EP0275929B1 - Farbentwicklungsblatt für druckempfindliche Aufzeichnungen und Farbentwicklungsmittel hierfür - Google Patents

Farbentwicklungsblatt für druckempfindliche Aufzeichnungen und Farbentwicklungsmittel hierfür Download PDF

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Publication number
EP0275929B1
EP0275929B1 EP88100466A EP88100466A EP0275929B1 EP 0275929 B1 EP0275929 B1 EP 0275929B1 EP 88100466 A EP88100466 A EP 88100466A EP 88100466 A EP88100466 A EP 88100466A EP 0275929 B1 EP0275929 B1 EP 0275929B1
Authority
EP
European Patent Office
Prior art keywords
colour developing
developing agent
acid
polyvalent metal
colour
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
EP88100466A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0275929A3 (en
EP0275929A2 (de
Inventor
Hiroaki Central Research Laboratory Umeda
Mamoru Central Research Laboratory Suzuki
Akira Central Research Laboratory Hasagawa
Kunio Central Research Laboratory Hata
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.)
Jujo Paper Co Ltd
Original Assignee
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
Application filed by Jujo Paper Co Ltd filed Critical Jujo Paper Co Ltd
Publication of EP0275929A2 publication Critical patent/EP0275929A2/de
Publication of EP0275929A3 publication Critical patent/EP0275929A3/de
Application granted granted Critical
Publication of EP0275929B1 publication Critical patent/EP0275929B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/124—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
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate

