EP0144472B1 - Ton als Farbentwicklerzusammensetzung für druckempfindliche Kopierblätter - Google Patents

Ton als Farbentwicklerzusammensetzung für druckempfindliche Kopierblätter Download PDF

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Publication number
EP0144472B1
EP0144472B1 EP19830307430 EP83307430A EP0144472B1 EP 0144472 B1 EP0144472 B1 EP 0144472B1 EP 19830307430 EP19830307430 EP 19830307430 EP 83307430 A EP83307430 A EP 83307430A EP 0144472 B1 EP0144472 B1 EP 0144472B1
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European Patent Office
Prior art keywords
color developer
acid
magnesium
color
clay mineral
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EP19830307430
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English (en)
French (fr)
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EP0144472A1 (de
EP0144472B2 (de
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Koichi Usui
Masahide Ogawa
Teiji Sato
Yasuo Mizoguchi
Nobuyuki Yamada
Noriyuki Takahashi
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MIZUSAWA KAGAKU KOGYO KK
Mizusawa Industrial Chemicals Ltd
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MIZUSAWA KAGAKU KOGYO KK
Mizusawa Industrial Chemicals Ltd
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Application filed by MIZUSAWA KAGAKU KOGYO KK, Mizusawa Industrial Chemicals Ltd filed Critical MIZUSAWA KAGAKU KOGYO KK
Priority to EP19830307430 priority Critical patent/EP0144472B2/de
Priority to DE8383307430T priority patent/DE3378200D1/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 a color developer composition which demonstrates pronounced color development effects when used in making pressure-sensitive recording sheets which can produce copies by handwriting, printing or typing without the use of conventional carbon paper.
  • Pressure-sensitive recording sheets except a few special cases, utilize a color development reaction ascribable to the transfer of electrons between a colorless organic dye compound having electron donating property and a color developer acting as an electron acceptor (U.S. Patent No. 2,548,366).
  • the colorless dye compound two kinds of dyes which assume different states of coloration are used together as the colorless dye compound.
  • a dye such as a triphenylmethane phthalide dye, which forms an intense color immediately upon contact with a solid acid, but the color fades easily (primary color-forming dye).
  • the other is a dye which does not immediately form a color upon contact with a solid acid but completely develops its color several days thereafter with sufficient fastness to sunlight.
  • An example is a leucomethylene blue dye (secondary color-forming dye).
  • Crystal violet lactone (CVL) is a typical primary color-forming dye.
  • BLMB benzoyl leucomethylene blue
  • fluoran-type green or black dyes Michler's hydrol derivatives such as Michler's hydryl- para-toluenesulfinate (PTSMH), diphenylcarbazolylmethane dyes and spirodibenzopyran dyes have also been used either singly or in combination with the aforesaid primary color-forming dye.
  • PTSMH Michler's hydrol derivatives
  • diphenylcarbazolylmethane dyes diphenylcarbazolylmethane dyes
  • spirodibenzopyran dyes spirodibenzopyran dyes
  • Solid acids are generally used as the color developer which is an electon acceptor. It is known that above all, dioctahedral montmorillonite clay minerals show excellent color-developing ability. Acid clay and sub-bentonite are especially preferred as the dioctahedral montmorillonite clay minerals.
  • the specific surface area of montmorillonite clay minerals such as acid clay and sub-bentonite can be increased to 180 m 2 /g or higher by treating them with acids, and the acid-treated clay minerals exhibit increased color-developing ability with respect to primary color-forming dyes such as triphenylmethane phthalide dyes.
  • the acid-treated acid clay is generally referred to as activated acid clay, and known widely as a coloring developer for pressure-sensitive recording paper.
  • inorganic and organic acids can be used in the acid treatment, but inorganic acids, particularly sulfuric and hydrochloric acids, are preferred because of their reasonable cost and the ease of handling.
  • the acid-treating conditions are not critical. If a diluted acid is used, either the treating time becomes longer or the quantity of the required acid increases. On the other hand, if an acid of high concentration is used, either the treating time becomes shorter or the quantity of the acid required becomes smaller. If the treating temperature is high, the treating time can be shortened. Hence, the acid concentration can be freely selected within the range of 1 to 98%. It is known however that in practice, the acid treatment is preferably carried out at an acid concentration of about 15 to 80% and at a temperature of 50 to 300°C because of the ease of handling.
  • JP-A-55-103994 and JP-A-55-97982 describe the use of magnesium compounds, such as the hydroxide or carbonate, to improve the storage stability of acid-treated clays, including montmorillonite clay, intended for use as color developers.
  • EP-A-44645 discloses a color developer composition for pressure-sensitive recording sheets, comprising a color developer (1) which is derived from a clay mineral having a layer structure composed of regular tetrahedrons of silica and which shows
  • the attached drawings are graphs showing the relation of the mole ratio between two metal compounds used in accordance with this invention to the light resistances of a colored dye.
