EP0105376B1 - Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen - Google Patents

Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen Download PDF

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Publication number
EP0105376B1
EP0105376B1 EP19830900802 EP83900802A EP0105376B1 EP 0105376 B1 EP0105376 B1 EP 0105376B1 EP 19830900802 EP19830900802 EP 19830900802 EP 83900802 A EP83900802 A EP 83900802A EP 0105376 B1 EP0105376 B1 EP 0105376B1
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European Patent Office
Prior art keywords
color
developing
sheet
parts
developing sheet
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Expired
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EP19830900802
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English (en)
French (fr)
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EP0105376A1 (de
EP0105376A4 (de
Inventor
Takahiro Torii
Hideaki Senoh
Hirokazu Tsukahara
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
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Filing date
Publication date
Priority claimed from JP57033237A external-priority patent/JPS58151292A/ja
Priority claimed from JP57076021A external-priority patent/JPS5952690A/ja
Priority claimed from JP57143014A external-priority patent/JPS5933190A/ja
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Publication of EP0105376A1 publication Critical patent/EP0105376A1/de
Publication of EP0105376A4 publication Critical patent/EP0105376A4/de
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Publication of EP0105376B1 publication Critical patent/EP0105376B1/de
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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
    • B41M5/124—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 color-developing sheets in the no-carbon pressure-sensitive recording system, and more particularly to a color-developing sheet, in the same system, having an inorganic color developer.
  • the pressure-sensitive recording system which comprises a combination of a color-forming sheet (hereinafter referred to as "CB” in some cases) provided with a surface layer containing microcapsules filled with a solution of an electron-donative colorless dye (hereinafter referred to as "color former”) in a high-boiling solvent and a color-developing sheet (hereinafter referred to as "CF”) provided with a surface layer containing an electron-acceptable acid material (hereinafter referred to as "color developer”), wherein an image is formed on the CF by bringing both the surface layers into contact with each other and applying printing pressure.
  • CB color-forming sheet
  • color former an electron-donative colorless dye
  • CF color-developing sheet
  • color developer an electron-acceptable acid material
  • the color developer used are; inorganic developers including a natural clay mineral such as acid clay, attapulgite, and common clay and activated clay, i.e. the acid clay, which is a montmorillonite group clay mineral, merely treated with a mineral acid in a slight or medium degree; as well as organic developers including various phenol compounds, phenolic resins of novolak type, polyvalent metal salts of aromatic carboxylic acids, etc.
  • inorganic developers including a natural clay mineral such as acid clay, attapulgite, and common clay and activated clay, i.e. the acid clay, which is a montmorillonite group clay mineral, merely treated with a mineral acid in a slight or medium degree
  • organic developers including various phenol compounds, phenolic resins of novolak type, polyvalent metal salts of aromatic carboxylic acids, etc.
  • the above inorganic color developers of clay mineral group and the color-developing paper coated therewith have disadvantages such that, when they are stored for a long period of time under high humidity atmospheric conditions, particularly under high temperature and high humidity conditions, their color developing effect will be rather lowered and these developer particles will agglomerate, thereby the dispersiveness thereof in water being deteriorated and the coating being made difficult various attempts have been made for the purpose of improving the color developing effect of the CF employing the inorganic color developer.
  • an inorganic color developer (EP-A-44645) is known to provide a CF having the ability to develop a brighter and deeper color than does the usual inorganic color developer.
