WO1994023346A1 - Procede et appareil de formation d'une image en couleur - Google Patents

Procede et appareil de formation d'une image en couleur Download PDF

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Publication number
WO1994023346A1
WO1994023346A1 PCT/JP1994/000507 JP9400507W WO9423346A1 WO 1994023346 A1 WO1994023346 A1 WO 1994023346A1 JP 9400507 W JP9400507 W JP 9400507W WO 9423346 A1 WO9423346 A1 WO 9423346A1
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WO
WIPO (PCT)
Prior art keywords
transfer layer
resin
transfer
layer
photoreceptor
Prior art date
Application number
PCT/JP1994/000507
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English (en)
Japanese (ja)
Inventor
Eiichi Kato
Sadao Osawa
Yusuke Nakazawa
Original Assignee
Fuji Photo Film Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Priority to DE69420714T priority Critical patent/DE69420714D1/de
Priority to EP94910558A priority patent/EP0692743B1/fr
Publication of WO1994023346A1 publication Critical patent/WO1994023346A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/01—Apparatus for electrographic processes using a charge pattern for producing multicoloured copies
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof

Definitions

  • the present invention relates to a color image forming method such as an electrophotographic color copying machine, a color printer, a color puller and a color checker, and an apparatus used therefor.
  • a color image forming method such as an electrophotographic color copying machine, a color printer, a color puller and a color checker, and an apparatus used therefor.
  • a multi-color toner is sequentially superimposed and developed directly on the electrophotographic photoreceptor surface using an electrostatographic developer to form a color image, and then transferred to a transfer material such as printing paper at a time.
  • a transfer material such as printing paper at a time.
  • Such a developing method includes a so-called dry developing method and a wet developing method.
  • the color image obtained by the wet development method is preferable because the color image of each color does not have a color shift and a high-resolution color image can be obtained as compared with the case of the dry toner, but the wet image is directly applied to the paper from the photoreceptor surface. It is extremely difficult to completely transfer an image.
  • Japanese Patent Application Laid-Open Nos. 2-115,665 and 2-115,666 each disclose in advance an electrophotographic process after laminating a transparent film on the surface of a photoreceptor.
  • a method is disclosed in which a wet toner image is formed on a film, and then the film is peeled off from a photoreceptor, and the image is transferred by attaching to a plain paper.
  • the thickness of the film to be laminated is 9; however, the production and handling of the film having such a thickness is extremely troublesome, and it is necessary to take additional measures for that.
  • Japanese Patent Publication No. 2-431185 discloses that H light is emitted from behind a transparent electrophotographic photoreceptor to form an overlapped color-separated image on a dielectric support.
  • a method for transferring onto a transfer material is disclosed. In this method, exposure is performed from the transparent support side of the photoreceptor, and the conductive layer must also be transparent, which is disadvantageous in terms of cost.
  • Japanese Patent Application Laid-Open No. 2-264280 describes a method in which a toner image on a photosensitive layer is transferred to a highly smooth primary intermediate transfer medium and then transferred to a final transfer receiving material. Furthermore, Japanese Patent Application Laid-Open Nos. 3-243973 and 4-9077 propose a method of obtaining a good final color image even with a wet toner by using a special transfer medium. I have. In the method using such an intermediate transfer medium, it is said that the toner image can be transferred clearly without being affected by the surface irregularities of the material to be transferred. Since the toner image is transferred onto the transfer material, the resulting color image has a missing toner image or uneven image density, and in particular, a fine image such as a fine line or a letter is observed.
  • the transfer of the toner image remains on the surface of the photoconductor or the intermediate medium after the transfer of the toner image. This means that if the photoreceptor or intermediate medium is used repeatedly, the surface needs to be cleaned, and furthermore, the setting of the device and damage to the surface of the photoreceptor and intermediate medium due to the cleaning will occur. Etc. becomes a problem.
  • the present invention solves the above-mentioned problems of the conventionally known electrophotographic transfer image forming method.
  • the present invention provides a color image with excellent transferability of a toner image, no color shift, high definition, and high image quality.
  • a new electrophotographic color image forming method using a transfer layer on an intermediate medium, which can be obtained easily and stably and can reproduce an excellent image without selecting the final transfer material An apparatus to be used is provided. Further, the transfer layer has good resilience from the photoreceptor and good adherence to the material to be transferred, and has good brushing / sealability and preservability of the color copy, and
  • An object of the present invention is to provide an electrophotographic color image forming method having good storage stability.
  • the photoreceptor is repeated using a transfer device having a thimble configuration in the electrophotographic apparatus. Disclosure of which is can be used, can achieve low-running cost, provided that (invented a method of forming a transfer layer in the transfer device
  • An object of the present invention is to form a toner image of one or more colors by an electrophotographic process on a releasable first transfer layer formed on an electrophotographic photosensitive member having a peelable surface, and forming the toner image on a transfer layer. Is transferred onto the primary receptor, and then the toner image on the primary receptor is transferred onto the final transfer material together with the transfer layer. Was issued.
  • FIG. 1 an outline of the process is shown in FIG. 1, in which a transfer layer 1 which can be separated from at least an electrophotographic photosensitive member 11 comprising a support 1 and a photosensitive layer 2 2 (i), a toner image 3 of one or more colors is formed thereon using a normal electrophotographic process (ii), and then the toner image 3 is transferred to the primary receptor 20 together with the transfer layer 12 ( i ii) Further, the toner image 3 is transferred together with the transfer layer 12 to the final transfer material 30 (iv) to obtain a color copy.
  • a transfer layer 1 which can be separated from at least an electrophotographic photosensitive member 11 comprising a support 1 and a photosensitive layer 2 2 (i)
  • a toner image 3 of one or more colors is formed thereon using a normal electrophotographic process (ii)
  • the toner image 3 is transferred to the primary receptor 20 together with the transfer layer 12 ( i ii)
  • the toner image 3 is transferred together with the transfer layer 12 to the final transfer material
  • the toner image By transferring the toner image 3 thus formed on the transfer layer 12 together with the transfer layer 12 to the primary receptor 20 and then to the final transfer material 30, the toner image can be transferred to the transfer layer.
  • a conventional intermediate medium that transfers directly from the intermediate medium to the transfer material without using the conventional method.
  • transfer can be easily performed. Further, excellent color images can be stably maintained, and much better images can be obtained.
  • a second transfer layer 12 ′ which can be further separated is formed on the toner image 3 (ii) formed on the transfer layer 12.
  • the toner image 3 is transferred in the same manner as described above. ') Can be transferred to the primary receptor 20 (iii) and then to the final transfer material 30 (iv).
  • a toner image 3 is formed on a transfer layer 12 formed on a photoreceptor 11, and the transfer layer 12 is transferred to an intermediate medium 20 and further to a final transfer material 30.
  • the transfer layer 12 does not adversely affect the electrophotographic characteristics in the electrophotographic process, and the transfer property (photosensitivity) in the transfer process.
  • a wide variety of conditions, such as good separation from the body and good adhesion to the material to be transferred, and good brushing / sealability and firing characteristics as a color copy, are provided in a single transfer layer. I needed to.
  • the toner image 3 is formed after the toner image 3 is formed.
  • Various conditions to be achieved can be satisfied by dividing each layer according to its function.
  • the toner image 3 of the color copy finally obtained is sandwiched between the first transfer layer 12 and the second transfer layer (12 ′ or 12 ⁇ ), so that Since the fixing strength of the toner image area is reinforced by the transfer layer, it can be used without considering the fixability of the toner itself.
  • the transfer layers 12, 12 ′ and 12 ⁇ ⁇ used in the present invention may mainly contain a thermoplastic resin (A) having a glass transition point of 140 ° C. or less or a softening point of 180 ° or less. preferable. As a result, the transferability of the transfer layer becomes better.
  • the surface of the electrophotographic photoreceptor 11 having releasability provided in the present invention has an adhesive strength of 10 O gram * force (g ⁇ 0) according to JISZ 0237-1980 “Adhesive tape / adhesive sheet test method”. Or less, more preferably 50 g ⁇ ⁇ or less, particularly preferably 10 g ⁇ ⁇ or less, and the adhesive force on the surface of the primary receptor 20 is larger than the adhesive force on the surface of the photoreceptor 11, particularly It must be larger than 10 g ⁇ f and more than 30 g ⁇ f preferable.
  • the adhesive strength of the surface of the primary receptor 120 is at most 200 g ⁇ f, and particularly preferably 180 g ⁇ f.
  • the photoreceptor 11 and the transfer layer 12 can be separated from the photoreceptor 11 and the transfer layer from the photoreceptor 11 to the primary receptor 20.
  • Easy transfer of toner image 3 for each 12 and transfer of toner image 3 for each transfer layer 1 2 (or 12 'or 12 ⁇ ) from primary receptor 20 to final transfer material 3 3 it is preferable that the adhesive strength between the surface of the primary receptor 20 and the surface of the final transfer material 30 is at least lower than that of the latter.
  • test plate An electrophotographic photoreceptor 11 on which a transfer layer is to be formed is used as a “test plate”.
  • the roller is reciprocated one time at a speed of about 300 Z from the top of the test piece, with the striking surface of the test piece facing downward, and pressed against the cleaned test plate.
  • a constant-speed tension-type tensile tester peel off about 25 mm, and then peel off at a speed of 120 o / min.
  • the test shall be performed on three test pieces, and the average value of 12 pieces measured from the three test pieces shall be obtained, and this shall be proportionally converted per 10 mm width.
  • an amorphous silicon electrophotographic photoreceptor or an electrophotographic photoreceptor to be adjacent to the transfer layer 12 or adjacent to the transfer layer 12
  • the layer containing a gay atom and a resin containing a Z or fluorine atom is the transfer layer.
  • Any layer adjacent to (or a layer adjacent to) 12 may or may not be a photosensitive layer.
  • a non-photosensitive layer (overcoat layer) having releasability may be provided on the photosensitive layer in order to impart releasability to the transfer layer 12.
  • the copolymer formed by bonding the polymer segment (3) containing a polymer component in an amount of 0 to 20% by weight with at least one block each further enhances the flexibility of the transfer layer 12. It is preferable to make it good.
  • a compound (S) containing at least a fluorine atom and / or a gayne atom is adsorbed on the surface of the electrophotographic photoreceptor.
  • a "photoreceptor having an insulative surface” can be obtained.
  • a general-purpose electrophotographic photoreceptor can be used without considering the hybrid nature of the surface of the electrophotographic photoreceptor itself.
  • the transfer layer 12 or the second transfer layer 12 may be previously provided on the electrophotographic photoreceptor 11 or the primary receptor 20, respectively, or may be formed each time.
  • the formation of the transfer layer 12 or the transfer layer 12 ⁇ may be performed by an apparatus separate from the electrophotographic process or the transfer process, respectively, or the photoreceptor may be formed in the same apparatus as these processes. It may be performed each time on 11 or primary receptor 20.
  • the transfer layer 12, 12 ′ or 12 ′ is formed on the photoreceptor 11 by at least one of hot melt coating, transfer from paper, and electrostatic adhesion and electrodeposition. It is preferably formed on the transfer layer 12 or the primary receptor 20.
  • the step of forming the transfer layer 12 and further the transfer layer 12 ′ or 12 ′′ is provided in the same apparatus as the electrophotographic process or the transfer process, and the transfer layer is formed each time.
  • the photoreceptor 11 and the primary receptor 20 after covering these transfer layers can be used repeatedly without disposable, and the electrophotographic process can be continuously performed in the apparatus. Therefore, it is advantageous for reducing running cost and is preferable. Therefore, a third preferred embodiment of the present invention is a color image forming method characterized by performing the following steps (i) to (iV) in the same apparatus.
  • step (a) is further performed in the same apparatus between the above steps (ii) and (iii).
  • step (a) a step of forming a second transfer layer 12 ′ further separable on the toner image 3;
  • step (b) is further performed in the same apparatus before the step (iii).
  • the present invention provides a color image forming method comprising a step of adsorbing or adhering the compound (S) to the surface of 1.
  • the step (i) of forming the first transfer layer 12 on the electrophotographic photoreceptor 11 is carried out in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less, in the organic solvent 1.0.
  • Resin particles containing at least one compound (S) containing at least 0.01 g of a fluorine atom and a Z or gayne atom that dissolves in the resin and having a glass transition point of 140 or less or a softening point of 180 or less (AR ) Is dispersed by electrodeposition or adhesion of the resin particles (AR) to the surface of the electrophotographic photoreceptor 11 by electrophoresis to form a film.
  • the compound (S) containing fluorine atoms and Z or gayne atoms contained in the electrodeposition dispersion liquid for forming the transfer layer is electrophoresed by the dispersed resin particles (AR), and the surface of the photoconductor 11 is charged.
  • the photosensitive layer 11 Before being attached, the photosensitive layer 11 is adsorbed or adhered to the photosensitive element 11, so that the surface of the photosensitive element 11 is imparted with a magnetic property before the transfer layer 12 is formed, and the transfer property of the transfer layer 12 is exhibited.
  • Has the effect of causing By using this method, it is possible to simultaneously impart the sensitivities of the photoreceptor 11 and the transfer layer 12 to the surface of the electrophotographic photoreceptor 11 to be used. No special technology is required.
  • the resin particles (AR) are supplied between opposing electrodes provided to face the electrophotographic photosensitive member 11, and electrophoresed according to a potential gradient applied from an external power supply to the electrophotographic photosensitive member.
  • the film by electrodeposition or adhesion on the substrate 11 it is easy to adjust a more uniform layer.
  • the present invention provides means for forming a transfer layer detachable on the surface of an electrophotographic photoreceptor, means for forming a toner image of one or more colors on the transfer layer by an electrophotographic process,
  • a color image forming apparatus comprising at least means for transferring an image together with a transfer layer and means for transferring the toner image together with a transfer layer from a primary receptor to a final material to be transferred.
  • a releasable second image is formed on the toner image formed on the transfer layer.
  • a color image forming apparatus further comprising: means for forming a second transfer layer; or a color image forming apparatus further comprising: means for forming a second transfer layer which can be formed on the next receptor. I do.
  • the present invention provides an image forming apparatus which further comprises means for adsorbing or adhering the compound (S) to the surface of the photoreceptor.
  • transfer layer 12 (including 12 ′ or 12 ′′) used in the present invention will be described in detail.
  • the transfer layer 12 of the present invention is mainly composed of the resin (A), is light-transmissive, and is transparent to at least a part of the wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member. It is not particularly limited as long as it has the following, and may be colored. If the image transferred to the final transfer material is a color image (particularly a full-color image), a colorless and transparent transfer layer is usually used.
  • Transfer layer 1 2 composed mainly of a resin (A) of the present invention, preferably; 1 8 0 ° C below the temperature and Roh or 3 O kgf / cm 2 or less pressure, more preferably 1 6 0 ° C It is preferable that separation can be performed under the following transfer conditions of temperature and / or pressure of 20 kgf / cm 2 or less. If the above conditions are exceeded, a device for separating and transferring the transfer layer from the photoreceptor surface is used. The device for maintaining the heat capacity and pressure in the inside becomes large, and the transfer speed becomes extremely slow, which is not preferable.
  • the above conditions are preferably a temperature of room temperature or higher and a pressure of 0.1 kgf / cm 2 or higher.
  • the resin (A) may be any one as long as it peels off under the above-mentioned transfer conditions.
  • the thermo-physical properties of the resin (A) may be a glass transition point of 140 ° C. or less or a softening point of 180 ° C. or less.
  • a resin is preferable, and a resin having a glass transition point of 100 ° C. or lower or a softening point of 150 ° C. or lower is more preferable.
  • resins (A) having different glass transition points or softening points.
  • a resin having a glass transition point of 30 to 140 or a softening point of 35 to 180 ° C (hereinafter referred to as “resin (AH)”) has a glass transition point of 4 O'C or less or a softening point of 45 ° C or less
  • the resin has a glass transition point or a softening point lower than the resin S (AH) by 2 ° C. or more (hereinafter referred to as “resin (AL)”).
  • the resin (AH) preferably has a glass transition point of 30 to 12 CTC or a softening point of 38′C or more.
  • the glass transition point or softening point of the resin (AL) is at least 5 C lower than that of the resin (AH).
  • the difference in glass transition point or softening point between the resin (AH) and the resin having the lowest glass transition point or softening point is as follows. It refers to the difference from the one with the highest glass transition point (Tg) or softening point in tree flum (AL).
  • the ratio of the resin (AH) to the resin (AL) in the transfer layer is 5 to 90/95 to 10 (weight ratio).
  • the transfer layer 12 when the transfer layer is divided into two with the toner image interposed therebetween, that is, when the transfer layer 1 ′ or the transfer layer 11 ′′ is provided in addition to the transfer layer 12,
  • the transfer layer 12 provided above is not particularly limited as long as it is transmissive and has transparency to at least a part of the wavelength light in the spectral sensitivity region of the photoreceptor.
  • a colorless and transparent transfer layer is usually used.
  • the transfer layer 12 provided in the present invention does not degrade electrophotographic properties (band compressibility, charge retention in darkness, light sensitivity, etc.) until a toner image is formed by an electrophotographic process.
  • it has thermoplasticity that easily covers the surface of the photoreceptor 11, and in the final transfer process, it is easily adhered to the transfer material 30 regardless of the type of the transfer material 30 This is very important.
  • good adhesion to the transfer material 30 is extremely important in improving the releasability of the interface between the second transfer layer 12 ′ or 12 ′′ and the surface of the receptor 20. is there.
  • the second transfer layers 12 ′ and 12 ′′ are provided separately from toner image formation, there are no restrictions on the electrophotographic process as in the transfer layer 12.
  • a colorless and transparent transfer layer is usually used because it becomes the uppermost layer in the color image after the transfer to 0.
