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EP0367265B1 - Développateur sec électrophotographique - Google Patents

Développateur sec électrophotographique Download PDF

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Publication number
EP0367265B1
EP0367265B1 EP19890120305 EP89120305A EP0367265B1 EP 0367265 B1 EP0367265 B1 EP 0367265B1 EP 19890120305 EP19890120305 EP 19890120305 EP 89120305 A EP89120305 A EP 89120305A EP 0367265 B1 EP0367265 B1 EP 0367265B1
Authority
EP
European Patent Office
Prior art keywords
resin
toner
developer
composition
produced
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
Application number
EP19890120305
Other languages
German (de)
English (en)
Other versions
EP0367265A2 (fr
EP0367265A3 (fr
Inventor
Masao Niki
Koji Akiyama
Yutaka Kanamaru
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Publication of EP0367265A2 publication Critical patent/EP0367265A2/fr
Publication of EP0367265A3 publication Critical patent/EP0367265A3/fr
Application granted granted Critical
Publication of EP0367265B1 publication Critical patent/EP0367265B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03G9/087—Binders for toner particles

Definitions

  • the invention relates to an electrophotographic dry developer for electrostatic latent images in the field of the electrophotography, electrostatic recording and electrostatic printing.
  • the visible image is transferred to transform materials including flimsy (transferring process).
  • the image is then fixed by appropriate fixing methods such as heating and pressing (fixing process).
  • the developing method applicable to the electronic photographic method can be broadly divided into the dry development method and wet development method. Further, the former can be separated into a method using one component developer and a method using two component developers.
  • the group of two component developers if classified by the toner transportiog system, includes the magnetic brush development method in which powder is applied as the carrier; cascade developing method using a more or less coarse bead carrier; and fur brush development method using less fiber.
  • toner As toner applicable to these development methods, fine powder made by dispersing coloring agents like dyestuffs or pigment into natural or synthesized thermoplastic resin was used. For example, various kinds of additives such as coloring agents, charge controllers and wax, are mixed into and dispersed in binding agents of the polystyrene or polyester family. The matter thus produced is crushed into particles of 1 ⁇ 30 ⁇ m. Then, the particles are applied as toner.
  • toner applicable to single component developer a toner containing magnetic particles such as magnetite, is used.
  • the toner itself is absorbed and held by the magnetic roll and transferred to the image surface.
  • the toner in case a double component developer is applied, the toner is usually mixed into carrier particles such as glass beads, iron powders, and by static attraction caused by friction at the time held in the carrier and transferred to the latent image surface.
  • carrier particles such as glass beads, iron powders
  • the polarity is determined by the charge polarity of the latent image and definite polarity, positive or nagative, and an amount of charge is requested to be given.
  • the frictionally charging property of the carrier, its external material and resin, which is a component of toner can be used but this method is not satisfactory because the toners' charge is too small and it is difficult to reach a desired amount of charge quickly. In these cases, images obtained by development are apt to have fog and are not clear.
  • a material called charge controller is added to control the charging property.
  • a compound with electron donor radical-like nigrosine dye is effective and for negative electrification, an electron accepting organic complex including oil-soluble metal-inclusive dyestuffs are widely used.
  • nigrosine dyes the compatibility with the resin is usually not good and, therefore, it is applied after being denatured by oleic acid, stearic acid, in many cases.
  • charge controllers of positive electrification we have fatty acid amine, quaternary ammonium salt, Fettshwarz HBW, Sudan teak schwarz BBC and brilliant spirit
  • charge controllers of negative electrification colloidal silica, fatty acid metallic salt, mono-azo coloring metal complex salt, chlorinated paraffin, chlorinated polyester, chromogen shwarz, ETCO, Azo oil black.
  • Many of these electrification controllers stem from the dyestuff and pigment group and generally have complicated structures and strong properties of coloring. In case of a chromatic toner, a colored compound cannot be used and colorless or light colored electrification controllers have been studied for use.
  • quaternary ammonium salt vinyl pyridine, dehydrated condensate of ortho positioned amine and decarbonate acid, are applied.
  • Dyes or pigments are, although not completely satisfactory, applied presently because better materials are not available.
  • charge controllers are applied usually after being mixed with a thermoplastic resin, dispersed by thermo melting and kneading, pulverized and adjusted to a proper particle size according to the requirements. Although it is inevitable that these dyes, pigments and charge controllers will be used, many problems arise therefrom.
