EP0629512A2 - Wiederverwendbares wärmeepfindliches bilderzeugendes Material - Google Patents

Wiederverwendbares wärmeepfindliches bilderzeugendes Material Download PDF

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Publication number
EP0629512A2
EP0629512A2 EP94401241A EP94401241A EP0629512A2 EP 0629512 A2 EP0629512 A2 EP 0629512A2 EP 94401241 A EP94401241 A EP 94401241A EP 94401241 A EP94401241 A EP 94401241A EP 0629512 A2 EP0629512 A2 EP 0629512A2
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EP
European Patent Office
Prior art keywords
color material
group
weight
parts
material layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94401241A
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English (en)
French (fr)
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EP0629512A3 (de
Inventor
Akira C/O Minnesota Mining And Muramoto
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3M Co
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Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0629512A2 publication Critical patent/EP0629512A2/de
Publication of EP0629512A3 publication Critical patent/EP0629512A3/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/282—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using thermochromic compounds
    • B41M5/284—Organic thermochromic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • the present invention relates to a erasable and re-recordable recording media for forming letters and images by electric signals, and a recording process using such a recording media.
  • it relates to a recording media and a recording process that can provide a reversible recorded image usable in printers, facsimiles, and copying apparatus, and is easily maintained and operated.
  • Japanese Unexamined Patent Publication No. 50-1732 discloses a so-colled negative-type recording material showing reverse photochromism, using spiropyran and color-developing by heat.
  • Such a recording material is negative-type and has wide applications, but provides an unstable image and is substantially difficult to use in natural light. Moreover, it provides low color density, and insufficient gradation.
  • This invention is to provide an imaging material that is re-writable, provides high color density and high gradation and is stable when exposed to heat and light.
  • this invention provides a heat sensitive color material possessing a substrate, a color material layer laminated on the surface of said substrate, and a protective layer on said color material layer, characterized in that said color material layer comprises 100 parts by weight of a binder resin and 0.1 to 30 parts by weight of an aromatic polycyclic compound containing a 9,10-diphenylanthracene structure represented by the following formula (I): or a corresponding endoperoxide construction represented by the following formula (II):
  • a transparent or translucent substrate may be used as the above substrate, including various kinds of paper, macromolecular films, plastics, glasses, metals, etc.
  • binder resin Any binder can be used as the above binder resin as long as it has a film forming ability, the resulting film having excellent transparency, and good compatibility with the color material.
  • cellulose, cellulose derivatives, polystyrene, polyester, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, poly(methyl methacrylate), polyvinyl acetate, etc. can be used.
  • polyester which has color-developing and -erasing properties.
  • the alkyl groups for R1-R5 are independently a lower alkyl group having 1-5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, or any other branched pentyl group.
  • the alkyl moieties of substituted alkyl groups for R1-R5 are independently a lower alkyl group, for example, and of the alkyl groups mentioned above.
  • the substituents in the substituted alkyl groups are independently, for example, a halogen atom, such as fluorine, chlorine or bromine, or nitro group.
  • the alkyl components of the alkoxy groups for R1-R5 are independently a lower alkyl group, for example, any of the alkyl groups mentioned above. Specifically, they are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, or the like.
  • the alkoxy components of the substituted alkoxy group for R1-R5 are independently, for example, any of the alkoxy groups mentioned above, and the substituents are independently, for example, a halogen atom, such as fluorine, chlorine, or bromine, or nitro group.
  • the aryl groups for R1-R5 are independently, for example, phenyl group or naphthyl group.
  • the aralkyl groups are independently, for example, a phenyl alkyl group for example a benzyl group.
  • the aryl components and aralkyl components in the substituted aryl groups and the substituted aralkyl groups respectively are, for example, those mentioned above being substituted with a substitutent, for example, a halogen atom, such as fluorine, chlorine, or bromine, or nitro group.
  • a preferable aromatic polycyclic compound according to this invention is benzo[1,2,3-kl : 4,5,6-k',l']dixanetene represented by the following formula (VII) or (VIII): or its methyl derivative, or a corresponding endoperoxide thereof.
  • the above-mentioned aromaic polycyclic compound forms a corresponding endoperoxide with the irradiation of a light having a wavelength of ⁇ 1 in the presence of oxygen, which further forms the original aromatic polycyclic compound by heating or with the irradiation of a light having a wavelength of ⁇ 2, as represented by the following reaction mechanism: Compounds exhibiting such a reaction are described in H. Durr, H. Bouas-Laurent, editors, "Photochromism” (1990), Chapter 15.
  • the color material according to the present invention can be decolored with the irradiation of a strong light in the presence of oxygen, and then colored by a heating means, such as a thermal head.
  • the colored material of this invention is very stable in comparison to conventional recording materials using spiropyrane, spirooxazine and fulgides, but decolored with a strong light, for example, of 1 to 1000 J/cm2. Accordingly, the color material of the present invention has a high stability in a room light and can be used repeatedly.
  • the coloration takes place by entailing the discharge of oxygen on one hand, and the decolaration takes place by entailing the absorption of oxygen. Consequently, to accelerate the decoloration a binder having a high oxygen permeability is preferably used, and to lower the decoloration a binder having a low oxygen permeability is preferably used.
