EP0072380A1 - Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen - Google Patents

Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen Download PDF

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Publication number
EP0072380A1
EP0072380A1 EP81303712A EP81303712A EP0072380A1 EP 0072380 A1 EP0072380 A1 EP 0072380A1 EP 81303712 A EP81303712 A EP 81303712A EP 81303712 A EP81303712 A EP 81303712A EP 0072380 A1 EP0072380 A1 EP 0072380A1
Authority
EP
European Patent Office
Prior art keywords
colour
styrene
developer sheet
weight
activated clay
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Withdrawn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
EP81303712A
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English (en)
French (fr)
Inventor
Takahiro Torii
Hideaki Senoo
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.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills 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 Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to EP81303712A priority Critical patent/EP0072380A1/de
Publication of EP0072380A1 publication Critical patent/EP0072380A1/de
Withdrawn legal-status Critical Current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
    • B41M5/1555—Inorganic mineral developers, e.g. clays

Definitions

  • This invention relates to colour-developer sheets for use in a carbonless copying system, and more particularly, to an improved colour-developer sheet characterised by preparation thereof using in the / a coating liquid consisting essentially of solid particulate activated clay which has been previously mixed together with a dispersing agent, calcium carbonate added for replacement of part of th; activated clay, and a binding agent of polyvinyl alcohol and a styrene-butadiene latex.
  • Microencapsulation is effected by known processes such as co ⁇ cervation, in situ polymerisation, interfacial polymerisation or the like.
  • Eligible examples of the colour-developers in the prior art practice include malachite green lactone, crystal violet lactone, benzoyl leuco methylene blue, rhodamine B lactam, 3-dialkylamino-7-dialkylamylfluoran, 3-methyl-2,2-spirapibenzo[f]cromene and the like.
  • Exemplary of the colour-developera in the prior art practice are an inorganic croup including solid acids such as acid clay, activated clay, ettapulgite, zeolite, bentonite and the like; and an organic group including phenolic resins such as p-tert-butylphenol resin, p-phenylphenol resin, p-octylphenol resin and the like; organic compounds such as succinic acid, tannic acid, malonic acid, gallic acid and the like, or metal salts thereof; and aromatic carboxylic acids such as benzoic acid, salicylic acid, substituted salicylic acids, naphthoic acid, diphenic acid and the like, or metal salts thereof.
  • solid acids such as acid clay, activated clay, ettapulgite, zeolite, bentonite and the like
  • organic group including phenolic resins such as p-tert-butylphenol resin, p-phenylphenol resin, p-octylphenol resin and the like
  • phenolic resins and substituted salicylic acid (salts) of an organic class may operate to allow coating liquids to be applied at a higher concentration, but do not give rise tc good printability.
  • these two colour-developers are costly because they are derived from chemical syntheses.
  • Activated clay of an inorganic class is found to work out in improving printability such for example as ink adsorption and to be economically inexpensive.
  • one disadvantage experienced with such activated clay colour-developer is that a coating liquid prepared therefrom is liable to become gelled, with ultimate difficulty in sheet coating at a higher concentration.
  • activated clay useful as a colour-developer is one having a surface area of more than 20u m 2 /g and obtained by treatment of acid clay or any other similar type of clay with mineral acid to elute any acid-soluble basic components such as alumina, iron and the like.
  • the activated clay colour- - developer thus produced, even if mixed with salts such for example as zinc, magnesium and the like, may be used successfully.
  • activated clay is of an amorphous shape and has a large specific surface area. Accordingly, activated clay is substantially characteristically different from pigments commonly used for coating sheets of paper. When activated clay is actually dispersed in water, a greater amount of water is required to complete the dispersion due to the shape, surface activity and other factors inherent to the powder particles of the activated clay.
  • kaolin clay typical of sheet coating when dispersed in water, can retain its fluidity up to a concentration of more than 70%, activated clay becomes highly viscous at a concentration in the vicinity of 45 % and encounters reduced fluidity, resulting in gelled condition.
  • sheet coating be performed at a higher concentration for purposes of increased rates of production and savings of energy.
  • a highly concentrated coating liquid is difficult to attain with activated clay, and an air knife coating system is currently employed using a coating liquid of low concentration.
  • An object of the present invention is to provide means to reduce the viscosity of a coating liquid to be applied to a cclour-developer sheet for use in a carbonless copying system and to otherwise improve the fluidity of the coating liquid so as to be rendered adequate for application at a higher concentration.
  • An aspect of this invention resides in applying a coating liquid onto a colour-developer sheet, which liquid consists essentially of solid particulate activated clay, admixed previously with a dispersant, calcium carbonate, and a binder of polyvinyl alcohol and a styrene-butadiene latex.
  • the practice of the present invention provides a substantial improvement wherein considerably superior dispersion and fluidity of activated clay in water as well as viscosity reduction of the resulting coating liquid are achieved, with the result that higher concentration sheet coating is made applicable.
  • Such improvement leads not only to simplified adjustment of the quantities of the coating liquid to be applied, and hence improved coating operation, but also to increased energy-saving and productivity.
