EP0083075B1 - Farbentwicklungsblatt für druckempfindliche Aufzeichnungsblätter - Google Patents

Farbentwicklungsblatt für druckempfindliche Aufzeichnungsblätter Download PDF

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Publication number
EP0083075B1
EP0083075B1 EP82111915A EP82111915A EP0083075B1 EP 0083075 B1 EP0083075 B1 EP 0083075B1 EP 82111915 A EP82111915 A EP 82111915A EP 82111915 A EP82111915 A EP 82111915A EP 0083075 B1 EP0083075 B1 EP 0083075B1
Authority
EP
European Patent Office
Prior art keywords
color
bis
developing
sheet
hydroxyphenyl
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
Application number
EP82111915A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0083075A2 (de
EP0083075A3 (en
Inventor
Noboru Central Research Lab. Yamato
Hiroaki Central Research Lab. Umeda
Akira Central Research Lab. Hasegawa
Mamoru Central Research Lab. Suzuki
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
Priority to AT82111915T priority Critical patent/ATE21356T1/de
Publication of EP0083075A2 publication Critical patent/EP0083075A2/de
Publication of EP0083075A3 publication Critical patent/EP0083075A3/de
Application granted granted Critical
Publication of EP0083075B1 publication Critical patent/EP0083075B1/de
Expired 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