Definitions

  • the invention relates to a color developing sheet and color developing agent for pressure-sensitive recording sheets based on phenolic resins and conventional components of color developing agents.
  • the drawbacks that a phenolic resin still has as a color developing agent are therefore eliminated.
  • Pressure sensitive recording sheets are known as carbonless copy papers. When using mechanical pressure or impact pressure when writing or typing on a typewriter, they produce a colored impression and thus allow the simultaneous production of several copies. A colored image is formed due to the color development reaction between an electron donating colorless dye and an electron accepting color developing agent.
  • Typical color developing agents are inorganic solid acids such as activated clay, attapulgite, etc. (described in USP 2712507); substituted phenols and diphenols (described in Japanese Patent Publication 9309/1965); p-Subst.-phenol-formaldehyde polymers (in Japanese Patent publication 20144/1967); Metal salts of aromatic carboxylic acids (described in Japanese Patent Publications 10856/1974 and 1327/1977, etc.); 2,2'-bis-phenol sulfone compounds (described in JP-OS 10 6313/1979 etc.).
  • EP-A-271 081 (prior art under Article 54 (3) EPC) describes color developing agents for pressure-sensitive recording sheets and recording sheets containing this agent.
  • the color developing agent contains a reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal. It can be used in admixture with an inorganic solid acid, a phenol formaldehyde novolak resin, a substituted phenol resin, a metal salt thereof or a metal salt of an aromatic carboxylic acid.
  • EP-A-218 810 (prior art under Article 54 (3) EPC, except for IT) describes a color developing agent for a pressure-sensitive recording sheet and a color developing sheet containing this agent.
  • the color developing agent contains a polyvalent metal salt of a carboxylated terpene phenol resin, which is obtainable by condensing a cyclic monoterpene with phenol in the presence of an acid catalyst, carboxylating the condensed product and then reacting this product with a polyvalent metal or metal salt.
  • the color developing agent can be used in admixture with an inorganic solid acid, a phenol formaldehyde novolak salt, a substituted phenolic resin, a metal salt thereof or a metal salt of an aromatic carboxylic acid.
  • Phenolic resins are commonly used in the above color developing agents because they are inexpensive to manufacture and provide a color developing sheet with superior color forming ability, particularly high image density and high durability of the colored image to light, moisture, and heat.
  • a color developing sheet containing a phenolic resin as a color developing agent has the disadvantages that the color developing speed and final color developing intensity decrease on storage (hereinafter referred to as deterioration in color formability with time), and that the stability of the colored image upon contact with oils, particularly with plasticizers (hereinafter referred to as plasticizer resistance) is unsatisfactory.
  • the invention has for its object to provide a color developing agent for pressure-sensitive recording sheets which is largely free from the above disadvantages, i.e. has less deterioration in color formability with time and superior plasticizer resistance.
  • the inventors have surprisingly found after many studies that the above phenolic resins in combination with a polyvalent metal salt of a carboxylated terpene phenol resin and / or a reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal, less deterioration in color formation ability and superior Resistant to plasticizers and the benefits of the phenolic resin are retained.
  • the invention therefore relates to a color developing agent as defined in claims 1 and 2.
  • the phenolic resins according to the invention are polymers of phenols and aldehydes which are known from Japanese Patent Publication 20144/1967, in particular resins of the novolak type and with polyvalent metal salts modified novolak type resins are used.
  • Typical examples of such phenolic resins are p-phenylphenol-formaldehyde polymers, p-octylphenol-formaldehyde polymers, P-cumylphenol-formaldehyde polymers, p-tert.-butylphenol-formaldehyde polymers, p-nonylphenol-formaldehyde polymers, p-cyclohexylphenol-formaldehyde polymers, p-octetyl polymers , p-phenylphenol acetaldehyde polymers, p-tert-butylphenol acetaldehyde polymers and the like.
  • the polyvalent metal salt of a carboxylated terpene phenol resin according to the invention and the reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal according to the invention are new color developing agents. They have better resistance to yellowing over time and superior plasticizer resistance.
  • the carboxylated terpene phenol resin is prepared as described in EP-A-218 810 by the following procedure.
  • cyclic monoterpene and phenol are carried out in a suitable solvent, for example a petroleum product, in the presence of an acidic catalyst, for example aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc., to obtain a condensation product.
  • an acidic catalyst for example aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc.
  • Typical examples of the cyclic monoterpene are pinene, limonene, terpinolene, mentadiene, gum turpentine oil, which contains ⁇ -pinene as the main component, dipentene, which contains ⁇ -limonene as the main component, and so on.
  • Typical examples of the phenol are monophenols, e.g.