  • the second transfer layers 1 2 ′ and 12 ′′ have good adhesion to the toner image layer 3 and the transfer layer 12 in the non-image area. It is important that the storage stability of the copy is good so that it does not cause any trouble and that the transfer layer does not peel even if it is placed on various sheets and then fired.
  • first transfer layer 12 and the second transfer layer 12 'or 12' of the present invention are preferable to select the first transfer layer 12 and the second transfer layer 12 'or 12' of the present invention so as to satisfy the above characteristics.
  • the toner image layer 3 and the transfer layer 12 are provided on the surface in contact with the intermediate transfer layer 20 without the second transfer layer 12 ′ or 12 ⁇ , and the transferability is further improved. The effect can be obtained.
  • first transfer layer 12 provided on the photoreceptor 11 or a layer made of a thermoplastic resin (AH) having a high glass transition point or softening point, and a thermoplastic layer having a low glass transition point or softening point further thereon
  • the second transfer layer 12 ′ or 12 ′ provided on the toner image 3 or the primary receptor 20 also forms a layer made of resin (AL), and the side in contact with the transfer layer 12 Layered structure consisting of a layer made of thermoplastic resin (AL) having a low glass transition point or softening point, and a layer made of thermoplastic resin (AH) having a high glass transition point or softening point on the side in contact with primary receptor 20.
  • the adhesion between the transfer layer 12 on which the toner image 3 is formed and the second transfer layer 12 ′ or 12 ′′ is significantly improved, and the primary receptor 20 and the transfer material 30 Transfer properties are further improved, and transfer conditions (heating temperature, pressure, transport speed, etc.) As the latitude further expands, the image can be easily transferred irrespective of the type of material to be transferred as a color image copy. By adopting the structure, the effect of improving the transferability is recognized.
  • the outermost surface side of the transfer layer formed on the transfer material 30 is mainly composed of a resin (AH) having a high glass transition point or softening point.
  • AH resin having a high glass transition point or softening point.
  • the filling characteristics are further improved, and by selecting the type of resin (AH), it is possible to provide writing and marking properties close to those of plain paper.
  • any resin may be used as long as it is a thermoplastic resin that satisfies the above physical properties.
  • specific examples include thermoplastic resins, resins known as adhesives and pressure-sensitive adhesives, For example, olefin polymers and non-polymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, aryl alkanoate polymers and copolymers, and polymers of styrene and its derivatives And copolymers, olefin-styrene copolymers, olefin-unsaturated carboxylic acid ester copolymers, atarilonitrile copolymers, methacrylonitrile copolymers, Acrylate polymers and copolymers, methacrylate polymers and copolymers, styrene-acrylate copolymers, Styrene monomethacrylate copolymer
  • the resin (A) used for the transfer layer of the present invention is a polymer containing a substituent containing a fluorine atom and a Z or gayne atom, which has an effect of improving the releasability of the resin (A) itself.
  • the component (F) may be further contained as a copolymer component in each of the resins described above.
  • the present invention includes both those incorporated into the polymer main chain of the polymer and those contained as a substituent of a high molecular side chain.
  • the content of the polymer component (F) is preferably 3 to 40% by weight, more preferably 5 to 25% by weight, based on 100 parts by weight of the whole polymer component of the resin (A). These polymer components (F) are preferably contained in the copolymer of the resin (A) as a lock.
  • the resin constituting the transfer layer is composed of two or more kinds having different glass transition points or softening points
  • the resin containing the polymer component (F) containing the fluorine atom and the chromium or gallium atom is used.
  • (A) may be contained in either the first resin (AH) or the second resin (AL), but is more effective than contained in the resin (AH).
  • Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues.
  • Examples of the substituent containing a gayne atom include the following monovalent or divalent organic residues.
  • R u , R ′ 2 , R ] R 14 and R 1S may be the same or different, and each may be a substituted or unsubstituted hydrocarbon group or 10R 1S group (R 16 represents a hydrocarbon group. 9).
  • Examples of the hydrocarbon group represented by R-R 15, optionally substituted Ryo alkyl group e.g. methyl group with carbon number ⁇ 1 8, Echiru group, propyl group, butyl group, hexyl group, O corruptible, decyl , Dodecyl group, hexadecyl group, 2-cycloethyl group, 2- —Mouth moethyl group, 2, 2, 2— trifluoroethyl group, 2-cymanonityl group, 3,3,3—trifluoropropylethyl group, 2-methoxethyl group, 3-fluoromethyl pill group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, etc., substituted alkenyl group having 418 carbon atoms ( For example, 2-methyl-1-propenyl, 2-butenyl group, 2-tenyi — — —,, —
  • a xenyl group, 4-methyl-2-xenyl group, etc., an optionally substituted aralkyl group having 7 12 carbon atoms eg, a benzyl group, a phenyl group, a 3-phenylpropyl group, a naphthylmethyl group, a 2-naphthylethyl group
  • a substituted or unsubstituted alicyclic group having 58 carbon atoms for example, A cyclohexyl group, a 2-cyclohexyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 12 carbon atoms (for example, a phenyl group, a naphthyl group, a to
  • the fluorine atom and the organic residue containing Z or gayne atom may be constituted in combination, and in that case, they may be directly bonded or further via another linking group. They may be combined.
  • Specific examples of the linking group include a divalent organic residue.
  • D ′ represent the same contents as R 11 described above: Examples of the divalent aliphatic group include the groups shown below.
  • e 1 and e 2 may be the same or different, and each is a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, a methyl group, Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.).
  • Q one 0 - one S- or - N (d 2) - represents, d 2 is an alkyl group having 1 to 4 carbon atoms, one CH 2 or - represents a CH 2 B r.
  • divalent aromatic group examples include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (hetero atoms constituting a heterocyclic ring are selected from an oxygen atom, a zeolite atom, and a nitrogen atom. Containing at least one heteroatom).
  • aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, Examples of the substituent include a propyl group, a butyl group, a hexyl group, an octyl group and the like, and an alkoxy group having 1 to 6 carbon atoms (such as a methoxy group, an ethoxyquin group, a propoxy group and a butoxy group).
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom, etc.
  • an alkyl group having 1 to 8 carbon atoms eg, a methyl group, an ethyl group
  • substituent include a propyl group, a butyl group, a
  • heterocyclic group examples include a furan ring, a thiophene ring, a pyridine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, a 1,3-oxazoline ring, and the like.
  • R f represents any of the following groups (1) to (11), and b represents a hydrogen atom or a methyl group.
  • R represents a group represented by the above (1) to (8), n represents an integer of! -18, and m represents an integer of 1-18. And p represents an integer of 1 to 5.
  • R U , R 12 , R 13 Alkyl S of charcoal 1 ⁇ 12 cn CD
  • any one may be used as long as the polymer component containing a fluorine atom and / or a silicon atom is composed of blocks.
  • the term “consisting of blocks” means that the polymer contains a polymer segment containing at least 0% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom, for example, as shown below.
  • a polymer chain is used as a polymerization initiator.
  • Chemical actinic radiation radiation, electron beam, etc.
  • grafting method by mechanochemical reaction in mechanical application, etc.
  • chemical bonding silica
  • grafting method and polymerization reaction using macromonomer
  • Known methods for grafting using polymers include T. Shota et al. J. Appl. Polym. Sci. 13, 2447 (1969) WH Buck.Rubber Chemistry and Technology, 50, 109 (1976), Tsuyoshi Endo, Tsutomu Uezawa, Japan Adhesion Association, 24, 323 (1988) Tsuyoshi Endo, ibid. 25, 409 (1989), etc. .
  • the method for synthesizing the block copolymer of the present invention is not limited to these methods.
  • the resin ( ⁇ ) is preferably used in an amount of 70% by weight or more, and more preferably 90% by weight or more, based on the total amount of the entire composition of the transfer layer. These resins (II) may be used alone or in combination of two or more.
  • the transfer layer 12, 12 ′ or 12 ′′ may be used in combination with other additives as necessary in order to improve various physical properties such as adhesiveness, film formability and film strength.
  • additives such as adhesiveness, film formability and film strength.
  • rosin, petroleum resin, silicone oil, etc. to adjust the adhesiveness, polybutene, D0P, DBP, low plasticizer and softener to improve the wettability to the photoconductor and lower the melt viscosity
  • Antioxidants such as high molecular weight styrene resin, low molecular weight polyethylene wax, microcrystalline wax, paraffin wax, etc. can be added as polymeric antioxidants, polyvalent phenols, triazine derivatives, etc. Hot Melt Adhesion in practice "(Hiroshi Fukada, published by The Society of Polymer Publishing, 1983), pp. 29-107.
  • the thickness of the transfer layer is suitably from 0.1 to 20 m, and preferably from 0.5 to 10 m. If the film thickness is too small, transfer failure tends to occur. If the film thickness is too large, troubles in the electrophotographic process are liable to occur, and sufficient image density cannot be obtained or image quality tends to deteriorate.
  • both the transfer layer 12 and the transfer layer 12 ′ or 12 ′′ are preferably 0.1 to 10 g. / m 2 , more preferably in the range of 0.5 to 7 g / m 2. If the film thickness is too thin, transfer failure tends to occur, and if it is too thick, the transfer layer 12 provided on the photoreceptor 11 will have It is easy to cause troubles in the photographic process, so that sufficient image density cannot be obtained and the image quality tends to be reduced When the transfer layer is 12 'or 12 ⁇ , there is no practical problem, but material is wasted. Not preferred.
  • the electrophotographic photoreceptor 11 any conventionally known electrophotographic photoreceptor can be used. What is important is that before the transfer layer 12 is formed, the photoreceptor 11 is formed so that the transfer layer 12 provided on the surface of the photoreceptor 11 or the toner image 3 can be easily separated later. Is that the surface of the material has a receptivity.
  • the adhesive strength of the surface of the photoreceptor 11 before forming the transfer layer 12 according to JIS Z0237-1980 “Adhesive tape 'adhesive sheet test method” is 100 g ⁇ f or less, particularly 50 g ⁇ F or less, more preferably 10 g ⁇ f or less.
  • the electrophotographic photoreceptor 11 may be one having surface releasability in advance, but before the toner image 3 is formed, the surface of the photoreceptor 11 has a fluorine atom and a no or gay
  • the photoreceptor surface may be made separable by adsorbing or adhering a compound (S) containing at least an element atom.
  • the photoreceptor 11 having an insulative surface specifically, a method of using the photoreceptor 11 having an insulative surface in advance, separating the photoreceptor 11 which is generally used in general from the surface of the electrophotographic photoreceptor 11
  • a method of simultaneously forming the transfer layer 12 and imparting releasability to the photoreceptor 11 by forming it on the photoreceptor 11 by a deposition method is exemplified.
  • a photoconductor using a photoconductor in which the surface of amorphous silicon is modified to have releasability is used.
  • a coupling agent containing a fluorine atom and Z or a gay atom (a silane coupling agent) is used.
  • a titanium coupling agent, etc.) to treat the surface of the morphous silicon layer for example, JP-A-55-8984, JP-A-4-1231318, JP-A-60 — No. 170850, No. 59-102224, No. 60-177750.
  • a release agent (S) according to the present invention described below, in particular, a release agent containing, as a block, a component containing a fluorine atom and / or a gayne atom as a substituent, for example, polyether-modified (For example, modified borondialkyl silicons, carboxylic acids, amino groups, and rubinol).
  • a release agent containing, as a block, a component containing a fluorine atom and / or a gayne atom as a substituent, for example, polyether-modified (For example, modified borondialkyl silicons, carboxylic acids, amino groups, and rubinol).
  • an electrophotographic photoreceptor containing a polymer containing a polymer component containing a fluorine atom and a no or gallium atom in the vicinity of the surface is mentioned.
  • the vicinity of the surface of the electrophotographic photoreceptor means the uppermost layer of the photoreceptor, and includes an overcoat layer provided on the photoconductive layer and the uppermost photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of a photoconductor having a photoconductive layer, and the above-mentioned polymer is contained in the overcoat layer to impart separation properties, or a photoconductive layer (photoconductor unit).
  • a polymer or a photoconductor laminate the uppermost layer of which contains the above-mentioned polymer, and the surface of which is modified so as to exhibit releasability.
  • a method for imparting release property to the overcoat layer or the uppermost photoconductive layer is to use a polymer containing a gay atom and Z or a fluorine atom as a binder resin for the layer.
  • a small amount of a block copolymer (a surface uneven distribution type copolymer) containing a polymer segment composed of a polymer component containing a silicon atom and / or a fluorine atom as described in detail below is used together with another binder resin. It is also preferred.
  • a gay element Particles and resins containing z or fluorine atoms can also be used in combination in the form of particles.
  • a method using a surface uneven distribution type copolymer is preferable because the adhesion between the photoconductor layer and the overcoat layer can be sufficiently maintained.
  • the above-mentioned surface uneven distribution type copolymer can be used in combination with another binder resin at a ratio of 0.1 to 20 parts by weight based on 100 parts by weight of the total composition of the overcoat layer.
  • a surface layer is provided on the photoreceptor, which is known as one means for maintaining the durability of the photoreceptor surface against repeated use of the photoreceptor.
  • a method similar to the content of the protective layer in the method of protecting can be used.
  • a protective layer using a silicone-based block copolymer JP-A-61-195358, JP-A-55-83049, JP-A-62-8779 No. 71, JP-A-6-19-189559, JP-A-62-75461, JP-A-62-75461, JP-A-61- Nos. 3,955,56, JP-A-62-I39557, JP-A-62-2008-55, and the like.
  • the protective layer using a fluorine-based block copolymer JP-A-61-166, JP-A-61-17653, JP-A-61-163, No. 2,770,688, and Japanese Unexamined Patent Application Publication No.
  • the method of modifying the surface of the uppermost photoconductive layer into a state in which the conductive property is developed is effective when a so-called dispersion type photoconductor using at least a photoconductor and a binder resin is used. Applied.
  • a block copolymer resin containing a polymer segment containing a polymer component containing a fluorine atom and a Z or gayne atom in a block By coexisting at least one of resin particles containing a polymer component containing a nitrogen atom or a gallium atom, these materials are concentrated and migrated to the surface and are unevenly distributed. Can be. Examples of the copolymer and the resin particles are the same as those described in JP-A-5-197169.
  • a binder resin for the overcoat layer or the photoconductive layer a polymer segment containing a fluorine atom and Z or a silicon atom, and heat and Z or photocuring
  • a block copolymer formed by bonding at least one polymer segment containing a functional group-containing component with at least one polymer segment can be used.
  • the polymer segment containing such a heat and / or photocurable group-containing component the same as those described in JP-A-5-197169 can be mentioned.
  • a light and / or thermosetting resin may be used in combination with the resin containing a fluorine atom and / or a silicon atom according to the present invention.
  • the fluorine atom and the fluorine atom of the present invention effective for modifying the photoreceptor surface by the above-described method.
  • the polymer containing a polymer component containing a silicon atom is composed of a resin (hereinafter, referred to as a resin ( ⁇ )) or resin particles (hereinafter, referred to as a resin particle (L)).
  • the polymer component containing a fluorine atom and a nitrogen atom or a nitrogen atom be contained in at least 60% by weight or more of all polymer components. It is preferably at least 80% by weight.
  • the polymer comprises a polymer segment containing 50% by weight or more of a polymer component containing a fluorine atom and / or a gallium atom, and the polymer component containing the fluorine and / or gallium atom. It is a block copolymer in which a polymer segment () containing 0 to 20% by weight is bonded by blocks. More preferably, the block copolymer is characterized in that the segment (/ 5) in the block copolymer contains at least one polymer component containing at least one light and / or thermosetting functional group. is there.
  • the segment (; 5) does not contain any polymer component containing a fluorine atom and / or a silicon atom.
  • a block copolymer (polymer having a surface uneven distribution type) containing polymer segments (H) and (; 5) is used, whereby the surface separation is improved.
  • the improvement of the property itself, and the maintenance of the releasability are maintained.
  • the resins ( ⁇ ) and ⁇ of the present invention containing a fluorine atom and ⁇ or a gayne atom.
  • the resin (P) and the resin particles (L) of the present invention can easily be applied to the surface of the film before the drying step after application. Migration ⁇ Concentration is performed and the membrane surface is reformed to a state where it can exhibit separability.
  • the other polymer segment (a fluorine atom and a Z atom or a gallium atom-containing polymer segment) is blocked.
  • a good compatibility with the binder resin for forming the film Therefore, sufficient interaction takes place, and these resins are formed even when the transfer layer coating film is formed. In this method, further transfer to the transfer layer is suppressed or eliminated, and the transfer layer can clearly form and maintain the interface of the photoconductive layer (ie, the anchor effect).
  • the polymer may be used as resin particles (L) as described above.
  • Preferred resin particles (L) are resin particles dispersed in a non-aqueous solvent.
  • the resin particles include a polymer segment containing a polymer component containing a fluorine atom and / or a nitrogen atom, insoluble in the non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. At most 20%, in which the polymer segment is combined with a polymer segment soluble in the non-aqueous solvent.
  • the polymer component having a substituent containing a fluorine atom and / or a gay atom of the present invention includes, as the substituent, one incorporated in the polymer main chain of the polymer and one as a substituent on the side chain of the polymer. It includes both of the above. Specific examples include those having the same contents as the polymer component (F) that can be contained in the resin (A) used for the transfer layer.
  • the resin (P) and the resin particles (L) of the present invention in order to be a so-called surface unevenly distributed copolymer, a block containing the polymer component containing the fluorine atom and the Z or gayne atom is used.
  • the polymer component contains at least 50% by weight, preferably 70% by weight or more, and more preferably 80% by weight or more of the total amount of the whole block (; 5).
