EP0390432B1 - Chromogen - Google Patents

Chromogen Download PDF

Info

Publication number
EP0390432B1
EP0390432B1 EP19900303121 EP90303121A EP0390432B1 EP 0390432 B1 EP0390432 B1 EP 0390432B1 EP 19900303121 EP19900303121 EP 19900303121 EP 90303121 A EP90303121 A EP 90303121A EP 0390432 B1 EP0390432 B1 EP 0390432B1
Authority
EP
European Patent Office
Prior art keywords
color
dye
former
diethylamino
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19900303121
Other languages
English (en)
French (fr)
Other versions
EP0390432A3 (de
EP0390432A2 (de
Inventor
Masahiro C/O Oiso Branch Sakamoto
Tsutomu C/O Oiso Branch Murano
Shozo C/O Oiso Branch Harada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paper Industries Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=13555488&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0390432(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Publication of EP0390432A2 publication Critical patent/EP0390432A2/de
Publication of EP0390432A3 publication Critical patent/EP0390432A3/de
Application granted granted Critical
Publication of EP0390432B1 publication Critical patent/EP0390432B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • B41M5/287—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 microcapsules or microspheres only
    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients

Definitions

  • the present invention relates to a color-former comprising microcapsules suitable for use as a pressure-sensitive recording material and a temperature-indicating material.
  • Recording materials using an electron-donating colorless dye are well known, such as pressure-sensitive recording papers, heat-sensitive recording papers, light-sensitive recording papers, electrical heat-sensitive recording papers and temperature-indicating papers, see GB-A-2,140,449, US-A-4,480,052, US-A-4,436,920, JP-B-60-23922, JP-A-57-179836, JP-A-60-123556 and JP-A-60-123557.
  • GB-A-2,026,425 discloses the preparation of microcapsules containing a water-insoluble liquid by forming an emulsion from an aqueous medium containing a nonionic emulsifier and a solvent which is substantially insoluble in the aqueous medium, adding an organic acid which is soluble in the aqueous medium, adding urea and formaldehyde, and heating to produce a wall film or membrane by polycondensation of the urea and formaldehyde.
  • the present invention provides a color-former comprising microcapsules containing an electron-donating colorless dye dispersed in a hydrophobic liquid by a nonionic surfactant, a polymerized surfactant, or an oil-soluble pelar compound of long chain.
  • the electron-donating colorless dyes there can be used any previously disclosed for pressure- or heat-sensitive recording papers, for example phthalide dyes, fluorane dyes, spiropyran dyes, diphenylmethane dyes, azine dyes and triarylmethane dyes.
  • phthalide dyes examples include 3,3-bis(P-dimethylamino)-6-dimethylamino phthalide, 3-(P-dibenzylamino phenyl)-3-(1',2'-dimethyl-3-indolyl)-7-azaphthalide, 3,3-bis(4'dimethylamino phenyl) phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-7-azaphthalide, 3,3-bis(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3,3-bis(1-ethyl-2-methylindol-3-yl)-7-azaphthalide, 3,3-bis(1-
  • fluorane dyes examples include 3,6-dimethoxyfluorane, 4-amino-8-diethylaminobenzo[a] fluorane, 2-amino-8-diethylaminobenzo[a]-fluorane, 4-benzylamino-8-diethylaminobenzo[a] fluorane, 3-diethylamino-6-methylfluorane, 3-diethylamino-7-aminofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 2-methyl-6-(N-p-tolyl-N-ethylamino)-fluorane, 10-diethylaminobenzo[c] fluorane, spio(xanthene-9,1′-phthalan)-6-diethylamino-2-phenyl
  • spiropyran dyes examples include 2,2′-spiro (benzo[f] chromene), spiro[3-methylchromene-2,2′-7′-diethylaminochromene], spiro[3-methyl-benzo(5,6-a) chromene-2,2′-7′-diethylaminochromene], spiro[3-methylchromene-2,2′-7′-dibenzylaminochromene] and 3-methyl-di- ⁇ -naphthospiropyran.
  • diphenylmethane dyes examples include 4,4′-bis(4,4′-tetramethyldiamino diphenylmethylamino) diphenylmethane, bis ⁇ 4,4′-bis(dimethylaminobenzhydryl ⁇ ether, N,N′-bis[bis(4′dimethylaminophenyl) methyl]-1,6-hexamethylene diamine, N-bis(4-dimethylaminophenyl) methylglycine ethyl ester and 4,4′-bis-dimethylaminobenzhydryl benzyl ether.
  • Examples for azine dyes include 3,7-bis(dimethylamino) 10-benzoylphenothiazine, 10-(3′,4′,5′-trimethoxy-benzoyl)-3,7-bis(dimethylamino) phenothiazine and 3-diethylamino-7 (N-methylanilino)-10-benzoylphenoxazine.
  • triarylmethane dyes examples include N-butyl-3-[bis ⁇ 4-(N-methylanilino) phenyl ⁇ methyl] carbazole, 4H, 7-diethylamino-4,4′-bis(9′-ethyl-3′-methyl-6′-carbazolyl)-2-t-butyloylamino-3,1-benzothiazine, 4H-7-diethylamino-4-(p-diethylaminophenyl)-4-(9′-ethyl-3′-methyl-6′-carbazolyl)-2-pivaloylamino-3,1-benzothiazine, 4H-6-methyl-4,4-bis(p-dimethylaminophenyl)-2-pivaloyl-3,1-benzothiazine, 4H-7-dibenzylamino-4,4-bis(p-dimethylaminophenyl)-2-phenyl-3,1-benz