  • the condensation product is made alkaline by adding alkali metal, alkali metal hydroxide or carbonate and is introduced at 140-180 ° C and 5-30 atm with introduction of carbon dioxide gas. treated in an autoclave (Kolbe-Schmitt reaction), the carboxy group being introduced into the condensation product.
  • the solvent is distilled away. After cooling to room temperature, the product is washed out to remove unreacted compounds. The product is further extracted with a dilute basic aqueous solution and then neutralized, whereby the carboxylated terpene phenol resin is excreted. The resin obtained is filtered off and washed out in order to obtain the purified carboxylated terpene phenol resin.
  • the polyvalent metal salt of a carboxylated terpene phenol resin is prepared by reacting a carboxylated terpene phenol resin with a polyvalent metal oxide, hydroxide, chloride, carbonate, sulfate or the like in the presence of an inorganic ammonium salt with melting, or a carboxylated terpene phenol resin with alkali metal hydroxide a solvent such as water, alcohol, etc., add and react with a polyvalent metal salt, or the like.
  • polyvalent metals examples include magnesium, aluminum, calcium, cadmium, titanium, zinc, nickel, cobalt, manganese, etc .; Magnesium, aluminum and zinc are preferred. Zinc is most preferred.
  • the reaction product between the above carboxylated Terpene phenolic resin, aromatic carboxylic acid and polyvalent metal compound is prepared by uniformly mixing the carboxylated terpene phenolic resin, aromatic carboxylic acid and polyvalent metal compound and then reacting with each other, or by mixing two of the above three ingredients and then with one other component can react.
  • Uniform mixing is achieved by dissolving these ingredients in a solvent with stirring, or melting with heating, or by using other methods.
  • Typical examples of the solvents are alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc .; and organic solvents such as alcohol, acetone, etc .; and mixtures thereof.
  • aromatic carboxylic acid (monocyclic or polycyclic) is one in which the carboxy group is bonded directly to the ring.
  • aromatic carboxylic acid are: benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, Toluic acid, ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, p-tert.-butylbenzoic acid, o-benzoylbenzoic acid, p -benzoic acid, p -benzoic acid, p -benzoic acid, p -benzoic acid, p -benzoic acid, p -benzoic acid, p -
  • carboxylic acids the monocarboxylic acids are preferred.
  • suitable polyvalent metal compounds are oxides, halides, carbonates, sulfates, nitrates, acetates, formats, oxalates, benzoates, acetylacetone salts and salicylates of magnesium, aluminum, Cadmium, calcium, titanium, zinc, nickel, cobalt, manganese, vanadium, etc .; Magnesium, aluminum and zinc compounds are preferred; Zinc compounds are most preferred.
  • the amount of the polyvalent metal salt of a terpene phenol resin and / or the reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal based on the phenol resin is not particularly limited, and is preferably at least 1% by weight, and more preferably 30% .-%.
  • a color developing sheet is prepared by applying the coating slip obtained above as a simple layer on a substrate.
  • multi-layer coating methods can also be used, in which case a coating composition containing a color developing agent is first applied to a substrate and then another coating composition containing another color developing agent, and the like.
  • the color developing agents of the present invention are used in all fields related to pressure sensitive recording sheets. Examples are: Pressure sensitive recording sheets, e.g. have a middle sheet, lower sheet, single recording sheet, etc., or in which the color developing agent of the present invention is coated on or mixed with the support material; Test means for a leuco dye after dissolving in an organic solvent; Spot printing ink mixed with a wax; pressure sensitive ink using the color developing agent and / or microcapsules containing the leuco dye.
  • the coating slip according to the invention is produced by mixing kaolin clay, calcium carbonate, treatment starch, polyvinyl alcohol, synthetic or natural latex etc. and imparting the mixture with suitable viscosity and spreadability. It is advantageous to use 10-70% by weight of color developing agent, based on the total solids in the coating slip. With less than 10% by weight of color developing agent, the color developing ability is insufficient, with more than 70% by weight of color developing agent, on the other hand, the surface properties of the color developing sheet deteriorate.
  • color development layer it is also advantageous to apply the color development layer to a support in a coating amount of at least 0.5 g / m 2, preferably 1.0-10.0 g / m 2.
  • the color developing agent of the present invention is suitable for many known dyes used in pressure sensitive recording sheets.
  • Triphenylmethane series dyes such as crystal violet lactone, malachite green lactone, 3-dimethylaminotriphenylmethanephthalide, etc .
  • Fluoran series dyes such as 3,6-dimethoxyfluorane, 3-N-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 1,2-benzo-6-dimethylaminofluorane, 1,2-benzo- ( 2 ⁇ -diethylamino) -6-diethylamino-fluoran, 3-diethylamino-7-dibenzylamino-fluoran, 3-diethylamino-6-methyl-7-dibenzylamino-fluoran, 3-diethylamino-5-methyl-7-dibenzylamino-fluoran, 3 -Diethylamino-7-anilino-fluoran, 3-die
  • the evaluation method of the color development sheet using the transfer sheet is as follows.
  • dilution water 90 parts was mixed with 90 parts of a 10% aqueous solution of ethylene-maleic anhydride copolymer (trade name EMA, manufactured by Monsanto Co.). 10 parts of urea and 1 part of resorcinol were dissolved in this mixed solution, then the pH of the solution was adjusted to 3.4.