  • the color developer of this patent is obtained by (1) acid treatment of a clay mineral such as a montmollironite group clay, kaolinite group clay, sepiolite-palygorskite group clay, or vermiculite group clay, having a layer structure built up of regular tetrahedron lattices of silica, so as to give a silica content of 82-96.5% by weight on a dry basis (dried at 105°C for 3 hours), (2) bringing the resulting day, in a water-base medium, into contact with a magnesium and/or aluminum compound soluble at least partially in said medium, (3) if the soluble compound is not in hydroxide form, neutralizing with an alkali or acid so as to transform it into the hydroxide thereby introducing the magnesium and/or aluminum component into the acid-treated clay mineral, and if desired drying the product.
  • the color developer obtained thereby has the following characteristics:
  • this known color developer (hereinafter referred to as "synthetic activated clay”) is effective in improving the color developing ability of CF and in retaining the developed color density under high humidity conditions; however the color-developing sheet employing such a synthetic activated clay was found to have a drawback in that the light fastness of color images formed therein is rather inferior.
  • the present inventors made therefore extensive studies for a means of improving the light fastness of color images on the color-developer sheet employing a synthetic activated clay.
  • this invention has been achieved through finding that the addition of various known antioxidants (hindered phenols and others) or ultraviolet absorbers is almost ineffective, but that only the addition of effective amounts of at least one alcohol ester of p-hydroxybenzoic acid to the synthetic activated clay gives a CF, really excellent for practical use, which is markedly improved in the light fastness of color images formed and undergoes no objectionable side action such as the photo-yellowing of white areas (areas other than image areas) thereof.
  • Figs. 1 and 2 are graphs showing rheological behavior of the coating liquids prepared in Example 3 of this invention and in Comparative Example 4.
  • Suitable examples of the p-hydroxybenzoic acid ester used in combination with the synthetic activated clay are as follows:
  • the so-called activated clay chiefly used hitherto although prepared by treating acid clay, which is a montmorillonite group clay, with a mineral acid in a slight or medium degree to extract and remove acid-soluble cations naturally coexisting, such as iron, magnesium, calcium, and aluminum ions therefrom to some extent, is a silic anhydride in which these cations still remain in detectable amounts and acid sites of acid strengths PKa ⁇ -3.0, -3.0 ⁇ PKa+0.8, and +0.8 ⁇ PKa ⁇ +4.8 are respectively present (these acid cites originate from the presence of contaminating metal cations); when an electron-donative colorless dye such as crystal violet lactone, benzoyl leucomethylene glue, or the like is adsorbed on these acid sites, electron transfer takes place to ionize the dye, thus forming a color image.
  • acid clay which is a montmorillonite group clay
  • a mineral acid in a slight or medium degree to extract and remove acid-soluble cations naturally coexisting, such
  • a typical example of the synthetic activated clay used in this invention is Silton SS-1 (tradename).
  • Silton SS-1 tradename
  • the CF according to this invention is prepared by the generally known method, that is, by dispersing an ester of p-hydroxybenzoic acid and the synthetic activated clay together with a known binder, dispersant, and auxiliary in water, and applying the dispersion on paper, followed by drying.
  • the CB used jointly with this CF for copying is preferably a sheet having on a surface layer microcapsules that contain a solution of an electron-donative colorless dye, for example, crystal violet lactone, in an aromatic hydrocarbon. It seems a cause of improvements in the rate of color development and in the color density that the aryl or aralkyl aromatic ring of the above benzoic acid ester has a strong affinity for aromatic hydrocarbon solvents.
  • a synthetic activated clay (tradename: Silton SS-1) and 50 parts of the above wet-milled benzyl p-hydroxy-benzoate suspension were dispersed in 200 parts of water containing 1 part of sodium pyrophosphate dissolved.
  • a coating liquid was made up by adding 50 parts of a 10% aqueous oxydized starch solution and 50 parts of 0.48% SBR latex to the resulting dispersion. This coating liquid was applied on a 40-g/m 2 base paper to a dry coating weight of 7 g/m 2 , forming a CF sheet (designated as sample B).
  • Example C Another CF sheet (sample C) was prepared by using methyl p-hydroxybenzoate in place of benzyl p-hydroxybenzoate.
  • CB sheets used were prepared in the following way: A solution of an electron-donative colorless dye in a high-boiling aromatic hydrocarbon solvent, i.e. a solution of the following composition. was micro-encapsulated according to the method of U.S. Patent No. 4233178 by using a melamine- formaldehyde resin as shell material. A mixture of 100 parts (on dry basis) of the microcapsules obtained, 25 parts of wheat starch, and 150 parts of a 10% aqueous oxidized starch solution was applied on a 40 g/m 2 base paper to a dry coating weight of 5 g/m 2 .
