N-diallyl-- methyl ammonium chloride and N,N-diallylethyl ammonium chloride.
Examples of the anionic resin constituting the resin ion complex in accordance with this invention are ,~ copolymees compeising units feom styrenes, alkyl ~meth)-;~ aceylates and anionically chaegeable functional co-~;I monomees. Those feee from a cationically chargeable functional comonomer are prefereed. Copolymers obtained ; 35 by emulsion polymerization and having an aveeage paeticle ~ diametee of O.OS to 1 micron, preferaly 0.07 to 0.5 micron, .,,, ~,, . .
' ~ , ~ 3 ~ 5 3 especially preferably 0.1 to 0.3 micron, are suitable.
Preferred examples are copolymers composed of (a') 90 to 20% by weight, preferably 60 to 40%
by weight, of the styrenes, ~b') 80 to 10% by weight, preferably 60 to 40%
by weight, of the alkyl (meth)acrylates, and (c') 0.05 to 10% by weight, preferably 0.5 to 5%
by weight, of the anionically chargeable functional co-monomers. The weight percentages of these monomers (a'), (b') and (c') are calculated based on the total weight of (a'), (b') and (c'). The copolymers may further include units from another comonomer which can be copolymerized without impairing the properties of the toner.
The styrenes in (a') are the same as the styrenes (a) in the cationic resin, and the alkyl (meth)-acrylates in (b') are the same as the alkyl (meth)-acrylates ~b) of the cationic resin.
The anionically chargeable functional comonomers ~c" may, for example, ~i') alpha,beta-ethylenically unsaturated compounds having the group -COO and ~ii') alpha,beta-ethylenically unsaturated compounds having the group -SO3H.
Examples of the alpha,beta-ethylenically un-saturated compounds having the group -COO in ~i') include ; 25 acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monobutyl maleate, monooctyl maleate, and metal salts ~such as Na and Za salts) of these compounds.
Examples of the alpha,beta-ethylenically un-saturated compound having the group -SO3H in ~ii') are sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt.
Further examples of the anionic resin consti-tuting the resin ion complex in accordance with this invention include emulsifiable polyolefinic resins such as oxidlzed polypropylene and oxidized polyethylene, and .
1 31~ ~r;l copolymers of olefins and ethylenic vinyl monomers having an acidic group, such as an ethylene/acrylic acid co-polymer and an ethylene/methacrylic acid copolymer.
The resin ion complex forming the inner layer of 5 the toner of this invention preferably contains the cat-ionic resin and the anionic resin in such proportions that the charges of these resins are nearly neutralized. Those resin ion complexes in which at least 70~, preferably at least 80%, more preferably at least 90%, of the charge of 10 one of the cationic resin or the anionic resin is neu-; tralized may also be used.
The resin ionda~complex has a glass transition C temperature of -90 to- 10~C, preferably -50 to 80C, more preferably -10 to 60C and a degree of gellation, ex-15 pressed as the insoluble resin content upon extraction with a Soxhlet extractor under acetone refluxing for 30 minutes, of from 0.5 to 50% by weight, preferably 5 to 30%
by weight, preferably 10 to 30% by weight. If the glass transition point is too high beyond 100C, the fixability 20 f the toner at low temperatures tends to be reduced. If it is too low below -90C, the flowability of the toner tends to be reduced undesirably. On the other hand, if the degree of gellation is too high beyond 50% by weight, the fixability of the toner at low temperatures tends to 25 be reduced undesirably. If it is too low below 0.5% by weight, scattering of the toner tends to increase un-desirably.
The flowability imparting agent constituting the outer layec of the toner of this invention is a hydro-30 phobic substance selected from the group consisting of hydrophobic fluorine resins, urethane resins, polyamide resins, aromatic condensation resins, inorganic oxides, clay minerals, surface-active agents and colored dyes and pigments. The fluorine resins and hydrophobic inorganic 35 oxides are preferred, and the fluorine resins are es-pecially preferred.
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Examples of the fluorine resins inclu~e polymers of (meth)acrylates of perfluoroalcohols having ~ to 12 carbon atoms in the alkyl moiety, vinylidene fluoride resins, vinyl fluoride resins, vinyl trifluoride resins and vinyl tetrafluoride resins.