  • EMA ethylene-maleic anhydride copolymer
  • an oil mixture of alkyl diphenylethane (trade name: Hisol SAS 296, manufactured by Nisseki Kogaku Co.) and diisopropylnaphthalene (trade name KMC-113, manufactured by Kureka Kogaku Co.) was prepared in a weight ratio of 1: 1.
  • the core substance to be encapsulated there were prepared: (a) an oil of a blue color developing pressure sensitive dye by dissolving 3% crystal violet lactone and 1% benzoyl leucomethylene blue in the above oil mixture; and (b) an oil of a black color developing pressure sensitive dye by dissolving 5% 3-diethylamino-6-methyl-7-anilinofluorane, 1% 3-diethylamino-6-methyl-7-diphenylmethylaminofluorane and 0.5% 3-diethylamino-6-methyl-7-chlorofluorane in the above oil mixture.
  • a coating composition 180 parts of capsule slurry, 35 parts of wheat starch and 85 parts of an 8% aqueous oxidized starch solution were mixed to prepare a coating composition.
  • the coating composition was applied in a coating amount of 4.5 g / m2 on a base paper of 45 g / m2 and dried. In this way, two transfer sheets, that is, (A) a transfer paper developing blue color, and (B) a transfer paper developing a black color.
  • a CB sheet in which a support is coated with a microcapsule containing pressure-sensitive dye and a color developing sheet in which a support is coated with a color developing agent are laid so that the coated surfaces of the sheets touch each other.
  • a color image is generated with the grid plate roll calender.
  • the reflectance of the sheet is measured with a Hunter reflectometer (D-type; from Toyo Seiki Co.) measured using an amber filter.
  • the color development speed (J1 or J2) is calculated from the reflectance I0 before the color development, the reflectance I1 of 10 seconds after the color development or the reflectance I2 of 24 hours after the color development.
  • the image density at 10 seconds after color development is calculated according to the following equation:
  • the color development speed after 24 hours or the intensity of the final color development is calculated according to the following equation; Higher color development speed and intensity of final color development are desirable.
  • a color development sheet is 6 months at 30 ° C and 60% relative humidity stored.
  • the color development sheet and a transfer sheet are placed so that the coated surfaces of the sheets touch each other.
  • a color image is generated with the grid plate roll calender.
  • a color development speed J3 and a final color development intensity J4 are determined in the same manner as in the test method (1).
  • a small amount of dioctyl phthalate is applied to the colored surface of the image 24 hours after color development by the test method (1).
  • the reflectance I5 after the actual exposure time is measured.
  • the color development intensity J5 is calculated in the same manner as in the test method (1).
  • the plasticizer resistance value is expressed by the following equation:
  • the coating composition was applied to a sheet of 50 g / m2, so that the amount of coating composition applied after drying was 5.5 g / m2.
  • a water suspension of a color developing agent, a coating composition and a color developing sheet were prepared in the same manner as in Example 1, except that a reaction product of carboxylated terpene phenolic resin (made from rubber turpentine oil and carbolic acid as raw materials), salicylic acid and zinc chloride instead of the zinc salt of the carboxylated terpene phenolic resin in the example 1 was used.
  • a reaction product of carboxylated terpene phenolic resin made from rubber turpentine oil and carbolic acid as raw materials
  • salicylic acid and zinc chloride instead of the zinc salt of the carboxylated terpene phenolic resin in the example 1 was used.
  • Example 1 Using the above water suspension, a coating composition and then a color developing sheet were prepared in the same manner as in Example 1.
  • Example 1 100 parts of p-phenylphenol-formaldehyde novolak resin, 2.5 parts of sodium polyacrylate and 150 parts of water were dispersed to an average particle size of 3.2 ⁇ by a sand grinder to form a color developing agent suspension.
  • a coating composition and a color developing sheet were prepared from the obtained color developing agent suspension in the same manner as in Example 1.
  • a color developing sheet was prepared using a zinc-modified p-octylphenol-formaldehyde novolak resin in place of the p-phenylphenol-formaldehyde novolak resin in the same manner as in Comparative Example 1.
  • the color development sheet whose color development layer contains a phenolic resin in combination with a carboxylated terpene phenol resin zinc salt and / or a reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a zinc compound has less deterioration in color formation with time and superior plasticizer resistance compared to a color development sheet that contains only a phenolic resin.
  • this invention results in a commonly used color developing sheet which has less deterioration in color with time and superior plasticizer resistance compared to the prior art, while taking advantage of the phenolic resin, i.e. high image density and great resistance of the colored image to the effects of light, humidity and heat are retained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
EP88100466A 1987-01-14 1988-01-14 Farbentwicklungsblatt für druckempfindliche Aufzeichnungen und Farbentwicklungsmittel hierfür Expired - Lifetime EP0275929B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7014/87 1987-01-14
JP62007014A JPS63173681A (ja) 1987-01-14 1987-01-14 感圧複写紙用顕色シ−ト