  • the molecular structure is so complicated that the property is unstable, the quality is changed by thermo melting and kneading, the performance is apt to change according to the conditions of temperature and humidity, and the quality and property of electronic pictures are easily lowered as a result of increased frequency of copying.
  • the second problem involves the difficulty in dispersing these charge controllers evenly in the thermoplastic resin as it causes a difference in the amount of frictional charges between particles and results in lowered image quality.
  • the third problem is that because most charge controllers are hydrophilic and not well dispersed in the resin, they are exposed to the surface of toner particles. Therefore, the volume of charged electricity in the toner is lowered due to charge controllers having absorbed humidity under high humidity conditions. A high quality image cannot be obtained.
  • the fourth problem is that most dyes and pigments generally known as charge controllers are of chromatic color or dark color and cannot be contained in toners which have bright and desired colors.
  • the fifth problem is if the toner which is mixed with charge controllers is used for a long time, that the charge controllers adhere to the face of the photoactive substances or promote adherence of the toner to the photoactive substances, and exert harmful effects upon their formation of electrostatic image, (photoactive substance filming) damage the face of the photoactive substnace or cleaning beads, or accelerate the abrasion of the material portion thereof. As stated above, not a few undesirable actions are exerted on the cleaning process of duplicating machines.
  • color toners those made by dispersing or dissolving various kinds of dyestuffs or pigments into a binder resin are used.
  • toners especially when the purpose is to reproduce full color images by using the three primary colors, the following is very important. That is, not only are all of the basic performances including the above mentioned charging property good, but it also reproduces color which the original images had and, therefore, spectral reflectancies of each color draw almost idealistic curves and very low saturation of black is created. These are very important.
  • Japanese patent publication No. 60-112051 disclosed an even and sufficient positively- charged developer made as follows:
  • the purpose is to avoid the offsetting phenomena in the heat-roller fixing method.
  • the binder resin to be used is a copolymer resin of a copolymer-natured monomer having a specific polyester resin and a tertiary amino group and a hydrophobic copolymer-natured monomer.
  • a copolymer resin of a copolymer-natured monomer having a specific polyester resin and a tertiary amino group and a hydrophobic copolymer-natured monomer.
  • the composing ratio between copolymer-natured monomer with polyester resin and tertiary amino group and copolymer resin of hydrophobic copolymer-natured monomer is 10 to 50 weight percent : 50 to 90 weight percent, and the softening point in the ring and ball system is within the limit of 100 to 180°C.
  • EP-A-0 122 650 describes an electrophotographic dry developer comprising carrier particles and toner particles.
  • the toner particles comprise a binder resin comprising a polyester resin and a styrene-acrylic resin obtained by co-polymerizing a styrene compound, an acrylic compound and a monomer having an amino group and a dyestuff or pigment or carbon black, wherein the weight ratio of the polyester resin and the styrene-acrylic resin is 82 parts to 10 parts.
  • PA of Japan, vol. 9, no. 20 discloses to mix carrier particles coated with a silicone resin with the toner particles containing a di- or triphenylmethane type dye.
  • US-A-4,560,635 discloses a toner composition
  • a toner composition comprising resin particles, pigment particles and a sulfate charge enhancing additive consisting of distearyl dimethylammonium methylsulfate and behenyl trimethylammonium methylsulfate.
  • the purpose of this invention is related to positively charged dry developers with a stable charging property by which the above mentioned traditional tasks can be settled. Especially, it is to provide a more improved positively charged full color developer.
  • Another purpose of this invention is to prepare a developer with excellent transparency at the time when it is laid on top of another and also when transferred to and fixed on a transparency.
  • the additional purpose of this invention is to provide a developer which enables development and transfer faithful to the static latent image, that is, a developer which is without fog or scattered toners at or around the edge and which can obtain high density image and reproduce excellent half-tones.
  • this invention is purposed to offer a developer which maintains its initial property even after having been used for a long period of time, which is without toner cohesion and which can be preserved safely.