  • dyes used in the present invention include 7-chloro-1,3-dihydro-1,1-bis(p-dimethylaminophenyl)-3-oxisobenzo[b] thieno[2,3-c] furane, spiro ⁇ chromeno[2,3-c]-4(H)-1'-phthalan ⁇ -7-diethylamino-3-methyl-1-(p-tolyl)-3'-on, spiro[11H-benzo[b] thieno [3,2-b] chromene-11,1'-phthalan]-3-diethylamino-7-methyl-3'-on, spiro[11H-benzo[b] thieno [3,2-6] chromene-11,1'-phthalan]-8-chloro-3-diethylamino-6-methyl-3'-on, lactone of 1-benzyl-2-(2-carboxy-4-dimethylaminophenyl)-2-hydroxyraphthostyryl,
  • Cationic or amphoteric surfactants easily prevent color-formation.
  • Anionic surfactants tend to form the color of a colorless dye.
  • non-ionic surfactants cause neither a self color forming nor the prevention of color-forming and thus are suitable for the present invention.
  • the surfactants suitable for the present invention are, e.g. sorbitan fatty acid esters, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan sesquistearate, sorbitan monotall oil fatty acid ester, sorbitan monoisostearate, etc.; polyoxyethylene sorbitan esters of fatty acids such as polyoxyethylene sorbitan hexastearate and polyoxyethylene sorbitan tetraoleate; polyethylene glycol esters of fatty acids, such as polyoxyethylene monooleate and diethyleneglycol stearate; polyoxyethylene alkylphenyl esters such as polyoxyethylene nonylphenylether and polyoxyethylene octylphenylether; derivatives of lanoline or bees wax such as polyoxyethylene sorbitan bees wax and polyoxyethylene lanoline.
  • sorbitan fatty acid esters such as sorbitan monolaurate, sorb
  • the so-called polymerized surfactants can be used to obtain a uniform and stable dispersion of an electron-donating colorless dye in a hydrophobic liquid, for example such polymerized surfactants as lauryl methacrylate/diethylamino acrylate copolymer polymethacrylate, polyacryl amide, vinylcarboxylate/dialkyl fumarate copolymer and alkyl-polysulfide. Also oil-soluble polar compounds of long-chain, such as dialkyl dithiophosphate, can be used.
  • nonionic surfactants polymerized surfactants and polar compounds of long chain can be used alone or together with another compound.
  • the hydrophobic liquid for dispersing an electron-donating colorless dye include natural and synthetic hydrophobic liquid and is used alone or in combination.
  • examples for the hydrophobic liquid include natural oils such as plant oils and animal oils; petroleum destillate and derivatives thereof, such as machine oil, kerosine, paraffin and naphthene oil; synthetic oils such as alkylbiphenyl, alkylterphenyl, chlorinated paraffin, alkyl-naphthalene and diphenyl alkane; and semi-synthetic oils.
  • the dispersing of the dye is carried out as follows. A certain amount of the electron-donating colorless dye is introduced into a hydrophobic liquid, and is dispersed by means of a dispersing machine without heating.
  • the dispersing machine there can be used, for example, ball mill, sand mill, horizontal sand mill attritor or colloid mill. It is suitable that the electron-donating colorless dye is dispersed in the hydrophobic liquid in a concentration of 2 - 60% by weight, preferably 10 - 50% by weight. With a concentration of less than 2% by weight, a sufficiently high color-formation is not obtained.
  • the hydrophobic liquid comprises the nonionic surfactant, the polymerized surfactant and/or the polar long-chain compound in a concentration of 2 - 40% by weight, preferably 5 - 35% by weight.
  • concentration of 2 - 40% by weight preferably 5 - 35% by weight.
  • dispersing of dye is insufficient.
  • more than 40% by weight the adjustment of emulsified particle size in the capsule-forming process after the dye-dispersing is difficult and the capsule wall tends to be insufficient.
  • the particle size of dye in the dye-dispersion is not otherwise limited. But with the particle size of less than 0.1 ⁇ , the stability of the emulsified particles is reduced and the coagulation occurs easily, and with the particle size of more than 5 ⁇ , color-formation is not sufficient and the smudging can be formed through dye-particles in application as a color-former for a pressure-sensitive recording paper. Accordingly, it is suitable to use a dye particle size of 0.1 - 5 ⁇ , preferably 0.5 - 2 ⁇ .
  • the electron-donating colorless dye dispersed in a hydrophobic liquid of the present invention can be colored, with the change of temperature or in contact with an electron-accepting color-developing agent, in the same way as the dye dissolved in a solvent.
  • the color-former is coated with a binder on a base material, and in the use as a top sheet for pressure-sensitive recording sheets, the color-former is coated with a binder and a buffer agent on a base sheet.