Publications (3)

Publication Number Publication Date
EP0275929A2 EP0275929A2 (de) 1988-07-27
EP0275929A3 EP0275929A3 (en) 1988-09-14
EP0275929B1 true EP0275929B1 (de) 1991-08-07

Family

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EP88100466A Expired - Lifetime EP0275929B1 (de) 1987-01-14 1988-01-14 Farbentwicklungsblatt für druckempfindliche Aufzeichnungen und Farbentwicklungsmittel hierfür

Country Status (5)

Country Link
US (1) US4835134A (enrdf_load_stackoverflow)
EP (1) EP0275929B1 (enrdf_load_stackoverflow)
JP (1) JPS63173681A (enrdf_load_stackoverflow)
CA (1) CA1285764C (enrdf_load_stackoverflow)
DE (1) DE3864028D1 (enrdf_load_stackoverflow)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02243384A (ja) * 1989-03-17 1990-09-27 Sumitomo Durez Co Ltd 感圧記録紙用顕色剤
US6124377A (en) * 1998-07-01 2000-09-26 Binney & Smith Inc. Marking system
US6657726B1 (en) * 2000-08-18 2003-12-02 Applied Materials, Inc. In situ measurement of slurry distribution
US7815723B2 (en) * 2006-04-19 2010-10-19 Crayola Llc Water-based ink system
US7727319B2 (en) * 2006-04-19 2010-06-01 Crayola Llc Water-based ink system
GB2586188B (en) 2013-11-25 2021-06-23 Crayola Llc Marking system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218810A2 (de) * 1985-07-19 1987-04-22 Jujo Paper Co., Ltd. Farbentwicklungsmittel für druckempfindliches Aufzeichnungsblatt und Farbentwicklungsblatt dafür
EP0271081A2 (de) * 1986-12-10 1988-06-15 Jujo Paper Co., Ltd. Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten

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Publication number Priority date Publication date Assignee Title
FR2315003A1 (fr) * 1975-06-18 1977-01-14 Laprade Bernard Dispositif de regulation du melange air-carburant des moteurs a combustion interne
FR2315004A1 (fr) * 1975-06-18 1977-01-14 Laprade Bernard Dispositif de regulation du melange air-carburant des moteurs a combustion interne
US4165103A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developing agent
JPS60159540A (ja) * 1984-01-30 1985-08-21 Matsushita Electric Ind Co Ltd 換気装置
US4546365A (en) * 1984-05-23 1985-10-08 Appleton Papers Inc. Record member
US4573063A (en) * 1984-05-23 1986-02-25 Appleton Papers Inc. Record member
US4540998A (en) * 1984-05-23 1985-09-10 Appleton Papers Inc. Record member
US4620874A (en) * 1984-06-28 1986-11-04 Btl Specialty Resins Corporation Metal modified phenolic resin color developers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218810A2 (de) * 1985-07-19 1987-04-22 Jujo Paper Co., Ltd. Farbentwicklungsmittel für druckempfindliches Aufzeichnungsblatt und Farbentwicklungsblatt dafür
EP0271081A2 (de) * 1986-12-10 1988-06-15 Jujo Paper Co., Ltd. Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten

Also Published As

Publication number Publication date
JPS63173681A (ja) 1988-07-18
EP0275929A3 (en) 1988-09-14
DE3864028D1 (de) 1991-09-12
JPH0466194B2 (enrdf_load_stackoverflow) 1992-10-22
CA1285764C (en) 1991-07-09
US4835134A (en) 1989-05-30
EP0275929A2 (de) 1988-07-27

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