Examples of the urethane resins are polyconden-sates of an alcohol component such as polyethylene glycol and polyacrylate and a polyisocyanate component such as toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Examples of the polyamide resins are nylon 66, nylon 6, nylon 11, and copolymers of these.
Examples of the aromatic condensation resins are benzoguanamine-formaldehyde resins, phenol-formaldehyde resin, melamine-formaldehyde resin and xylene-formaldehyde resin.
Examples of the hydrophobic inorganic oxides include hydrophobic silica, alumina powder, calcium carbonate, apatites, and oxides of divalent or higher metals such as zinc, tin, iron, titanium, or manganese.
Examples of the clay minerals are mixtures of naturally occurrng metal oxides such as bentonite, talc and clay.
The colored dyes and pigments may, for example, include carbon black, nigrosine dye, aniline dye, chrome yellow, ultramarine blue, methylene blue chloride, Rose Bengale, magnetite and ferrite.
Examples of the surface-active agents are silicone-type surface-active agents and fluorine-type surface-active agents.
In the toner of this invention, the outer layer of the flowability imparting agent is covered in thin layer with the outside of the inner layer composed of the resin ion complex and the coloring agent, etc. It is not necessary for the thin layer to cover the entire surface of the inner layer of the resin ion complex. It is only :, ;"
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necessary that the thin layer covers the surface of the inner layer to such an extent as is necessary for the toner to have good flowability. The thin layer of the flowability imparting agent may be in the form of a thin film, or a layer of a powder intimately adhering to the surface or the surface layer of the inner layer.
The outer layer may be formed by using a known method. According to this invention, it may be conveni-ently formed by mixing two resin emulsions having opposite charges, subjecting the mixture to an aging treatment, uniformly mixing the resulting dispersion with the flow-ability imparting agent, and then spray-drying the mix-ture.
Especially preferably, the flowability imparting agent also has the ability to control positive or negative chargeability. Such a flowability imparting agent is, for example, a polymer of a perfluoroalcohol acrylate, a fluorine-containing surface-active agent, benzoguanamine-formaldehyde resin, and hydrophobic silica. When the ` 20 charge-controlling flowability imparting agent is used, it i8 not necessary to incorporate a charge con~rolling agent in the resin ion complex in the inner layer, and the ; amount of the charge controlling agent used can be dras-tically reduced.
The toner of this invention compeises 80 to 99.9% by weight, preferably 95 to 99.5% by weight, of the inner layee composed of the eesin ion complex and the coloring agent, etc. and 20 to 0.1% by weight, preferably ,b, 5~0 to 0.5~ by weight, of the outer layer of the flow-ability imparting agent.
The toner of the invention is peefeeably sub-stantially in the foem of spherical paeticles having a paeticle diameter of 1 to 30 miceometees, peeferably 5 to 20 miceometers, and has a softening point of 60 to 200C, preferably B0 to 150C. The softening point, as used heeeln, denotes a temperature at which one half of a ~ , ::
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sample weighing 1 g flows in a test using a Koka-type flow tester ~made by Shimazu Seisakusho) under conditions involving a load of 30 kg, a die nozzle diameter of 1 mm, a die length of 10 mm and a temperature elevation rate of 3C/min.
The coloring agent used in this invention needs not to be special, and includes, for example, carbon black, nigrosine dye, aniline dye, chrome yellow, ultra-marine blue, methylene blue chloride, Rose Bengal, magnetite and ferite.
Examples of the charge controlling agent which can be optionally included into the inner layer of the toner of this invention are electron-donating dyes of the nigrosine type, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salts, alkylamides, chelates, pigments and fluorine treat-ment activating agents for controlling positive charging;
and electron-accepting organic complexes, chlorinated paraffin, chlorinated polyesters, polyesters having an excess of an acidic group, and sulfonylamine of copper phthalocyanine for controlling negative charge.
The magnetic material which may optionally be included in the inner layer of the toner of this invention may, for example, be magnetite or ferrite.