Definitions

  • the invention relates to pressure-sensitive recording sheets, in particular a color developing sheet for pressure-sensitive recording sheets, which gives a recording image with increased image density and superior light fastness.
  • the pressure-sensitive recording sheets consist of an upper sheet (CB-coated underside) and a lower sheet (CF-coated upper side).
  • the underside of the upper sheet is coated with microcapsules which contain an electron-donating, colorless or slightly colored chromogenic dye which is dissolved in an organic solvent (capsule oil).
  • the surface of the lower sheet is coated with a color development layer containing an electron-accepting color development agent.
  • the surface of the middle sheet (CFB coated top and bottom) is coated with a layer comprising a color developing agent, and the bottom of the middle sheet is coated with microcapsules containing the chromogenic dye. If you put one or more CFB sheets between the CB and CF sheets, you can get one or more copies.
  • the activated clay is made by using the for the purpose of dissolving aluminum, iron and other basic components. acidic clay or the like treated with a mineral acid, thereby increasing its specific surface. A specific surface area of over 200 m 2 / g gives a preferred color development effect.
  • Activated clay has the advantage that it is much cheaper than known organic color developing agents.
  • the color for the image of the pressure-sensitive recording sheets was only blue, since crystal violet lactone (CVL), benzoyl leuco methylene blue (BLMB), etc. were used as color formers.
  • Such color formers are used in the recording sheet according to GB-A-2 060 017.
  • the color developing layer in this known recording sheet may contain, among other things, activated clay, a thiourea compound, zinc oxide and / or zinc hydroxide and a novolak resin.
  • the dye developing a black color can be a combination of blue and yellow-orange dye, blue and yellow and yellow orange and red dye, three basic dyes such as blue-green-red dyes, etc., or two dyes that form counter-colors with each other.
  • fluoran dyes which themselves form a black color have been developed.
  • dyes of this type are 3 - diethylamino - 6 - methyl - 7 - anilinofluoran, 3 - (N - cyclohexyl - N - methylamino) - 6 - methyl - 7 - anilinofluoran, 3 - diethylamino - 6 - methyl - 7 - (ortho , para - dimethylanilino) - fluoran, 3 - (N - ethyl - p - toluidino) - 6 - methyl - 7 - anilinofluoran, etc.
  • fluoran dyes when used with inorganic color developing agents such as activated clay, have the disadvantages that they give a reddish-black or greenish-black image, the resulting image undergoes hue change or fading, becoming reddish brown, and that an image with a persistent Hue cannot be obtained.
  • the invention is based on the object of creating a color development sheet which, with a transfer sheet and a fluoran dye forming a black color, gives a purely black colored image with increased image density, superior light fastness and little color change. It is another object of the present invention to provide a color development sheet which, with an transfer sheet and a blue color developing dye, gives a blue colored image with superior color developing ability, durability and light fastness.
  • a color development sheet for pressure-sensitive recording sheets which has a color development layer on a support which is capable of developing color images on contact with a color former, the color development layer containing at least activated clay, zinc carbonate, a thiourea compound and a bisphenol compound.
  • the color development sheet of the present invention gives a recording image with increased image density and superior light fastness.
  • Typical examples of dyes according to the invention which develop a black color are 3 - (N - ethyl - N - isoamyl) amino - 6 - methyl - 7 - anilinofluoran, 3 - pyrrolidino - 6 - methyl - 7 - anilinofluoran, 3 - pyrrolidino - 6 - methyl - 7 - anilinofluoran, 3 - (N - cyclohexyl - N - methylamino) - 6 -methyl -7 -anilinofluoran, 3 -diethylamino -7 - (m -trifluoromethylanilino) fluorane, 3 - (N-ethyl - p - toluidino) - 6 - methyl - 7 - anilinofluoran, 3 - (N - ethyl - p - to
  • blue color developing dyes are triphenylmethanephthalide dyes, such as 3,3 '- bis (diethylaminophenyl) - 6 - dimethylaminophthalide (crystal violet lactone: CVL); Phenothiazine dyes such as 3,7 - bis (dimethylamino) - 10 - benzoylphenothiazine (benzoylleucomethylene blue: BLMB); Phenoxazine dyes such as 3,7-bis (dimethylamino) -10-benzoylphenoxazine; and the like
  • dyes can be used alone or in a mixture with other dyes. Furthermore, dyes which lead to the formation of a red, green or the like color can also be used in this invention.
  • the dyes are dissolved in an organic solvent and by coacervation processes (see, for example, US Pat. No. 2,800,457), interfacial polymerization processes (see, for example, Japanese Patent Publication 19578/1963), "in-situ” polymerization processes (see, for example Japanese Patent Publication 45133/1974) and the like. Encapsulated. They are then applied to a support to make a transfer sheet.
  • coacervation processes see, for example, US Pat. No. 2,800,457
  • interfacial polymerization processes see, for example, Japanese Patent Publication 19578/1963
  • "in-situ” polymerization processes see, for example Japanese Patent Publication 45133/1974
  • Encapsulated They are then applied to a support to make a transfer sheet.
  • the use of zinc carbonate, thiourea compounds and bisphenol compounds in addition to activated clay in the color development layer leads in connection with the fluoran dye to a purely black colored image with an increased image density, and an improved light
  • thiourea compounds are thiourea, trimethylthiourea, diethylthiourea, dibutylthiourea, dilaurylthiourea, ethylene thiourea, diphenylthiourea and the like.
  • thiourea compounds trimethylthiourea, diethylthiourea, diethylthiourea are preferred.
  • Typical examples of bisphenol compounds are 2,2 '- bis (4' - hydroxyphenyl) propane, 2,2 '- bis (4' - hydroxyphenyl) butane, 2,2 '- bis (3' - methyl - 4 '- hydroxyphenyl ) propane, 1,1 '- bis (4' - hydroxyphenyl) methane, 1,1 '- bis (4' - hydroxyphenyl) - ethane, 1,1 '- bis (4' - hydroxyphenyl) butane, 1,1 ' Bis (4 '- hydroxyphenyl) heptane, 2,2' - bis (3 '- phenyl - 4' - hydroxyphenyl) propane, 2,2 '- bis (3' - ethyl - 4 '- hydroxyphenyl) propane, 2, 2 '- bis (3' - isopropyl - 4 '- hydroxyphenyl) propane and 2,2' - bis (3 '-
  • bisphenol compounds can be used alone or in a mixture.
  • 2,2'-bis (4'-hydroxyphenyl) propane (bisphenol A) 2,2'-bis (4'-hydroxyphenyl) butane are preferred according to the invention.
  • the use of the zinc carbonate thiourea compounds and bisphenol compounds leads to significant effects, namely to a pure black image with increased image density, superior light fastness and little color change when using a transfer sheet with a black color developing fluoran dye and to a colored image with superior color developability, durability and light fastness when using a transfer sheet with a dye developing a blue, red or green color.
  • the color development layer can also contain binders and inorganic pigments.
  • binders are natural or synthetic polymers such as starch, carboxymethyl cellulose, methyl cellulose, gelatin, gum arabic, polyvinyl alcohols, casein, styrene-butadiene copolymer latices and the like.
  • inorganic pigments are natural or synthetic inorganic pigments such as clay, talc, kaolin, calcium carbonate, basic magnesium carbonate, barium sulfate, barium carbonate, aluminum hydroxide, zinc white and the like.
  • the color development sheet of the present invention it is preferable to use 3 to 20 parts by weight of zinc carbonate, 1 to 30 parts by weight of the thiourea compound and 0.1 to 5 parts by weight of the bisphenol compound per 100 parts by weight of the activated clay, and 10 to 40 Parts by weight of binder, based on 100 parts by weight of total solids content, are to be used.
  • the pH of the coating is usually about 7 to 10, but it is desirable to use a low pH to achieve more favorable fluidity and coating function.
  • the color development sheet of the present invention has the advantage of using the low pH coating paint to give a superior blue image density.
  • the amount of color in the color development layer is advantageously 3 to 10 glm 2 .
  • a solution of 20 parts by weight of gum arabic in 160 parts by weight of water was added to the dispersion, and 550 parts by weight of water were added with further stirring. Then, a 10% aqueous acetic acid solution was added to adjust the pH of the solution to 4.4 while the complex coacervation was carried out. All of the above processes were carried out at a solution temperature above 50 ° C. After the solution had cooled to 10 ° C., 3.8 parts by weight of a 37% strength aqueous formalin solution were added as a stiffening agent. After stirring, the pH of the system was adjusted to 9 with a 20% aqueous sodium hydroxide solution. In this way, a coating color was obtained from microcapsules containing a color former. The coating color was applied on a base paper with a weight of 40 g / m 2 in a coating amount of 5 g / m 2 , this gave a transfer sheet.
  • a black image transfer sheet was prepared in the same manner but using 80 parts by weight of the oil by dissolving 4% by weight of 3-diethylamino-6-methyl-7-anilinofluorane . was used in place of the above CVL and BLMB containing oil.
  • the coating color obtained was applied to a base paper having a weight of 40 g / m 2 in a coating amount of 7 g / m 2 , whereby a color developing sheet was obtained.
  • a transfer sheet and a color development sheet are placed on top of each other so that the coated surfaces of the sheets touch each other.
  • the stacked sheets are written on with a typewriter so that a color forms.
  • the reflectance of the sheet 24 hours after color development is measured using a Hunter reflectometer (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) using an amber filter.
  • the hue of the color-developing sheet on which an 'image is formed according to the method described under 1) is evaluated with the naked eye 24 hours after the color development.
  • the color developing sheet on which an image was formed according to the method described in 1) is irradiated with sunlight for 2 hours, after which the light fastness is evaluated.
  • the color developing sheet on which an image was formed according to the method described in 1) is irradiated with sunlight for 2 hours, the change in color tone is assessed with the naked eye.
  • Examples 1-6 give a blue and black image with high image density, superior image color tone and excellent light fastness and improved color tone change.
  • the comparative experiments yield images with insufficient light fastness in blue images and with a deterioration in color tone. Furthermore, the comparative tests yield 1-4 images with a reddish-black hue for black images, insufficient lightfastness and a large change in color. Therefore, they have no practical use.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
EP82111915A 1981-12-24 1982-12-22 Farbentwicklungsblatt für druckempfindliche Aufzeichnungsblätter Expired EP0083075B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82111915T ATE21356T1 (de) 1981-12-24 1982-12-22 Farbentwicklungsblatt fuer druckempfindliche aufzeichnungsblaetter.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP208149/81 1981-12-24
JP56208149A JPS58110290A (ja) 1981-12-24 1981-12-24 感圧複写用顕色シ−ト