  • This invention provides an electrophotographic dry developer, which comprises carrier particles and colored toner particles comprising a binder resin comprising (A) a polyester resin and (B) a styrene-acrylic resin obtainable by co-polymerizing a styrene compound, an acrylic compound and a monomer having an amino group, at a weight ratio of (A) to (B) ranging from 55:45 to 95:5, both resins (A) and (B) having a softening point of 110°C or less, and a dyestuff or pigment, wherein the carrier particles consist of core particles coated with a silicone resin being curable at room temperature and being heated to at least 180°C or with a fluoro resin having at least 80 mole percent of fluorine atoms related to the sum of the monovalent atoms attached to the carbon atoms.
  • a binder resin comprising (A) a polyester resin and (B) a styrene-acrylic resin obtainable by co-polymerizing a
  • the carrier has been coated with a silicone resin being curable at the room temperature and heated at 180 degree C or higher.
  • An alternative coating is a fluoro resin having 80 mole percent or more of fluorine atoms in the monovalent atoms attached to the carbon atoms.
  • this invention is to prepare positively charged dry developers with the following properties:
  • the binder resin (the main content of toners) consists of polyester resin (A) and styrene acrylic resin (B) produced by copolymerizing copolymer-natured monomer containing the amino group.
  • the weight ratio of resin (A) and (B) is within the range of 55 : 45 to 95 : 5, and the softening point (ring and ball method) is 110 degrees centigrade or less.
  • the carrying agents to be mixed with the binder resin are dyes or pigments of chromatic colors.
  • the main ingredients of the binder resin in this invention are a mixture of polyester resin (A) and styrene-acrylic resin (B), which are produced by polymerizing-polymerization-natured monomer containing the amine group.
  • Polyester resin (A) applied here is synthesized by a polycondensation reaction between polycarboxylic acid and polyhydric alcohol.
  • group of polyvalent carboxylic acid the following carboxylic acid, carboxylic acid anhydride and low class alkylester of carboxylic acid can be applied; e.g., fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 3-isodecyl-1, 2, 5, 6 - hexanetetra carboxylic acid, succinic acid, isooctyl-succinic acid and adipic acid.
  • polyhydric alcohol group the following are applied, e.g., ethylene glycol, diethylene glycol, triethylene alcohol, propylene glycol, butanediol, neopentyl glycol, polyoxyethylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane, polyoxy propylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane, hydrogenated bisphenol A, glycerol and trimethylol propane.
  • mono carboxylic acid or mono alcohol can be added as polyester materials.
  • a copolymerizing monomer containing the amino group which is used in the production of styrene acrylic resin (B)
  • a copolymerized compound of copolymerization-natured monomer containing the amino group the following can be applied:
  • monomers of the styrene family such as styrene, P-methylstyrene, ⁇ -methylstyrene; esters of acrylic acid and methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate.
  • the weight composition of resin (A) and resin (B), (A) : (B) is 55 : 45 ⁇ 95 : 5, more preferably 65 : 35 ⁇ 90 : 10. If the ratio of resin (B) is 5 or less, the charged electrostatic capacity is not enough or the electrostatic charge becomes negative. If the ratio of resin (B) is 45 or more, the property of dispersing or dissolving dyestuffs and/or pigment of polyester resin will be lost, and in case it is applied in color toners, saturation will be lost and the color will become dull. Furthermore, a defect of OHP's projected image becoming dark will be produced. Therefore, it is undesirable.
  • the softening point (SP) of resin (A) and (B) under the ring and ball method (JIS K-2207) should be 110°C or less. SP beyond the said limit will result in too much molar weight and spoiling due to entwinement of the high polymer chain, the rapidly melting property. Thus, the resulting image will lack transparency and be of dull color with low saturation. Especially those of SP over 130 degrees centigrade are not desirable.
  • coloring agents for color toners in this invention widely known dyes or pigments of chromatic colors can be used as listed hereunder:
  • Cyan C.I. Solvent Blue-25, C.I. Solvent Blue-94, C.I. Pigment Blue-15.3.
  • developer toners in this invention can offer more stabilized images by combination with carriers covered with specific cladding materials.
  • carriers to be applied in this invention widely known carriers can be used, e.g., ferromagnetic materials including iron, ferrite, steel, magnetite, nickel, or glass, etc.
  • ferromagnetic materials including iron, ferrite, steel, magnetite, nickel, or glass, etc.
  • specific cladding materials are straight silicon resin, fluoro resin.
  • Silicon varnish curing under ordinary temperatures is silicon resin of the following chemical structural formula, including KR-114, KR-220, KR-251 and KR-255 (all of which are manufactured by Shin-etsu Chemical Co., Ltd.) (In this formula, R1 ⁇ R4 are hydrogen atoms, hydroxyl group, low class alkoxyl group with the number of carbons being 1 ⁇ 4, methyl group or phenylgroup.)
  • the specific cladding material is a fluoro resin
  • the resin it is desirable for the resin to be a fluoro resin, whose ratio of fluorine atoms in univalent atom connecting with carbon principal and side chains is 80 mole percent.
  • fluoro resins examples include poly (tetra fluoro ethylene-vinylidene fluoride), poly (tetra fluoro ethylene - fluoro propylvinyl-ether) copolymer of methacrylic acid 2 - fluoro octyl ether and methacrylic acid n-butyl, and poly (tetra fluoro ethylene-hexa fluoro propylene).
