Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
  • C01B33/42—Micas ; Interstratified clay-mica products
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
  • C01B33/40—Clays
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/46—Amorphous silicates, e.g. so-called "amorphous zeolites"
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/259—Silicic material

Definitions

• a color former for pressure sensitive recording paper which comprises a member selected from the group consisting of acid-treated dioctahedral montmorillonite clay minerals and mixtures of said minerals with natural dioctahedral montmorillonite clay minerals and a process for producing the same.
• This invention relates to a color former which demonstrates pronounced color development effects when used in making manifold record paper, i.e. the pressure sensitive recording paper, which can reproduce copies by handwriting, printing or typing without the necessity of the conventional carbon paper,
• the invention also relates to a process for producing such a color former.
• the pressure sensitive recording papers with a few exception in the case of special papers, are in all cases those in which the color development reaction ascribable to the transfer of electrons between the colorless compound of organic coloring matter having electron donating property and a color former, the electron acceptor. (US. Pat. No. 2,548,366).
• the color reaction substance As the colorless compound of organic coloring matter, the color reaction substance, two classes of coloring matter each of which exhibit different behaviors of coloration are used cojointly. One of them is that which, as in the case, for example, of the triphenyl methane coloring matter, develops color intensity immediately upon contacting a solid acid, but which has a tendency to fade easily (primary color development coloring matter).
• the second coloring matter used is one which does not immediately develop color upon contacting a solid acid but develops its color completely after several days have elapsed and exhibits adequate fastness to sunlight.
• the acyl leucomethylene blue coloring matter are used (secondary color development coloring matter).
• the solid acids are generally used.
• known are such, for example, as kaolin, bentonite, attapulgite, aluminum sulfate, natural zeolite, silica gel, feldspar, pyrophyllite, halloysite, magnesium trisilicate, zinc sulfate, zinc sulfide, calcium fluoride, calcium citrate as well as the organic acids as tannic acid and benzoic acid.
• the pressure sensitive recording paper using these color development coloring matter and color formers is made up of two classes of papers: one the transfer sheet (referred to as the coated back of CB), a paper which has been coated with the coloring matter in solution in oil and encapsulated by such as gelatin, gum arabic or synthetic resin the size of which capsules is several microns in diameter, and the other the receiving sheet (referred to as the coated front or CF a paper coated with the color former.
• the coated back of CB a paper which has been coated with the coloring matter in solution in oil and encapsulated by such as gelatin, gum arabic or synthetic resin the size of which capsules is several microns in diameter
• the coated front or CF a paper coated with the color former.
• an one or more intermediate sheets which we generally referred to as a coated front and back back sheet (or CFB) i.e. one which has the front coated with the color development coloring matter and the back coated with the color former, are used interleaved between the transfer sheet and the receiving sheet.
• CFB coated front and back back sheet
• a color former for pressure sensitive recording paper which comprises a dioctahedral montmorillonite clay mineral and/or the acid-treated products thereof the specific surface area of which is at least mF/g. of the total particles at least 75 percent by weight having a particle diameter 10 microns or less, and not more than 45 percent by weight being those of diameter one micron or less, said mineral and/or its acid-treated products having a secondary color development property, K of at least 1.40, preferably at least 1.60, the value of K being represented by the formula wherein R and R are reflectances of light having wavelengths 430 my. and 555 mp., respectively when said mineral and/or its acid-treated products are developed by benzoyl leucomethylene blue.
• the color development effects of the color former in the secondary color development coloring matter e.g. acyl leucomethylene blue
• the color development property of the natural solid acid relative to the secondary color development coloring matter could be improved somewhat by such chemical treatments as, say, acid, alkali, oxidation and reducing treatments, a substantial improvement of the color development property could not be attained.
• the solid acids which are the color former
• the natural clay minerals such as hereinbefore indicated, e.g. kaolin, bentonite, attapulgite and natural zeolite, are known, but actually attapulgite is principally used.
• a color former for pressure sensitive recording paper use which excels in both in its primary and secondary color development property could be obtained by first choosing from among the dioctahedral montmorillonite clay minerals those which excel in secondary color development property and thereafter subjecting these chosen montmorillonite clay minerals to an acid treatment until the desired specific surface area is obtained.
• the particle diameter of the color former is measured by means of the Andreasen sedimentation pipet.
• the particle diameters used herein have all been made by this method of measurement.
• the degree of color development of the specimen whose color has been developed in the foregoing manner is measured with a spectrophotometer.
• the specimen is packed in a powder cell of quartz and its reflectances of lights having wavelengths of 430 and 550 mp. are measured.
• the reflectance is expressed in percent using as the basis percent for the reflectance of an alpha-alumina shaped product. 5. Method of indicating the secondary color development property.