  • Figure 1 is a graph showing the relation of the mole ratio between calcium hydroxide and magnesium oxide to the light resistance of a colored dye in Examples 1 to 5.
  • the total amount of the two metal compounds per gram of the color developer is 0.1 millimole for curve a, 0.2 millimole for curve b, 0.4 millimole for curve c, 0.6 millimole for curve d, 0.8 millimole for curve e, 1.0 millimole for curve f, and 2.0 millimoles for curve g.
  • Figure 2 is a graph showing the relation of the mole ratio between calcium hydroxide and zinc oxide to the light resistance of a colored dye in Examples 6 to 10.
  • Figure 3 is a graph showing the relation of the mole ratio between magnesium hydroxide and zinc oxide to the light resistance of a colored dye in Examples 11 and 15.
  • Figure 4 is a graph showing the relation of the mole ratio between calcium hydroxide and magnesium hydroxide to the light resistance of a colored dye in Example 11 and Example 16 to 19.
  • the curves a, b, c, d, e, f and g refer to the case of the total amount of the two metal compounds being 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 2.0 millimoles, respectively, as in Figure 1.
  • the color developer (1) and a method of its production are disclosed in detail in EP-A-44645.
  • the color developer (1) in accordance with this invention can be produced, for example, through the steps of acid-treating a clay mineral having a layered structure composed of regular tetrahedrons of silica until its Si0 2 content reaches 82-96.5% by weight, preferably 85-95% by weight on dry basis (drying at 105°C.
  • the first step for convenience
  • a magnesium and/or aluminum compound neutralizing the treated product with an alkali or an acid to form a hydroxide when the magnesium and/or aluminum compound is not a hydroxide, thereby introducing a magnesium and/or an aluminum component into the acid-treated clay mineral, and if desired, drying the product
  • the second step for convenience
  • compositions of typical clay minerals having the layer structures composed of regular tetrahedrons of silica are as shown in Table A below, in which the contents (%) of Si0 2 , A1 2 0 3 and MgO as the main components are given.
  • clay minerals having a layer structures composed of regular tetrahedrons of silica show a unique diffraction pattern characteristic of the crystals of the layer structure, when subjected to an X-ray diffraction analysis.
  • a diffraction pattern attributable to the crystal faces having Miller's indices of (020), (200) and (060) appears most distinctly.
  • the clay mineral having a layer structure composed of regular tetrahedrons of silica is intensely acid-treated until its Si0 2 content reaches 82-96.5% by weight, preferably 85-95% by weight, on dry basis (drying at 105°C. for 3 hours).
  • the acid treatment should be continued until the acid-treated clay mineral (in dry state) shows substantially no diffraction pattern attributable to the already specified crystals faces of the crystals having a layer structure composed of regular tetrahedrons of silica which the untreated clay mineral has, when subjected to an X-ray diffraction analysis.
  • the acid treatment should be performed until not only the X-ray diffraction analysis but also an electron diffraction analysis of the acid-treated clay mineral no longer substantially show the characteristic diffraction patterns attributable to the crystals of the layer structure composed of regular tetrahedrons of silica which the untreated clay mineral has.
  • the clay mineral which has been acid-treated as above is then contacted in an aqueous medium with a magnesium and/or an aluminum compound. If the magnesium and/or aluminum compound is not a hydroxide, the contacted product is neutralized with an alkali or acid so that a hydroxide of magnesium and/or aluminum is formed therein, thereby introducing a magnesium and/or aluminum component into the acid-treated clay mineral.
  • the product is thereafter dried, if desired.
  • the color developer (1) used in this invention contains at least silicon and magnesium in addition to oxygen in regard to the requirement (C).
  • the color developer (1) used in this invention which satisfies the conditions (A), (B) and (C), further meets the requirement that it contains silicon and magnesium and/or aluminum in such proportions that the atomic ratio of silicon to magnesium and/or aluminum is from 12:1.5 to 12:12, particularly from 12:3 to 12:10 [requirement D].
  • Typical examples of the clay mineral of a layer structure composed of regular tetrahedrons of silica which is used as a raw material for the production of the color developer (1) are given below.
  • dioctahedral montmorillonite clay minerals such as acid clay, kaolinite clay minerals such as kaolin and halloysite, and chain clay minerals such as attapulgite.
  • the color developer (2) i.e., montmorillonite clay minerals, particularly acid clay, which have been treated with mineral acids such as sulfuric, nitric and hydrochloric acids, most commonly sulfuric acid, as a color developer, for pressure-sensitive recording sheets.