  • the fluorine- and / or gay-element-containing polymer component accounts for 20% by weight or less of the total amount of the block (yS). 0% by weight.
  • the weight ratio of the block (hi) to the other block (yS) is 1-95 to 5 to 99 (weight ratio), preferably 5 to 90 to 10 to 95 (weight ratio). Outside this range, both the resin (P) and the resin particles (L) of the present invention decrease the concentration effect and the anchor effect on the surface of the uppermost layer of the photoconductive layer, and as a result, the separation property of the transfer layer is reduced. Will decrease.
  • the weight average molecular weight of the resin (P) is preferably 5 x 1 0 3 ⁇ 1 X 1 0 6, more preferably a 1 X 1 0 4 ⁇ 5 X 1 0 5.
  • the weight average molecular weight of the block part in the resin (P) is at least 1 ⁇ 10 3 or more.
  • the resin particles (L) have an average particle diameter of preferably from 0.01 to 1 m, more preferably from 0.05 to 0.5 m.
  • the resin may be shifted.
  • the term “consisting of blocks” means that the polymer contains a polymer segment containing 50% by weight or more of fluorine atoms and Z or gayne atoms.
  • the resin for the transfer layer As described in A), A-B type block, A-B-A type block, B-A-B type block, graft type block, star type block and the like can be mentioned.
  • the resin (A) containing the polymer component (F) as a block can be synthesized according to a conventionally known polymerization method. Specifically, it can be referred to as the resin (A) containing the polymer component (F) as a block. A similar method can be used.
  • the resin particles (L) of the present invention will be described. As described above, the resin particles (L) are preferably made of a polymer portion ( ⁇ ) containing a fluorine atom and Z or a gallium atom, which is insoluble in a non-aqueous solvent; Or a polymer part () containing substantially no gay atom, and the average particle diameter of the particles is as small as 1 m or less. Further, the polymer component ( ⁇ ) portion constituting the insoluble portion of the resin particles may form a crosslinked structure.
  • a non-aqueous dispersion polymerization method described with the thermoplastic resin dispersion particles described in the electrodeposition coating method described below can be used.
  • the same contents as those described below can be mentioned.
  • the non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more.
  • organic solvent examples include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol; ketones such as acetone, methylethyl ketone, cyclohexanone, and getyl ketone; dimethyl ether, tetrahydrofuran, and dioxane.
  • alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol
  • ketones such as acetone, methylethyl ketone, cyclohexanone, and getyl ketone
  • dimethyl ether tetrahydrofuran, and dioxane.
  • 6 to 1 carbon atoms such as ethers such as methyl ester, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, etc.
  • Aliphatic hydrocarbons aromatic hydrocarbons such as benzene, toluene, xylene, and benzene, methylene chloride, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylmethylform, dichlorobrono, ⁇ , And halogenated hydrocarbons such as trichloroethane.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and benzene
  • methylene chloride methylene chloride
  • dichloroethane tetrachloroethane
  • chloroform chloroform
  • methylmethylform methylmethylform
  • dichlorobrono dichlorobrono
  • ⁇ halogenated hydrocarbons
  • the average particle size of the resin particles can easily be 1 Aim or less, and the distribution of the particle size is very narrow and the dispersion is monodispersed. can do.
  • the monomer (a) corresponding to the polymer component constituting the block (H) and the monomer (b) corresponding to the polymer component constituting the block (S) are simply referred to as Using a non-aqueous solvent that dissolves but becomes insoluble when polymerized, peroxides (eg, benzoyl peroxide, lauroyl peroxide, etc.), azobis compounds (eg, abbisisobutyronitrile, abbis) It is possible to carry out heat polymerization in the presence of a polymerization initiator such as isovaleronitrile), an organometallic compound (eg, phthalyl lithium), etc.
  • a polymerization initiator such as isovaleronitrile
  • an organometallic compound eg, phthalyl lithium
  • the polymer (P / S) composed of the above may be polymerized in the same manner as described above.
  • the inside of the insolubilized polymer particles of the resin particles (L) of the present invention may have a crosslinked structure.
  • any of the conventionally known methods can be used.
  • the polymerization reaction between the polymer component (H) and the polymer containing a component containing a reactive group can be carried out by a method such as a method of crosslinking by a polymer reaction.
  • cross-linking agent in the above method (2) examples include compounds that are usually used as a cross-linking agent. Specifically, it is described in Shinzo Yamashita, Tosuke Kaneko, "Holding Agent Handbook” Taisei Publishing (1981), The Society of Polymer Science, “Polymer Data Handbook, Basic Edition", Baifukan (1986), etc. Compounds can be used.
  • an organic silane compound e.g., Binirutorime Tokishishiran, Biniruto Ributokishishiran, 7-glycidoxy pro built Increment Tokishishiran, 7 - Melka -but trimethoxy E butoxy silane, 7-Aminopuropiru Bok triethoxysilane silane cutlet bling agents such like
  • Polyisocyanate-based compounds for example, tolylen difocyanate, 0-toluene diisocyanate, diphenylmethane diisocyanate, triphenyl methane triisocyanate, polymethylene borifeniuiluisocyanate, hexamethylene diisocyanate) , Isophorone diisocyanate, polymer polyisocyanate, etc.
  • polyol compounds eg, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol
  • polyamine compounds eg, ethylenediamine, 7-hydroxyquinpropyl-modified thiylenediamine, phenylenediamine, hexamethylenediamine, N —Aminoethylpiperazine, modified aliphatic polyamines, etc.
  • polyepoxy group-containing compounds and epoxy resins eg, edited by Hiroshi Kakiuchi “New epoxy resin” Shokodo (1985), edited by Kuniyuki Kashimoto “Epoxy resin” Compounds described in Nikkan Kogyo Shimbun (1969), etc.
  • melamine resins for example, "Urea 'Melamine Resin” edited by Ichiro Miwa and Hideo Matsunaga) Compounds described in Nikkan Kogyo Shimbun (1969), etc.
  • Monomers having two or more of the same or different polymerizable functional groups may be oligomers.
  • the monomer having two or more polymerizable functional groups include, for example, monomers or oligomers having the same polymerizable functional group, such as styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohols (for example, Ethylene glycol, ethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, Esters of methacrylic acid, acrylic acid or crotonic acid, such as trityl pentane, pentaerythritol, etc.) or polyhydroxy D-kinphenol (eg, hydroquinone, resorcin, catechol and their derivatives); Diester ethers or aryl ethers: vinyl esters of dibasic acids (eg, malonic acid, succinic acid, phthalic acid,
  • Examples of the monomer or oligomer having a different polymerizable functional group include, for example, a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl propion). Reactants of acids, diconiloyl acids, itaconiloyl propionic acids, carboxylic anhydrides, etc.
  • alcohols or amines eg, aryloxycarbonylpropionic acid, aryloxycarbonyl st acid, 2 —Ester derivatives or amide derivatives containing vinyl groups such as aryloxycarbonylbenzoic acid and arylaminocarbonylpropionic acid (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconate, acrylyl methacrylate, acrylyl) Aryl acid, Anorelli itaconic acid, Methacryloyl vinyl acetate, vinyl methacryloyl propionate, methacryloyl propionate, methacryloyl vinyloxycarbonyl methyl ester, meth vinyl oxycarbonylmethyl quinine carbonyl ethylene ester, N-arylacryl Amides, N-aryl methacrylamide, N-arylic amide amide, methacryloyl propionyl amide, etc., or amino alcohols (for example, aminoethanol, 1-aminopropanol,
  • the monomer or oligomer having two or more polymerizable functional groups used in the present invention is based on the total amount of the monomer (a) and the other monomer coexisting with the monomer (a). To 10% by mole, preferably 5% by mole or less to form a resin. Furthermore, when a chemical bond is formed by the reaction between the reactive groups of the polymer in the above method (3) to form a bridge between the polymers, the reaction must be performed in the same manner as the reaction of ordinary organic low-molecular compounds. Can be.
  • the method (1) used is preferred. That is, synthesis is carried out by performing a polymerization granulation reaction in the presence of the polyfunctional monomer (d) in addition to the monomer (a), the monomer (b) and Z or the polymer (PyS). can do. Further, when a polymer (P / 3) composed of the above-mentioned block (yS) is used, a monomer is added to a side chain in the polymer main chain of the polymer (PyS) or one end of the main chain. A polymer (PS ') having a polymerizable double bond group copolymerizable with (a) is preferred.
  • polymerizable groups may be directly bonded to the polymer chain, or may be bonded via another divalent organic residue.
  • Specific examples of these polymers are described, for example, in JP-A-6-43375, JP-A-11-257969, JP-A-2-74956, JP-A-2825666, The method can be carried out in the same manner as the method described in each gazette such as 2-173667, 3-15862 and 4-70669.
  • the total amount of the polymerizable compound is about 5 to 8 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent.
  • the amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound.
  • the polymerization temperature is about 30 to 180 ° C, preferably 40 to 120 ° C.
  • the reaction time is preferably 1 to 15 hours.
  • Examples of the polymer component which can be contained in the binder resin (P) and which contains at least one kind of light and Z or a thermosetting group include those described in the above-mentioned known documents. Specifically, for example, the same as those described as the polymerizable functional group can be used.
  • the polymer component containing at least one kind of light and Z or a curable group contained in these polymers is contained in 0.1 to 40 parts by weight in 100 parts by weight of the polymer segment (S) of the block copolymer. Parts by weight, preferably 1 to 30 parts by weight.
  • the content is less than the lower limit of the content, the curing after the formation of the photoconductive layer does not proceed sufficiently, and the retention of the film interface with the surface of the photoconductive layer during coating of the transfer layer becomes insufficient. Affects the laminar nature of the layer.
  • the content exceeds the above upper limit, the electrophotographic characteristics of the binder resin of the photoconductive layer may deteriorate, resulting in a decrease in the reproducibility of the original image of the copied image and the occurrence of background fog in the non-image portion. Occurs.
  • the block copolymer (P) containing light and Z or a thermosetting group it is preferable to use 40% by weight or more of the block copolymer (P) containing light and Z or a thermosetting group in 100 parts by weight of the total binder resin.
  • the content of the resin (P) is less than 40% by weight, the electrophotographic characteristics are deteriorated.
  • a light and Z thermosetting resin (D) may be used in combination with the above-mentioned resin containing a fluorine atom and a no or gallium atom.
  • the light and Z or the thermosetting group contained in the resin (D) may be any one, and specific examples thereof include those having the same content as the curable group contained in the block copolymer described above.
  • the light and Z or the thermosetting resin (D) may be any of the conventionally known curable resins, for example, the same functional group-containing as the curable group described for the block copolymer (P) of the present invention.
  • the resin of the above is mentioned as an example.
  • binder resins for the electrophotographic photosensitive layer include, for example, Ryuji Shibata, Jiro Ishiwatari, Kobunshi, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imagen ' , 1973 (No. 8).
  • olefin polymers and copolymers vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, aryl alkanoate polymers and copolymers, styrene and its derivatives , Polymers and copolymers, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carbonate ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether Copolymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene / methacrylic acid ester copolymers, styrene / methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers Polymer, maleic anhydride cop
  • the overcoat layer or the photoconductive layer contains at least one binder resin ( ⁇ ) and at least one block copolymer for surface boundary substances ( ⁇ ). Further, in order to improve the curing of the film, it is preferable that a small amount of the photo- and / or thermosetting resin (D) and Z or a crosslinking agent coexist.
  • the amount used is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, based on the total amount of the binder resin (B) and the block copolymer (P). . If the amount is less than 0.01% by weight, the effect of improving the hardening of the film is diminished. On the other hand, if it exceeds 20% by weight, the electrophotographic properties are adversely affected.
  • a crosslinking agent in combination, and as the crosslinking agent, a compound usually used as a crosslinking agent can be used. More specifically, it is described in “Hotbook of Crosslinking Agents” edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), edited by The Society of Polymer Science, “Basic Edition of Polymer Data Handbook”, Baifukan (1986), etc. It is better to use a compound.
  • organic silane compounds for example, silane coupling such as vinyltrimethoxysilane, vinyltributoxysilane, aglycidoxypropyltrimethoxysilane, 7-mercaptopropyltriethoxysilane, 7-aminopropylethoxysilane, etc.
  • Agents, etc. polyisocyanate compounds (for example, toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenyl methane triisocyanate, polymethylene borrifeniluisocyanate) , Hexamethylene diisocyanate, isophorone diisocyanate, high-molecular polyisocyanate, etc.), boryl compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, etc.) , 1, 1.1-trimethylolpropane, etc.),
  • monomers containing polyfunctional polymerizable groups eg, vinyl methacrylate, acryl methacrylate, ethylene Glycol diacrylate, polyethylene glycol diatalylate, divinyl succinate, divinyl adipate, diacrysuccinate, 2 Mechirubi two Rume evening click Li rate, preparative trimethylolpropane tri methacrylates, divinyl benzene, Pentaerisuri tall Helsingborg Atari rate, etc.
  • polyfunctional polymerizable groups eg, vinyl methacrylate, acryl methacrylate, ethylene Glycol diacrylate, polyethylene glycol diatalylate, divinyl succinate, divinyl adipate, diacrysuccinate, 2 Mechirubi two Rume evening click Li rate, preparative trimethylolpropane tri methacrylates, divinyl benzene, Pentaerisuri tall Helsingborg Atari rate, etc.
  • the uppermost layer (the layer adjacent to the transfer layer 12) of the photoconductive layer of the present invention is preferably cured after film formation.
  • the binder resin (B), the block copolymer (P), the curing resin (D), and the cross-linking agent to be provided are preferably used in a combination of functional groups that are chemically bonded between polymers.
  • a well-known method can be mentioned as a polymer reaction by a combination of functional groups, and for example, a combination of a functional group of Group A and a functional group of Group B as shown in the following table is exemplified. However, it is not limited to this.
  • R represents ⁇ hydrogen 3 ⁇ 4.
  • ⁇ represents a child-withdrawing group, for example, -CN, -CF 3 , -COR 2C1 , -C ⁇ R 20 , — S0 2 OR 0 , (R 20 is C n H 2n + 1 (n: an integer from 1 to 4), -CH 2 C6H5, -C5H5 and the like.
  • a reaction accelerator may be added as necessary to the binder resin in order to promote a crosslinking reaction in the photosensitive layer film.
  • a reaction mode in which the cross-linking reaction forms a chemical bond between functional groups for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chloroform) Mouth phenol, nitrophenol, thiophenol, bromophenol, naphthol, dichlorophenol, etc., organic metal compounds (acetylacetonato zirconium salt, acetylacetone divinyl salt, acetyl acetate cobalt) Salts, dibutoxytin dilaurate, etc.), dithiolvamic acid compounds (eg, getyl dithiocarbamate), tinouram disulfide compounds (eg, tetramethyltinouram disulfide), carboxylic acid anhydrides (eg, Anhydrous phthalic acid, maleic anhydride, succinic anhydride, but
  • Such a binder resin is cured by light and / or heat after the photosensitive layer forming material is applied.
  • the drying conditions are made stricter than the drying conditions for the conventional photoreceptor.
  • the drying conditions are high temperature and Z or long time.
  • treatment is performed at 60 to 15 CTC for 5 to 120 minutes.
  • the treatment can be performed under milder conditions.
  • a step of light irradiation with “chemically active light rays” may be included.
  • the “chemically active light beam” used in the present invention may be any of visible light, ultraviolet light, far ultraviolet ray, electron beam, X-ray, 7-ray, ⁇ -ray and the like, and preferably an external ray. More preferably, it emits light in the wavelength range from 310 nm to 50 O nm, and low-pressure, high-pressure or ultra-high-pressure mercury lamps, halogen lamps and the like are generally used. Light irradiation treatment can be sufficiently performed by irradiation for 10 seconds to 10 minutes from a distance of usually 5 cm to 5 O cm.
  • a second method for obtaining a photoreceptor having a detachable surface is the formation of a transfer layer 12.
  • a method for imparting releasability to the surface of the normal electrophotographic photosensitive member 11 by adsorbing or adhering a release compound (S) on the surface of the photosensitive member 11 will be described.
  • Examples of the releasing compound (S) include compounds containing at least a fluorine atom and / or a gaussium atom, and may be any of low molecular weight compounds, oligomers and polymers.
  • the substituent having a fluorine atom and / or a gallium atom includes both those incorporated in the main chain of the polymer and those contained as a substituent for the side chain of the polymer. Is included.
  • the repeating unit containing the substituent may be a block-containing repeating unit, and these are particularly effective in exhibiting the adsorption and releasability to the surface of the electrophotographic photosensitive member. .
  • substituents containing a fluorine atom and / or a gallium atom include the same substituents that can be contained in the resin (A) used in the transfer layer.
  • the compound (S) of the present invention is obtained by the method described in Nobuo Ishikawa, "Synthesis and Function of Fluorine Compounds” CMC Co., Ltd. (1987), edited by Jiro Hirano et al. Technical Information Association (1991), supervised by Mitsuo Ishikawa “Organic Gay Strategic Materials” Chapter 3 Using the synthesis method described in the literature such as Science Forum Co., Ltd. (1991), the present invention satisfies the above physical properties. Compound (S) can be synthesized.
  • polymer component containing a substituent containing a fluorine atom and / or a gayne atom as an oligomer or a polymer are also the same as the polymer component (F) described in the resin (A). Things can be mentioned as examples. But, The scope of the present invention is not limited to these.
  • the compound (S) of the present invention is an oligomer or a polymer, and is a so-called block copolymer
  • any one may be used as long as the polymer component containing a fluorine atom and a Z or gayne atom is composed of blocks.
  • the term “consisting of a block” means that the polymer has a polymer segment containing 70% by weight or more of a component having a fluorine atom and / or a gallium atom, for example, as described in the resin (A).