A preferred example of the process for producing the toner of this invention is as follows: The coloring agent, and optionally the charge controlling agent and/or the magnetic material are dispersed in a cationic or anionic resin emulsion, and then a resin emulsion having an opposite charge is mixed with it in an amount nearly equal to one required for neutralizing the charge of the first-mentioned resin to form a uniform dispersion of the resin ion complex. The flowability imparting agent is mixed with the dispersion. The mixture is spray-dried and as required, classified.
More preferably, after obtaining a uniform !
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optimal ~or complexing, and then the dispersion is sub-jected to an aging treatment at 60 to 90C, preferably 70 to 80C for about 0.5 to 2 hours, and then the flowability imparting agent is added.
The toner of this invention has excellent fix-ability at room temperature to relatively low tempera-~- tures, for example at 20 to 150C. Since it has excellent flowability, no non-uniformity occurs in triboelectric chargeability, and scattering or fogging does not occur.
It also gives an image having a high resolution.
Since the process for producing the toner of this invention does not require a melt-kneading/pul-verizing step, the toner having the excellent propertiesas stated above can be produced at low cost.
The following examples illustrate the present invention more specifically. Unless otherwise specified, all amounts and percentages in these examples are by ~ ~s ; 20 Weight.
~; Preparation of a cationic emulsion-polymeriza-tioh resin ~resin A) Styrene monomer ~ST) 60 parts ~iS 25 Butyl acrylate ~BA) 40 pats 2-Hydroxy-3-methacryloxypropyl-5 parts trimethyla onium chloride A mixture of the above monomers was added to an aqueous solution composed of the~following ingredients.
30 ~ ~ Water 150 parts Nonionic emulsifier ~Emulgen 950) 1 part Cationic emulsifier ~Sanizol B-50) 1.2 parts Potasslum~persulfate 0.5 part With stirring, the mixture was subjected to '~ 35~ polymerization at 70C for 8 houes to give a cationic ." . j j, ., emulsion~;polymerization resin having a solids content of 40S.~ ~
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Pre~aration of an anionic emulsion-polymeriza-tion resin tresin B) Styrene monolner ~ST) 60 parts Butyl acrylate ~A) 40 parts Me~h~crylic acid ~M~A) 1 part A mixture of the above monomer~ was added to an aqueous solutlon composed of the following ingredients.
Water 100 parts Nonionic emulsi~ier ~mulgen~950~ 1 part Anionic emulsiEier (Neogen~R~ 1.5 paets Potassium per~ulate 0.5 part The mixture was subjected to polymerization with stirring at 70C for 8 hours to give an anionic emulsion-poly-merization cesin having a solids content of 50~.
Preparation of a toner ~e6in A 125 parts Carbon black ~Diablack~100) 10 paets Nigrosine dye ~Bontron~N-04) 10 parts A mixture of the above ingredient~ was dispeesed 20 in a ball mill for 48 hours, and the di~peraion was ad-justed to pH 12 with aqueous ammonia. Sub~equently, 100 parts of resin 8 and 500 partR of water were added, and with stirring, the mixture was maintained at 70C for 1 hour. 8y microscopic observation, it was confirmed that 25 the resin included carbon and the nigrosene dye and grew to particles with a diameter of about 10 micrometers.
Subsequently, 4 parts of hydroxyapatite (Supertite~10 made by Nihon Chemical Co., Ltd.) wa~ added as a 1Owability imparting agent. The liquid di&persion wa~ cooled, and - 30 dried by using a spray dryer ~Mobile Mino a product of A~hizawaniro Atomizer) at an inlet temperature of 120C, an outlet temperature o~ 90C and a eed rate of 1.5 liters/min. by operating the atomizer at 3 x 10 e/m to obtain a test toner. The toner h~d a Tg of 40C, a degree of gellation of 20~, and a sotening point of 148C and as in the form o nearly true spherical particle~ with an !
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13~ 67566-1031 average particle diameter o'~ 12 microm~tec~. The toner showed excellent flowability.
Copving test Four parts of the toner obtaine~ as above was mixed with 800 parts of an iLon pow~cr ~DSP-257@9made by Dowa Iron Powder Industry Co., Ltd.) to prepare a de-veloper. The mixture was set in a commercial copying machine ~SF-75 ~made by Sharp Co.), and copying was per-formed. Copied images having a high density and reduced fogging were obtained. The test was carried out by vary-ing the temperatute o~ fixing rollers. Good fixa~ility was obtained at temperature~ o~ 100C and above.