  • the acid-soluble basic metal components in the developer for example, such metal components as aluminum, magnesium, iron, calcium, sodium, potassium and manganese (which are present predominantly in the form of oxides or hydroxides) dissolve in the mineral acid, and consequently the Si0 2 content of the acid clay increases.
  • the resulting acid-treated acid clay (which also known as activated acid clay) decreased in its color-developing ability with respect to a secondary color development, and the light resistance of a developed color of a primary color development dye (e.g., CVL) in the main is markedly deteriorated.
  • a primary color development dye e.g., CVL
  • the degree of acid treatment of acid clay is inherently limited, and under the conventionally adopted acid-treating conditions, the resulting acid-treated product (activated clay) has a Si0 2 content of 68-78% by weight. Even under considerably rigorous acid-treating conditions, the Si0 2 content is at most 80% by weight.
  • the correlations among the degree of acid treatment, destruction of the crystals having the layer-structure and the ultimately occurring substantial disappearance of the characteristic diffraction patterns vary depending on the type and purity of clay minerals, pre-treating conditions which may be applied before the acid treatment (e.g., sintering and grinding conditions), etc. and are by no means definite. In all cases, however, as the acid treatment proceeds beyond a certain degree, the destruction of crystals having the layer-structure begins and progresses to result ultimately in the substantial disappearance of the diffraction patterns attributable to the aforesaid crystals.
  • the color developer (1) can be produced by a method comprising the first and second steps referred to above.
  • the acid-treatment of the first step should be performed to such an extent that the Si0 2 content of the acid-treated clay mineral should not exceed 96.5% by weight.
  • the resulting product does not necessarily exhibit improved color-developing ability, and some types of clay minerals even show a reduced color-developing ability.
  • the acid-treatment is carried out preferably to such an extent that the SiO 2 content of the acid-treated clay mineral becomes 85 to 95% by weight, in order to secure economic advantages and to protect the layer composed of regular tetrahedrons of silica from excessive destruction.
  • the acid-treated clay mineral is treated, for example, with an aqueous magnesium chloride or aluminum chloride solution according to the second step, neutralized with an aqueous caustic soda solution, washed with water and dried, the product again shows diffraction pattern characteristic of the layered crystalline structure when examined by electron diffractometry, as shown in Figs. 3 and 4.
  • This fact is believed to show that although the crystals having the layer-structure composed of regular tetrahedrons of silica are destroyed by the acid-treatment of the first step, the layers themselves remain without complete destructions and that the remaining layers composed of regular tetrahedrons of silica are re-constructed into crystals by the magnesium and/or aluminum component.
  • the color developer (1) used in this invention which shows the diffraction pattern of the crystals reconstructed by a magnesium or an aluminum component in electron diffractometry (the product of the second step) exhibits an improved color-developing ability particularly with respect to a primary color-forming dye over the acid-treated product, and also shows an improved color-developing ability with respect to a secondary color-forming dye. Furthermore, the color developer (1) scarcely decreases in color-developing ability after storage in an atmosphere kept at a high humidity and a high temperature, and evidently, a marked improvement in color-developing ability is noted.
  • the amount of the metal compound to be incorporated in the color developer (1) is 0.2 to 2 millimoles, preferably 0.4 to 1 millimole, per gram of the color developer (1), (2) when present, and the metal compound (3) combined.
  • hydroxide of calcium, the oxide or hydroxide of magnesium and the oxide of zinc are preferred as the metal compound, and calcium hydroxide is especially preferred.
  • metal oxides or hydroxides can be used either singly or in combination with each other.
  • a combination of calcium hydroxide and magnesium oxide (or magnesium hydroxide), (b) a combination of calcium hydroxide and zinc oxide, and (c) a combination of magnesium hydroxide (or magnesium oxide) and zinc oxide are preferred.
  • the mole ratio of calcium hydroxide to magnesium oxide, magnesium hydroxide and/or zinc oxide is adjusted to from 0.9:0.1 to 0.2:0.8.
  • the metal compound and the color developer (1) are mixed as uniformly as possible to obtain the composition of this invention.
  • the metal compound preferably has such a particle size that when its particle size is measured by the Andreasen pipette, the proportion of particles having a particle diameter of not more than 10 pm is at least 70% by weight. It is particularly advantageous that the metal compound contains at least 90% by weight of particles which have a size 325 mesh under according to the Tyler's mesh.
  • the color developer (1) can be used as a mixture with an acid-treated dioctahedral montmorillonite clay mineral or a mixture of it with a naturally occurring dioctahedral montmorillonite clay mineral [to be referred to as the color developer (2)] which minerals have heretofore been known as color developers for pressure-sensitive recording sheets.
  • an acid-treated dioctahedral montmorillonite clay mineral or a mixture of it with a naturally occurring dioctahedral montmorillonite clay mineral [to be referred to as the color developer (2)] which minerals have heretofore been known as color developers for pressure-sensitive recording sheets.
