US3330722A - Method for preparing pressure-sensitive filler-containing copying paper and paper thereof - Google Patents
Method for preparing pressure-sensitive filler-containing copying paper and paper thereof Download PDFInfo
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- US3330722A US3330722A US39232964A US3330722A US 3330722 A US3330722 A US 3330722A US 39232964 A US39232964 A US 39232964A US 3330722 A US3330722 A US 3330722A
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- United States
- Prior art keywords
- paper
- clay
- salt
- lead
- weight
- Prior art date
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 20
- 239000000945 filler Substances 0.000 title description 9
- 239000004927 clay Substances 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011133 lead Substances 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- VHNFAQLOVBWGGB-UHFFFAOYSA-N benzhydrylbenzene;3h-2-benzofuran-1-one Chemical class C1=CC=C2C(=O)OCC2=C1.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 VHNFAQLOVBWGGB-UHFFFAOYSA-N 0.000 claims description 4
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical class C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 14
- 150000002611 lead compounds Chemical class 0.000 description 13
- 239000000370 acceptor Substances 0.000 description 11
- 239000007900 aqueous suspension Substances 0.000 description 11
- 235000013495 cobalt Nutrition 0.000 description 9
- -1 triphenyl methane phthalide compound Chemical class 0.000 description 8
- 229960000892 attapulgite Drugs 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052625 palygorskite Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 229940097267 cobaltous chloride Drugs 0.000 description 3
- 229940046892 lead acetate Drugs 0.000 description 3
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- GAMPNQJDUFQVQO-UHFFFAOYSA-N acetic acid;phthalic acid Chemical compound CC(O)=O.OC(=O)C1=CC=CC=C1C(O)=O GAMPNQJDUFQVQO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005506 phthalide group Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- a water insoluble inorganic salt which is produced by the reaction of aqueous solution in colloidal forms in the aqueous suspension containing paper grade pulp and clays of electron acceptor, is most preferable as a compound which performs the function of sensitizer physically and chemically.
- the cobalt-, manganese-, and lead-compounds which are usable are: water-insoluble salts of inorganic or organic acids e.g. borate, phosphate, silicate, carbonate, sulfate, chromate, salts of resin acids, and salts of carboxylic acids or the like. Both bivalent and trivalent lead compounds or the like are useful. A mixture of different lead compounds is also useful.
- An internally filled paper for use in forming presuresensitive copying paper, said internally filled paper comprising cellulosic fibers, a clay, and a water insoluble lead salt, the clay and salt being present in an amount of 1040% by weight of the filled paper and the lead salt being from 2 to 15% by weight based on the weight of clay and salt, said clay being an electron acceptor clay capable of developing color by adsorbing colorless electron donor selected from triphenylmethane phthalide compounds and acyl leuco methylene blue compounds.
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Paper (AREA)
- Coloring (AREA)
Description
United States Patent 0 3,330,722 METHOD FOR PREPARING PRESSURE-SENSITIVE FILLER-CONTAINING COPYING PAPER AND PAPER THEREOF Masahiro Amano and Hideo Ohye, Kobe, Japan, assignors to Mitsubishi Paper Mill, Ltd., Tokyo, Japan, a corporation of Japan No Drawing. Filed Aug. 26, 1964, Ser. No. 392,329 Claims priority, appiication Ja an, Get. 31, 1963, 38/ 57,653 12 Claims. (Cl. 162-181) This invention relates to a method for preparing an internally filled paper adapted for forming a pressuresensitive copying paper by filling a paper stock with clays of electron acceptor, which develop color by adsorbing colorless compounds of electron donor together with at least one cobalt-, manganese-, or lead-compound and to a paper thus prepared. More particularly this invention relates to a novel method for preparing an internally filled paper for forming a pressure-sensitive, copying paper in which compounds of cobalt, manganese, and lead which have been used extensively as a dryer of printing ink for a long time, are incorporated as sensitizers for color developing reaction with clays of electron acceptor, and to a paper thus prepared.