  • the amount of the above aromatic polycyclic compound or the endoperoxide to be used is in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the binder resin. If the amount is too small, the color density is not sufficient, and if it is too large, the dissolution in the binder is not sufficient, thereby bringing about coagulation.
  • Any resin can be used as the above protective layer as long as it has heat resistance and slidabling to the thermal head, is transparent, and is free of UV curing and heat curing (at 100°C or more).
  • a fluorine resin or silicone resin can be used as such a resin.
  • the heat sensitive color material it is possible to dissolve the above aromatic polycyclic compound or the endoperoxide and the binder in an appropriate solvent capable of dissolving both components, and to apply the solution on the surface of the substrate, followed by drying.
  • an appropriate solvent capable of dissolving both components
  • the solvent for example, tetrahydrofuran, toluene, chloroform, etc. may be used.
  • concentration of the binder resin in the solution which is not specifically restricted, is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 20% by weight.
  • the application of binder resin solution on the surface of the substrate may be carried out in a usual manner, for example, using a Meyer bar, knife coater, gravure coater, die coater, etc.
  • the drying after the application may be carried out, for example, at 50-70°C for 10-60 minutes.
  • the resulting color material layer possesses a thickness of 1 to 50 ⁇ m, preferably 3 to 30 ⁇ m.
  • a fluorine resin or silicone resin may be dissolved or uniformly dispersed in a poor solvent that does not affect the color material layer, applied on the surface of the color material layer, and then dried.
  • the poor solvent that can be used in this case includes, for example, an alcohol, hexane or heptane, a furon type solvent, water, or the like.
  • the application of the forming liquid on the surface of the color material layer may be carried out in a usual manner, for example, using a Meyer bar, knife coater, gravure coater, die coater, etc.
  • the drying after the application may be carried out, for example, at 50-70°C for 10-60 minutes.
  • After drying the color material dye layer possesses a thickness of 0.001 to 0.1 ⁇ m, preferably 0.01 to 0.1 ⁇ m.
  • the colored image can be obtained using a totally decolored material and irradiation of visible light by a heating means, such as a thermal head.
  • the colored image can be erased with irradiation of strong visible light.
  • the colorless material containing a colorless type of aromatic polycyclic compound can form a color image by a heating means, such as a thermal head, and the color image can be decolored with irradiation of strong visible light.
  • the rate of decoloration depends on the kind of binder used (particularly the oxygen permeability), and the quantum efficiency of the decoloration reaction of the aromatic polycyclic compound. Moreover, when light irradiation for the purpose of the decoloration is carried out, if light irradiation is carried out on the side of the color material layer of the image material the decoloration can take place in a shorter time than when irradiation is carried out on the side of the substrate.
  • the energy required for the decoloration is within the range of 1 to 1000 J/cm2.
  • the heat sensitive color material according to this invention can be used repeatedly by repeating the image formation by heating and the decoloraticn of the image with light irradiation.
  • Toray silicone (H.V.G.) (produced by Toray Silicone) dissolved in 95 parts by weight heptane was applied as a protective layer with a #40 Meyer bar, and dried at 65°C for 10 minutes to form a red film having a transmission optical density (TOD) of approximately 1.2.
  • TOD transmission optical density
  • a sixteen step gradation was formed on the heat sensitive color material thus obtained using a test printer of 3M (200 DPI) by placing a weight of about 4 kg on a thermal head (produced by Kyocera). Thereafter, the entire surface was decolored on the OHP with irradiation of visible light for about 20 minutes, and then a gradation image was formed using the test printer again. The procedure could be carried out repeatedly.
  • the sensitivity curve at this time is shown in Fig. 1, and the maximum transmission optical density and the transmission optical density at the time of decoloration are shown in Fig. 2.
  • Example 2 TABLE 1 Content of Compound based on 100 parts by weight of resin Transmission optic density
  • Example 2 0.5 0.15
  • Example 3 1.0 0.29
  • Example 4 2.0 0.53
  • Example 5 3.0 0.72
  • Example 6 7.2 1.17
  • Example 7 15.0 1.43
  • Example 1 0.05 0.03
  • Example 2 0.1 0.05
  • a tetrahydrofuran solution of Vylon 290 was added to a given amount of compound A, and tetrahydrofuran was added until compound A was dissolved, then the solvent was removed in a dryer, and the solubility of compound A in the resin was visibly observed. As a result, the coagulant was formed when the amount of compound A exceeded 30 parts by weight.
  • Compound B represented by the following formula: was prepared by dehydration condensation between 5-dinitrosalicylic aldehyde and 1.3,3-trimethyl-2-methyleneindolin.
  • Example 8 A visible light was irradiated on the films obtained in Example 8 and Comparative Example 4 using a color transmission densitometer (produced by X-Rite, Model X-Rite 309), and the decrease in the transmission optical density was measured. The results are shown in Fig. 3. The colored image from Example 8 was found to be more stable than that from Comparative Example 4.
  • Fig. 1 shows the change is gradation of an image in the heat sensitive color material of Example 1 in the case where the image formation and image decoloration were repeated three times.
  • Fig. 2 shows the changes in image density and density after decoloration (TOD) in the heat sensitive color material of Example 1 when image formation and image decoloration were repeated six times.
  • Fig. 3 is a graph comparing the stability (color-fading due to irradiation of visible light) of the image of heat sensitive color material prepared in Example 5 with that from Comparative Example 5.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP94401241A 1993-06-07 1994-06-06 Wiederverwendbares wärmeepfindliches bilderzeugendes Material. Withdrawn EP0629512A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5135868A JPH079766A (ja) 1993-06-07 1993-06-07 繰り返し使用可能な感熱発色材料
JP135868/93 1993-06-07