~XA~PLES 2-10 Example 1 wa~ repeated using the ~aterials indicated in ~able 1. The results shown in Table 1 were obtained. ~he abbreviations u~ed in ~able 1 were as follow6: ' ; 2-EHA: 2-ethylhexyl acrylate BD: butadiene DMAA: dimethylaminoethyl acrylate ~" M8M: monobutyl maleate ,,~i VP; vinylpyridine ~, ASSN: ~odiu~ allyl~ulEosuccinate LMA: lauryl ~ethacrylate ' 2S DMPC: N,N-diallylmethyl ammonium chloride ,, IA: itaconic acid BQA: benzoguanamine re6in ~made by Japan Catalytic Chemical Co., Ltd.) ' Alumina powder: aluminum oxide C made by Japan i~ ' 30 Aero~il Co., Ltd.
Nylon: X4001 made by ~oray Inc.
In 6xample 10, the nylon u6ed a6 a flowability ,~ impa~rting agent was added a6 a l~ l60propanol 601ution.
XAMYL~S 11-13 ; ~ 35Example 1 wa~ repeated except that the carbon black and the niqro~ine dye,added to the resin A in the - ~" ~, ~ ' ~; ' ~ . , i ....... . . .
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1~ 67566-1031 preparation of th~ toner were cl~anged to 65 parts of magnetite (BL-120~made by Titanium Industry Co., Ltd.) ~nd 1.5 parts of a chromium-type dye (Bontron S-34, a product of Orient Chemical Co. Ltd.~; and in the copying test, a copying machine (NP-20~made by Canon Co., Ltd.) was used instead of the copying machine described in Example 1. The results are shown in Table 1. The ab-breviations used were as ~gllows:-Silica: Aerosi ~R972 made by Japan Aerosil Co., Ltd. ~
Urethane: Bondic 1310F made by Dainippon Ink and Chemicals, Inc.
FR: resin obtained by copo~merizing a per-fluoroacrylate ~Su~fron~*SC-101 made by Asahi Glass Co., Ltd.) In Example 13, FR as the flowability imparting agent was added after it was diluted with isopropanol to a solids content of 15~
Example 11 was repeated except that the flow-ability imparting agent was not added. The resulting toner had no significant flowability, and the copying test was impo6sible.
Method of evaluatinq flowabilitv ,;
Twenty grams of the toner was pUt in a plastic bottle and left to stand in a constant-temperature chamber at 50C for 9 hours. The degree of agglomeration of the toner was then measured by a powder tester ~made by Hosokawa Micron Co., Ltd.), and used as a measure of flowability.
By using a t4Z-mesh sieve, the test was con-ducted by vibration channel 4 For 30 seconds, and then the weight of the toner remaining on the sieve was measured, and evaluated on the following scale.
A: less than 0.5 g B: 0.5 to 1 g , !
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C: l~to 5 g D: more than 5 g E: all the toner agglomerated firmly in the plastic bottle.
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EX~MPLE 14 l~ourty-six ~ arts oE oxidizcd propylene wax emulsion resin (~lite~E-433N, a product a Toyo Chemical Co., Ltd.), 40 parts of magnetite (~apico~ L-220, a pro-duct of Titanium Industry Co., Ltd.), l part of a nigro-sine dye (Bontron N-04, a product of Orient Chemical Co., Ltd.) and 400 parts of water were dispersed for 1.5 hours by a disper to give an anionic resin emulsion.
The dispersion was transferred to a glass flask equipped with a stirring device, and heated to 70C.
Then, 11 parts of the cationic emulsion-polymerization resin tresin B) prepared in Example l was added, and the mixture was stirred for 2 hours. After confirming that the particle diameter grew to about lO micrometers, the temperature was lowered to 50C to give a resin ion complex.
Two parts of hydroxyapatite ~Supertite lO, a product of Nippon Chemical Co., Ltd.) was added as a flowability imparting agent, and the mixture was deied under the same conditions as in Example l to prepare at a test toner. The toner had a rg of -25C, a degree of gellation of 15~ and a softening point o 110C and was nearly in the form of spherical particles having an average particle diameter of lO micrometers.