The conventional pressure-sensitive copying paper which utilizes color development by electron donating and accepting consists of a sheet of paper, the back surface of which constitutes an electron donating surface and another sheet of paper, the surface of which constitutes an electron accepting surface. The electron donating surface is coated with a particulated and individually insulated solution of colorless electron donor compounds such as a triphenyl methane phthalide compound, e. g. crystal violet lactone, and an acyl leuco methylene blue compound, e.g. benzoyl leuco methylene blue or the like dissolved in nonpolar solvents such as chlorinated diphenyl or the like, the insulation of particulated solution being performed by the coating thereof with film forming materials such as gelatine, agar-agar, albumin, salt of alginic acid, fibrinogen, casein, soya-bean protein, pectin, gum arabic, starch, starch acetate-phthalate, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polystyrene, polyacrylic ester, polymethacrylic ester, polyvinyl acetate, polyethylene imine, divinyl benzene polymer, polyethylene-m-aleic anhydride copolymer, polymethylether-maleic anhydride copolymer, etc. and the electron accepting surface is coated with electron accepting clays such as attapulgite, terra alba, activated clay, finely divided silicic acid, kaoline, pyrophillite, halloysite, zeolite, bentonite etc.
Color is developed when the insulating coating of the electron donating surface, -i.e., the capsule is broken at the contact of the two surfaces due to the local pressure exerted by writing, printing, etc., and the exuded solution is adsorbed by the electron accepting surface. Such electron accepting surfaces of pressure-sensitive copying paper have been made by coating papers with electron accepting clays such as attapulgite, terra alba, acid-treated product thereof (material produced by grinding crude or dried terra alba or similar clay, treating it by hydrochloric ac-id, nitric acid, sulfuric acid or the like at a temperature higher than 90 C., at atmospheric pressure or above and if necessary neutralizing with alkali, and after filtration and washing, drying at a temperature of from 120 C. to 200 C. and grinding) together with adhesives such as starch, casein, latex or the like. The manufacture of these accepting surfaces, however, requires two steps, i.e., paper making and coating and due to various accidents which may occur frequently during the coating step, the reduction of production efficiency has been inevitable. Assuming that electron accepting clays be filled in paper, it seems to have the possibility of improving the production efficiency, but in reality electron accepting clays filled in paper are exceedingly inferior to that coated on paper.
An object of the present invention is to provide a method for preparing a filler-containing copying paper having the same color developing function as the conventional coated paper by a filling process, in other Words, by the paper making step of the process alone, thereby to increase the production efiiciency.
Another object of the present invention is to provide such a filler-containing paper adapted for use as a pressure-sensitive copying paper.
These and other objects will be attained by the present method.
According to the present invention, a filler-containing copying paper is made by filling clays of electron acceptor into paper together with compounds of cob-alt, manganese, and lead or a mixture thereof which have been used extensively as dryers of printing ink for a long time.
Compounds of cobalt, manganese, and lead used in the present invention strengthen the color developing reaction not only by their function as electron acceptors by themselves, but, also because of their function as a dryer of printing ink whereby they promote such reaction by the oxidation performed by such metallic constituents as an oxygen carrier. In other words, for the electrondonating surface of a pressure-sensitive copying paper, two kinds of compounds have been conventionally employed. One is a triphenyl methane phthalide compound such as crystal violet lactone which develops color as soon as it is adsorbed but later gradually loses this color by fading. The other is an acyl leuco methylene blue compound such as benzoyl leuco methylene blue which is gradually oxidized at the adsorbed state to develop color and maintains the color stability.
The compounds of cobalt, manganese, lead or the like used in the present invention strengthen the color development of the former and simultaneously promote the color development of the latter. In this regard, the present invention improves the life of copying paper the function of color development in a marked degree.
As for forms of the cobalt-, manganese, and leadcompound, a water insoluble inorganic salt which is produced by the reaction of aqueous solution in colloidal forms in the aqueous suspension containing paper grade pulp and clays of electron acceptor, is most preferable as a compound which performs the function of sensitizer physically and chemically.
The cobalt-, manganese-, and lead-compounds which are usable are: water-insoluble salts of inorganic or organic acids e.g. borate, phosphate, silicate, carbonate, sulfate, chromate, salts of resin acids, and salts of carboxylic acids or the like. Both bivalent and trivalent lead compounds or the like are useful. A mixture of different lead compounds is also useful.