Publications (3)

Publication Number Publication Date
EP0083075A2 EP0083075A2 (de) 1983-07-06
EP0083075A3 EP0083075A3 (en) 1983-08-10
EP0083075B1 true EP0083075B1 (de) 1986-08-13

Family

ID=16551446

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82111915A Expired EP0083075B1 (de) 1981-12-24 1982-12-22 Farbentwicklungsblatt für druckempfindliche Aufzeichnungsblätter

Country Status (5)

Country Link
US (1) US4480260A (enrdf_load_stackoverflow)
EP (1) EP0083075B1 (enrdf_load_stackoverflow)
JP (1) JPS58110290A (enrdf_load_stackoverflow)
AT (1) ATE21356T1 (enrdf_load_stackoverflow)
DE (1) DE3272638D1 (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755501A (en) * 1984-05-18 1988-07-05 Amoco Corporation Color developing composition for carbonless paper copying system
US11345183B2 (en) * 2019-12-03 2022-05-31 Iron Orchid Designs, Llc Decorative transfer methods and apparatus

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3560229A (en) * 1961-08-31 1971-02-02 Burroughs Corp Colorforming compositions and methods for preparing and controlling same
CA944559A (en) * 1970-09-24 1974-04-02 Makoto Yoshida Recording sheet and color developer therefor
AT309473B (de) * 1971-04-20 1973-08-27 Yamamoto Kagaku Gosei Kk Druckempfindliches Kopierpapier
DE2442576A1 (de) * 1973-10-09 1975-04-17 Kores Holding Zug Ag Mikrokapseln
US4180405A (en) * 1977-02-25 1979-12-25 Graphic Controls Corporation Heat-sensitive recording composition with mixed color precursors
JPS5811142B2 (ja) * 1977-09-09 1983-03-01 松下電器産業株式会社 デイジタルチユ−ナ
JPS54108706A (en) * 1978-02-14 1979-08-25 Mitsubishi Paper Mills Ltd Pressureesensitive recording paper
JPS5637189A (en) * 1979-09-05 1981-04-10 Oji Paper Co Ltd Tinting paper for pressure sensitive recording
GB2088889B (en) * 1980-10-24 1984-09-05 Fuji Photo Film Co Ltd Recording materials having a clay-containing developer layer

Also Published As

Publication number Publication date
DE3272638D1 (en) 1986-09-18
JPS645838B2 (enrdf_load_stackoverflow) 1989-02-01
US4480260A (en) 1984-10-30
EP0083075A2 (de) 1983-07-06
ATE21356T1 (de) 1986-08-15
EP0083075A3 (en) 1983-08-10
JPS58110290A (ja) 1983-06-30

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