  • Another performance advantage is that a sheet of paper thus coated is of good quality with excellent smoothness and resistance to smudge blurry spots arising from rubbing its coated sheet surface) and with improuved surface strength.
  • activated clay useful for the practice of the invention is produced by treating acidic clay with a suitable acid, followed by washing with water, drying and then grinding of the acid treated clay.
  • a first method is to treat acidic clay with an acid and to add an aqueous solution of the dispersant to the resulting clay after being washed with water.
  • a seco ⁇ d method is to mix particulates of the dispersant with the acid treated clay prior to drying, and a third method lies in admixing the particulate dispersant with the acid treated clay after drying, followed by subsequent gridning of the admixture.
  • the sequence of a fourth method is such that the dispersant particulates are admixed with the acid treated clay before grinding. While any of the methods of the type described may be used satisfactorily, no limitation should not be considered to be imposed upon these methods.
  • Eligible dispersants according to the invention are e.g. sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium silicate and the like, all of which are of an inorganic class; and carboxylates (acrylic acid salt, etc.), maleates (styrenemaleic anhydride salt, etc.), sulfonates (naphthalenesulfonic acid salt, etc.) and the like, all of which are of an organic class.
  • carboxylates acrylic acid salt, etc.
  • maleates styrenemaleic anhydride salt, etc.
  • sulfonates naphthalenesulfonic acid salt, etc.
  • Suitable amounts of the dispersant for the practice of the invention fall e.g. in the range of 0.1 to 15%, preferably 1.0 to 8.0%, based on the weight of activated clay. Smaller amounts may not give satisfactory results, whereas greater amounts may result in reduced colour-forming concentration.
  • sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate are preferred which exhibit significantly superior activity.
  • Calcium carbonate according to the invention may e.g. be used both in heavy form and in light form. Particularly preferable are light calcium carbonate which is cubic in shape and has a particle diameter of 0.1 to 1.0 ⁇ , ard heavy calcium carbonate which has an average particle diameter of 1.0 p, but these two specific forms are not limiting to the invention.
  • Suitable amounts of calcium carbonate are e.g. in the weight range of 5 to 25%, preferably 10 to 15%, based on the total of carbonate and clay, whose amounts are thus from 95 to 75%, and 90 to 85%,respectively. Less amounts of calcium carbonate may exert no desirable effect, while greater amounts may reduce colour-forming concentration and thereby result in unsatisfactory coating liquid for application onto a colour-developing sheet.
  • Polyvinyl alcohol according to the invention preferably has a saponification value of more than 98% by mole and a polymerisation degree of less than 7000 Other values may give poor fluidity of a coating liquid.
  • Suitable amounts of polyvinyl alcohol are e.g. 1.0 to 10.0%, preferably 2.5 to 6.0%, based on the weight of activated clay. Smaller amounts may achieve no sufficient fluidity, and greater amounts may result in extremely viscous coating liquid.
  • Styrene-butadiene latexes according to the invention preferably contain the essential ingredient styrene in an amount of 55 to b5% by weight of the polymer Departure from this range may involve reduced water resistance of a coated paper sheet and adversely affect printability of the sheet.
  • carboxyl- modified styrene-butadiene latexes resulting from copolymerisation of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and the like may also be used with satisfactory results.
  • suitable amounts of the styrene-butadiene latex give e.g.5.0 to 20.0% polymer based on the weight of activated clay. An amount of 8.0 to 15.0% by weight is most satisfactory. Less amounts may not work well in improving fluidity of a coating liquid. Greater amounts may reduce colour-forming concentration.
  • a coating liquid contemplated by the invention for use on a colour-developer sheet which coating liquid consists essentially of activated clay, calcium carbonate, polyvinyl alcohol, and a styrene-butadiene latex
  • coating liquid consists essentially of activated clay, calcium carbonate, polyvinyl alcohol, and a styrene-butadiene latex
  • An additional advantage is that a substrate such as paper coated with the coating liquid is at optimum almost completely smudge-proof since such coated sub- strated is of good smoothness with minimal capsular rupture even when brought into rubbed contact with its corresponding capsulated surface.
  • the substrate shows a further improvement in its surface strength.
  • the resulting liquid was applied by a blade coater to paper of 40 g/m 2 in a coat weight of 8 g/m 2 (solid).
  • the resulting liquid was applied by a blade coater to paper of 40 g/m 2 in a coat weight of 8 g/ m 2 .
  • the resultin liquid was applied by a blade coater to paper of 40 g/m 2 in a coat weight of 8 g/m 2 .
  • the coating liquid of Inventive Example 1 is of considerably low viscosity and also is of good fluidity as compared to the coating liquids of Comparative Examples 1 and 2. As shown in Figs. 1 to 3 the comparative liquids are more viscous than the inventive liquid at high-speed revolution rate and become gelled at low-speed revolution rate.
  • Figs. 1 to 3 are rheograms of a coating liquid embodying the present invention and illustrated in Inventive Example 1 and coating liquids exemplified in Comparative Examples 1 and 2.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
EP81303712A 1981-08-14 1981-08-14 Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen Withdrawn EP0072380A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP81303712A EP0072380A1 (de) 1981-08-14 1981-08-14 Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP81303712A EP0072380A1 (de) 1981-08-14 1981-08-14 Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen

Publications (1)

Publication Number Publication Date
EP0072380A1 true EP0072380A1 (de) 1983-02-23

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EP81303712A Withdrawn EP0072380A1 (de) 1981-08-14 1981-08-14 Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen

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EP (1) EP0072380A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105376A1 (de) * 1982-03-03 1984-04-18 Mitsubishi Paper Mills, Ltd. Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen
EP0275326A1 (de) * 1986-07-31 1988-07-27 Goyo Paper Working Co. Ltd. Farbentwicklungsblatt
DE4342140A1 (de) * 1993-12-10 1995-06-14 Zanders Feinpapiere Ag Akzeptorschicht für druckempfindliche Aufzeichnungsblätter

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB760080A (en) * 1953-09-15 1956-10-31 Ncr Co Process for producing pigment-containing paper-coating compositions
DE1152429B (de) * 1951-05-26 1963-08-08 Ncr Co Beschichtungsmaterial fuer Farbreaktions-Durchschreibpapiere
US3223546A (en) * 1962-01-17 1965-12-14 Minerals & Chem Philipp Corp Color-reactable inorganic adsorbent pigment and coating composition containing the same
US3622364A (en) * 1968-11-12 1971-11-23 Mizusawa Industrial Chem Color former for pressure sensitive recording paper and process for producing same
GB2028888A (en) * 1978-08-23 1980-03-12 Mitsubishi Paper Mills Ltd Colour-developing sheet for pressure-sensitive copying paper
GB2050407A (en) * 1979-03-28 1981-01-07 Mitsubishi Paper Mills Ltd Colour developer coating colours for carbonless copying papers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1152429B (de) * 1951-05-26 1963-08-08 Ncr Co Beschichtungsmaterial fuer Farbreaktions-Durchschreibpapiere
GB760080A (en) * 1953-09-15 1956-10-31 Ncr Co Process for producing pigment-containing paper-coating compositions
US3223546A (en) * 1962-01-17 1965-12-14 Minerals & Chem Philipp Corp Color-reactable inorganic adsorbent pigment and coating composition containing the same
US3622364A (en) * 1968-11-12 1971-11-23 Mizusawa Industrial Chem Color former for pressure sensitive recording paper and process for producing same
GB2028888A (en) * 1978-08-23 1980-03-12 Mitsubishi Paper Mills Ltd Colour-developing sheet for pressure-sensitive copying paper
GB2050407A (en) * 1979-03-28 1981-01-07 Mitsubishi Paper Mills Ltd Colour developer coating colours for carbonless copying papers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105376A1 (de) * 1982-03-03 1984-04-18 Mitsubishi Paper Mills, Ltd. Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen
EP0275326A1 (de) * 1986-07-31 1988-07-27 Goyo Paper Working Co. Ltd. Farbentwicklungsblatt
EP0275326A4 (de) * 1986-07-31 1989-03-16 Goyo Paper Working Co Ltd Farbentwicklungsblatt.
DE4342140A1 (de) * 1993-12-10 1995-06-14 Zanders Feinpapiere Ag Akzeptorschicht für druckempfindliche Aufzeichnungsblätter

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Inventor name: SENOO, HIDEAKI

Inventor name: TORII, TAKAHIRO