The amounts of these metallic compounds to be incorporated into fillers of the present invention expressed by weight percent relative to weight of fillersare as follows:
Percent Lead 2-15 Manganese 0.5-4.5 Cobalt 0.3-2.0
A most remarkable effect can be attained when two or three kinds of metallic constituents such as cobalt-, manganese-, and lead compounds are used simultaneously as a mixture.
As for the kinds of clay, the above-mentioned electron accepting clays are useful.
The amounts of clays and cobalt, manganese-, or lead compound very according to paper making methods. They are dependent upon the retention of fillers. W'hen expressed by ash in finished paper, they are in the follow- When a cobalt-, manganese-, or lead compound is to be incorporated in paper, any of the following methods can be employed.
' (1) A method which synthesizes water-insoluble lead compound or the like in aqueous suspension containing pulp and clay, followed by paper making.
(2) A method which synthesizes water-insoluble lead compound or the like in aqueous suspension of pulp and then adds clay, followed by paper making.
(3) A method which synthesizes water-insoluble lead compound or the like in aqueous suspension of clay and then adds pulp, followed by paper making.
(4) A method which admixes pulp, clay and water insoluble lead compound or the like simultaneously, followed by paper making.
A more comprehensive understanding of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of various conditions such as kind, form, amount, etc. of the fillers.
It is to be understood that any modifications derived from the following examples belong to the spirit and scope of this invention so long as they do not depart from the scope of the claims.
EXAMPLE 1 To 2% aqueous suspension of paper grade pulp, 10% aqueous suspension of attapulgite and 5% aqueous solution of cobaltous chloride were admixed uniformly and then while stirring, an aqueous solution of 41 B sodium silicate (approximately Na O-3-2 SiO diluted times as much water was added thereby to produce colloidal cobaltous silicate. The amounts of the above-mentioned raw materials were adjusted to afford the following proportions by Weight:
Paper grade pulp 100 Attapulgite 50 Cobaltous chloride 3 41 B sodium silicate solution 10 The pH of resulting aqueous mixed suspension was 8.9 and the weight and the ash content of filled paper made by the laboratory cylinder machine were 50 g./m. and 20.5% respectively.
EXAMPLE 2 Paper grade pulp 100 Terra alba 50 Manganous chloride 5 Sodium pyrophosphate 6 Locust bean gum 1 The pH of the resulting mixed aqueous suspension was 8.4. Filled paper made by the laboratory cylinder machine had a weight of 50 g./m. and an ash content of 25.0%.
EXAMPLE 3 To 2% aqueous suspension of paper grade pulp, 10% aqueous suspension of finely divided silicic acid produced by treating terra alba with sulfuric acid and 5% equeous solution of lead acetate were admixed uniformly. While stirring, 5% aqueous solution of borax was added thereby to produce colloidal lead borate. Further 10% colloid of melamine resin which had been made acidic by hydrochloric acid was added to improve the retention of fillers. The amounts of the above-mentioned raw materials were adjusted to afford following proportions by weight:
Paper grade pulp Finely divided silica 50 Lead acetate 10 Borax 9 Melamine resin 2 The pH of resulting aqueous mixed dispersion was 6.7. Filled paper made by the laboratory cylinder machine had a weight of 50 g./m. and ash content of 26.4%.
What is claimed is:
1. An internally filled paper for use in forming pressure-sensitive copying paper, said internally filled paper comprising cellulosic fibers, a clay, and a member selected from the group consisting of water insoluble salts of cobalt, manganese, lead and mixtures thereof, the clay and insoluble salt being present in an amount of 10-40% by weight of the filled paper, the salt being from 0.3 to 15% by weight of the total of the clay and salt, said clay being an electron acceptor clay capable of developing color by absorbing colorless electron donor selected from triphenylmethane phthalide compounds and acyl leuco methylene blue compounds.