The toner was subjected to the same copying test as in Example l except that the copying machine was ~; changed to a copying machine PC-3 ~f Canon Co., Ltd.
adapted for pressure fixation of toners. The lowest temperature at which fixation was possible was -10C, and the toner had a flowability of C. Images having a high density and excelling clarity was obtained. The images were not contaminated even by rubbing it with a finger.
~ The ~ixed images were not peeled even when bent.
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EX~MPLE 14 l~ourty-six ~ arts oE oxidizcd propylene wax emulsion resin (~lite~E-433N, a product a Toyo Chemical Co., Ltd.), 40 parts of magnetite (~apico~ L-220, a pro-duct of Titanium Industry Co., Ltd.), l part of a nigro-sine dye (Bontron N-04, a product of Orient Chemical Co., Ltd.) and 400 parts of water were dispersed for 1.5 hours by a disper to give an anionic resin emulsion.
The dispersion was transferred to a glass flask equipped with a stirring device, and heated to 70C.
Then, 11 parts of the cationic emulsion-polymerization resin tresin B) prepared in Example l was added, and the mixture was stirred for 2 hours. After confirming that the particle diameter grew to about lO micrometers, the temperature was lowered to 50C to give a resin ion complex.
Two parts of hydroxyapatite ~Supertite lO, a product of Nippon Chemical Co., Ltd.) was added as a flowability imparting agent, and the mixture was deied under the same conditions as in Example l to prepare at a test toner. The toner had a rg of -25C, a degree of gellation of 15~ and a softening point o 110C and was nearly in the form of spherical particles having an average particle diameter of lO micrometers.
The toner was subjected to the same copying test as in Example l except that the copying machine was ~; changed to a copying machine PC-3 ~f Canon Co., Ltd.
adapted for pressure fixation of toners. The lowest temperature at which fixation was possible was -10C, and the toner had a flowability of C. Images having a high density and excelling clarity was obtained. The images were not contaminated even by rubbing it with a finger.
~ The ~ixed images were not peeled even when bent.
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Claims (18)
1. A toner for developing an electrostatically charged image, comprising:
(A) an inner layer comprising a resin ion complex which is a resin particle-to-particle ionically crosslinked resin complex and a coloring agent and (B) an outer layer containing a flowability imparting agent.
(A) an inner layer comprising a resin ion complex which is a resin particle-to-particle ionically crosslinked resin complex and a coloring agent and (B) an outer layer containing a flowability imparting agent.
2. The toner of claim 1 wherein the resin ion complex has a Tg of -90 to 100°C.
3. The toner of claim 1 wherein the resin ion complex has a degree of gellation of 0.5 to 50%.
4. The toner of claim 1 wherein the flowability imparting agent is a hydrophobic flowability imparting agent selected from the group consisting of hydrophobic fluorine-type resins, urethane resins, polyamide resins, aromatic condensation resins, hydrophobic inorganic oxides, clay minerals, colored dyes and pigments and surface-active agents.
5. The toner of claim 4 wherein the flowability imparting agent has an ability to control positive or negative chargeability.
6. The toner of claim 1 which comprises 80 to 99.9% by weight of the inner layer and 20 to 0.1% by weight of the outer layer.
7. The toner of claim 1 which is substantially in the form of spherical particles having a particle diameter of 1 to 30 micrometers.
8. The toner of claim 1 which has a softening point of 60 to 200°C.
9. A process for producing a toner for developing an electrostatically charged image as defined in claim 1, which comprises dispersing a coloring agent in a resin emulsion having a charge, mixing the dispersion with a resin emulsion having an opposite charge to prepare a dispersion of a resin ion complex, adding a flowability imparting agent to the dispersion, and spray-drying the resulting dispersion.
10. The process of claim 9 wherein after adding the resin emulsion having an opposite charge, the dispersion is subjected to an aging treatment at 60 to 90°C.