  • a mixture of the color developer (1) and the color developer (2) with the proportion of the color developer (1) being at least 3% by weight based on the mixture when formed into an aqueous composition for coating on a receiving sheet, has a much lower viscosity than that of an aqueous composition of the color developer (2) alone. Accordingly, the aqueous composition in a high concentration can be coated on the receiving sheet, and the coating operation and drying become easy.
  • the presence of the color developer (1) increases the color-developing ability of the mixture and its aqueous composition decreases in viscosity.
  • this color developer is very useful in practical applications. Even when such a color developer mixture is used, the inclusion of the aforesaid metal compound makes it possible to prevent effectively a color formed by the color developer mixture from fading or discoloration.
  • the metal compound specified above can be incorporated also in -the mixture of the color developer (1) and the color developer (2) in the same way as described above with regard to the color developer (1).
  • the color developer (2) will be described below in detail.
  • the color developer (2) used in this invention may be any of conventional known color developers for pressure-sensitive recording sheets which are composed of acid-treated products of dioctahedral montmorillonite clay minerals such as acid clay and sub-bentonite, or mixtures thereof with naturally occurring dioctahedral montmorillonite clay minerals.
  • the acid-treated products of the montmorillonite clay minerals especially an active clay obtained by acid-treatment of acid clay, are preferred.
  • the acid treatment for production of these is carried out under such conditions that the treated product does not lose the diffraction pattern attributed to the crystals of a layer structure composed of regular tetrahedrons of silica, which the starting clay has.
  • the acid-treatment under the relatively mild conditions described above increases the specific surface area of the starting clay mineral.
  • the color developer (2) used in this invention preferably has a specific surface area of at least 180 m 2 /g.
  • a typical method for producing the color developer (2) is described in the specification of U.S. Patent No. 3,622,364.
  • the color developer (2) has a secondary color developing performance K 2 , defined by the following equation, of at least 1.40.
  • R 430 and R 550 are the reflectances of light having a wavelength of 430 mu and 550 mp respectively.
  • the color developer composition of this invention comprises the color developer (1) or a mixture of the color developer (1) and the color developer (2) and 0.2 to 2 millimoles, preferably 0.4 to 1 millimole, of the aforesaid metal compound per gram of the color developer or developers and the metal compound combined.
  • the composition is prepared by blending in the dry state the metal compound with a dried product of the color developer (1) or a mixture of it with the color developer (2).
  • the color developer (2) is used together, it is possible to blend the color developer (2) with the metal compound and then adding the color developer (1) to the mixture.
  • the metal compound is blended with the color developer (1) and then a suitable amount of the color developer (2) is added to the mixture. Blending can be effected by any known method.
  • the color developer composition of this invention comprising the color developer (1) and the metal compound, or the color developer (1), the color developer (2) and the metal compound has such a particle size that at least 99% by weight thereof consists of particles having a size 325 mesh under in accordance with the Tyler's mesh.
  • the metal compound blended with the color developer (1) or the mixture of the color developers (1) and (2) dissolves in the aqueous ammonium chloride solution.
  • the amount of the metal compound in the color developer composition can be determined by this method (for details, see the testing method described hereinafter).
  • the color developer (1) used in this invention is obtained by intensely acid-treating a clay mineral of a layer structure composed of regular tetrahedrons of silica (preferably such that the treated product does not substantially show the diffraction pattern attributed to the crystals of layer structure composed of regular tetrahedrons of silica which the clay mineral before the acid-treatment has), and contacting the treated product with at least partially soluble magnesium and/or aluminum compound to reconstruct the crystals of the layer structure so that they show a diffraction pattern attributed to the layer structure composed of regular tetrahedrons of silica in electron diffractometry.
  • the magnesium and/or aluminum consumed in the reconstruction of these crystals is not dissolved out by the aforesaid treatment with the aqueous ammonium chloride solution, but is still retained in the color developer (1). But that portion of the magnesium compound used in the reconstruction which remains free in the color developer (1) in a very small amount dissolves in the aqueous ammonium chloride solution as does the metal compound blended in the color developer (1).
  • That portion of the magnesium compound used in the reconstruction which remains free in the color developer (1) and dissolves in the aqueous ammonium chloride solution is usually very small in amount, and insufficient to improve the light resistance of a color formed by the color developer (1). But when combined with the metal compound included in the color developer (1), it serves to increase the light resistance.
  • the clay minerals used as raw materials for the production of the color developers (1) and (2) contain calcium or magnesium, but calcium and magnesium are not dissolved out by treatment with the aqueous ammonium chloride solution.
  • the concentration of the color developer composition can be adjusted to about 20 to about 50% by weight.