  • the color-former of the present invention can be used in the same way as the microcapsules comprising an electron-donating colorless dye dissolved in a solvent.
  • microcapsules obtained by dispersing an electron-donating colorless dye in a hydrophobic liquid are not easily ruptured.
  • the use as the temperature-indicating material or the color-former for a pressure-sensitive recording sheet, under coating the material of the present invention on a substrate, provides a clear dense color-formation with little smudging and stable preservability in storage. The reason for the above excellent features is unclear. However, it is assumed that in the conventional dye-dissolution-type color-former, dye is deposited as crystals with the lapse of time, and the capsule wall is ruptured by a slight pressure on the end or a corner of the obtained crystal.
  • a sheet (a top sheet) coated with microcapsules was laid on a bottom sheet (W-40-R, produced by JUJO PAPER CO., LTD.) and treated by a calender in a pressure of 50kg/cm2 to develop a color. After 6 seconds, Y-value of the color image was measured by means of Color-Difference Meter, and expressed as color-forming velocity. The smaller the value, the greater the color-forming velocity.
  • a sheet coated with microcapsules was laid on the above bottom sheet and treated by a calender in a pressure of 50kg/cm2 to develop a color. After 1 hour, Y-value of the color image was measured by means of Color-Difference Meter and expressed as image density. The smaller the value, the denser the image.
  • a sheet coated with microcapsules was laid on the bottom sheet and treated by a calender in a static pressure of 5kg/cm2 to develop a color. After 1 hour, Y-value of the color image was measured by means of Color-Difference Meter. The difference between the above Y-value and the Y-value of non color-developed part of the bottom sheet was expressed as smudging under static pressure. The smaller the value, the slighter the smudging.
  • a sheet (top sheet) coated with microcapsules was laid on the bottom sheet. Also, 6 sheets were superposed and typewritten. The cleaness of the letter on the 6th sheet was determined by means of eyes.
  • a color-former for pressure-sensitive recording sheets was obtained in the same manner as in Example 1, except that 3,6-di-(N-dimethylaminofluorane-9-spiro-3′-(6′-dimethylamino) phthalide (Green 118, produced by Yamamoto Kagaku (0) was used as an electron-donating colorless dye.
  • Example 1-(1) 50g of 3-cyclohexylamino-6-chlorofluorane (OR-55, produced by Yamada Kagaku Co.) as an electron-donating colorless dye and 20g of dialkyl tindithiophosphate (an oil-soluble polar long-chain compound) as a dispersing agent were added to 30g of plant oil (colza oil), and dispersed to an average particle size of 1.5 ⁇ by means of a sand mill. This dispersed liquid was added to 450g of diaryl alkane oil (Hysol SAS 296), and further dispersed. 150g of the obtained liquid were encapsulated in the same manner as in Example 1. Then, a top sheet for pressure-sensitive recording sheet was obtained and evaluated in the same way as in Example 1.
  • OR-55 produced by Yamada Kagaku Co.
  • dialkyl tindithiophosphate an oil-soluble polar long-chain compound
  • Microcapsules and a top sheet for pressure-sensitive recording sheets were obtained and evaluated in the same manner as in Example 1, except that 4g of a liquid dispersing CVL (Crystal Violet Lactone) (Example 6) or ODB (3-dimethylamino-6-methyl-7-anilinofluorane) (Example 7) in mineral turpentine oil were further dispersed in the solvent of Example 1 or 3, and thus a dispersed liquid having a dye concentration of 2.5% was used.
  • CVL Crystal Violet Lactone
  • ODB 3-dimethylamino-6-methyl-7-anilinofluorane
  • Examples 1 - 7 and Comparative Examples 1 and 2 were summarized in Table 1, and their evaluated results were indicated in Table 2.
  • Table 2 the Examples using as a color-former the dye-dispersion-capsules of the present invention provide practically sufficient abilities with respect to image density, color-forming velocity, smudge under static pressure and copying ability.
  • Examples 2, 4 and 5 using the electron-donating colorless dyes with a poor solution-stability the dye-dispersion capsules provide better effects in comparison with the dye-dissolution capsules giving an insufficient image density.
  • Examples 6, 7 and Comparative Examples 3, 4 using the electron-donating colorless dyes with a good solution-stability the dye-dispersion-capsules provide the same effects as the dye-dissolution capsules.
  • the color-former of the present invention provides the following superior effects, compared with the conventional color-former obtained by a dye dissolved in a solvent.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (7)