11. The process of claim 10 wherein the aging time is 0.5 to 2 hours.
12. A toner for developing an electrostatically charged image, which comprises:
(A) 80 to 99.9% by weight of an inner layer composed of a mixture that contains (1) a resin ion complex which is a substantially neutral ionically-crosslinked resin particle produced by mixing a cationic resin emulsion and an anionic resin emulsion in such amounts that the charges of the resins are at least 70% neutralized and then drying the resulting mixed emulsions, where the said resin ion complex has a glass transition temperature of -90 to +100°C and a degree of gellation expressed as the content of an insoluble resin upon extraction with a Soxlet extractor under acetone reflux for 30 minutes of from 0.5 to 50%
by weight, and (2) a coloring agent, and (B) 20 to 0.1% by weight of a thin outer layer comprising a flowability imparting agent selected from the group consisting of hydrophobic fluorine-type resins, urethane resins, polyamide resins, aromatic condensation resins, hydrophobic inorganic oxides, clay minerals, colored dyes and pigments and surface-active agents
(A) 80 to 99.9% by weight of an inner layer composed of a mixture that contains (1) a resin ion complex which is a substantially neutral ionically-crosslinked resin particle produced by mixing a cationic resin emulsion and an anionic resin emulsion in such amounts that the charges of the resins are at least 70% neutralized and then drying the resulting mixed emulsions, where the said resin ion complex has a glass transition temperature of -90 to +100°C and a degree of gellation expressed as the content of an insoluble resin upon extraction with a Soxlet extractor under acetone reflux for 30 minutes of from 0.5 to 50%
by weight, and (2) a coloring agent, and (B) 20 to 0.1% by weight of a thin outer layer comprising a flowability imparting agent selected from the group consisting of hydrophobic fluorine-type resins, urethane resins, polyamide resins, aromatic condensation resins, hydrophobic inorganic oxides, clay minerals, colored dyes and pigments and surface-active agents
13. The toner of claim 12 which is substantially in the form of spherical particles having a particle diameter of 1 to 30 micrometers.
14. The toner of claim 13 which has a softening point of 60 to 200°C.
15. A toner of claim 14, wherein:
the cationic resin employed for producing the resin ion complex is a copolymer obtained by emulsion polymerization and having an average particle diameter of 0.05 to 1 micron the said copolymer being composed of:
(A) 90 to 20% by weight of stylene which may be substituted by one or more substituents selected from the group consisting of alkyl, alkoxy, phenyl and chloro, (B) 80 to 10% by weight of an alkyl (meth)acrylate, and (C) 0.05 to 10% by weight of a cationic chargeable functional comonomer having an amino or quaternary ammonium group.
the cationic resin employed for producing the resin ion complex is a copolymer obtained by emulsion polymerization and having an average particle diameter of 0.05 to 1 micron the said copolymer being composed of:
(A) 90 to 20% by weight of stylene which may be substituted by one or more substituents selected from the group consisting of alkyl, alkoxy, phenyl and chloro, (B) 80 to 10% by weight of an alkyl (meth)acrylate, and (C) 0.05 to 10% by weight of a cationic chargeable functional comonomer having an amino or quaternary ammonium group.
16. A toner of claim 15 wherein, the anionic resin employed for producing the resin ion complex is a copolymer obtained by emulsion polymerization and having an average particle diameter of 0.05 to 1 micron, the said copolymer being composed of:
(A') 90 to 20% by weight of stylene which may be substituted by one or more substituents selected from the group consisting of alkyl, alkoxy, phenyl and chloro, (B') 80 to 10% by weight of an alkyl (meth) acrylate, and (C') 0.05 to 10% by weight of an anionically chargeable functional comonomer having -COOH or -SO3H group.
(A') 90 to 20% by weight of stylene which may be substituted by one or more substituents selected from the group consisting of alkyl, alkoxy, phenyl and chloro, (B') 80 to 10% by weight of an alkyl (meth) acrylate, and (C') 0.05 to 10% by weight of an anionically chargeable functional comonomer having -COOH or -SO3H group.
17. A toner of claim 15, wherein:
the anionic resin employed for producing the resin ion complex is a member selected from the group consisting of oxidized polypropylene, oxidized polyethylene and a copolymer of an olefin and an ethylenic vinyl monomer having an acidic group.
the anionic resin employed for producing the resin ion complex is a member selected from the group consisting of oxidized polypropylene, oxidized polyethylene and a copolymer of an olefin and an ethylenic vinyl monomer having an acidic group.