  • a suitable amount of a water-soluble or water-dispersible binder can be added to the aqueous coating composition.
  • water-soluble binder examples include starch, carboxy methyl cellulose (CMC), polyvinyl alcohol (PVA), casein and gelatin. Starch and carboxymethyl cellulose are preferably used.
  • water-dispersible binder examples include a styrenebutadiene type latex, an acrylic latex, a vinyl acetate-type emulsion and vinyl chloride-type emulsion. The styrene-butadiene type latex is preferred.
  • the combined use of the water-soluble binder and the water-dispersible binder is especially preferred.
  • the amount of the binder used, as solids content is 10 to 30% by weight, preferably 13 to 20% by weight, based on the solids content of the aqueous coating composition.
  • the aqueous coating composition may further contain at least one of pH adjusting agents, dispersing agents and viscosity adjusting agents.
  • the pH adjusting agents may include the hydroxides and carbonates of alkali metals or alkaline earth metals such as sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and lithium carbonate; sodium silicate; and ammonia.
  • dispersing agents examples include polyphosphates such as sodium hexametaphosphate and sodium pyrophosphate, and polycarboxylic acid salts such as sodium polycarboxylate and ammonium polycarboxylate.
  • viscosity adjusting agents talc, mica and asbestos (Japanese Patent Publication No. 23177/ 1970), and kaolin, and calcium carbonate (Japanese Patent Publication No. 47992/1980) may be used.
  • an extender or a color developer other than the color developers (1) and (2) may further be included in the aqueous coating composition in accordance with this invention.
  • the color developer compositions of this invention have a great color-developing ability with respect to primary color-forming dyes and secondary color-forming dyes, and their color-developing ability shows only a very low degree of reduction after storage at high temperatures and humidities.
  • the supernatent liquid separated was taken in an amount of 5 ml into a 100 ml Erlenmeyer flask by a whole pipette. A very small amount of aluminum, etc. was masked with triethanolamine, and the pH of the liquid was adjusted by NH 3 -NH Q CI buffer solution to about 10. The liquid was then titrated with a 1/100 M standard solution of EDTA using Eriochrome Black T (BT) as an indicator. The titrated amount (V ml) to the total amount of calcium, magnesium and zinc was determined. The amount (mmoles/g) of the metal compound which dissolved at this time from the color developer sample into the 1 M NH 4 CI solution can be calculated from the following equation. where f represents the titer of the 1/100 mole standard solution of EDTA.
  • the resulting coating slurry was coated on 8 sheets of paper (4 sheets coated at a high rate and 4 sheets coated at a low rate) by means of two coating rods (wire diameter: 0.10 mm and 0.05 mm, respectively).
  • the coated papers were dried in the air and then dried at 110°C for 3 minutes.
  • the amount of the coating solution applied was measured (determined from the dry weight difference between a sample ofthe uncoated paper and a sample of a uniformly coated portion of the coated paper, both samples having the same area).
  • the coated sheets of paper were cut into halves to form two 4-sheet sets (having the same coating amount).
  • the amounts of coating of the two types were slightly more and slightly less than 6 g/m 2 .
  • One of the two 4-sheet sets of receiving sheets was put in a desiccator (relative humidity 75%) containing a saturated aqueous solution of sodium chloride, and stored in the dark at 25°C. After the lapse of about 24 hours from the coating, it was taken out and exposed indoors (kept constantly at about 25°C and a relative humidity of about 60%) for 16 hours, and then subjected to color development. Color development was carried out by the following procedure.
  • the receiving sheets were superposed on two different types of transfer sheets, either (1) a transfer sheet coated with microcapsules containing CVL (Crystal Violet Lactone) which is an instantaneously color-forming leuco dye (CVL dye sheet) or (2) a commercial transfer sheet coated with microcapsules containing a mixture of CVL, BLMB (Benzoyl Leuco Methylene Blue) and a fluoran-type dye (mixed dye sheet), with their coated surfaces facing each other, and together inserted between a pair of steel rolls, and revolving the rolls under pressure to rupture the microcapsules completely.
  • CVL Crystal Violet Lactone
  • BLMB Benzoyl Leuco Methylene Blue
  • fluoran-type dye mixed dye sheet
  • the color-developing ability of each of the receiving sheets was evaluated by measuring the density of the color one hour after color formation by means of a densitometer (Fuji Densitometer Model-P, made by Fuji Shashin Film K.K.), and averaging the measured values on four sheets. High densities show high color-developing ability.
  • the color-developing ability of a sample color developer (density [A]) is expressed by the density [A] on the receiving sheet coated with 6 9 .m 2 of the color developer calculated from the density [A 1] of the thinly coated (a 1 g/m 2 ) receiving sheet and the density [A 2] of the thickly coated (a 2 g/m 2 ) receiving sheet.