2. An internally filled paper for use in forming presuresensitive copying paper, said internally filled paper comprising cellulosic fibers, a clay, and a water insoluble lead salt, the clay and salt being present in an amount of 1040% by weight of the filled paper and the lead salt being from 2 to 15% by weight based on the weight of clay and salt, said clay being an electron acceptor clay capable of developing color by adsorbing colorless electron donor selected from triphenylmethane phthalide compounds and acyl leuco methylene blue compounds.
3. An internally filled copying paper according to claim 2, in which the clay is finely divided silicic acid and the lead compound is lead borate.
4. An internally filled paper for use in forming pressure-sensitive copying paper, said internally filled paper comprising cellulosic fibers, a clay, and a water insoluble manganese salt, the clay and salt being present in an amount of 10-40% by weight of the filled paper and the manganese salt being from 0.5 to 4.5% by weight based on the Weight of clay and salt, said clay being an electron acceptor clay capable of developing color by adsorbing colorless electron donor selected from triphenylmethane phthalide compounds and acyl leuco methylene blue compounds.
5. An internally filled copying paper according to claim 4, in which the clay is terra al-ba and the manganese compound is manganese pyrophosphate.
6. An internally filled copying paper for use in forming pressure-sensitive copying paper, said internally filled paper comprising cellulosic fibers, a clay and a water insoluble cobalt salt, the clay and salt being contained in an amount of 10-40% by weight of the filled paper and the cobalt salt being from 0.3 to 2.0% by weight based on the weight of filler, said clay being an electron acceptor clay capable of developing color by adsorbing colorless electron donor selected from triphenylrnethane phthalide compounds and acyl leuco methylene blue compounds.
7. An internally filled copying paper according to claim 6, in which the clay is attapulgite and the cobalt compound is cobaltous silicate.
8. A method for preparing an internally filled paper suitable for forming pressure-sensitive copying paper, said method comprising adding to an aqueous suspension of cellulosic fiber, clay of electron acceptor capable of developing color by adsorbing colorless electron donor, a water insoluble salt selected from the group consisting of salts of cobalt, manganese, lead and mixtures thereof, and thereafter forming from the fiber suspension a paper, said clay and water insoluble salt being added to the suspension in respective amounts such that the quantity of clay and water insoluble salt is between 10 and 40% by weight of the filled paper and the water insoluble salt is from 0.3 to 15% by weight of the clay.
9. A method for preparing an internally filled paper suitable for forming pressure-sensitive copying paper, said method comprising adding to an aqueous suspension of cellulosic fiber, clay of electron acceptor capable of developing color by adsorbing colorless electron donor, a substance selected from the group consisting of water soluble salts of cobalt, manganese, lead and mixtures thereof, and a compound which reacts with said salt substance to convert the same in sit-u to water insoluble salt, and thereafter forming from the fiber suspension a paper, said clay, Water soluble salt and compound being added to the suspension in respective amounts such that the quantity of clay and water insoluble salt is between 10 and 40% by weight of the filled paper and the water 5 insoluble salt is from 0.3 to 15% by weight of the clay.
10. A method as claimed in claim 9 wherein the water soluble salt is cobaltous chloride and the insoluble saltproducing compound is sodium silicate whereby water insoluble cobaltous silicate is formed, the latter being present in an amount between 0.3 and 2% by weight of the clay.
11. A method as claimed in claim 9 wherein the water soluble salt is manganous chloride and the insoluble saltproducing compound is sodium pyrophosphate whereby insoluble manganous pyrophosphate is formed, the latter being present in an amount between 0.5 to 4.5%.
12. A method as claimed in claim 9 wherein the water soluble salt is lead acetate and the insoluble salt-producing compound is borax whereby water insoluble lead borate is formed, the latter being present in an amount between 2 to 15%.
References Cited UNITED STATES PATENTS 2,654,673 1 0/1953 Steinhardt 1l63 6.2 X 2,663,653 12/1953 Zimmerman ll7--3 6.2 2,902,399 9/1959 Paquin ll7-36.2 X 3,049,468 8/1962 Hinton et a1 l62181 S. LEON BASHORE, Primary Examiner.