  • CF (4 types) specimens were each superposed upon the CB specimen so as to contact the coating surfaces with each other.
  • the superposed specimens were first pressed through a medium- pressure calender (the nip pressure is in the range of pen tip pressures). After one minute, one hour, and 24 hours, the developed color density on the surface of the CF specimen was determined from the following equation by reflectance measurements with a colorimetric color-difference meter of Nippon Denshoku Co., Ltd. (Table 1);
  • each CF-CB combination was similarly pressed through a high-pressure calender (supercalender) for obtaining images of saturated color density, and after one or more days, was subjected to tests of exposing to carbon arc light (one-hour exposure to light from a carbon arc lamp Fade-O-Meter) and to airborne oxidizing gas (10-minute exposure to 150 ppm of NO X gas).
  • the color density retention was determined from the following equation by reflectance measurements with the color-difference meter (Table 2):
  • sample (B) and (C) of this invention were much superior to the sample A employing the synthetic activated clay alone as color developer and were little inferior to the sample D, in light fastness and NO X gas fastness.
  • the sunlight fastness of white areas was evaluated by exposing blank areas of the color-developing sheets to direct rays of sunlight for 4 hours, and measuring reflectances (%) on the areas with the color-difference meter using a blue filter.
  • the nitrogen oxide gas fastness of white areas was evaluated by exposing white areas of the color-developing sheets to 3000 ppm of NOX gas for 20 minutes, and measuring reflectances (%) on the areas with the color-difference meter using a blue filter (Table 3).
  • the CF according to this invention exhibits a high initial rate of color development (Table 1), the color developed thereon is good in fastness (Table 2), and additionally the white area thereof scarcely undergoes yellowing (Table 3).
  • Table 1 the initial rate of color development
  • Table 2 the color developed thereon is good in fastness
  • Table 3 the white area thereof scarcely undergoes yellowing
  • Nitrogen oxide gas is produced by filling a gas reservoir with water, putting 300 ml of sulfuric acid adjusted to a specific gravity of 1.603 in a gas generator, placing 100 ml of a saturated solution of sodium nitrite in a dropping funnel, dropping this solution into the sulfuric acid to generate nitrogen oxide gas, and leading the gas through a trap containing a 10% sodium hydroxide solution to the gas reservoir; color-developing sheets are placed in a desicator; the nitrogen oxide gas is introduced into the desicator to a prescribed concentration (ppm); and specimens of the color-developing sheets were placed and held therein for 10 or 20 minutes to see the fading.
  • ppm concentration
  • the white area of the CF of this invention can be more protected from the light-or NO x- caused yellowing, by further incorporation of an inorganic or organic ammonium salt into the color-developing layer.
  • an inorganic or organic ammonium salt as follows: Desired objects can be achieved by adding 1-100 parts by weight of at least one of those ammonium salts for 100 parts by weight of the synthetic activated day.
  • Ammonium salts of organic acids such as ammonium acetate, ammonium formate, ammonium n-butyrate, ammonium oxalate, diammonium citrate, triammonium citrate, diammonium tartrate, ammonium succinate, ammonium lactate, ammonium adipate, ammonium sebacate, ammonium phthalate, and ammonium benzoate;
  • Ammonium salts of inorganic acids such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium thiosulfate, ammonium hydrogensulfate, ammonium persulfate, mono-ammonium phosphate, diammonium phosphate, and triammonium phosphate.
  • the mixture was adjusted to pH 8.5 by adding caustic soda to make up a coating liquid.
  • This coating liquid was applied on a 40 g/m 2 base paper (plain paper) by means of an air-knife coater to a dry coating weight of 5.5 g/m 2 .
  • a synthetic activated clay (SS-1) was slowly added with stirring to form a dispersion. Further, 100 parts of a 10% aqueous solution of an oxidized starch (MS-3800) and 20 parts of a 48% SBR latex (Dow 670) were added. After thorough stirring the mixture was adjusted to pH 8.5 by adding caustic soda to make up a coating liquid. This coating liquid was applied on a 40 g/m 2 plain paper by means of an air-knife coater to a dry coating weight of 5.5 g/m 2 .