  • A-B-type blocks, A-B-A-type blocks, B-A-B-type blocks, graft-type blocks, star-type blocks, etc., which are the same as solids, are synthesized by the same method as described above. Can be.
  • any conventionally known method may be applied, and the compound (S) may be appropriately incorporated into the apparatus used in the present invention. Is preferred.
  • Yuji Hara Coating Engineering
  • Asakura ⁇ Store (1971) Yuji Harasaki ⁇ Coating Method
  • Hiroshi Fukada The Actuality of Hot Melt Bonding
  • the non-aqueous solution of the compound (S) can be uniformly wetted on the surface of the photoreceptor 11 by an ink jet method and then dried to be adsorbed or adhered.
  • the ink-jet method can be achieved, for example, by the principle and means described in Shin Ono, “Non-impact Printing” Co., Ltd. (1986).
  • continuous injection type Sweet method, Hertz method, intermittent injection type Winston method examples include an ink-demand type pulse jet system, a bubble jet system, and an ink mist type mist system.
  • the compound (S) is used directly or diluted with a solvent, and used in the ink tank and the .Z or ink head cartridge.
  • the viscosity of the ink is 1 to 10 cP and the surface tension is 30 to 60 dyneZcm.
  • a surfactant or the like may be added, and the ink may be heated.
  • the conventional ink jet printer uses a head orifice system of about 30 to 100 ⁇ m for finer character drawing, and the particle size of flying ink is about the same. In the invention, it may be larger. In this case, the amount of ink discharged increases, so that the time required for application can be reduced. Further, the use of a multi-nozzle is extremely effective for shortening the coating time.
  • silicone rubber can also be used as the compound (S).
  • a silicone rubber roller is wound around a metal core roller, which may be directly pressed against the surface of the photoconductor 11.
  • the nip pressure is 0.5 to 1 O kgf / cm 2 , and the contact time is 1 second to 30 minutes.
  • the photoconductor and / or the silicone rubber roller may be heated to 150 ° C. or lower. It is considered that a part of the low molecular weight component in the silicone rubber is transferred from the roller surface to the photoconductor 11 surface by the pressing.
  • the silicone rubber may be swelled with silicone oil.
  • the silicone rubber may be in the form of a sponge, or the sponge may be further impregnated with silicone oil, a silicone surfactant solution or the like.
  • these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) used (liquid, waxy, solid), and if necessary, a heating medium is used in combination.
  • the fluidity of the compound (S) can also be adjusted.
  • the compound (S) before the transfer layer 12 is formed, the compound (S) is adsorbed or adhered to the electrophotographic photoreceptor 11 to impart releasability to the surface, and preferably, the adhesive force of the surface is reduced. It is sufficient that the amount be 100 g ⁇ f or less, and it is not necessary to always repeat this step in the color image forming step of the present invention.
  • the photoreceptor 11 and the ability to maintain the releasability by adsorption or adhesion of the compound (S) or the compound (S) to be used may be appropriately selected depending on the combination of the means and the means.
  • the amount of the compound (S) adsorbed or applied to the surface of the photoreceptor 11 is not particularly limited, but an adverse effect on the electrophotographic characteristics of the photoreceptor 11 is not a practical problem. I just need. Normally, a film thickness of 1 m or less is sufficient, and the expression of the adhesive force of the present invention is sufficient in the condition of "Weakboundary Layer j (defined by Bikerman The Science of Adhesives Joints Academic Press (1961)"). It is.
  • a third method for obtaining the photoreceptor 11 having a detachable surface when the transfer layer 12 is formed on the photoreceptor 11 by an electrodeposition method, A method in which the inclusion of a hybridizable compound (S) in the photoconductor 11 simultaneously imparts the photoconductive member 11 with the hybridizable property and forms the transfer layer 12 is exemplified.
  • an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less at least 0.01 g of a compound containing a fluorine atom and / or a gallium atom that is dissolved in 1.0 g of the organic solvent (S ), And resin particles (AR) are electrically converted using a wearing dispersion in which resin particles (AR) having a glass transition point of 14 O'C or lower or a softening point of 18 O'C or lower are dispersed.
  • a releasable transfer layer 12 can be formed.
  • the releasable compound (S) contained in the dispersing liquid for forming the transfer layer is subjected to electrophotography before the dispersed resin particles (AR) are electrophoresed and electrodeposited on the surface of the photoconductor 11. Since it is adsorbed or adhered to the body 11, the photosensitive body 11 having elasticity can be obtained as a result before the transfer layer 12 is formed. The specific method will be described later.
  • the configuration and materials of the electrophotographic photoreceptor 11 used in the present invention can be any of conventionally known ones, and are not limited.
  • a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin may be mentioned.
  • the dispersed photoconductive layer may be a single layer type or a laminated layer. It may be a type or any type.
  • the photoconductive compound used in the present invention may be either an inorganic compound or an organic compound.
  • Examples of the inorganic compound used as the photoconductive compound of the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium monotellurium, silicon, and lead sulfide. These may form a photoconductive layer together with the binder resin, or may form the photoconductive layer alone by vapor deposition or sputtering.
  • inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium monotellurium, silicon, and lead sulfide.
  • the ratio of the binder resin is 100 to 100 parts by weight with respect to 100 parts by weight of the inorganic photoconductive compound. It is preferably used in a proportion of 15 to 40 parts by weight.
  • any of the conventionally known compounds may be used.
  • Japanese Patent Publication No. 37-171162, 62-51642, JP-A-52-2437, 54 A photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin, as described in each of the publications such as 1-9803, 56-107246, and 57-161663.
  • 60-230147, 60-230148, and 60-60 each having a photoconductive layer mainly composed of a charge generating agent, a charge transport agent, and a binding resin as described in Japanese Patent Publications
  • a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers as described in each of the publications such as 238853 is also known.
  • the electrophotographic photoreceptor of the present invention may take any form of the above-described photoconductive layer.
  • the organic photoconductive compound in the present invention is not limited to
  • the organic photoconductive compound is not limited to the compounds listed in (a) to (t), and any known organic photoconductive compound can be used. These organic photoconductive compounds can be used in combination of two or more in some cases.
  • the sensitizing dye contained in the photoconductive layer conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are “electrophotographs”! ⁇ , 9 (1973), “Synthetic Organic Chemistry", 24 (11). 1010 (1966). For example, U.S. Pat. Nos.
  • the upper limit of the content ratio of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. When added, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the lower the content of the organic photoconductive compound, the lower the electrophotographic sensitivity, it is preferable to include as much of the organic photoconductive compound as possible as long as crystallization of the organic photoconductive compound does not occur.
  • the content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin. . Further, the organic photoconductive compound may be used alone or in combination of two or more.
  • the binder resin (B) that can be used for the photoreceptor 11 of the present invention may be any of the resins used for conventionally known electrophotographic photoreceptors, and preferably has a weight average molecular weight of 5 ⁇ 10—1 ⁇ 1. 0 6, and more preferably from 2 1 0 4 ⁇ 5 X 1 0 5.
  • the glass transition point of the binder resin is preferably from 14 O'C to 10 200, and more preferably from 11 O'C to 14 O'C.
  • olefin polymer and non-polymer vinyl chloride copolymer, vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer, aryl alkanoate polymer
  • Polymers and copolymers styrene and its derivatives, polymers and copolymers, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carbonate ester copolymer, atarilonitrile copolymer , Methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer Coalesce, itaconic acid diester polymer and copolymer, maleic anhydride copolymer, acrylamide copo
  • the binder resin of the photoconductive material (B) a carboxyl group, a sulfo group
  • resin having a relatively low molecular weight containing an acidic group such as a phospho amino group (1 0 3 to 1 0 about 4)
  • the electrostatic characteristics can be improved.
  • the resin include a resin contained in a graft portion of the union, and an AB-type block copolymer having an acidic group as a block described in JP-A-3-1848.
  • thermosetting resin which forms a bridge structure between polymers described in JP-A-2-65861, a part of which has a crosslinked structure described in JP-A-2-65862 Resin, JP-A-2-69 Resins formed by bonding the acidic group described in No. 759 to the main chain terminal of the graft copolymer are exemplified.
  • the environment is remarkable; stable performance can be maintained even when the environment fluctuates.
  • the photoconductor can be uniformly dispersed and a photoconductive layer having good smoothness can be formed, and a change in environment or a scanning exposure method using semiconductor laser light can be used. In this case, excellent static characteristics can be maintained.
  • the thickness of the photoconductive layer is preferably from 1 to 100 / zm, particularly preferably from 10 to 50m.
  • the thickness of the charge generation layer is from 0.01 to 5 zm, particularly from 0.05 to 2 wm. Is preferred.
  • various dyes can be used in combination as a spectral sensitizer, if necessary, depending on the type of light source such as exposure to visible light or exposure to semiconductor laser light.
  • Carbium dyes diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, bolimethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, oral dashyanine dyes, styryl dyes) And phthalocyanine dyes (which may contain a metal).
  • Japanese Patent Publication No. 51-452 Unexamined Japanese Patent Publication Nos. 50-93033, 50-114, 227, 53-391, and 53-82, 533, U.S.A. Patent Nos. 3, 0 52, 540, 4, 0 54,
  • JP 5 7 - 1 6 4 5 6 No. etc. c Okisonoru dye include those described in, merocyanine dyes, Shianin dyes, as a polymethine dye such as mouth Dashianin dyes, FM Pigments described in Hamer "The Cyanine Dyes and Related Compounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110,591 No. 3, 1 2 1, 0 08, No. 3, 1 2 5, 4 47, No. 3, 1 2, 8, 1 79, No. 3, 1 3, 2, 9 4 2, 3,622,3,17, UK Patent Nos. 1,2,6,892, 1,309,274, 1,4,5,988 No., JP-B-48-7814, same
  • polymethine dyes that spectrally sense the near-infrared to infrared light region of 700 nm ⁇ long wavelengths
  • the photoreceptor of the present invention is also excellent in that even when various sensitizing dyes are used in combination, the performance thereof is not easily changed by the sensitizing dye.
  • additives for electrophotographic photosensitive members can be used in combination.
  • additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, and surfactants.
  • Chemical sensitizers include, for example, halogen, benzoquinone, chloranil, fluoranyl, bromanyl, dinitrobenzene, anthraquinone, 2,5-dichlorobenzenebenzoquinone, nitrophenol, tetrachloromouth phthalic anhydride, phthalic anhydride, maleic anhydride, N-Hydroquine maleimide, N-Hydroquinephthalimid, 2,3-Dichloro-1,5-dicyanobenzoquinone, Dinitrofluorenone, Trinitrofluorenone, Tetracyanoethylene, Nitrobenzoic Acid, dinitrobenzoic acid Electron-withdrawing compounds such as Hiroshi Komon et al.
  • plasticizer examples include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebaguete, dibutyl sebagate, butyric laurate, methyl phthalyl glycolate, Dimethyldaricol phthalate or the like can be added to improve the flexibility of the photoconductive layer.
  • plasticizers can be contained within a range that does not deteriorate the electrostatic properties of the photoconductive layer.
  • the addition amount of these various additives is not particularly limited, but is usually 0.01 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.
  • the photoconductive layer 2 of the present invention can be provided on a conventionally known support 1.
  • the support 1 of the electrophotographic photosensitive layer is preferably electrically conductive, and the conductive support may be made of a low-resistance substance such as a metal, paper, plastic sheet, etc. Conductive treatment by impregnation etc., and at least one or more layers coated for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and preventing curling.
  • a support provided with a water-resistant adhesive layer on the surface of the support, a support provided with at least one or more pre-coat layers as necessary on the surface layer of the support, Plastics laminated on paper can be used.
  • the transfer layer 12 is formed on the electrophotographic photoreceptor 11 having an elastic surface.
  • the formation of the transfer layer 12 on the photoreceptor 11 may be performed separately from the steps of the electrophotographic process and the transfer process, or may be formed in advance or formed each time. Is also good.
  • an ordinary method for forming a coating film may be mentioned.
  • a solution or dispersion containing the transfer layer composition may be formed on the surface of the photoreceptor 11 by a known method. Just apply.
  • the transfer layer 12 is preferably formed each time using the same apparatus as the electrophotographic process or the like.
  • the photoconductor 11 can be used repeatedly in the same apparatus, and the photoconductor 11 can be used without being disposable.
  • a hot melt coating method, a transfer method or an adhesive coating method is preferably used.
  • a hot-melt coating method as one method for forming a transfer layer will be described.
  • the hot-melt coating method is a method in which a transfer layer composition is hot-melt-coated by a known method, and is a solvent-free type coating machine, for example, a hot melt described in the above-mentioned material “Hot-melt bonding” on pages 197 to 215.
  • the mechanism of the hot melt coater (hot melt coater) for adhesives can be diverted to a photosensitive drum coating specification. Examples include a direct roll coater, an offset gravure roll coater, a lottery coat, an extruder, a slot orifice coater, a curtain coater, and the like.
  • Melting temperature of the thermoplastic resin during coating is to optimize the composition of the thermoplastic resin to be used is usually in the range of 5 0 ⁇ 1 8 0 e C. It is desirable to use a pre-heating device having a closed automatic temperature control means to melt in advance and then raise the temperature to an appropriate temperature at a position to be applied to the photoreceptor in a short time. By doing so, it is possible to prevent deterioration and coating unevenness due to thermal oxidation of the thermoplastic resin.
  • the coating speed is suitably from 1 to 10 seconds, and more preferably from 5 to 40 seconds, depending on the fluidity of the thermoplastic resin at the time of thermal melting, the coater method, the amount of application, and the like.
  • a transfer method using release paper as one method of forming a transfer layer will be described.
  • a transfer layer is previously formed on release paper by hot melt coating, solvent coating, latex electrodeposition, or the like, and then the transfer layer is thermally transferred to the surface of the photoreceptor.
  • the release paper on which the transfer layer is formed is in the form of a roll or sheet, making it easy to use in electrophotographic equipment. Can supply.
  • the release paper used in this method can be any known paper, such as new adhesive (adhesive) technology and its use ⁇ Development materials for various applied products (published by Management Development Center Publishing Dept.) , May 20, 1983), Product Encyclopedia of All Paper Guides, Volume 1, Cultural Industries) Published; Paper Industry Times, December 1, 1983) One.
  • the release paper is made by applying a release agent mainly composed of silicone, to unbleached clupak paper laminated with polyethylene resin, to high-grade paper and kraft paper coated with a solvent-based resin, and to undercoat. It is applied to a PE base or directly to glassine paper.
  • Silicone is generally used in the form of a solvent, and is coated and dried with a gravure roll and a wire with a degree of pus of 3 to 7%, then heat-treated at 150 ° C or more and cured.
  • the application amount is about 1 g Znf.
  • a usual thermal transfer method can be used. That is, it is sufficient that the transfer paper holding the transfer layer is pressed against the electrophotographic photosensitive member and the transfer layer is thermally transferred.
  • the conditions for transferring the transfer layer to the surface of the photoreceptor from the paper are preferably as follows.
  • the nip pressure of the mouth is 0.1 to 10 kgfZai, more preferably 2 to 8 kgf Zcnf, and the transfer temperature is 25 ° C to 100 ° C, more preferably 40 ° C. ⁇ 80 ° C.
  • Transport speed is from 0,5!
  • the time is preferably 0.03 seconds, more preferably 3 to 50 seconds, which may be different in each of the transfer layer forming step, the electrophotographic step, and the thermal transfer step to the primary receptor or the material to be transferred.
  • thermoplastic resin as described above is electrodeposited or adhered on the surface of the photoreceptor 11 in the form of resin particles (AR), and a uniform thin film is formed by, for example, heating to form a transfer layer. 1 and 2.
  • thermoplastic resin particles have a charge of either a positive charge or a negative charge, and the detectability is arbitrarily determined by the chargeability of the electrophotographic photosensitive member 11 to be combined. It is determined.
  • the resin particles (AR) have a range satisfying the above-mentioned physical properties, and usually have an average particle size in the range of 0.01 m to 15 ⁇ , preferably 0.05 m to 5 m. u ⁇ , more preferably 0.1 ⁇ ! In the range of ⁇ 1 z m.
  • the particles may be in the form of particle powder (dry type) or non-aqueous resin particles (wet type).
  • non-aqueous dispersion resin particles which can easily adjust the film thickness of the separation transfer layer to a thin film with a uniform thickness, can be mentioned.
  • At least two kinds of resins having different glass transition points preferably at least two kinds of the above-mentioned resin having a high glass transition point (AH) and the above-mentioned resin having a low glass transition point (AL) are contained in the same particle.
  • the contained resin particles (A RW) By using the contained resin particles (A RW), the transferability of the formed transfer layer is further improved.
  • the fine resin particles of the present invention can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. These production methods can be used for dry electrodeposition or wet electrodeposition, and for misaligned particles.
  • a mechanical pulverization method a method of directly pulverizing with a conventionally known pulverizer into fine particles (for example, a ball mill, a paint mill, a jet mill, etc.) Method, etc.). If necessary, mix the materials to be resin particles, pulverize through melting and kneading, or after pulverization Classification for uniforming the particle size or post-treatment of the particle surface Etc. can be appropriately combined. Also, a spray drying method is known.
  • polymerization granulation method conventionally known methods such as a production method by an emulsion polymerization reaction performed in an aqueous system, a hand polymerization reaction, a suspension polymerization reaction, and a dispersion polymerization reaction performed in a non-aqueous solvent system are known.
  • a conventionally known coating method of electrostatic powder or a developing method of dry electrophotographic developer can be used. Specifically, as described in “Electrostatic powder coating” by JF Hughes (translated by Hideo Nagasaka and Machiko Midorikawa), methods such as corona charging, friction charging, induction charging, ion wind charging, and reverse ionization phenomenon are used.