  • the density [A] can be determined from the equation below.
  • the color-developed sheet used in the initial color-developing ability test was irradiated with an artificial light (carbon arc lamp) for two hours, as set in a weatherometer (Suga Shikenki K.K., Standard Sunshine Weatherometer, WE-SUN-HC model).
  • the density of the developed color which faded upon the irradiation was measured.
  • the density [B] of the developed color on the receiving sheet coated with 6 g/m 2 of sample color developer, after fading, was calculated from the similar densities of thinly coated and thickly coated receiving sheets ([B 1] and [B z] , respectively) as in the foregoing.
  • the light resistance is expressed by the ratio of [B] to the initial color-developing density ([A]), i.e. ([B]/[A]).
  • the color developer (2) is a known color developer for pressure-sensitive recording sheets. By the methods described in the specification of U.S. Patent No. 3,622,364, it was found to have a specific surface area of 295 m 2 /g and a secondary color-developing performance, K 2 , of 1.78.
  • the color developer (1a) obtained in Comparative Example 1a and the known clay mineral-type color developer (2) obtained in Referential Example 1 were uniformly mixed in a ratio of 50:50 by weight in a fluidizing-type mixer (Supermixer) to obtain a white color developer powder (this is the same as sample E of Example 1 given in U.S. Patent No. 4,405,371 (European Laid-Open Patent Publication No. 0044645A1 ).
  • a powder of calcium hydroxide from which coarse particles had been removed by winnowing was added to the color developer (1a) obtained in Comparative Example 1a a in an amount of 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 2.0 millimoles respectively per gram of the entire dry mixture (upon drying at 110°C). They were uniformly mixed by a fluidizing-type mixer to form a white color developer powder.
  • Example 2 was repeated except that the mixing mole ratio of calcium hydroxide to magnesium oxide was changed to 0.5:0.5 (1:1).
  • Example 2 was repeated except that the mixing mole ratio of calcium hydroxide to magnesium oxide was changed to 0.25:0.75 (1:3).
  • Example 1 was repeated except that magnesium oxide was used instead of calcium hydroxide.
  • a powder of calcium hydroxide form which coarse particles had been removed by winnowing was added to the color developer powder obtained in Comparative Example 2 in an amount of 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 2.0 millimoles respectively per gram of the entire dry mixture (upon drying at 110°C), and they were uniformly mixed in a fluidizing-type mixer to obtain a white develop color developer powder.
  • Example 7 was repeated except that the mixing mole ratio of calcium hydroxide to zinc oxide was changed to 0.5:0.5 (1:1).
  • Example 7 was repeated except that the mixing mole ratio of calcium hydroxide to zinc oxide was changed to 0.25:0.75 (1:3).
  • Example 6 was repeated except that zinc oxide was used instead of calcium hydroxide.
  • a powder of magnesium hydroxide from which coarse particles had been removed by winnowing was added to the color developer (1 b) obtained in Comparative Example 1 b in an amount of 0.1,0.2,0.4,0.6,0.8, 1.0 and 2.0 millimoles per gram of the entire dry mixture (upon drying at 110°C), and they were mixed uniformly in a fluidizing-type mixer to form a white color developer powder.
  • a powder of magnesium hydroxide and powder of zinc oxide from which coarse particles had been removed by winnowing were uniformly mixed in a mole ratio of 0.75:0.25 (3:1
  • the resulting mixture was added to the color developer (1 b) obtained in Comparative Example 1 b in an amount of 0.1,0.2,0.4,0.6,0.8, 1.0 and 2.0 millimoles respectively per gram of the entire dry mixture (upon drying at 110°C), and they were mixed uniformly in a fluidizing-type mixer to obtain a white color developer powder.
  • Example 12 was repeated except that the mixing mole ratio of magnesium hydroxide to zinc oxide was changed to 0.5:0.5 (1:1).
  • Example 12 was repeated except that the mixing mole ratio of magnesium hydroxide to zinc oxide was changed to 0.25:0.75 (1:3).
  • Example 11 was repeated except that zinc oxide was used instead of magnesium hydroxide.
  • a powder of calcium hydroxide from which coarse particles had been removed by winnowing was added to the powdery developer (1 b) obtained in Comparative Example 1b in an amount of 0.1,0.2,0.4,0.6, 0.8, 1.0 and 2.0 millimoles, respectively, per gram of the entire dry mixture (upon drying at 110°C). They were uniformly mixed by a fluidized-type mixer to obtain a white color developer powder.
  • Example 17 was repeated except that the mixing mole ratio of calcium hydroxide to magnesium hydroxide was changed to 0.5:0.5 (1:1).
  • Example 17 was repeated except that the mixing mole ratio of calcium hydroxide to magnesium hydroxide was changed to 0.25:0.75 (1:3).