  1. Chromogen, das Mikrokapseln umfaßt, enthaltend einen Elektronen abgebenden farblosen Farbstoff, der in einer hydrophoben Flüssigkeit mittels eines nicht-ionischen Tensids, eines polymerisierten Tensids oder einer langkettigen öllöslichen polaren Verbindung dispergiert ist.
  2. Chromogen nach Anspruch 1, bei dem die Konzentration des besagten Farbstoffes in besagter hydrophober Flüssigkeit 2 bis 60 Gewichts-% beträgt.
  3. Chromogen nach Anspruch 1 oder 2, bei dem besagter Farbstoff in besagter hydrophober Flüssigkeit durch, als nichtionisches Tensid, wenigstens eine Verbindung ausgewählt aus Sorbitanfettsäureester, Polyoxyethylensorbitanester von Fettsäuren, Polyethylenglykolester von Fettsäuren, Polyoxyethylenalkylphenylether und Derivaten von Lanolin oder Bienenwachs dispergiert ist.
  4. Chromogen nach Anspruch 1, 2 oder 3, bei dem die Menge an nicht-ionsichem Tensid, polymerisiertem Tensid oder einer langkettigen öllöslichen polaren Verbindung 2 bis 40 Gewichts-% basierend auf besagter hydrophober Flüssigkeit beträgt.
  5. Chromogen nach irgendeinem der vorherigen Ansprüche, bei dem der Farbstoff eine durchschnittliche Teilchengröße von 0,1 bis 5 µm besitzt.
  6. Chromogen nach Anspruch 5, bei dem der Farbstoff eine durchschnittliche Teilchengröße von 0,5 bis 2 µm besitzt.
  7. Verwendung des Chromogens nach irgendeinem der vorherigen Ansprüche in einem druckempfindlichen Aufzeichnungsmaterial oder einem Temperaturanzeigematerial.
EP19900303121 1989-03-27 1990-03-23 Chromogen Expired - Lifetime EP0390432B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP74725/89 1989-03-27
JP1074725A JPH0741738B2 (ja) 1989-03-27 1989-03-27 発色材料