  • the non-aqueous latex used in the wet electrodeposition method
  • the non-aqueous latex can also be produced by a deviation between the mechanical method and the polymerization granulation method as described above.
  • a method in which a dispersing polymer is used in combination and further dispersed by a wet dispersing machine for example, a ball mill “Intoshi”, Keddy mill, Dyno mill, etc.
  • a material serving as a resin particle component for example, a ball mill “Intoshi”, Keddy mill, Dyno mill, etc.
  • a dispersion assisting polymer or a coating polymer
  • a method for producing a paint or a developer for electrostatography can be used.
  • Kenji Ueki “Flow of paint and pigment dispersion” Kyoritsu Shuppan (1971), —Solomon, Paint Science, “Paint and Surface Coating Theory and Practice,” Yuji Harazaki “Coating 'Engineering” Asakura Shoten (1971), Yuji Harasaki “Basic Science of Coating” (1977) .
  • the polymerization granulation method it can be produced by a conventionally known non-aqueous dispersion polymerization method.
  • a conventionally known non-aqueous dispersion polymerization method Specifically, the above-mentioned “Latest technology of ultrafine particle polymer”, Chapter 2, “Recent electrophotographic development systems” And development of toner materials 'Practical use', Chapter 3, KEJ Barvett, "Dispersion Polymerization in Organic Mediaj John Wiley (1975)” and other publications.
  • resin particles (ARW) containing at least two kinds of resins having different glass transition points in the same particle it can be easily produced by using a seed polymerization method.
  • resin (AL) or (AH) fine particles are synthesized by the above-described conventionally known non-aqueous dispersion polymerization method, and then the fine particles are used as seeds.
  • (AL) is preferably produced by feeding monomers and polymerizing them.
  • the polymer component (F) for improving the plasticity into the resin (A) is soluble in the organic solvent to be a thermoplastic resin and polymerized.
  • a monomer corresponding to the polymer component (F) coexists with the monomer to be insolubilized to carry out a polymerization reaction, whereby the copolymer is copolymerized in the resin (A). Obtained easily.
  • polymer component (F) in the form of a polymer block
  • a method of using at least a block copolymer containing the polymer component (F) in a block in the dispersion stabilizing resin to be used a method of using at least a block copolymer containing the polymer component (F) in a block in the dispersion stabilizing resin to be used.
  • polymer monofunctional component weight average (F) you structure as main repeating unit molecular weight 1 X 1 0 3 ⁇ 2 x 1 0 4 ( preferably 3 X 1 0 3 ⁇ to 5 X 1 0 4)
  • the resin (A) can easily be made into a block copolymer by coexisting with a hydrophilic macromonomer and copolymerizing it with monomers.
  • Another method is to use a polymer initiator (azobis high molecular initiator or peroxide high molecular initiator) containing the polymer component (F) as a main repeating unit, similarly to the block copolymer.
  • a polymer initiator azobis high molecular initiator or peroxide high molecular initiator
  • the combined resin particles can be obtained.
  • the non-aqueous solvent used for the production of the non-aqueous solvent-based dispersed resin particles has a boiling point of 20 o. Any of the following organic solvents can be used: It can be used alone or in combination of two or more.
  • organic solvents include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol; ketones such as acetone, methylethylketone, cyclohexanone, and getylketone; Aether, ethers such as tetrahydrofuran, dioxane, etc., carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, etc.
  • alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol
  • ketones such as acetone, methylethylketone, cyclohexanone, and getylketone
  • Aether, ethers
  • Aliphatic hydrocarbons having 6 to 14 carbon atoms aromatic hydrocarbons such as benzene, toluene, quinylene, and benzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, and dichloropropane Halogenated hydrocarbons such as trichloride Roetan the like.
  • aromatic hydrocarbons such as benzene, toluene, quinylene, and benzene
  • methylene chloride dichloroethane, tetrachloroethane, chloroform, methylchloroform, and dichloropropane
  • Halogenated hydrocarbons such as trichloride Roetan the like.
  • the present invention is not limited to the compound examples described above.
  • the average particle diameter of the resin particles can be easily reduced to 1 / m or less, and the distribution of the particle diameter is very narrow and the dispersion is monodisperse. can do.
  • non-aqueous dispersed resin particles are subjected to a wet electrostatographic development method or a method in which they are electrophoresed by electrophoresis in an electric field, an electric resistance of 1 ⁇ m is used as a dispersion medium. It is adjusted to a non-aqueous solvent system with a resistivity of not less than 0 8 ⁇ ⁇ ⁇ and 3.5 or less. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used.
  • the above-mentioned insulating organic solvent was used from the beginning as the solvent used during polymerization granulation. However, after granulation with a solvent other than these solvents, it can be adjusted by replacing the dispersion medium.
  • a nonaqueous latex comprising a polymer component comprising a soluble, non-soluble in the solvent to the electric resistance 1 0 8 ⁇ cm or more and a dielectric constant of 3.5 or less non-aqueous solvent described above polymer
  • the block copolymer composed of the components can be provided as fine resin particles by wet dispersion in the solvent. That is, a block copolymer composed of a soluble polymer component and an insoluble polymer component is prepared by polymerizing a block copolymer in an organic solvent in which the block copolymer is dissolved in advance using the above-described block polymer synthesis method. And then dispersing it in a non-aqueous solvent for electrodeposition.
  • the particles are positively or negatively chargeable electrophoretic particles.
  • This can be achieved by appropriately using the technique of an electrophotographic developer. Specifically, see “Recent developments and developments of electrophotographic development systems and toner materials” on pages 139-148, edited by the Society of Electrophotographic Engineers, “Basics and Application of Electrophotographic Technology,” pages 497-505 (Corona, 1988), Yuji Harazaki, "Electrophotography” (.2), p. 44 (1977), etc., using the electricity detection materials and other additives.
  • composition of the non-aqueous latex to be subjected to electrodeposition is as follows: 0.1 to 20 g of particles mainly containing a thermoplastic resin and 0.01 to 50 g of dispersion stabilizing resin in at least the electrically insulating dispersion medium 1 ⁇ .
  • the charge control agent added according to, ranges from 0.0001 to 10 g.
  • additives may be added to maintain the dispersion stability and charge stability of the particles.
  • rosin petroleum resins, higher alcohols, polyethers, silicone oils, paraffins Waxes and triazine derivatives.
  • rosin petroleum resins, higher alcohols, polyethers, silicone oils, paraffins Waxes and triazine derivatives.
  • polyethers polyethers
  • silicone oils paraffins Waxes
  • the upper limit of the total amount of these additives depends on the electrical resistance of the electrodeposition latex. Be regulated. That is, electric resistance since the amount of adhesion of the thermoplastic resin particles becomes lower than 1 0 8 ⁇ ⁇ cm is hardly obtained sufficient amount, the amount of each additive is controls in this limit ⁇ .
  • thermoplastic resin particles dispersed in the electrically insulating liquid by being charged into fine particles in this manner exhibit the same behavior as the electrophotographic wet developer.
  • electrophoresis can be performed on the surface of a photoreceptor using a developing device, for example, a slit developing electrode device described in “Basics and Application of Electrophotographic Technology”, pp. 275-285, supra. That is, particles mainly containing a thermoplastic resin are supplied between the opposing electrodes provided to face the electrophotographic photoreceptor 11, and electrophoresed according to a potential gradient applied from an external power supply. A film is formed by being attached or electrodeposited on the photoreceptor 11.
  • a voltage is applied from an external power source between the conductive support of the photoconductor and the developing electrode of the developing device so that the photoconductor 11 side has a negative potential. And electrostatically deposit the particles on the surface of the photoconductor 11.
  • the toner can be applied by wet toner development by a normal electrophotographic process.
  • wet toner development by a normal electrophotographic process.
  • burn-off in which the photoreceptor is uniformly charged and no exposure is performed or only the unnecessary areas are exposed. Then, normal wet toner development is performed.
  • the adhesion amount of the thermoplastic resin particles on the photoconductor 11 can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoconductor, and the development time.
  • the developer is wiped off with a squeeze using a known rubber roller, gap roller, reverse roller, or the like, and the developer is removed. Methods such as Corona Quiz and Air Squeeze are also known. Further, the transfer layer is formed by drying with cold or warm air or an infrared lamp or the like, preferably by forming thermoplastic resin particles into a film.
  • the compound (S) containing at least a fluorine atom and / or a gallium atom is added to the dispersion for electrodeposition for forming the transfer layer.
  • the compound (S) containing at least a fluorine atom and / or a gallium atom is added to the dispersion for electrodeposition for forming the transfer layer.
  • the compound (S) used here is the same as described for the releasable compound (S) above. It is a compound that dissolves in at least 0.05 g or more (at a temperature of 25 ° C) in 1 lb of an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less.
  • the amount of the compound (S) is dissolved in the solvent 1 ⁇ is less than 0. 0 1 g, tend to cause adsorption unevenness of the photoreceptor of the compound (S), preferably Do Re, 0
  • the compound (S) of the present invention is obtained by wetting a solution in which the compound (S) is dissolved in the above-mentioned electrically insulating organic solvent at a concentration of 0.01 ig £-, onto an electrophotographic photoreceptor to be used.
  • the adhesive strength is 100 gf or less, preferably 50 gf or less, particularly preferably the adhesive strength according to JI S Z0237-1980 "Tightening tape 'Adhesive sheet test method". Is not more than 10 g ⁇ : f or less. Specifically, those similar to the aforementioned compound (S) can be mentioned.
  • the addition amount of the compound (S) of the present invention in the electrically insulating organic solvent varies depending on the compound (S) used, the electrically insulating organic solvent, and the like. (Lower liquid resistance, higher viscosity, etc.). Preferably, it is about 0.01 g ⁇ to 20 g Z ⁇ .
  • a toner image 3 is formed on the photoreceptor 11 having the transfer layer 12 through a normal photolithography process. That is, each process of charging, developing, and fixing is performed by a conventionally known method.
  • a conventionally known developer for electrophotography can be used, and any of a dry-type developer for electrophotography and a liquid developer may be used.
  • a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner, or the like has been put into practical use, and any of these can be used.
  • a combination of a scanning exposure method using a laser beam for exposure based on digital information and a development method using a liquid developer forms a high-definition image. This is an effective process. An example is shown below.
  • the photoreceptor 11 is positioned on the flatbed by a register pin method, and then is suctioned and fixed by air suction from the back surface. Then, for example,
  • toner development is performed using a liquid developer.
  • the photoreceptor charged and exposed on the flatbed can be removed therefrom and used by the direct wet development method shown on page 275 et seq.
  • the II light mode is performed in correspondence with the toner image development mode.
  • the negative image that is, the same charge polarity as when the photosensitive material is charged by irradiating the image area with laser light.
  • a developing bias voltage is applied so that the toner adheres to the exposed portion. Details of the principle are described on page 157 et seq.
  • the basic composition of the material of the wet developer is as follows: an electrically insulating organic solvent ⁇ for example, isoparaffinic aliphatic hydrocarbon: Ansoper H, Risopar G (manufactured by Etsuso), Cherlaub 70, Cherenstein 7, 1 (manufactured by Shell Co., Ltd.), IP-solvent 1620 (manufactured by Idemitsu Petrochemical), etc. ⁇ as a dispersion medium, and an inorganic or organic pigment or dye as a colorant and an alkyd resin, an acrylic resin, a polyester resin, or the like. Dispersion stability of styrene butadiene resin, rosin, etc. Dispersing resin for imparting fixability and chargeability, and adding various additives as needed to enhance charge characteristics or improve image characteristics In addition, there may be mentioned.
  • an electrically insulating organic solvent for example, isoparaffinic aliphatic hydrocarbon: Ansoper H, Risopar G (manufactured by Et
  • dyes and pigments are arbitrarily selected, for example, benzidine, azo, zomethine, xanthene, anthraquinone, and phthalocyanine.
  • Dyes or pigments such as Nin-based (including metals), titanium white, Niguchi Shin, aniline black, and carphone black.
  • additives for example, those specifically described in Yuji Harazaki, “Electrophotography,” Vol. 16, No. 2, page 44 can be used.
  • the amounts of the main components of these wet developers are generally as follows.
  • the amount of the toner particles containing a resin (and a colorant used as desired) as a main component is preferably 0.5 to 50 parts by weight based on 100 parts by weight of the carrier liquid.
  • the amount is less than 0.5 part by weight, the image density is insufficient, and when the amount is more than 50 parts by weight, caprily tends to occur in the non-image portion.
  • the above-mentioned carrier liquid soluble resin for dispersion stabilization is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 100 parts by weight of the carrier liquid.
  • the charge controlling agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on 100 parts by weight of the carrier liquid.
  • various additives may be added.
  • the upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, since continuous tone images of good quality if the electric resistance of the liquid developer in a state of removing the toner particles is lower than 1 0 8 ⁇ ⁇ cm is hardly obtained, the amount of each additive, this limit Is controlled within.
  • a method for producing colored particles by mechanically dispersing a colorant and a resin using a dispersing machine such as a sand mill, a ball mill, a jet mill, or a Ryoichi Yuichi is available.
  • a dispersing machine such as a sand mill, a ball mill, a jet mill, or a Ryoichi Yuichi is available.
  • the dispersed resin particles are produced using a non-aqueous dispersion polymerization method for obtaining a fine particle having good monodispersity and coloring the resin particles is exemplified.
  • the coloring methods there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738.
  • when producing by a polymerization granulation method there is a method of using a monomer containing a dye in advance to obtain a dye-containing copolymer.
  • the toner image 3 on the photoreceptor 11 is thermally transferred onto the primary receptor 20 together with the transfer layer 12.
  • a transfer layer 12 ′ is further formed on the toner image 3 formed on the transfer layer 12, and the toner image 3 is transferred to the primary receptor 20 together with the transfer layers 12 and 12 ′.
  • a transfer layer 12 ⁇ may be formed on the primary receptor 20 separately, and the toner image 3 on the photoreceptor 11 may be transferred together with the transfer layer 12 (FIG. 2a). (See Figure 2b.) If a transfer layer 12 1 is to be formed on the primary receptor 20 at the end of the process of forming the toner image 3 on the photoreceptor 11 By this, it is necessary that the transfer layer 12 is provided on the primary receptor 20.
  • the detachable second transfer layer 12 ′ formed on the toner image 3 and the transfer layer 12 is Usually, the toner image is formed on the toner image each time in the same apparatus as the electrophotographic process or the transfer process. For example, it may be formed in advance on the receiving surface separately from the electrophotographic process or the transfer process by a usual coating film forming method or the like, or may be formed on the receptor 20 each time in the same apparatus as these processes. It is preferable that the primary receptor 20 be used repeatedly without disposable use in the same apparatus.
  • the second detachable transfer layer 12 ′ or 12 ′ is formed by at least one of hot-melt coating, transfer from release paper, and electrostatic adhesion and electrodeposition. By using one of the two methods as appropriate, it can be formed on the toner image 3 or on the primary receptor 20.
  • the transfer layer 12 and the transfer layer 1 ′ or 12 ⁇ may be formed by different means, respectively. The same means may be used. In the present invention, the above-mentioned three methods are mentioned as preferable methods for forming the transfer layer 12, the transfer layers 12 'and 12', but the transfer device can be simplified, and a uniform thin film can be formed stably and easily.
  • the wet electrodeposition method is particularly preferable because it can be performed.
  • the primary receptor 20 receives the toner image 3 formed on the transfer layer 12 on the side of the photoreceptor 11 by electrostatic transfer or by closely transferring the image under heat and heat or pressure.
  • the transfer layer 12 (further 12 ′ or 12 ′′) is separated from the toner image 3 onto the final transfer material 30 by heating and applying Z or pressure to form a final color image. It is an intermediate medium.
  • the releasability of the surface of the primary celebrator 20 is lower than that of the surface of the photoreceptor 11 and that the releasability for the separation and transfer to the final transfer receiving material 30 is maintained. Therefore, it must be larger than the adhesive strength of the surface of the photoconductor 11, preferably larger than 10 g ⁇ f, more preferably larger than 30 g ⁇ ⁇ . Further, the adhesive strength of the receptor 20 surface is preferably at most 200 g ⁇ f, more preferably at most 180 g ⁇ f.
  • a known method and apparatus can be appropriately used for this ripening transfer.
  • the nib pressure in the transfer is usually in the range of 0.2 to 20 kgf / cnf, preferably 0.5 to 15 kgfZcnf.
  • the air cylinder using spring or compressed air at both ends of the roller shaft as the roller pressing means Can be used.
  • the transport speed is usually 0! It is within the range of 100 seconds to Z seconds, preferably 0.5 to 50 mm seconds, more preferably 1 to 30 seconds, and may be different between the electrophotographic process and the thermal transfer process.
  • the roller surface temperature is preferably maintained within a predetermined range by a known surface temperature detecting means, a temperature controller, or the like. Further, a preheating means for the photosensitive material may be provided before the heating roller portion, and a cooling means after the heating roller portion. Further, as the inter-roller pressurizing means, an air cylinder using a spring or compressed air at both ends of a shaft of at least one of the rollers can be used.
  • the transfer of the toner image 3 from the photoreceptor 11 to the primary receptor 20 and the transfer from the primary receptor 20 to the final transfer material 30 may be simultaneous within one screen, or After the entire screen has been transferred to receptor 20, transfer to final transfer material 30
  • this thermal transfer step can be appropriately incorporated in a series of electrophotographic process apparatuses.
  • any material may be used.
  • examples of a method used for transferring the toner image 3 from the photoreceptor 11 to the primary receptor 20 include a drum method and a reusable endless belt method.