  • the above examples are used individually or in mixture.
  • toluene 60.0 and dodecyl mercaptan 3.0 were placed in a reaction receptacle equipped with a stirrer, a refluxing pipe, a dropping funnel and a nitrogen blowing pipe.
  • a mixed solution of styrene 120.0 n-butyl methacrylate 70.0, diethyl amino ethyl methacrylate 10.0, , and ⁇ , ⁇ '-azobis isobutyronitrile 4.0 was instilled and polymerized for 2 hours. After an additional 2 hours of aging, the temperature was risen to 200°C and the pressure was decreased to 30 mm Hg., to eliminate toluene by topping.
  • the resin obtained had a softening point at 104.5°C and Tg at 62.3°C.
  • Iron powder (TSV-300) 1000 made by Nippon Teppun Co., Ltd., as being fluidizated on a fluid bed, was heated up to 60°C, maintained at the same temperature and sprayed with silicon resin (KR-252 of Shin-etsu Silicone Co., Ltd.) 10 (figured on the basis of resin contained therein) solution melted into 5% with toluene. After drying for 20 minutes, it was heat treated at 200°C for 30 minutes in an electric furnace. Thus, a silicone resin coat carrier was obtained.
  • Nippon Teppun-made iron powder (TSV-300) 1000 which was fluidized on a fluid bed and heated up to 80°C, was sprayed with fluoro resin 10 (made by Daicel Chemical Industries, Ltd., Daifuron ND-4) and diluted with water to a 5% solution. Then, after drying for 30 minutes, it was heat treated for 20 minutes in an electric furnace at 300°C. In this manner, a fluoro resin coated carrier was obtained.
  • Polyester resin in Composition Example 1 70.0 Styrene-acrylic resin in Composition Example III 80.0 C.I. Pigment Yellow-14 5.0 Viscol 660P (Made by Sanyo Chemical Industries, Ltd., polypropylene wax) 2.0
  • the quantity of charged electricity was 16.5 ⁇ c/g at the initial stage, and a bright and intense image without fog was produced. Moreover, after consecutive copying of 10,000 sheets, the quantity of charged electricity was 17.6 ⁇ c/g, and good quality images without any differences from the initial one were produced. Also, images copied on OHP sheets had good transparency and images projected with OHP had good yellow color.
  • magenta toner was made by the same method as in Execution Example I. Next, a developer was produced from said magenta toner 50.0 and silicone resin coat carrier 950 in Manufacturing Example I.
  • Polyester resin in Composition Example I 70 Styrene-acrylic resin in Composition Example IV 30 C.I. Solvent Red-49 5.0 Viscol 660 (Made by Sanyo Chemical Industries, Ltd.) 2.0
  • a magenta toner was produced by the same method as in Execution Example I. Then, a developer was manufactured from said magenta toner 50.0 and fluoro resin coat carrier 950 in Manufacturing Example 2.
  • a cyanic toner was produced from the compounds of the above ingredients by the same method as that of Execution Example 1. Next, a developer was produced from said cyanic toner 50.0 and fluoro resin coat carrier 950 stated in Manufacturing Example 2.
  • Polyester resin in Composition Example I 75.0 Styrene acrylic resin in Composition Example III 25.0 C.I. Solvent Yellow-114 5.0 Viscol 660P (Made by Sanyo Chemical Industries, Ltd.) 2.0
  • a yellow toner was produced from compounds of the above ingredients by the same method as stated in Execution Example I. Next, a developer was produced from said yellow toner 50.0 and silicone resin coat carrier 950 in Manufacturing Example 1.
  • Polyester resin in Composition Example II 80.0 Styrene acrylic resin in Composition Example IV 20.0 C.I. Pigment Red-13 5.0 Viscol 660P (Made by Sanyo Chemical Industries, Ltd.) 2.0
  • a magenta toner was produced from compounds of the above ingredients by the same method as stated in Execution Example 1. Next, a developer was produced from said magenta toner 50.0 and silicone resin coat carrier 950 in Manufacturing Example 1.
  • Polyester resin in Composition Example II 75.0 Styrene acrylic resin in Composition Example III 25.0 C.I. Solvent Blue-15.3 5.0 Viscol 660P (Made by Sanyo Chemical Industries, Ltd.) 2.0
  • a cyanic toner was produced from compounds of the above ingredients by the same method as stated in Execution Example 1. Next, a developer was produced from said cyanic toner 50.0 and fluoro resin coat carrier 950 in Manufacturing Example 2.
  • a cyanic toner was produced from compounds of the above ingredients by the same method as stated in Execution Example I. Next, a developer was produced from said cyanic toner 50.0 and coat carrier 950 (made by Nippon Teppun TSV-300).
  • a yellow toner was produced from compounds of the above ingredients by the same method as stated in Execution Example I. Next, developer was produced by said yellow toner 50.0 and fluoro resin coat carrier 950 stated in Manufacturing Example 2.
  • a magenta toner was produced from compounds of said ingredients by the method stated in Execution Example I. Next, a developer was produced from said magenta toner 50.0 and silicon resin coat carrier 950 stated in Manufacturing Example I.
  • a cyanic toner was produced from compounds of the above ingredients by the same method as stated in Enforcement Example I. Next, a developer was produced from said cyanic toner 50.0 and fluoro resin coat carrier 950 in Manufacturing Example 2.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)