Publications (3)

Publication Number Publication Date
EP0390432A2 EP0390432A2 (de) 1990-10-03
EP0390432A3 EP0390432A3 (de) 1991-05-22
EP0390432B1 true EP0390432B1 (de) 1994-10-19

Family

ID=13555488

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900303121 Expired - Lifetime EP0390432B1 (de) 1989-03-27 1990-03-23 Chromogen

Country Status (4)

Country Link
EP (1) EP0390432B1 (de)
JP (1) JPH0741738B2 (de)
AU (1) AU630680B2 (de)
DE (1) DE69013383T2 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9113086D0 (en) * 1991-06-18 1991-08-07 Wiggins Teape Group Ltd Solvent compositions for use in pressure-sensitive copying paper
DE69321765T3 (de) * 1992-06-04 2006-08-24 Arjo Wiggins Ltd., Basingstoke Druckempfindliches Aufzeichnungsmaterial
GB9221621D0 (en) * 1992-10-15 1992-11-25 Wiggins Teape Group Ltd Solvents for use in pressure-sensitive record material
GB9318369D0 (en) * 1993-09-04 1993-10-20 Carrs Paper Ltd Pressure-sensitive record materials
GB9318371D0 (en) * 1993-09-04 1993-10-20 Carrs Paper Ltd Pressure-sensitive record materials
US6071852A (en) * 1994-09-05 2000-06-06 Carrs Paper Limited Pressure-sensitive record materials

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB184992A (en) * 1921-07-29 1922-08-31 Henry Alfred Oake Improvements in or relating to advertising devices
JPS558856A (en) * 1978-07-05 1980-01-22 Mitsubishi Paper Mills Ltd Covering of finely dispersed liquid droplet with thin film
JPS55158998A (en) * 1979-05-29 1980-12-10 Mitsubishi Paper Mills Ltd Manufacturing of microcapsule
JPS5634495A (en) * 1979-08-31 1981-04-06 Kureha Chem Ind Co Ltd Pressure sensitive copying paper
JPS5711085A (en) * 1980-06-25 1982-01-20 Nippon Petrochem Co Ltd Recording material
JPS57116686A (en) * 1981-01-13 1982-07-20 Kureha Chem Ind Co Ltd Pressure-sensitive recording paper
JPS59214691A (ja) * 1983-05-21 1984-12-04 Mitsubishi Paper Mills Ltd 感熱記録紙
JPS6122985A (ja) * 1984-07-12 1986-01-31 Toa Nenryo Kogyo Kk 感圧複写紙用溶剤
JPS61242886A (ja) * 1985-04-22 1986-10-29 Fuji Photo Film Co Ltd 多色感熱記録材料
JPS61286337A (ja) * 1985-06-13 1986-12-16 Kureha Chem Ind Co Ltd １−トリル−２−フエニルプロパン
JPS62129141A (ja) * 1985-11-29 1987-06-11 Fuji Photo Film Co Ltd マイクロカプセルの製造方法
FR2591124B1 (fr) * 1985-12-10 1988-02-12 Rhone Poulenc Spec Chim Procede de microencapsulation par polyaddition-interfaciale.
JPS62257879A (ja) * 1986-05-02 1987-11-10 Kureha Chem Ind Co Ltd 感圧記録紙用染料溶剤及びその溶剤を用いた感圧記録紙
JPS62257880A (ja) * 1986-05-02 1987-11-10 Kureha Chem Ind Co Ltd 感圧記録紙用染料溶剤及びその溶剤を用いた感圧記録紙
JPS63118288A (ja) * 1986-11-07 1988-05-23 Kawasaki Steel Corp 感圧複写紙用溶剤及びその製造方法
JPH07121611B2 (ja) * 1986-11-20 1995-12-25 日本石油化学株式会社 複写材料
JPH07121612B2 (ja) * 1986-11-20 1995-12-25 日本石油化学株式会社 複写材料
JPH0737179B2 (ja) * 1986-12-30 1995-04-26 日本石油化学株式会社 感圧複写材料
JP2559112B2 (ja) * 1987-02-09 1996-12-04 東燃株式会社 感圧複写紙用溶剤
FR2610537A1 (fr) * 1987-02-11 1988-08-12 Rhone Poulenc Chimie Procede ameliore de microencapsulation par polyaddition interfaciale
JPS63203376A (ja) * 1987-02-19 1988-08-23 Kureha Chem Ind Co Ltd 感圧記録紙用染料溶剤
JPH02106387A (ja) * 1988-10-14 1990-04-18 Kanzaki Paper Mfg Co Ltd 感圧複写シート
JP2675594B2 (ja) * 1988-10-18 1997-11-12 三菱製紙株式会社 マイクロカプセル製造用乳化剤、該乳化剤を用いてなるマイクロカプセル及びその製造方法並びに該マイクロカプセルを用いたノーカーボン感圧複写紙