  • Example 1 was repeated except that calcium oxide was used instead of calcium hydroxide.
  • Example 1 was repeated except that zinc hydroxide was used instead of calcium hydroxide.
  • the zinc hydroxide used was a powder obtained by adding an aqueous solution of sodium hydroxide to an aqueous solution of zinc sulfate, washing the resulting white precipitate with water, drying it at less than 100°C, pulverizing it and removing coarse particles by winnowing.
  • Example 1 was repeated except that zinc oxide was used instead of calcium hydroxide.
  • a powder of calcium hydroxide with varying particle sizes obtained by winnowing was added to the color developer powder (1a) obtained in Comparative Example 1a in an amount of 0.6 millilmole per gram of the entire dry mixture (upon drying at 110°C). They were mixed uniformly by a fluidized mixture to obtain a white color developer composition.
  • Table 10 shows the effect of the content of particles having a particle diameter of not more than 10 microns and the content of particles having a size 325 mesh under in the metal compound on the color-developing performance of each of the resulting color developer compositions.
  • Tables 1 to 7 summarize the results of the test of color developing ability of the color developer samples obtained by the above examples.
  • Table 8 shows the results of measuring the content of particles having a particle diameter of not more than 10 microns, the content of particles having a size 325 mesh under, and the viscosities of the coating slurries.
  • Table 9 shows the results of the quantitative analysis of the metal compounds.

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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)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (15)

1. Farbentwickerlermasse für druckempfindliche Aufzeichnungsblätter, enthaltend einen Farbentwickler (1) auf der Basis eines Tonminerals mit einer Schichtstruktur aus regulären Si02-Tetraedern, welcher
(A) ein Beugungsmuster zeigt, das den Kristallen einer Schichtstruktur aus regülaren Si02-Tetraedern zukommt, wenn einer Elektronenbeugungsanalyse unterwofen, jedoch
(B) im wesentlichen kein Beugungsmuster zeigt, das den Kristallen dieser Schichtstruktur zukommt, wenn einer Röntgenbeugungsanalyse unterworfen, und
(C) als Bauelement neben Sauerstoff, zumindest Silicium, Magnesium und/oder Aluminium enthält, dadurch gekennzeichnet, daß die masse zumindest umfaßt
(1) den Farbentwickler (1), enthaltent Magnesium und/oderAluminium, wobei der Magnesiumgehalt in wässriger Ammoniumchloridlösung nicht löslich ist,
(2) gegebenenfalls einen Farbentwickler mit einem Si02-Gehalt von nicht mehr als 80% auf Trockengewichtbasis aus mit einer Säure behandeltem doppeltoktaedrischem Montmorillonit-Tonmineral oder einem Gemisch davon mit natürlich vorkommendem doppeltoktaedrischem Montmorillonit-Tonmineral, wobei der Farbentwickler (2)
(D) ein Beugungsmuster aufweist, das den Kristallen dieser Schichtstruktur zukommt, wenn der Röntgenbeugungsanalyse unterworfen, und
(3) 0,2 bis 2 mmol/g der Komponenten (1), (2) und (3) zusammen zumindest einer Metallverbindng in form der Oxide und/oder Hydroxide von Calcium, Magnesium und Zink, wobei die Metallverbindung, wenn sie Magnesiumoxid oder -hydroxid ist, in wässriger Ammoniumchloridlösung löslich ist.
2. Masse nach Anspruch 1, worin das Tonmineral, aus dem sich der Farbentwickler (1) ableitet, wenigstens eines aus der Reihe der Montmorillonit-, Kaolinit-, Sepiolit-Palygorskit-, Chlorit- und Vermiculi-Tonmineralien ist.
3. Masse nach Anspruch 1 oder 2, worin der Farbentwickler (1) Silicium und Magnesium und/oder Aluminium in einem Atomverhältnis Silicium/(Magnesium und/oder Aluminium) von 12:1,5 bis 12:12 enthält.
4. Masse nach Anspruch 1, 2 oder 3, wobei der Farbentwickler (2) eine spezifische Oberfläche von zumindest 180 m2/g besitzt.
5. Masse nach einem der vorstehenden Ansprüche, worin der Farbentwickler (2) ein säurebehandelter saurer (aktiver) Ton oder seine Mischung mit natürlich vorkommendem sauren Ton ist.
6. Masse nach Anspruch 1 bis 4, worin der Farbentwickler (2) ein säurebehandeltes doppeltoktaedrisches Montmorillonit-Tonmineral oder seine Mischung mit natürlich vorkommendem doppeltoktaedrischem Montmorillonit-Tonmineral ist und er, wenn einer zweiten Farbentwicklung mit Benzoylleukomethylenblau unterwofen, ein sekundäres Farbentwicklungsvermögen K2 gemäß nachstehender Gleichung von zumindest 1,4 besitzt wobei
Figure imgb0028
worin R430 und R550 die Lichtreflexionen bei Wellenlängen von 430 um bzw. 550 um bedeuten.