18. A toner of any one of claims 1 to 8 and 12 to 17, wherein the inner layer also comprises at least one member selected from the group consisting of a charge controlling agent and a magnetic material substantially uniformly dispersed in the inner layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP246,322/85 | 1985-11-05 | ||
| JP60246322A JPH0740142B2 (en) | 1985-11-05 | 1985-11-05 | Toner for electrostatic image development |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1311957C true CA1311957C (en) | 1992-12-29 |
Family
ID=17146830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000522029A Expired - Lifetime CA1311957C (en) | 1985-11-05 | 1986-11-03 | Toner for developing electrostatic images |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4797339A (en) |
| EP (1) | EP0225476B1 (en) |
| JP (1) | JPH0740142B2 (en) |
| CA (1) | CA1311957C (en) |
| DE (1) | DE3685309D1 (en) |
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| US5166027A (en) * | 1990-07-12 | 1992-11-24 | Minolta Camera Kabushiki Kaisha | Fine particles composing developer for electrophotography |
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| EP2710431B1 (en) | 2011-05-18 | 2017-09-13 | Canon Kabushiki Kaisha | Toner |
| JP6351296B2 (en) | 2014-02-24 | 2018-07-04 | キヤノン株式会社 | toner |
| US10705442B2 (en) | 2016-08-03 | 2020-07-07 | Xerox Corporation | Toner compositions with white colorants and processes of making thereof |
| WO2019225207A1 (en) | 2018-05-22 | 2019-11-28 | 三洋化成工業株式会社 | Toner binder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3326848A (en) * | 1964-07-02 | 1967-06-20 | Xerox Corp | Spray dried latex toners |
| US4105572A (en) * | 1976-03-31 | 1978-08-08 | E. I. Du Pont De Nemours And Company | Ferromagnetic toner containing water-soluble or water-solubilizable resin(s) |
| JPS5348740A (en) * | 1976-10-15 | 1978-05-02 | Ricoh Co Ltd | Pressure sensitive adhesive electrostatic photographic toner |
| US4161454A (en) * | 1977-06-02 | 1979-07-17 | Xerox Corporation | Coating magnetite with polyacid |
| NL7711623A (en) * | 1977-10-24 | 1979-04-26 | Oce Van Der Grinten Nv | TONER POWDER FOR DEVELOPING LATENT ELECTROSTATIC IMAGES. |
| AU521423B2 (en) * | 1977-11-10 | 1982-04-01 | Moore Business Forms, Inc. | Microcapsular electroscopic marking particles |
| JPS56110947A (en) * | 1980-02-06 | 1981-09-02 | Konishiroku Photo Ind Co Ltd | Toner for electrostatic charge image development and its production |
| JPS57150855A (en) * | 1981-03-13 | 1982-09-17 | Konishiroku Photo Ind Co Ltd | Toner for developing electrostatic charge image |
| JPS57188045A (en) * | 1981-05-15 | 1982-11-18 | Fuji Xerox Co Ltd | Developer composition |
| JPS58199355A (en) * | 1982-05-17 | 1983-11-19 | Toray Ind Inc | Two component type developer |
| JPH0629987B2 (en) * | 1983-06-03 | 1994-04-20 | 富士ゼロックス株式会社 | Toner for electrostatic image development |
| JPS61122657A (en) * | 1984-11-20 | 1986-06-10 | Fuji Xerox Co Ltd | Developer composition |
-
1985
- 1985-11-05 JP JP60246322A patent/JPH0740142B2/en not_active Expired - Lifetime
-
1986
- 1986-10-30 US US06/924,738 patent/US4797339A/en not_active Expired - Lifetime
- 1986-10-31 EP EP86115168A patent/EP0225476B1/en not_active Expired - Lifetime
- 1986-10-31 DE DE8686115168T patent/DE3685309D1/en not_active Expired - Lifetime
- 1986-11-03 CA CA000522029A patent/CA1311957C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0225476A1 (en) | 1987-06-16 |
| DE3685309D1 (en) | 1992-06-17 |
| JPS62106473A (en) | 1987-05-16 |
| US4797339A (en) | 1989-01-10 |
| EP0225476B1 (en) | 1992-05-13 |
| JPH0740142B2 (en) | 1995-05-01 |
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