Publications (2)

Publication Number Publication Date
EP0629512A2 true EP0629512A2 (de) 1994-12-21
EP0629512A3 EP0629512A3 (de) 1996-01-10

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EP94401241A Withdrawn EP0629512A3 (de) 1993-06-07 1994-06-06 Wiederverwendbares wärmeepfindliches bilderzeugendes Material.

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EP (1) EP0629512A3 (de)
JP (1) JPH079766A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0779559A1 (de) * 1995-12-13 1997-06-18 Fuji Xerox Co., Ltd. Wiederverwendbares Bildaufzeichnungsmaterial und Bild herstellende Vorrichtung sowie Methode zur Wiederverwendung
WO2004065520A1 (ja) * 2003-01-17 2004-08-05 Nippon Kayaku Kabushiki Kaisha 発光素子、それに用いる縮合多環系化合物及びその製造方法
CN100366623C (zh) * 2003-01-17 2008-02-06 日本化药株式会社 发光元件、其中使用的稠多环类化合物及其制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8748629B2 (en) 2010-07-09 2014-06-10 Mitsubishi Gas Chemical Company, Inc. Photochromic material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3794512A (en) * 1969-08-08 1974-02-26 American Cyanamid Co Product for the formation of fluorescent images
DE2910668A1 (de) * 1979-03-19 1980-09-25 Brauer Hans Dieter Photochrome aufzeichnungsmaterialien und verbindungen
SU900247A1 (ru) * 1980-02-05 1982-01-23 Институт Физики Ан Усср Светочувствительный материал
JPS6253885A (ja) * 1985-09-02 1987-03-09 Kao Corp 光学記録媒体
EP0518470A1 (de) * 1991-05-08 1992-12-16 Minnesota Mining And Manufacturing Company Negativ-arbeitende thermographische Materialien