• the dried color former After the dried color former has been fully comminuted in a mortar or pot mill, it is winnowed and prepared such that a least 85 percent by weight of the total particles are those having a particle diameter 10 microns or less and not more than 35 percent by weight are those of a particle diameter one micron or less. Five grams of this powder are then weighed into a weighing bottle, dried for 1 hour in a 1 [0 C. constant temperature dryer and thereafter allowed to cool in a desiccator.
• crystal violet lactone a triphenylmethane coloring matter
• 0.5 Gram of this coloring matter is dissolved in 99.5 grams of g.p. benzene.
• the chemical nomenclature and structural formula of crystal violet lactone are as follows:
• Crystal violet lactone [3,3-bis(p-dimethylaminophenyl)-6- dimethylphthalide] 2. Color development conditions.
• the degree of color development of the specimen whose color has been developed under the hereinbefore indicated conditions is measured using a spectrophotomer.
• the specimen is packed in a quartz cell having a diameter of 21 mm. and a height of [0 mm. and with the width of the slit 1 mm. the refiectances at wavelengths 390, 550 and 590 mp. are measured.
• the reflectance is indicated in percent using as the basis 100 percent for the reflectance of an alpha-alumina shaped article.
• dioctahedral montmorillonite clay minerals which are unsuitable for use as the color former of the present invention because they are inferior in their secondary color development property although they excel in their specific surface area, primary color development property and decolorizing property (see specimen Nos. l0, l3 and 15 5.
• dioctahedral montmorillonite clay minerals which excel in their secondary color development property as in the case with attapulgite but whose specific surface area does not increase by means of the acid treatment and hence whose primary color development property is not improved (see specimen No. 8 in table I).
• the secondary color development property being an inherent property of the material clay itself cannot essentially be improved though some improvement can be had by the acid treatment.
• the decolorizing property is not related at all to the secondary color development property.
• a dioctahedral montrnorillonite clay mineral having the highest possible K a dioctahedral montrnorillonite clay mineral having the highest possible K
• dioctahedral montmorillonite clay minerals can be mentioned the natural clay minerals such, for example, as the so-called bentonite, subbentonite, fullers earth, Florida earth and Japanese acid clay.
• the dioctahedral montmorillonite clay minerals, as used herein, are not limited to only those which have been illustrated.
• any whether inorganic or organic may be used which is able to increase the specific surface area of the aforesaid montmorillonite clay minerals to above I80 m. /g.
• the inorganic acids are generally to be preferred over the organic acids for reasons of cost and ease of handling, and of the inorganic acids sulfuric and hydrochloric acids are particularly convenient.
• the acid concentration may be any in the range of the order of 180, percent, but from the standpoint of convenience in handling practice the acid treatment is preferably carried out at a concentration of the order of 1545 percent and a temperature ranging between 50 and l05 C. in short, in this invention, the acid treatment of the aforesaid dioctahedral montmorillonite clay mineral until its specific surface area becomes at least 180 mF/g. is the sole basically important conditions.
• the acid treatment conditions be so controlled that the specific surface area of the clay after treatment comes within the range between 180 mF/g. and 350 mF/g.
• the color development effect was greatly enhanced to yield an excellent color former for pressure sensitive recording paper use in which moreover the undesirable tendency to smudging and exfoliation of the applied particles was less.
• the color former should be preferably one containing at least 75 percent by weight of particles of a diameter 10 microns or less for achieving the color development efi'ect and prevention of the smudging phenomenon.
• One hundred grams of the color former are suspended in 250 ml. of water, to which are then added 10 grams of starch.
• thedioctahedral mSBESrii-" lonite clay minerals as used in the present invention are increased in their specific surface area by means of the acid treatment, and it can be seen that the primary color develop. ment property becomes good when the specific surface area becomes greater than 180 mF/g. When the specific surface area increases in this manner, the capacity to absorb and adsorb oil increases at the same time. Hence, the acid treatment is necessary and indispensable in the present invention.
• This suspension is applied to paper of fine quality in an amount such that 7 grams of the color former are adhered per square meter of the paper, after which the paper is dried to thus obtain a coated front sheet.
• a coated back sheet is superposed on this coated front sheet, and a stainless steel cylinder 5 cm. in diameter and weighing 4 kg. is then placed on top of the superposed sheets and gently pulled across the sheets.
• the soiling of the coated front sheet thus resulting is measured for its reflectance of light of a wavelength 430 mp. using a spectrophotometer.
• the soil-resistant following equation:
• the property is defined by the Soil-resistant property That is to say, the greater the numerical value of the soil-resistant property (percent), the less is the soiling.
• the foregoing l.G.T. test was conducted on the specimen prepared in the following manner in accordance with the below-described measurement method.
• One hundred grams of the color former are suspended in 250 ml. of water, to which are then added 10 grams of starch.
• This suspension is applied to high quality paper such that the adhesion of the color former to the paper amounts to 7 grams per square meter, followed by drying the paper to obtain the coated front sheet.