  • the material of the primary receptor to be provided on the drum may be any material as long as it satisfies the above conditions, and a preferred embodiment is an elastic layer and Z or A laminated structure including an elastic layer and a reinforcing layer support is desirable, and the surface of the laminated structure should satisfy the above-mentioned properties.
  • These laminates may be provided directly on the drum, for example, or may be detachable so that they can be replaced.
  • the elastic body examples include conventionally known natural resins and synthetic resins, which can be used alone or in combination of two or more to form a single layer or a plurality of layers.
  • synthetic resins for example, D. Roberts "Natural Rubber Science and Technology” Oxford Science Publicat ions (published annually), W. Hofmann rRubber Technology Handbookj Hanser Publ ishers (published in 1989), Plastic Materials Structure, 18 volumes, Nikkan Kogyo Shimbun Various resins are described in companies and the like.
  • styrene-butadiene rubber for example, styrene-butadiene rubber, butadiene rubber, acrylonitrile rubber, cyclized rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluoro rubber, polysulfurized rubber, natural rubber , Isoprene rubber, urethane rubber, and the like, but are not limited thereto, and may be arbitrarily selected in consideration of the releasability from the transfer layer, durability, and the like.
  • the adjustment of the adhesive strength of the surface of the receptor can be easily performed by the same method as described in the above-described easily-separable photosensitive member.
  • the reinforcing layer of the elastic layer is used as the reinforcing layer of the elastic layer.
  • a sponge-like rubber layer may be provided between the surface elastic layer and the reinforcing layer.
  • the average roughness of the surface of the primary receptor 20 is preferably not more than 0.01 country, and the thickness of the surface elastic layer is preferably from 0.01 mm to 10 cm.
  • known members can be used for the belt type primary receptor.
  • there is a method of providing a layer serving as a heating medium in the belt carrier layer of the belt type primary receptor for example, a method described in Japanese Patent Application Laid-Open No. 4-503265 is known.
  • the final transfer material 30 used in the present invention is not particularly limited, and may be any of various papers, polymer sheets (films), metals, and the like.
  • papers include coated paper, high-quality paper, plain paper, copy paper for PPC (including recycled paper for PPC), which are well-known conventional printing papers, and an adhesive whose surface is coated with a glue-adhering agent.
  • Sheets for example, copy labels manufactured by Plus Co., Ltd., TF sheet TF sheets manufactured by Lion Co., Ltd., adhesive paper sheets for word processing manufactured by Kokuro Co., Ltd.
  • PET film sheets paper
  • Various film sheets such as an ethylene sheet and a polypropylene sheet are exemplified.
  • thermoplastic resin layer may be further provided on the surface of the various final transfer materials 30 (that is, on the side where the toner image of the present invention is in close contact with the transfer layer).
  • the resin layer provided has a thickness of 1 ⁇ ! The range is preferably from 20 m to 20 m, and more preferably from 2 m to 10 m.
  • the resins to be used include those having the same contents as the transfer layer resin (A) of the present invention, and resins known as conventional pressure-sensitive adhesives and adhesives.
  • the adhesion between the final transfer material 30 and the toner images 3 and Z on the primary receptor 20 or the transfer layers 12, 12 ′, and 12 ′′ is improved, and the transfer is further improved.
  • the transfer temperature and the transfer pressure can be reduced, and the transfer speed can be dramatically increased, especially when the surface of the transfer material 30 is rough. Or when the transfer material 30 is hard and has a small cushioning property, the effect is more enhanced.
  • a known method and apparatus can be used to thermally transfer the toner image 3 to the transfer material 30 together with the transfer layer 12 (and further the transfer layer 12 'or 12' as necessary).
  • the above-described step of performing the electrophotographic process, the step of forming the transfer layer, and the step of transferring the transfer layer or the transfer layer to the primary receptor may be performed separately. It can also be appropriately incorporated into an apparatus for performing these steps.
  • a general apparatus for thermally transferring the transfer layer 12 (including the transfer layer 12 'or 12 ") to the material to be transferred separately from the apparatus for performing other steps is shown in Fig. 3. 5
  • the roller is driven without applying a predetermined nip E force between a pair of built-in rubber-coated rollers 4.
  • the surface temperature of the roller 14 is preferably 40 to 150 ° C.
  • nip pressure between rollers is preferably 0.2 to 20 kgf Zcnf, more preferably 0.5 to 10 kgf Zcnf
  • transport speed is preferably 0.1 to
  • the roller surface temperature is preferably kept within a predetermined range by a known surface temperature detecting means 6 and a temperature controller 7. Further, a cooling means may be provided before the heating roller and before the photosensitive material.
  • roller-to-roller pressurizing means it is possible to use a spring or an air cylinder using compressed air at both ends of a shaft of at least one of the rollers.
  • a preferable heating temperature range during transfer, the primary receptor 20 and the transfer material are preferably the same as the ranges of the thermal transfer conditions of the photoconductor 11 and the primary receptor 20 described above.
  • the transfer to the primary receptor 20 and the transfer to the transfer material 30 may be the same or different.
  • the thermal transfer behavior to the final transfer material 30 is estimated as follows. That is, when the transfer layer 12 (including the transfer layer 12 ′ or 12 ′′), which has been softened to some extent, is heated, the adhesiveness increases, and the transfer layer 12 adheres to the final transfer material 30. After passing through, the toner image 3 and the transfer layer 12 (including 1 2 'or 12 ”) adhere to the final transfer material 30 with the temperature lowered, the fluidity and tackiness reduced, and the film remains as it is. Separated from the surface of the primary receptor 20 in this state. Therefore, conditions should be set so as to realize such a hiding.
  • the toner image 3 on the final transfer material 30 is consequently the second transfer layer 1 2 2 'or 1 2 " Since the toner image 3 is overcoated, the toner image 3 can be protected from scratches and dirt.
  • FIG. 4 is a schematic diagram of a color image forming apparatus using a hot-melt coating method as a method of forming the transfer layer 12 and a drum method as a primary receiving element
  • FIG. 5 is a diagram showing the formation of the transfer layer 12.
  • the transfer layer 12 is formed on the photoreceptor 11 as it is. If the surface of the photoreceptor 11 is not sufficiently flexible, a device for adsorbing or adhering the compound (S) before the formation of the transfer layer 12 may be provided. Releasability can be imparted. That is, the compound (S) is supplied to the surface of the photoreceptor 11 by appropriately providing the compound (S) coating unit 10 of the present invention using any of the above-described specific embodiments.
  • the coating unit 10 for adsorbing or adhering the compound (S) to the surface of the photoconductor 11 may be either a fixed unit or a movable unit.
  • thermoplastic resin 12 a is heated by a hot melt coater 13, for example, on the photosensitive drum surface. It is applied to the surface of the body 11 and cooled to a predetermined temperature by passing under the intake / exhaust unit 15. After the hot melt coater 13 has moved to the standby position 13a, the liquid developing unit set 14 is moved there, and enters the electrophotographic process.
  • the electrodeposition / development unit set 14 ′ containing the resin particle dispersion is applied to the photoreceptor 11. Close and fix so that the distance between the electrode and the developing electrode of 'developing unit set 14' is one image. A particle dispersion liquid is supplied from the electrodeposition unit 14T between the gaps, and rotated while applying a voltage from the outside, so that the particles are adsorbed on the entire surface of the photoreceptor 11.
  • Squeeze unit 14 R built into electrodeposition and development unit set 14 '
  • FIG. 6 is a schematic view of an apparatus for easily forming the transfer layer 12 on the photoreceptor 11 using release paper.
  • the release paper 24 provided with the transfer layer 12 is heated and pressed by a heating roller 25 b to transfer the transfer layer 12 to the surface of the photoconductor 11.
  • the pattern paper 24 is cooled by the cooling roller 25c and collected.
  • the photoreceptor 11 itself may be heated by the preheating means 25a to improve the transferability of the transfer layer 12 by ripening and pressing.
  • the apparatus shown in FIG. 6 may be appropriately incorporated into the apparatus for the hot-melt coating method in FIG.
  • the photoreceptor 11 on which the transfer layer 12 made of a thermoplastic resin is formed as described above then enters an electrophotographic process.
  • An example in which a wet developer is used for toner development will be described below with reference to FIG.
  • the photoreceptor 11 is corona-charged by a corona charging device 18, for example, after being uniformly charged into a brass, and then exposed by an exposure device (for example, a semiconductor laser) 19 based on yellow image information. Is reduced, and a potential contrast between the unexposed portion and the unexposed portion is obtained. Only the yellow liquid developing unit 14 y containing the liquid developer in which the yellow pigment having a brass electrostatic charge is dispersed in the electrically insulating dispersion medium is applied from the developing unit set 14 to the surface of the photoconductor 11. Close and set the gap to l mm.
  • the photoreceptor 11 is pre-bused by a pre-bus means provided in the developing unit, and then wet developing is performed while applying a developing bias voltage between the photoreceptor 11 and the developing electrode by a bias power supply and electric connection (not shown).
  • the agent is supplied to the surface of the photoconductor 11.
  • the bias voltage is connected so that the developing electrode side is positive and the photoreceptor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, sufficient toner image density cannot be obtained.
  • the developing solution attached to the surface of the photoconductor 11 is washed away by the rinsing means built in the developing unit set 14, and then the rinsing liquid attached to the surface of the photoconductor 11 is removed by the squeezing means. Dry by passing under the exhaust unit 15.
  • magenta 14 m
  • cyan 14 c
  • black 14 k
  • the method of forming the second transfer layer 12 ′ on the first transfer layer 12 having the toner image 3 can be performed in the same manner as in the case of forming the transfer layer 12.
  • the method of forming the transfer layer 12 and the transfer layer 12 ′ may be the same or different.
  • the transfer layer 12 ′ is formed on the primary receptor 20 by the end of the toner image forming process on the photoreceptor 11. It is provided by a forming device 21.
  • the transfer layer 12 can also be formed on the primary receptor 20 by appropriately applying the above-mentioned method of the transfer layer 12.-The secondary receptor 20 is shown in FIG. As shown in FIG. 5, a drum system may be used, or an endless belt system may be used as shown in FIG.
  • the suction / exhaust unit 15 provided for the electrophotographic photoreceptor 11 is used to exhaust the dispersion solvent of the dispersion liquid. May be laid out at a position that can also be used for the primary receptor 20, or a similar unit may be provided on the primary receptor 20.
  • a carrier of a usual wet type developer is used for the pre-bath and the rinsing liquid.
  • the transfer layer 12 and the transfer layer 12 ′ or 12 ′ of the present invention are formed in the same apparatus as the electrophotographic process, and the photoreceptor 11 and the receptor 20 are repeatedly used.
  • the transfer layer 12 and the transfer layer 12 ′ or 12 ′ may be provided with a transfer layer having the same composition by appropriately moving the same forming apparatus, or may be provided with transfer layers having different compositions. Is also good.
  • two sets of transfer layer forming units can be used. In this case, the same transfer layer forming method may be used, or different methods may be combined. In other words, when forming the transfer layer, any one of the other process units may be arranged so that it can be arranged by moving. It can be performed arbitrarily in the installation design, and is not limited.
  • the apparatus can be operated during the next operation of the apparatus. You can immediately start from the electrophotographic process.
  • FIG. 7 shows a schematic partial view of the transfer step. For convenience, only the transfer layer 12 is described.
  • a predetermined preheating is performed by heating means 16 and 17 or 17 for thermal transfer of the photosensitive drum, and if necessary, the transfer layer 12 "on the primary receptor 20 is also heated by heating means 16 and Z or 1 The toner surface image 3 on the transfer layer 12 is pressed against the primary receptor 20 and thermally transferred by performing a predetermined preheating by using 7.
  • the heating means 16 it is preferable to use a non-contact type, for example, an infrared line heater or a flash heater, and the heating surface temperature of the photosensitive layer at the time of thermal transfer is 40 to 150 ° C., especially 50 ° C. ⁇ 12 O'C is preferred.
  • an air cylinder using spring or compressed air at both ends of the roller shaft can be used as the roller pressing means.
  • FIG. 8 shows a schematic partial view of the final transfer step.
  • FIG. 8A employs a drum system and FIG. 8B employs an endless belt system. For convenience, only the transfer layer 12 is described. .
  • predetermined preheating by the heating means 16 and 17 or 17 of the secondary receptor 20, and predetermined preheating of the transfer material 30 by the transfer backup roller 31, and the primary receptor 20 After thermal transfer by pressing against the transfer layer 12 having the toner image 3 of the toner image 3, the toner image 3 together with the transfer layer 1 2 is separated and transferred onto the transfer material 30 while being cooled by the separating back roller 32. End the process.
  • each transfer step can be performed under the same operation method and conditions as in the case of the drum type.
  • the conditions for each transfer of 1 2 "are as follows: the photoreceptor 11 used (photosensitive layer and support), the physical properties of the primary receptor 20 surface, the transfer layers 12, 12 'and 12 ⁇ It is natural to optimize the properties of the material, such as the material to be transferred 30, etc. Particularly, the temperature conditions during the thermal transfer process are the glass transition point, softening temperature, fluidity, and sharpness of the transfer layer. It is necessary to take into account such factors as film thickness, film properties, film thickness, etc. In other words, the transfer layer, which has been softened to some extent as a preheating means, passes under the heating port to increase the adhesiveness and increase the transfer material. Then, after passing under the cooling roller, the conditions are set so that the temperature drops, the fluidity and tackiness are reduced, and the toner remains in the film and the toner adheres to the transfer layer in a flat state. Should.
  • the material of the cooling roller 1 be a heat conductive metal such as aluminum or copper coated with a silicone rubber, and that the heat be radiated to the inside of the roller or the outer peripheral portion not in contact with the transfer paper using a cooling means.
  • a cooling means it is preferable to use a cooling fan, a refrigerant circulation or an electronic cooling element or the like, and to keep the temperature within a predetermined temperature range in combination with a temperature controller.
  • the transfer layer 12 on the photoreceptor 11 As described above, according to the present invention, in the electrophotographic color image forming method using the intermediate medium (primary receptor) 20, by providing the transfer layer 12 on the photoreceptor 11, there is no color shift, Fine, high-quality color images can be obtained easily and stably. It is also convenient for the storage stability of the obtained color copy.
  • a further detachable transfer layer 12 ′ or 12 ′′ is provided on the toner image 3 formed on the transfer layer 12 or on the primary receptor 20.
  • various conditions to be provided for the transfer layer can be satisfied for each layer in accordance with its function, and the storage stability of the toner image 3 is further improved.
  • the transfer layer 12, 12 'or 1 "used in the present invention is formed on the photoreceptor 11 or the primary receptor 20 each time in the same apparatus as the electrophotographic apparatus for forming a toner image. This makes it possible to repeatedly use the photoreceptor 11 and the primary receptor 20. This makes it possible to reduce the running cost, and furthermore, this can be implemented with a simple image forming apparatus. is there.
  • the transferability is further improved, the latitude during transfer is expanded, and the final transfer material is
  • the flexibility of the transfer layer is further improved. And a better image can be obtained.
  • the formation of the surface-receptive photoreceptor and the formation of the transfer layer are the same. Sometimes it can be done. With these methods, a general-purpose electrophotographic photoreceptor can be used, and the running cost can be further reduced.
  • thermoplastic resin layer on the surface of the final transfer material 30 to be used, the final transfer material 30 and the toner image 3 on the primary receptor 20 and the transfer layer 12, 12, 12 'or 12 And the transferability is further improved.
  • a toner image of one or more colors is formed by an electrophotographic process on a transferable transfer layer formed on an electrophotographic photoreceptor having an imageable surface, and the toner image is transferred to the transfer layer,
  • a color image forming method comprising: transferring the toner image on a primary receptor to a final transfer material;
  • the surface of the electrophotographic photoreceptor has an adhesive force of 100 gram 'force or less according to the “test method of adhesive tape' adhesive sheet 'of JIS Z0237-1980” and the surface of the primary receptor The color image forming method according to the above (1), wherein the adhesive strength is larger than the adhesive strength of the surface of the photoreceptor.
  • the peelable transfer layer is made of resin (AH) having a glass transition point of 30 ° C to 140 ° C or a softening point of 35 ° C to 180 ° C, and a glass transition point of 40 eC or less. Or (5) a resin having a softening point of 45 ° C or lower and a resin (AL) whose glass transition point or softening point is lower by 2 ° C or more than the resin (AH).
  • AH resin having a softening point of 45 ° C or lower
  • A resin whose glass transition point or softening point is lower by 2 ° C or more than the resin (AH).
  • the releasable transfer layer is formed by at least one of hot-melt coating, transfer from paper, and electrostatically applying and electrodepositing. (1) The method of forming an empty image as described in (3).
  • the resin layer having a glass transition point of 10 to 14 O'C or a softening point of 35 to 180 ° C. and a glass transition point of 45 or less or a softening point of 60 ° C.
  • Thermoplastic resin particles (ARW) having a glass transition point of 14 O'C or less or a softening point of 180 or less containing at least two kinds of resin fl
  • the detachable transfer layer contains, in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less, at least 0.01 g of a fluorine atom and / or a gallium atom dissolved in 1.0 ⁇ of the organic solvent.
  • the resin particles (AR) containing at least one compound (S) and having a glass transition point of 140 or lower or a softening point of 180 or lower and dispersed therein are used as an electrodeposition dispersion liquid.
  • the resin particle (AR) force is supplied between the opposing electrodes provided opposite the electrophotographic photosensitive member, and electrophoreses according to the potential gradient applied from the external electrode, and is applied to the electrophotographic photosensitive member.
  • the image forming method according to the above Q0 wherein the film is deposited or adhered.
  • the method for forming an image according to the above (1), wherein the final material to be transferred further has a thermoplastic resin layer on the side in close contact with the transfer layer.
  • IS A method for forming a color image, wherein the steps (i) to () v) are performed in the same apparatus.