  • a synthetic activated clay (SS-1) was slowly added with stirring to form a dispersion. Further, 50 parts of a dispersion of benzyl p-hydroxybenzoate and then 100 parts of a 10% aqueous solution of an oxidized starch (MS-3800) and 20 parts of a 48% SBR latex (Dow 670) were added and stirred. After thorough stirring, the mixture was adjusted to pH 8.5 by adding caustic soda to make up a coating liquid. This coating liquid was applied a 40 g/m 2 plain paper by means of an air-knife coater to a dry coating weight of 5.5 g/m2.
  • this invention provides, by combined use of the above ammonium salt with the foregoing b-hydroxybenzoic acid ester and inorganic developer, a useful article quite excellent as a color-developing sheet for recording purposes which is superior, above all, in the fastness of developed color to sunlight, humidity, and oxidizing gas and additionally is almost completely free from the white area yellowing due to sunlight or nitrogen oxide gas.
  • the coating liquid, containing the synthetic activated clay, used for producing the CF of this invention is much higher in viscosity than the coating liquid containing the usual clay mineral color-developer and exhibits therefore a notably lowered workability in paper coating.
  • the method is to use as a flow improver for the coating liquid of high concentration (at least 40% by weight of solids), jointly with the synthetic activated clay, at least one inorganic filler selected from the group consisting of pyrophyllite clay (Al 2 O 3 ⁇ AS i O 2 ⁇ 2H 2 O), kaolinite clay (Al 2 O 3 ⁇ 2S i O 2 ⁇ 2H 2 O), halloysite clay (Al 2 O 3 ⁇ 2S i O ⁇ 4H 2 O), sericite clay (K 2 O ⁇ 3Al 2 O 3 ⁇ 6S i O 2 ⁇ 2H 2 O), montmollonite clay (Al 4 [M g ](S ig [Al]O 20 (OH) 4 ⁇ XH 2 O), aluminum hydroxide, gohun, chalk, heavy calcium carbonate, fine precipitated calcium carbonate, superfine precipitated calcium carbonate, super
  • Suitable amount ratios of the synthetic activated clay to the inorganic filler, in this invention are in the range from 30:70 to 95:5, particularly from 50:50 to 85:15, % by weight. Amounts of the synthetic activated clay less than 30% by weight are not practically useful since the resulting color-developing ability are markedly low. If the amount exceeds 20% by weight, no coating liquid of high concentration and low viscosity can be obtained.
  • the coating liquid combining, as shown above, the synthetic activated clay color-developer with an effective amount of at least one of the above-cited inorganic fillers exhibits improved flow and can be applied on paper to a light gauge (5 g/m 2 or less) without leaving any bared fiber of paper at the coating surface. Accordingly, the resulting color-developing sheet can be printed by thin deposition of a desensitizing ink. Since the thin layer of ink can be quickly dried, a speed-up of the printing becomes possible. Further, the coating liquid, applicable to a light gauge, has great advantages in cost reduction possible by productivity improvement and energy saving. These are great effects of this invention.
  • the color-forming sheets used were commercial CBs for pressure sensitive recording (Mitsubishi-NCR Overlying Sheet-40 Blue) (dyes: crystal violet lactone (CVL) and Benzoyl leucomethylene blue (BLML)).
  • the mixture was adjusted to pH 8.5 with 20% aqueous caustic soda to make up a coating liquid.
  • This coating liquid applied on a 40 g/m 2 base paper by means of a blade coater to a dry coating weight of 4.5 g/ M 2 , giving a color-developing sheet.
  • a dispersion prepared by wet-griding 100 parts of benzyl p-hydroxybenzoate and 5 parts of hydroxyethylcellulose in 145 parts of water using a ball mill and subsequently 20 parts (as solids) of a SBR latex (Dow 670) were added to the above dispersion and dispersed by good stirring.
  • the mixture was adjusted to pH 8.5 with 20% aqueous caustic soda to make up a coating liquid.
  • This coating liquid was applied on a 40 g/ m 2 base paper by means of a blade coater to a dry coating weight of 4.5 g/m 2 , giving a color-developing sheet.
  • Table 6 shows found viscosities, solid contents, and fluid features of the coating liquids of Example 3 and Comparative Examples 3 and 4.
  • Figs. 1 and 2 show viscosity curves of coating liquids of Example 3 and Comparative Example 4, respectively.
  • the coating liquid of Example 3 As is shown in Table 6, the coating liquid of Example 3, as compared with that of Comparative Example 4, has markedly low viscosity and exhibits very high flow while containing nearly the same amount of solids.
  • Figs. 1 and 2 it is obvious that the coating liquid of Comparative Example 4 exhibits high viscosities, as compared with that of Example 3, at high revolutions of the rotor and gels at a low revolution, exhibiting also a high viscosity.