Also Published As

Publication number Publication date
EP0390432A3 (de) 1991-05-22
DE69013383D1 (de) 1994-11-24
JPH0741738B2 (ja) 1995-05-10
DE69013383T2 (de) 1995-02-23
EP0390432A2 (de) 1990-10-03
JPH02252576A (ja) 1990-10-11
AU630680B2 (en) 1992-11-05
AU5210390A (en) 1990-09-27

Similar Documents

Publication Publication Date Title
EP0247816B1 (de) Wärmeempfindliches Farbe-Aufzeichnungsmaterial mit Mikrokapseln
US4352855A (en) Transfer-onto-plain paper type pressure-sensitive copying paper
US4087284A (en) Color-developer coating for use in copy systems
US5178949A (en) Color-former
EP0390432B1 (de) Chromogen
WO2000016985A1 (en) Microcapsules comprising solvent for chromogenic material
DE19717651B4 (de) Kohlenstoff-freies, druckempfindliches Kopierpapier und dessen Verwendung
CA2092233C (en) Desensitizable record material
EP0697292B1 (de) Druckempfindliches Aufzeichnungsmaterial
CA1049709A (en) Pressure-sensitive record material employing alkyl naphthalene dye-precursor solvent
US4181328A (en) Recording element
JP3611094B2 (ja) 発色剤マイクロカプセル
US4800193A (en) Recording material
JPH06340169A (ja) 記録材料
CA1224627A (en) High print intensity marking fluid
JP2010173087A (ja) 発色剤マイクロカプセル及びそれを用いた感圧複写紙
US4743579A (en) Recording sheet having a chlorinated alpha-olefin solvent
EP0718116B1 (de) Aufzeichnungsmaterial
JP3882436B2 (ja) マイクロカプセル
JP2010194776A (ja) 発色剤マイクロカプセル及びそれを用いた感圧複写紙
JPH08169178A (ja) 記録材料
JPS62152780A (ja) 感圧複写紙およびその製法
JPS58148789A (ja) 感圧複写紙
JPH11268411A (ja) ノーカーボン感圧複写紙
JPH08142507A (ja) 感圧記録用シート

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE FR GB LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE FR GB LI

17P Request for examination filed

Effective date: 19911018

17Q First examination report despatched

Effective date: 19930915

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI

REF Corresponds to:

Ref document number: 69013383

Country of ref document: DE

Date of ref document: 19941124

ET Fr: translation filed
RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: NIPPON PAPER INDUSTRIES CO., LTD.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: NIPPON PAPER INDUSTRIES CO., LTD

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: STORA - FELDMUEHLE AG

Effective date: 19950621

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

R26 Opposition filed (corrected)

Opponent name: STORA PUBLICATION PAPER AG

Effective date: 19950621

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 19970313

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20070314

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070315

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070321

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070308

Year of fee payment: 18

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080323

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081001

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080323