  • step (a) is further performed in the same apparatus between the steps (i i) and (i i i).
  • step (b) The color image forming method as described in as above, wherein the following step (b) is performed in the same apparatus before the step (iii).
  • a color image forming apparatus comprising at least means for transferring each layer, and means for transferring the toner image together with a transfer layer from a primary receiver to a final material to be transferred.
  • FIG. 1 is a schematic diagram for explaining one method of the present invention.
  • FIG. 2 is a schematic diagram for explaining one method of the present invention.
  • FIG. 3 is a diagram showing an example of an apparatus for thermally transferring a transfer layer to a material to be transferred.
  • Figure 4 shows the hot-melt coating method and the primary sevator method for forming the transfer layer on the photoreceptor.
  • FIG. 1 is a schematic diagram showing an example of an apparatus for implementing the method of the present invention, which employs a drum system.
  • FIG. 5 is a schematic view showing an example of an apparatus for carrying out the method of the present invention, employing a wet electrodeposition method as a method for forming a transfer layer on a photoreceptor and an endless belt method as a primary receptor. .
  • FIG. 6 is a schematic view showing an example of a partial device for forming a transfer layer on a photoreceptor using release paper.
  • FIG. 7 is a schematic partial view showing a step of transferring the toner image together with the transfer layer to the primary receptor.
  • FIG. 8 is a schematic partial view showing each step of the process of transferring the toner image on the primary receptor together with the transfer layer to the material to be transferred.
  • FIG. 9 is a schematic partial view showing an example of a compound (S) supply apparatus.
  • a mixed solution of 15 g of a dispersion stabilizing resin (Q-1) having the following structure, 100 g of vinyl acetate and 384 g of isopropyl is heated to a temperature of 70 ° C. while stirring under a nitrogen stream.
  • Dispersion stabilizing resin (Q-1) having the following structure, 100 g of vinyl acetate and 384 g of isopropyl is heated to a temperature of 70 ° C. while stirring under a nitrogen stream.
  • a polymerization initiator 0.8 g of 2.2'-azobis (isovaleronitrile) (abbreviated as A.I.V.N.) was added and reacted for 3 hours. Twenty minutes after the initiator was added, cloudiness occurred and the reaction temperature rose to 88 ° C. Furthermore, after adding 0.5 g of the initiator and reacting for 2 hours, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 90% and an average particle diameter of 0.17 and having good monodispersibility. Particle size is 0? It was measured with Hachi-500 (manufactured by Horiba, Ltd.).
  • a part of the white dispersion with centrifuged (rotational number 1 XI 0 4 rpm, rotation time 60 minutes), collecting the resin particles content of sediment, dried, weight average molecular weight of the resin particles was ( Mw) and was measured glass transition point (Tg), IV ⁇ i2 xi 0 5 ( Bo polystyrene GPC value converted to value), Tg was 38'C.
  • a mixed solution of 18 g of a dispersion stabilizing resin (Q-2) having the following structure and 553 g of Isopar H was heated to a temperature of 55 ° C while stirring under a nitrogen stream.
  • the white dispersion obtained through a 200-mesh nylon cloth was a latex having a degree of polymerization of 99% and an average particle diameter of 0.15 m and having good monodispersibility.
  • the Mw of the resin particles was 1.5 ⁇ 10 4 and the Tg was 45′C.
  • Synthesis Example 2 was similar to Synthesis Example 2 of resin particles (AR) except that each monomer shown in Table A below was used instead of 80 g of methyl methacrylate and 20 g of ethyl acrylate. Resin particles were synthesized in the same manner as described above.
  • the average particle size of each of the obtained resin particles was in the range of 0.15 m to 25 m, and all were good in monodispersity. Further, the Mw of each resin particle was in the range of 9 ⁇ 10 3 to 2 ⁇ 10 4 , and the Tg was in the range of 35 ° C. to 65 ° C.
  • the macromonomer (M-1) 10 g Resin particles (AR-18) to (AR-23) were produced in the same manner as in Synthesis Example 3 except that each macromonomer shown in Table 1B below was used instead of
  • the polymerization rate of the obtained particles was 98 to 99%, the average particle size was in the range of 0.15 to 0.2, and the particle size distribution was narrow and the monodispersity was good.
  • the Mw of the resin particles was 2.5 1 0 4 ⁇ 4 xl 0 4 , a glass transition temperature from 35 to 70. C range.
  • a mixture of 12 g of the dispersion stabilizing resin (Q-1), 70 g of vinyl acetate, 30 g of vinyl butyrate and 88 g of Isopar H 380 g was stirred at 80 ° C. under a nitrogen stream. Heated to C. To this was added 1.5 g of azobisisobutyronitrile (abbreviation: A... BN) as an initiator and reacted for 2 hours, and 0.8 g of A.I. BN was added twice every 2 hours and reacted. Was. After cooling, obtained through a 200 mesh nylon cloth
  • each resin particle (AR) was manufactured.
  • Each of the obtained white dispersions had a polymerization rate of 90 to 99% and an average particle size of 0.13 to 0.20 m.
  • the Tg of each resin particle ranged from 10 to 25 ° C.
  • Methyl acrylate 60 Methyl methacrylate 60
  • Resin particles (AR-24) were synthesized according to Synthesis Example 24 of transfer layer resin particles (AR).
  • a mixed solution of the resin particle dispersion (ie, seed particles) and the dispersion stabilizing resin (Q-2) (10 g) was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this was added a mixture of 60 g of methyl methacrylate, 40 g of methyl methacrylate, 2.0 g of methyl 3-mercaptopropionate, 0.8 g of A.I.VN and 400 g of Aitpar G. After 2 hours, the reaction was continued for another 2 hours. Next, 0.8 g of an initiator was added, the temperature was raised to 70 ° C., and the mixture was reacted for 2 hours. Further, 0.6 g of an initiator was added and reacted for 3 hours. cold After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 98% and an average particle size of 0.25 with good monodispersibility.
  • a film prepared by dispersing resin particles on PET film was heated at 50 ° C and 80 ° C for 5 minutes, and then each sample was processed by JEOL, JSL — Using a T330 Scanning Microscope at a magnification of 20,000, the temperature was 5 (particles were observed in the TC sample, but no particles were observed in 8 O'C. Was melted by heating.
  • resin particles (AR-2) Tg 45 ° C
  • resin particles (AR-24) Tg l8) composed of each of the two kinds of resins (copolymers) constituting the particles of the present invention. ° C), and a dispersion of the two types of particles mixed at a 1/1 weight ratio.
  • the sample consisting of resin particles (AR-24) is not heated The sample is in a particle state, but the temperature is 50, no particle state is observed, and the sample of resin particles (AR-2) is at a temperature of 80 ° The particles disappeared in C.
  • the resin particles synthesized according to the examples of the present invention are not a mixture of two kinds of resin particles, but two kinds of resin particles in one particle. In this case, it was confirmed that the high Tg resin was core-shell particles in which the low Tg resin was distributed in the outer layer and the low Tg resin was distributed in the inner layer.
  • the high-Tg resin (AH) and the low-Tg resin (AL) may have a core-shell structure having the above-described configuration, a core-shell structure having the reverse combination, or an uneven distribution. Any of the existing particles may be used without any particular limitation.
  • a Tg—25 ° C [vinyl acetate Z ethylene [4 675 4 weight ratio] copolymer (Evaflex 45X: Mitsui 'Dupont Chemical Co., Ltd.') and Tg 38 ° C was melt-kneaded with polyvinyl acetate in a three-roll mill at a temperature of 120 ° C. using a (1/1) weight ratio.
  • the kneaded material was coarsely ground with a trio blender, and 5 g of the ground material, 4 g of resin for dispersion stabilization: Sorprene 125 (manufactured by Asahi Kasei Corporation) and 1 g of Aisper H5 were approximately 4 inm in diameter.
  • the mixture was charged into a paint shinny riichi (manufactured by Toyo Seiki Co., Ltd.) using the glass beads as a medium, and preliminarily dispersed for 20 minutes.
  • This preliminary dispersion was wet-dispersed at 450 Or.pm for 6 hours using a Dynomill KDL type (manufactured by Shinmaru Enterprises Co., Ltd.) using glass beads having a diameter of 0.75 to 1 mm as a media. These were flattened with a white dispersion obtained through a 200 mesh nylon cloth.
  • the average particle size was 0.4 latex.
  • Example of synthesis of resin particles (ARW) 10 to 14: (ARW-10) to (ARW-1) In place of the two resins (A) used in Example 9 of synthesis of resin particles (ARW), A dispersion was prepared by the same wet dispersion method as in Synthesis Example 9 except that each compound shown in Table-E was used. The white dispersion ranged in average particle size from 0.3 to 0.6 m.
  • a mixed solution of 70 g of methyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream, and cooled to -20.
  • 0.8 g of 1,1-dibutylbutyllithium was added and reacted for 12 hours.
  • a mixed solution of 30 g of the following monomer (m-1) and 60 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream, and added, followed by further reaction for 8 hours.
  • This mixture was rubbed at 0 ° C: methanol was added thereto, and the mixture was reacted for 30 minutes to terminate the polymerization.
  • the resulting polymer solution was stirred at a temperature of 30 ° C.
  • a mixture of 50 g of ethyl methacrylate, 10 g of glycidyl methacrylate and 4.8 g of benzyl ⁇ , N-getyldithiocarbamate was tightly closed in a vessel under a nitrogen stream, and heated to a temperature of 50 g. This was irradiated with light from a high-pressure mercury lamp of 400 W through a glass filter from a distance of 10 on for 6 hours to carry out photopolymerization. This was dissolved in 100 g of tetrahydrofuran, and after adding 40 g of the following monomer (m-3), the mixture was replaced with nitrogen and irradiated with light again for 10 hours. The obtained reaction product was reprecipitated in methanol 1, collected, and dried. The resulting polymer was Mw4.8 X 1 0 4 in a yield 73 g.
  • Example 2 Was synthesized in the same manner as in Example 1 to obtain a copolymer having an Mw of 4.5 ⁇ 10 4 .
  • a mixed solution of 68 g of methyl methacrylate, 22 g of methyl acrylate, 10 g of glycidyl methacrylate, 17.5 g of an initiator having the following structure (1-3) and 150 g of tetrahydrofuran was heated under a nitrogen stream. Heated to 50 ° C. This solution was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 10 hours to carry out photopolymerization. The resulting reaction product was reprecipitated in methanol 1 ⁇ , and the precipitate was collected dried to obtain Mw4.0 X 1 0 4 of the polymer in a yield 72 g.
  • a dispersion stabilizing resin As a dispersion stabilizing resin, a mixed solution of 5 g of (AB-6) (manufactured by Toagosei Co., Ltd .: monofunctional macromonomer composed of butyl acrylate units) and methylethyl ketone 140 was stirred under a nitrogen stream. The mixture was heated to a temperature of 6 (TC).
  • AB-6 manufactured by Toagosei Co., Ltd .: monofunctional macromonomer composed of butyl acrylate units
  • TC temperature of 6
  • a monomer (LM-2) having the following structure 1.5 g of ethylene glycol diacrylate, 0.2 g of A.I.VN and 0.2 g of methyl ethyl ketone 40 g of the mixed solution was added dropwise over 1 hour After the reaction for 2 hours, 0.1 g of AIVN was further added and reacted for 3 hours to obtain a white dispersion After cooling, the mixture was passed through a 200 mesh nylon cloth. Distributed The average particle size of the product was 0.35 m.
  • Monomer (LM-2): CH 2 CH
  • X-type metal-free phthalocyanine (Dai Nippon Ink Co., Ltd.) 2 g, binding resin (B-1) 8 g having the following structure, resin (P-1) 2 g , compound (A) 0 having the following structure
  • a mixture of 15 g and 80 g of tetrahydrofuran was placed in a 500 glass container together with a glass bead, dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and then phthalic anhydride was added to the mixture. After adding 1 g and 0.02 g of 0-chlorophenol and dispersing for 5 minutes, the glass beads were filtered off to obtain a photosensitive layer dispersion.
  • Binder resin (B-1) Binder resin (B-1)
  • this dispersion was applied to a conductive-treated 0.2 mm thick aluminum plate with a wire bar, dried by touch, and then heated in a circulation oven at 110 ° C. for 20 seconds. Heated at 0 ° C for 1 hour.
  • the thickness of the obtained photoreceptor was 8 m.
  • the adhesive strength of the photoreceptor was measured using the “Testing method for adhesive tape / adhesive sheet” of JISZ 0237-198, the value was 2 g ⁇ f.
  • the transfer layer was formed at g ⁇ f or more, no separation property was exhibited.
  • the above photoreceptor having an easily peelable surface is mounted on the apparatus shown in FIG. 5 as an electrophotographic photoreceptor 11, and a blanket for offset printing 9600 — A (adhesive strength 80 g) is used as a primary receptor 20.
  • ⁇ Dispersion of resin (A) [; L-1] with the following content on c photoreceptor drum equipped with f / 10 mm width, overall thickness 1.6 mm, made of Meiji rubber) Is supplied to the wet electrodeposition unit 14 T, which is a transfer device, and the transfer layer 12 is formed by the wet electrodeposition method.
  • the resin particles (AR-24) 5 g (as solid content) Charge adjusting compound (D-1) 0.03 g
  • the electrophotographic process was performed as follows.
  • the photoconductor 11 is passed under the corona charger 18 at a location, charged with corona to +450 V, read in advance from the original with a color scanner, and color-separated to obtain a system-specific After applying some corrections related to color reproduction, the digital image data was stored in the hard disk of the system as a one-night negative image mode. Exposure was performed with 8 8 ⁇ ⁇ so that the amount of exposure on the photoreceptor was 3 O erg / cnf.
  • the positively charged yellow toner for the signature system (manufactured by Kodak) is diluted 75 times with Isopar H (manufactured by Etsuso Standard Petroleum), supplied to the yellow liquid developing unit 14 y, and the developing unit 14 y is developed. +350 V bias voltage is applied to the exposed side, and reversal development is carried out so that the toner is electrodeposited on the exposed area. After being removed, it was dried by passing it under an intake / exhaust unit 15 and a preheating unit 16.
  • the above toner development process is applied to magenta (14m), cyan (14c), black (14k :)
  • the photosensitive member 11 was heated using the preheating means 16 and the temperature adjusting means 17 so that the surface temperature became 60 ° C.
  • the photosensitive drum 11 and the primary receptor 20 drum were brought into contact with each other. Heating and pressurizing were performed under the conditions of a nip pressure of 4.5 kgf / cnf and a drum peripheral speed of 10 tsec.
  • Image 3 was completely transferred onto primary receptor 20 together with transfer layer 12 c.
  • the coated paper 30 for printing which is the final transfer material, is introduced between the backup roller 32 for industrial use set at C, the nip pressure is 5 kgf / cnf, and the drum peripheral speed is 1 O mmZ.
  • the entire color toner image 3 was transferred onto the coated paper 30 together with the transfer layer 12, and a clear, high-quality color image was obtained.
  • a color image was formed on the coated paper 30 by a method of transferring onto the photoreceptor 11 without providing the transfer layer 12, and compared with the present invention.
  • the toner from the photoreceptor can be sufficiently transmitted from the photoreceptor by using the resin layer as the transfer layer, and the image can be easily and sufficiently transferred from the primary receptor to the final transfer-receiving material. It can be seen that the fact that the image is protected by the transfer layer is good.
  • An amorphous silicon photoreceptor (manufactured by Kyocera Corporation) was mounted on the apparatus shown in Fig. 5 as an electrophotographic photoreceptor.
  • the variation of the photoreceptor surface was 200 g ⁇ g.
  • the release property was imparted to the photoreceptor by immersing it in a solution of the compound (S) of the present invention in the same apparatus (immersion method).
  • the photosensitive member surface temperature was set to 50 ° C., and the peripheral speed of the photosensitive drum was rotated at an arbitrary Z second for 10 seconds, and the positively charged resin particle dispersion having the following contents was applied to the photosensitive member surface using a slit electrodeposition device. While supplying [: L-2], the photoconductor side was grounded, and a voltage of -130 V was applied to the electrode side of the slit electrodeposition apparatus to electrodeposit and fix the resin particles. A transfer layer having a thickness of 2.0 m was formed.
  • the amorphous silicon photoreceptor 11 having a hybrid shape is read in advance from a manuscript by a color scanner, and color-separated to obtain some system-specific characteristics. After corrections related to color reproduction were made, digital image data was stored on the hard disk in the system. Of the yellow, magenta, unen, and black colors, the semiconductor laser was first used based on information about yellow. Exposure was performed using 780 nm light. The potential of the II light portion was 122 V and the unexposed portion was +600 V.
  • the resin particles (AR-18) and (ARW-1) were formed as a second transfer layer 12 'on the photoreceptor on which the color image was formed, in the resin particle dispersion [L-12].
  • a transfer layer 12 ′ having a thickness of 3 ⁇ m was formed in the same manner as in the wet electrodeposition method.
  • a primary receptor 7 parts by weight of the resin (P-2) and 100 parts by weight of phthalic anhydride were added to 100 parts by weight of isoprene rubber on the roll surface of the blanket 9600-A used in Example 1.
  • a film having a thickness of 10 m was coated with 0. 1 g, and a cured film was formed by heating at 140 ° C for 2 hours. which was) then in the coated paper 3 0, combined it heavy and primary receptor 2 0 having a color one toner image 3, 4 kgf / cnf always control the surface temperature in contact with pressure to 1 0 0 e C of It passed under the heated rubber spout 31 at a speed of 50 occ.
  • the coated paper 30 was peeled off, and the toner 3 of the primary receptacle 20 was transferred to the coated paper 30 together with the transfer layers 12 and 12 ′. Heat transferred. Further, since the toner 3 on the coated paper 30 was completely covered with the thermoplastic resin 12 ′ as the transfer layer, it did not rub off.