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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)

Claims (6)

1. Farbentwicklungsblatt in einem kohlenstoffreien, druckempfindlichen Aufzeichnungssystem mit einer farbentwickeinden Oberflächenschicht, enthaltend einen synthetischen aktivierten Ton mit den folgenden Eigenschaften:
(A) er zeigt eine Elektronenbeugungsanordnung, bezogen auf die Kristalle von Silicium mit einer Schichtstruktur, diesich auf regulären Tetraeder-Gittern aufbaut;
(B) er zeigt kein Röntgenstrahl-Beugungsspektrum, welches sich auf der obigen Schichtstruktur aufbaut; und
(C) es enthält zumindest Silicium, Magnesium und/oder Aluminium als Element, das sich von Sauerstoff unterscheidet; und weiterhin
(D) es enthält Silicium, Magnesium und/oder Aluminium in Atomverhältnissen (Silicium)/(die Summe von Magnesium und/oder Aluminium) von 12/1,5 bis 12/12, insbesondere 12/3 bis 12/10, wobei die Summe von Magnesium und/oder Aluminium, wenn nur eines davon enthalten ist, die Menge des einen enthaltenen darstellt;

dadurch gekennzeichnet, dass es in der Oberflächenschicht ausserdem einen p-Hydroxybenzoesäureester der allgemeinen Formel
Figure imgb0020
worin R einen Alkyl-, Aryl- oder einen Aralkylrest bedeutet, enthält.
2. Farbentwicklungsblatt gemäss Anspruch 1, worin der p-Hydroxybenzoesäureester Benzyl-p-hydroxybenzoat ist.
3. Farbentwicklungsblatt gemäss Anspruch 1, dadurch gekennzeichnet, dass die Farbentwicklungsschicht zusätzlich ein Ammoniumsalz enthält.
4. Farbentwicklungsblatt gemäss Anspruch 3, worin das Ammoniumsalz Ammoniumchlorid ist.
5. Farbentwicklungsblatt gemäss Anspruch 1 oder 3, dadurch gekennzeichnet, dass die farbentwickelnde Schicht ausserdem einen anorganischen Füllstoff enthält.
6. Farbentwicklungsblatt gemäss Anspruch 1, 2, 3, 4 oder 5, welches in Kombination mit einem farbbildenden Blatt, in welchem der Elektronendonor Crystal-Violet-Lacton ist, angewendet wird.
EP19830900802 1982-03-03 1983-03-02 Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen Expired EP0105376B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP33237/82 1982-03-03
JP57033237A JPS58151292A (ja) 1982-03-03 1982-03-03 感圧記録システム
JP57076021A JPS5952690A (ja) 1982-05-08 1982-05-08 ノ−カ−ボン記録紙用顕色剤シ−ト
JP76021/82 1982-05-08
JP143014/82 1982-08-18
JP57143014A JPS5933190A (ja) 1982-08-18 1982-08-18 画像記録材料用顕色シ−ト

Publications (3)

Publication Number Publication Date
EP0105376A1 EP0105376A1 (de) 1984-04-18
EP0105376A4 EP0105376A4 (de) 1984-09-28
EP0105376B1 true EP0105376B1 (de) 1986-12-10

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EP19830900802 Expired EP0105376B1 (de) 1982-03-03 1983-03-02 Farbentwicklungsblatt zur verwendung in kohlenfreien aufzeichnungssystemen

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EP (1) EP0105376B1 (de)
AU (1) AU1330983A (de)
DE (1) DE3368231D1 (de)
WO (1) WO1983003077A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58222880A (ja) * 1982-06-22 1983-12-24 Mitsubishi Paper Mills Ltd 感圧記録用顕色層
JPH0627425Y2 (ja) * 1983-01-26 1994-07-27 三菱製紙株式会社 漢字プリンタ−用ノ−カ−ボン紙
AT399126B (de) * 1987-03-31 1995-03-27 Ruetgerswerke Ag Farbentwicklermassen für farbreaktionssysteme

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5715996A (en) * 1980-07-03 1982-01-27 Mizusawa Ind Chem Ltd Novel clay mineral based color former for heat-sensitive copying paper and production thereof
EP0058262A1 (de) * 1981-02-13 1982-08-25 Mitsubishi Paper Mills, Ltd. Entwicklungsblatt für kohlefreies Kopierpapier
EP0072380A1 (de) * 1981-08-14 1983-02-23 Mitsubishi Paper Mills, Ltd. Farbentwicklungsfolie für kohlefreie Aufzeichnungsbögen
JPS58138689A (ja) * 1982-02-13 1983-08-17 Mitsubishi Paper Mills Ltd 感圧記録系

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DE3368231D1 (en) 1987-01-22
EP0105376A1 (de) 1984-04-18
AU1330983A (en) 1983-10-18
WO1983003077A1 (en) 1983-09-15
EP0105376A4 (de) 1984-09-28

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