7. Masse nach einem der vorstehenden Ansprüche, worin der Farbentwickler (1) erhalten wird durch Behandeln eines Tonminerals mit einer Schichtstruktur aus regulären Si02-Tetraedern mit einer Säure, so daß nach dem Trocken bei 105°C währen 3 Stunden der Si02-Gehalt 82 bis 96,5 Gew.-% beträgt, Inberührungbringen des behandelten Tons in einem wässrigen Medium mit einer Magnesium- und/oder Aluminiumverbindung, Neutralisieren des erhaltenen Produkts mit Alkali oder Säure unter Bildung eines Hydroxids, wenn die Magnesium- und/oder Aluminiumverbindung kein Hydroxid ist, um dadurch in das säurebehandelte Tonmineral Magnesium und/oder Aluminium einzuführen und - falls erwünscht - Trocknen des Produkts.
8. Masse nach Anspruch 7, worin die Säurebehandlung so lange vorgenommen wird, bis das säurebehandelte Tonmineral in der Röntgenanalyse im wesentlichen kein Beugungsmuster mehr zeigt, das Kristallen der aus regulären Si02-Tetraedern zusammengesetzten Schichtstruktur des Tonminerals vor der Säurebehandlung zuzuschreiben ist.
9. Masse nach einem der vorstehenden Ansprüche, worin der Anteil der Metallverbindung 0,4 bis 1 mmol/g der Komponenten (1), wenn vorhanden (2) und (3) zusammen ist.
10. Masse nach einem der vorstehenden Ansprüche, worin die Metallverbindung (3) Calciumhydroxid ist.
11. Masse nach einem der vorstehenden Ansprüche, worin die Metallverbindung (3) eine solche Korngröße hat, daß wenigstens 70% davon aus Teilchen mit einem Teilchendurchmesser von nicht mehr als 10 um bestehen, bestimmt mit der Andreasen-Pipette.
12. Masse nach einem der vorstehenden Ansprüche, worin die Metallverbindung (3) zu wenigstens 90 Gew.-% aus Teilchen besteht, die durch ein 325 mesh Tyler-Standard-Sieb fallen.
13. Masse nach einem der vorstehenden Ansprüche, welche wenigstens 99 Gew.-% Teilchen enthält, die durch ein 325 mesh Tyler-Standard-Sieb fallen.
14. Druckempfindliche Aufzeichnungsblätter mit einer Beschichtung aus einer Farbentwickermasse, wie in einem der vorstehenden Ansprüche beansprucht.
EP19830307430 1983-12-06 1983-12-06 Ton als Farbentwicklerzusammensetzung für druckempfindliche Kopierblätter Expired EP0144472B2 (de)

Priority Applications (2)

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EP19830307430 EP0144472B2 (de) 1983-12-06 1983-12-06 Ton als Farbentwicklerzusammensetzung für druckempfindliche Kopierblätter
DE8383307430T DE3378200D1 (en) 1983-12-06 1983-12-06 Clay mineral-type color developer composition for pressure-sensitive recording sheets

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Application Number Priority Date Filing Date Title
EP19830307430 EP0144472B2 (de) 1983-12-06 1983-12-06 Ton als Farbentwicklerzusammensetzung für druckempfindliche Kopierblätter

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EP0144472A1 EP0144472A1 (de) 1985-06-19
EP0144472B1 true EP0144472B1 (de) 1988-10-12
EP0144472B2 EP0144472B2 (de) 1992-06-24

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JP3054153B2 (ja) * 1989-02-28 2000-06-19 水澤化学工業株式会社 感圧複写紙用顕色剤
GB9313790D0 (en) * 1993-07-03 1993-08-18 Wiggins Teape Group The Ltd Pressure-sensitive copying material
DE4327158A1 (de) * 1993-08-12 1995-02-16 Sued Chemie Ag Verfahren zur Herstellung von neutralen bis alkalischen Farbentwicklerpigmenten
GB9414637D0 (en) * 1994-07-20 1994-09-07 Wiggins Teape Group The Limite Presure-sensitive copying material
WO2007087649A1 (en) * 2006-01-27 2007-08-02 Qualcomm Incorporated Repeater open loop gain measurement
CN101417563B (zh) * 2008-10-21 2010-09-22 莫文生 一种环保型无碳复写纸显色剂的生产方法

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JPS5637189A (en) * 1979-09-05 1981-04-10 Oji Paper Co Ltd Tinting paper for pressure sensitive recording
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

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