  • Example 2 the compound was formed in the same apparatus that performs an electrophotographic process on the photoreceptor surface.
  • the following method was used instead of the above immersion method as a method for imparting release properties to the surface of the photoreceptor by adhering or adsorbing the substance (s).
  • the compound (S-2) 113 is supplied between the metalling roll 112 and the transfer roll 111 as shown in FIG. Even when the method was applied to the compound (S) -coated portion 110, similarly good results were obtained.
  • Binder resin (B-2) X-type metal-free phthalocyanine 2 g, binder resin having the following structure (B-2) 8 g, binder resin having the following structure (B-3) 2 g, compound (B) having the following structure 0.15 g, and tetrahydrogen
  • a mixture of 80 g of mouth furan was placed in a 50 glass container together with glass beads, and dispersed with a paint shaker (manufactured by Toyo Seiki Seisaku-sho) for 60 minutes. The glass beads were filtered off to obtain a photosensitive layer dispersion.
  • Binder resin (B-2) binder resin having the following structure (B-3) 8 g, binder resin having the following structure (B-3) 2 g, compound (B) having the following structure 0.15 g, and tetrahydrogen
  • this dispersion is coated on a 0.2 mm thick paper master for stencil, which has been subjected to conductive treatment and solvent resistance treatment, with a wire bar, dried with a resin, and then dried with a 11 O'C circulation type oven. Ripened for 20 seconds.
  • the thickness of the obtained photosensitive layer was 8 m.
  • a photoreceptor having an easily releasable surface was obtained by providing a 1.5 m-thick film-forming surface layer on the photoreceptor as described below. Formation of easily removable surface layer>
  • a coating containing 0.1 g in 100 g of ⁇ -hexane was applied using a wire-round rod to a film thickness of 1.5 mm. Heated for 0 minutes.
  • the adhesive force of the obtained surface was 1 g ⁇ f or less.
  • the photosensitive member 11 was mounted on an apparatus having a movable developing unit set 14 and a movable hot melt coater 13 shown in FIG.
  • the transfer layer 12 was formed using a hot melt resin set at 120 ° C using an ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, softening point 9 O'C by the ring and ball method) as a thermoplastic resin.
  • the coating was applied to the surface of the photosensitive layer at a speed of 20 picoseconds per night, and cooling air was blown from the intake / exhaust unit 15 to cool, and then the surface temperature of the photoconductor was maintained at 30 ° C. Was. At this time, the thickness of the transfer layer 12 was 2.5 m.
  • the method of transferring from the paper pattern 24 shown in FIG. 6 onto the primary receptor 20 as in Example 1 is applied to the transfer layer forming means 21 to the primary receptor 20 as appropriate, and the transfer layer 12 was formed.
  • Separate paper manufactured by Oji Paper Co., Ltd.
  • AH high Tg resin
  • Nivaflex 45X [(vinyl acetate Z-ethyl (46Z54)) is formed as a low-Tg resin (AL) on top of a 1.5-m-thick film consisting of a polymer (Tg 60 ° C).
  • Weight ratio) Copolymerization (Tg—25 ° C .: manufactured by Mitsui DuPont Polychemical Co., Ltd.) was pressed into the same primary receptor 20 as in Example 1 to form a coating having a thickness of 5 m.
  • one color transmembrane pressure 3 kgf / cnf, the surface temperature 6 0 e C and passing speed 1 0 negation / sec conditions with the primary receptor 2 0 on the surface to form a transfer layer 1 2 having a thickness of 3 ".
  • Example 2 Using the photoreceptor 1 having the transfer layer 12 formed thereon and the primary receptor 20 having the transfer layer 12 "formed thereon, a color image was formed on the coated paper 30 in the same manner as in Example 1. The obtained color copy was a good image without capri as in Example 4, and the image strength was sufficient.
  • Example 2 The same amorphous silicon photoreceptor as used in Example 2 was mounted on an apparatus as shown in FIG. 5, and the wet electrodeposition method was used to simultaneously release the photoreceptor 11 and form the transfer layer 12. It was carried out in a manner to be performed.
  • a transfer layer having a thickness of 2.0 m was formed on the photoreceptor using the following resin particle dispersion [L-4] in the same manner as in Example 1.
  • a pair of heating rollers each coated with a 100-m-thick silicon rubber whose surface adhesive strength was adjusted to 60 g ⁇ and having an infrared lamp heater incorporated inside the hollow roller, were used.
  • the next receptor was 20 and this infrared line heater was used to measure the surface temperature with a radiation thermometer to about 80 ° C.
  • acetic acid 'cellulose butyrate a resin consisting of Cellulidor Bsp (manufactured by Bayer AG) and a [styrene / vinyl acetate] copolymer (copolymer weight ratio (80 to 20)) in a 1 Z 1 weight ratio
  • a hot melt coater set at 80 ° C apply the solution to the surface of the secondary receptor at a speed of 2 nm / s, and cool by blowing cooling air from the intake / exhaust unit.
  • the thickness of the transfer layer 12 was 5 m.
  • the color image 3 on the photoreceptor 11 was transferred to the primary receptor 20 and a high-quality final transfer material was further transferred.
  • the paper was transferred onto paper 30 to obtain a blank copy.
  • the transfer conditions were as follows: transfer pressure 4 Kgf / crf, transfer Degrees 7 0 ° C, ⁇ of ivy in transfer speed 1 5 O mmZ seconds.
  • a mixture of 5 g of bisazo pigment having the following structure, 95 g of tetrahydrofuran, 5 g of polyester resin: Byron 200 (manufactured by Toyobo Co., Ltd.) and 30 g of tetrahydrofuran solution was sufficiently pulverized in a ball mill. Next, the mixture was taken out, and under stirring, 500 g of tetrahydrofuran was added. This dispersion was coated on the conductive support used in Example 1 using a wire round rod to form a charge generation layer of about 0.7 m.
  • the tackiness of the surface of the obtained photoreceptor was 5 g ⁇ : f.
  • the photoreceptor 11 is mounted on an apparatus in which the transfer layer forming apparatus shown in FIG. 6 is applied to the apparatus shown in FIG. 4, and the transfer layer 1 is transferred onto the photoreceptor 11 by transfer from release paper as follows. 2 was formed.
  • Sun release manufactured by Sanyo Kokusaku Pulp Co., Ltd. was used as the release paper 24, and poly (vinyl acetate) and poly (phenethyl methacrylate) were added to the above film with a thickness of 3 m consisting of (5/5) weight ratio.
  • the paper with the coating formed thereon was pressed against the photoreceptor 11 as shown in Fig. 6, and the pressure between rollers was 3 kgf / cnf, the surface temperature was 60 ° C, and the passing speed was 10 ⁇ /
  • a transfer layer 12 having a thickness of 3 m was formed on the surface of the photoconductor 11 under the condition of seconds.
  • This photosensitive material is charged to a surface potential of ⁇ 500 V at a location, and then irradiated with light of 633 nm using a He—Ne laser with an exposure amount of 30 erg / A color toner image was formed on the photoreceptor by operating in the same manner as in Example 1 except that the exposure was performed so as to be cnf.
  • the drum type shown in FIG. 4 was replaced with the endless belt type receptor shown in FIG.
  • Offset printing blanket 9600-A adheresive strength 80 g ⁇ ⁇ / 10 width, overall thickness 1.6 marauder, made of Meiji Rubber
  • [L-15] and [L-16] were supplied to a wet electrodeposition unit, which is a transfer layer type apparatus 21, respectively, and a two-layer transfer layer 12 ⁇ was formed by a wet electrodeposition method.
  • the primary receptor 20 was charged to 1150 V to electrodeposit resin particles to form a first layer having a thickness of 2.5 m.
  • Resin particles (AR-3) 10 g (as solid content) Charge adjusting compound (D-3) 0.0 2 g
  • this dispersion liquid [L-15] except that 10 g of the resin particles (ARL-3) were used instead of 10 g of the resin particles (ARH-3), it was completely the same as the first layer.
  • the electrodeposition dispersion liquid [L-16] prepared in the same manner, the dispersion was charged to 115 V, and the resin particles were electrodeposited to form a second layer having a thickness of 2 m.
  • the second layer of the transfer layer 12 "on the primary receptor 20 which was to be in contact with the toner image was formed so as to be composed of a resin having a low Tg.
  • the drum 1 and the primary drum 20 were brought into contact, and heating and pressurization were performed under the conditions of a nip pressure of 3 kgi / cnf and a drum peripheral speed of 100 mm / s.
  • the toner image 3 was all transferred to the transfer layer 12 ⁇ ⁇ on the primary receptor 20 together with the transfer layer 12.
  • the primary receptor 20 drum whose surface temperature was set to 60 ° C. by the temperature control means 17, and 130.
  • the coated paper 30 for final printing which is the final material to be transferred, is introduced between the backup roller 31 for transfer set at C and the backup roller 32 for separation set at 10 ° C. Heating and pressurization were performed at a pressure of 4 kgi / cnf and a drum peripheral speed of 100 mmsec.Toner image 3 was completely transferred onto coated paper 30 with transfer layer 12 and transfer layer 12 ⁇ . Transferred, high-quality clear color image was obtained. Furthermore, when the coated paper, which is the main paper for printing, was replaced with a commercially available copy paper for a copying machine as the final transfer material 30, a color image was formed in the same manner. Color image quality with no difference was obtained. That is, even if the paper quality of the final transfer material 30 was changed, a good color copy was obtained without being affected by the change.
  • the X-type metal-free phthalocyanine photoreceptor having an easily peelable surface and the primary receptor used in Example 1 were mounted on the same apparatus as in Example 1.
  • a first layer in contact with the photoreceptor side has a high T g resin (AH) and a second layer formed thereon has a low T g resin (AL) as described below.
  • AH high T g resin
  • AL low T g resin
  • the surface of the photoreceptor was charged to 110 V to electrodeposit resin particles, thereby forming a first layer having a thickness of 2 m.
  • Resin particles (AR-9) 10 g (as solid content) Charge adjusting compound (D-3) 0.02 g
  • the electrodeposition dispersion liquid [; L-19] having the following content was also supplied to the apparatus 21 in FIG. 4 for the formation of a transfer layer.
  • a transfer layer 12 ⁇ having a thickness of 2 m was formed.
  • the infrared line heater is turned on and passed under it, and the surface temperature is measured with a radiation thermometer to be approximately 80 ° C.
  • the primary receptor with the above transfer layer 12 ⁇ is provided. Heat the (drum) 20 to a temperature of 100 C, bring the photoreceptor 11 drum into contact with the primary receptor 20, and set the nib pressure to 4 kgf / ⁇ and the drum peripheral speed to 100 Under the conditions, the color toner image 3 was all transferred onto the primary receptor 120.
  • the high-quality paper 30 is superimposed on the primary receptor 20 having the color toner image 3, and the heated rubber roller whose surface temperature, which is in contact with a pressure of 4 kgf / cnf, is always controlled to 120 ° C It passed under 3 1 at a speed of 100 thighs. Then, when the high-quality paper was pulled off by passing under the cooling roller 32, the toner 3 on the primary receptor 20 was completely transferred to the high-quality paper 30 along with the transfer layers 12 and 12 1. . Further, since the toner 3 on the high-quality paper 30 was completely covered with the thermoplastic resin 12 "as the transfer layer, it did not rub off, and the image strength was sufficient.
  • Example 8 2 7 Even if it is added or stamped on paper, it can be done in the same way as for plain paper.
  • Example 1 instead of 2.0 g of the resin (P-1), the resin (PJ A blank image was prepared in the same manner as in Example 1 except that each of Z and Z or the resin particles (L) were used.
  • Each of the obtained color images was a copy of clear image quality with no ground force blur, and the strength of the image portion was sufficient.
  • Example 1 The procedure of Example 1 was repeated, except that each of the compounds shown in Table 1N below was used in place of the resin (P-1), fluoric anhydride, and 0-chloromouth fininol. Error images were created.
  • Example 3 9 to 4 6 the resin particles (AR-18) and (ARW-1) for the transfer layer 12 formed on the electrophotographic photoreceptor and the resin particles (ARW-1) for the transfer layer 12 'formed on the toner image were prepared.
  • a color image copy was prepared in the same manner as in Example 2 except that each resin particle (AR) and / or (ARW) shown in Table 1 below was used instead of ARW-3).
  • Example 5 instead of the compound (S-5) 0.8 g / ⁇ and the resin particles (ARW-48 g), the compound (S) and the resin particles (AR) or (ARW) shown in Table 1P below are used. Except for using 8 g (as a total amount), the same operation as in Example 5 was performed to obtain a color image copy.
  • Example 5 a transfer image forming operation was performed in the same manner as in Example 5 except that the resins (A) used in the transfer layer 12 on the primary receptor were replaced with the resins shown in Table-Q below. As a result, good results equivalent to those of Example 5 were obtained.
  • Example 6 instead of separation paper having a transfer layer provided on the photoreceptor, release paper: Sun Release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was used. A blank image was created in the same manner as in Example 6, except that the paper provided with the resin [A] was used.
  • Sun Release manufactured by Sanyo Kokusaku Pulp Co., Ltd.
  • the obtained color image was a clear image with no ground force, and almost no deterioration of the image quality was recognized as compared with the original. no
  • Example 1 instead of using coated paper as the final transfer material 30, a blank image copy was created using the following transfer material.
  • Example 2 a color image was obtained under the same conditions as in Example 1 by using a transfer material 30 in which EVAflex 45X resin was applied to a thickness of 5 m on the surface of the coated paper. As a result, a good color image was formed on the transfer material in the same manner as in Example 1.
  • transfer condition I was performed by changing the transfer conditions from the primary receptor 120 to the material 30 to be transferred as follows (transfer condition I).
  • Transfer speed (Drum peripheral speed) 1 O mmZ sec. 150 sec. Even under the above condition H, the toner image 3 is completely transferred onto the coated paper 30 provided with the resin layer with the transfer layer 12 completely. There was no disturbance such as missing image parts.
  • the transfer conditions are relaxed and the transfer speed is further improved. Becomes possible. The same effect was observed not only on coated paper but also on other materials to be transferred, that is, high-quality paper, plain paper, transfer paper for copying, various resin films, and the like.
  • Example 66 the transfer material having the content shown in Table S below was used in place of the cut paper provided with Evaflex 45 as the final transfer material. Got it.
  • the method and apparatus of the present invention can be effectively used for forming a color image such as an electrophotographic color copier, a color printer, a color puller, and a color checker.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Electrostatic Charge, Transfer And Separation In Electrography (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

Le procédé consiste à: (i) déposer une couche de transfert décollable (12) sur un matériau électrophotographique sensible (11) constitué au moins d'un élément de support (1) et d'une couche photosensible (2); (ii) former une image (3) à base de toner comportant une ou plusieurs couleurs sur cette couche de transfert (12) par un procédé électrophotographique classique; (iii) transférer l'image (3) à base de toner sur un récepteur primaire (20) avec la couche de transfert (12); et (iv) transférer l'image (3) à base de toner sur un matériau de transfert final (30) avec la couche de transfert (12). On obtient ainsi une image en couleur et on peut produire une copie de cette image en couleur qui présente une haute définition et une haute qualité mais aucune erreur de reproduction des couleurs, et il est donc facile de transférer cette image en couleur quel que soit le matériau de transfert final retenu. De plus, il ne subsiste aucune trace de l'image à base de toners, ce qui permet une utilisation répétitive de l'élément photosensible et du support intermédiaire.
PCT/JP1994/000507 1993-03-29 1994-03-29 Procede et appareil de formation d'une image en couleur WO1994023346A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE69420714T DE69420714D1 (de) 1993-03-29 1994-03-29 Verfahren zur erzeugung eines mehrfarbigen bildes und gerät dazu
EP94910558A EP0692743B1 (fr) 1993-03-29 1994-03-29 Procede et appareil de formation d'une image en couleur

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP5/91913 1993-03-29
JP9191393 1993-03-29
JP5/146770 1993-05-27
JP14677093 1993-05-27
JP5/240279 1993-09-02
JP24027993 1993-09-02
JP5/246048 1993-09-08
JP24604893 1993-09-08
JP35462493 1993-12-28
JP5/354624 1993-12-28

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PCT/JP1994/000507 WO1994023346A1 (fr) 1993-03-29 1994-03-29 Procede et appareil de formation d'une image en couleur

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DE (1) DE69420714D1 (fr)
WO (1) WO1994023346A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4833183B1 (fr) * 1968-05-10 1973-10-12
JPS60179751A (ja) * 1984-02-28 1985-09-13 Fuji Photo Film Co Ltd 静電写真用液体現像剤
JPH03142472A (ja) * 1989-10-27 1991-06-18 Brother Ind Ltd 画像転写形成方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176974A (en) * 1989-10-16 1993-01-05 Xerox Corporation Imaging apparatuses and processes
US5075186A (en) * 1989-12-13 1991-12-24 Xerox Corporation Image-wise adhesion layers for printing
US5108865A (en) * 1990-04-18 1992-04-28 Minnesota Mining And Manufacturing Company Offset transfer of toner images in electrography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4833183B1 (fr) * 1968-05-10 1973-10-12
JPS60179751A (ja) * 1984-02-28 1985-09-13 Fuji Photo Film Co Ltd 静電写真用液体現像剤
JPH03142472A (ja) * 1989-10-27 1991-06-18 Brother Ind Ltd 画像転写形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0692743A4 *

Also Published As

Publication number Publication date
EP0692743A4 (fr) 1997-02-12
DE69420714D1 (de) 1999-10-21
EP0692743B1 (fr) 1999-09-15
EP0692743A1 (fr) 1996-01-17

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