• This sheet is submitted to the l.G.T. test and the rate at which the exfoliation of the color former takes place is measured. It can be seen that when the content of particles one micron or less in size exceeds 45 percent by weight the results of the l.G.T. test suddenly become worse.
• a color former for pressure sensitive recording paper by a procedure comprising choosing from among the dioctahedral montmorillonite clay minerals one whose secondary color development property, K value, relative to benzoyl leucomethylene blue as measured in accordance with the hereinbefore described measurement method is at least 1.40, and preferably at least 1.60, subjecting this chosen montmorillonite clay mineral to an acid treatment to increase its specific surface area to at least 180 m. /g., and preferably to a value in the range between 180 m. /g. and 350 mF/g.
• K value does not become less than 1.40, and preferably not less than 1.60, followed by water-washing and drying, and thereafter either comminuting or classifying the foregoing clay mineral to render it into particle size in which of the total particles at least 75 percent by weight are those having a particle diameter 10 microns or less and moreover not more than 45 percent by weight of the total particles are those one micron or less in diameter.
• the invention color former cal also be produced by mixing (A) a dioctahedral montmorillonite clay mineral which has been acid treated until its specific surface area is at least 180 m.”/g., and preferably at least 220 m./g., with (B) a dioctahedral montmorillonite clay mineral or an acid-treated product thereof whose secondary color development property, K has a value of at least 1.40, and preferably at least 1.80 to obtain as a whole a specific surface area of at least 180 mF/g.
• the aforesaid clay mineral (A) need not necessarily be one whose K value is at least 1.40.
• the aforesaid clay mineral (B) or its acid-treated product need not necessarily be one whose specific surface area is at least 180 m.'*/g.
• the invention color former prepared as hereinbefore described can be applied to paper using the natural or artificial pastes such, for example, as starch, casein, tragacanth gum, CMC, synthetic latex having a bonding property, such as styrene butadien latex and butadiene-acrylonitrille resin latex and polyvinyl alcohol to thus make the coated front sheet of pressure sensitive recording paper.
• the natural or artificial pastes such as starch, casein, tragacanth gum, CMC, synthetic latex having a bonding property, such as styrene butadien latex and butadiene-acrylonitrille resin latex and polyvinyl alcohol
• additives for improving the color development effect still further or for increasing the amount of color former added, it is possible to suitably add such additives as other natural clay minerals or synthetic inorganic substances, e.g. calcium carbonate, silica, silicate; organic or inorganic pigments, e.g. ultramarine, persian blue, chrome yellow, iron oxide, lndanthrene, Rhodamine and Methyl violet; dyestuffs such as fluorescent bleaching agent, e.g. diaminostilbene and benzoimidazole; oxidants, e.g.
• additives e.g. calcium carbonate, silica, silicate
• organic or inorganic pigments e.g. ultramarine, persian blue, chrome yellow, iron oxide, lndanthrene, Rhodamine and Methyl violet
• dyestuffs such as fluorescent bleaching agent, e.g. diaminostilbene and benzoimidazole
• oxidants e.g.
• EXAMPLES l-5 The material clays indicated in table V were chosen, which were each dried, comminuted and winnowed to prepare them into specimens in which percent of the total weight were particles whose diameter was 10 microns or less and 30 percent of the total weight were those whose diameter was one micron or less.
• Specimen l (specimen No. l of table I) and specimen ll (Japanese acid clay specimen 8 of table II which had been acid treated for 12 hours) were each winnowed and specimens
• the Value of K in the Specimens L 4, 10 and l 1 in having the following particle sizes were prepared.
• table V were above 1.40. Hence, the acid treatment of these was carried out under the following conditions.
• Specific surface area 340 m. /g. K, 3.15 K, 1.89
• R and R are reflectances of light having wavelengths 430 mu and 550 mu, respectively, when said minerals are developed by benzoyl leucomethylene blue.
• a process for producing the color former for pressure sensitive recording paper comprising treating a dioctahedral montmorillonite clay mineral having a secondary color development property, K of at least 1.40, the value of K being represented by the formula wherein R and R are reflectances of light having wavelengths 430 my and 550 m,u., respectively, when said mineral is developed by benzoyl leucomethylene blue, with an acid to increase the specific surface area of said mineral to at least 180 mF/g.
• a process for producing a color former for pressure sensitive recording paper comprising mixing:

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• 1968
  • 1968-11-12 US US775126A patent/US3622364A/en not_active Expired - Lifetime
  • 1968-11-14 GB GB54042/68A patent/GB1213835A/en not_active Expired
  • 1968-11-18 BE BE724046D patent/BE724046A/xx not_active IP Right Cessation
  • 1968-11-19 DE DE19681809778 patent/DE1809778B2/de not_active Ceased
  • 1968-11-20 FR FR174573A patent/FR1592438A/fr not_active Expired
• 1971
  • 1971-08-31 US US00176743A patent/US3753761A/en not_active Expired - Lifetime

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