Claims (1)

  1. Révélateur électrophotographique à sec, comprenant des particules de support et des particules de tonner colorées comprenant une résine en tant que liant comprenant (A) une résine de polyester et (B) une résine de type styrène-acrylique pouvant être obtenues par copolymérisation d'un composé styrénique, d'un composé acrylique et d'un monomère présentant un groupe amino, dans un rapport molaire de (A) à (B) compris entre 55:45 et 95:5, les résines (A) et (B) présentant toutes deux un point de ramollissement de 110°C ou moins, et une substance colorante ou un pigment, les particules de support étant constituées de particules formant noyaux revêtues d'une résine de silicone durcissable à la température ambiante et chauffée à au moins 180°C ou revêtues d'une résine fluorée présentant au moins 80% en moles d'atomes de fluor relativement à la totalité des atomes monovalents reliés aux atomes de carbone.
EP19890120305 1988-11-02 1989-11-02 Développateur sec électrophotographique Expired - Lifetime EP0367265B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP278105/88 1988-11-02
JP63278105A JP2733073B2 (ja) 1988-11-02 1988-11-02 正帯電性乾式現像剤

Publications (3)

Publication Number Publication Date
EP0367265A2 EP0367265A2 (fr) 1990-05-09
EP0367265A3 EP0367265A3 (fr) 1991-12-18
EP0367265B1 true EP0367265B1 (fr) 1996-02-14

Family

ID=17592699

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890120305 Expired - Lifetime EP0367265B1 (fr) 1988-11-02 1989-11-02 Développateur sec électrophotographique

Country Status (3)

Country Link
EP (1) EP0367265B1 (fr)
JP (1) JP2733073B2 (fr)
DE (1) DE68925670T2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2928370B2 (ja) * 1990-10-03 1999-08-03 花王株式会社 電子写真用現像剤組成物用の結着樹脂及びその製造方法
US6288166B1 (en) * 1993-09-03 2001-09-11 Kao Corporation Binder resin for toner and positively chargeable toner containing the same
DE102004028022B4 (de) 2004-06-09 2006-11-16 Perkinelmer Optoelectronics Gmbh & Co.Kg Sensor
JP5195361B2 (ja) * 2008-12-02 2013-05-08 コニカミノルタビジネステクノロジーズ株式会社 二成分現像剤

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5492326A (en) * 1977-12-29 1979-07-21 Ricoh Co Ltd Electrophotographic carrier material
JPS57155552A (en) * 1981-03-20 1982-09-25 Ricoh Co Ltd Developer for electrophotography
DE3465384D1 (en) * 1983-04-13 1987-09-17 Agfa Gevaert Nv Toner composition for use in the developing of electrostatic charge patterns
US4560635A (en) * 1984-08-30 1985-12-24 Xerox Corporation Toner compositions with ammonium sulfate charge enhancing additives
JPS62127749A (ja) * 1985-11-29 1987-06-10 Konishiroku Photo Ind Co Ltd 静電像現像剤

Also Published As

Publication number Publication date
DE68925670T2 (de) 1996-09-26
EP0367265A2 (fr) 1990-05-09
JP2733073B2 (ja) 1998-03-30
DE68925670D1 (de) 1996-03-28
JPH02124582A (ja) 1990-05-11
EP0367265A3 (fr) 1991-12-18

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