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3794512A (en) * 1969-08-08 1974-02-26 American Cyanamid Co Product for the formation of fluorescent images
DE2910668A1 (de) * 1979-03-19 1980-09-25 Brauer Hans Dieter Photochrome aufzeichnungsmaterialien und verbindungen
SU900247A1 (ru) * 1980-02-05 1982-01-23 Институт Физики Ан Усср Светочувствительный материал
JPS6253885A (ja) * 1985-09-02 1987-03-09 Kao Corp 光学記録媒体
EP0518470A1 (de) * 1991-05-08 1992-12-16 Minnesota Mining And Manufacturing Company Negativ-arbeitende thermographische Materialien

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 4, 26 July 1982, Columbus, Ohio, US; abstract no. 31346z, V.V.BONDAR ET AL 'Light-sensitive material' page 512 ;column RIGHT ; & SU-A-900 247 (INSTITUTE OF PHYSICS, ACADEMY OF SCIENCES, UKRAINIAN S.S.R.) *
PATENT ABSTRACTS OF JAPAN vol. 11, no. 241 (M-614) 7 August 1987 & JP-A-62 053 885 (KAO CORP) 9 March 1987 & DATABASE WPI Week 8715, Derwent Publications Ltd., London, GB; AN 87-105797 *
STUDIES IN ORGANIC CHEMISTRY, vol.40, 1990, AMSTERDAM pages 631 - 653 H.D]RR ET AL *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0779559A1 (de) * 1995-12-13 1997-06-18 Fuji Xerox Co., Ltd. Wiederverwendbares Bildaufzeichnungsmaterial und Bild herstellende Vorrichtung sowie Methode zur Wiederverwendung
US5958559A (en) * 1995-12-13 1999-09-28 Fuji Xerox Co., Ltd. Peelable image recording member and image forming apparatus and method of reusing the peelable image recorder member
WO2004065520A1 (ja) * 2003-01-17 2004-08-05 Nippon Kayaku Kabushiki Kaisha 発光素子、それに用いる縮合多環系化合物及びその製造方法
EP1589089A1 (de) * 2003-01-17 2005-10-26 Nippon Kayaku Kabushiki Kaisha Lichtemittierende vorrichtung, darin eingesetzte kondensierte polycyclische verbindung sowie verfahren zu deren herstellung
JPWO2004065520A1 (ja) * 2003-01-17 2006-05-18 日本化薬株式会社 発光素子、それに用いる縮合多環系化合物及びその製造方法
CN100366623C (zh) * 2003-01-17 2008-02-06 日本化药株式会社 发光元件、其中使用的稠多环类化合物及其制造方法
EP1589089A4 (de) * 2003-01-17 2008-08-27 Nippon Kayaku Kk Lichtemittierende vorrichtung, darin eingesetzte kondensierte polycyclische verbindung sowie verfahren zu deren herstellung
US7494721B2 (en) 2003-01-17 2009-02-24 Nippon Kayaku Kabushiki Kaisha Light-emitting device, condensed polycyclic compound used therein and method for producing same
JP4606328B2 (ja) * 2003-01-17 2011-01-05 日本化薬株式会社 発光素子、それに用いる縮合多環系化合物及びその製造方法

Also Published As

Publication number Publication date
EP0629512A3 (de) 1996-01-10
JPH079766A (ja) 1995-01-13

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