Claims (1)
1. AN INTERNALLY FILLED PAPER FOR USE IN FORMING PRESSURE-SENSITIVE COPYING PAPER, SAID INTERNALLY FILLED PAPER COMPRISING CELLULOSIC FIBERS, A CLAY, AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF WATER INSOLUBLE SALTS OF COBALT, MANGANESE, LEAD AND MIXTURES THEREOF, THE CLAY AND INSOLUBLE SALT BEING PRESENT IN AN AMOUNT OF 10-40% BY WEIGHT OF THE FILLED PAPER, THE SALT BEING FROM 0.3 TO 15% BY WEIGHT OF THE TOTAL OF THE CLAY AND SALT, SAID CLAY BEING AN ELECTRON ACCEPTOR CLAY CAPABLE OF DEVELOPING COLOR BY ABSORBING COLORLESS ELECTRON DONOR SELECTED FROM TRIPHENYLMETHANE PHTHALIDE COMPOUNDS AND ACYL LEUCO METHYLENE BLUE COMPOUNDS.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5765363 | 1963-10-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3330722A true US3330722A (en) | 1967-07-11 |
Family
ID=13061848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US39232964 Expired - Lifetime US3330722A (en) | 1963-10-31 | 1964-08-26 | Method for preparing pressure-sensitive filler-containing copying paper and paper thereof |
Country Status (5)
Country | Link |
---|---|
US (1) | US3330722A (en) |
BE (1) | BE653728A (en) |
DE (1) | DE1471717B2 (en) |
GB (1) | GB1082293A (en) |
NL (1) | NL6410989A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3753761A (en) * | 1968-11-12 | 1973-08-21 | Mizusawa Industrial Chem | Pressure sensitive recording paper |
US3864146A (en) * | 1971-06-16 | 1975-02-04 | Kanzaki Paper Mfg Co Ltd | Sensitized record sheet material |
US3933578A (en) * | 1973-05-30 | 1976-01-20 | Fuji Photo Film Co., Ltd. | Method of recovering pressure sensitive copying paper waste paper |
US3963852A (en) * | 1973-08-04 | 1976-06-15 | Moore Business Forms, Inc. | Clay-coated record material of improved image durability |
DE2731418A1 (en) * | 1977-07-12 | 1979-01-18 | Feldmuehle Ag | COLOR-REACTIVE RECORDING MATERIAL AND METHOD OF ITS MANUFACTURING |
US4435004A (en) | 1980-06-13 | 1984-03-06 | The Wiggins Teape Group Limited | Record material carrying a color developer composition |
US4458922A (en) * | 1980-06-12 | 1984-07-10 | The Wiggins Teape Group Limited | Record material carrying a color developer composition |
US4462616A (en) * | 1981-12-04 | 1984-07-31 | The Wiggins Teape Group Limited | Record material |
US4509065A (en) * | 1981-12-04 | 1985-04-02 | The Wiggins Teape Group Limited | Record material |
US5209947A (en) * | 1989-12-16 | 1993-05-11 | The Wiggins Teape Group Limited | Process for the production of record material |
US5304242A (en) * | 1991-05-16 | 1994-04-19 | The Wiggins Teape Group Limited | Color developer composition |
US5880063A (en) * | 1995-05-22 | 1999-03-09 | Wallace Computer Services, Inc. | Method of improving coverage of chromogenic reaction product |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE794617A (en) * | 1972-01-28 | 1973-05-16 | Mizusawa Industrial Chem | AQUEOUS COMPOSITION CONTAINING A COLOR FORMER FOR PRESSURE RECORDING PAPER, AND PROCESS FOR ITS MANUFACTURING |
DE2450720C3 (en) * | 1974-10-25 | 1982-01-28 | Pelikan Ag, 3000 Hannover | Correction agents for color reaction papers |
DE2601864C3 (en) * | 1976-01-20 | 1981-11-12 | Feldmühle AG, 4000 Düsseldorf | Recording paper |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2654673A (en) * | 1951-10-20 | 1953-10-06 | Ncr Co | Colorless printing fluid |
US2663653A (en) * | 1948-03-17 | 1953-12-22 | Standard Register Co | Manifold sheet and process of making same |
US2902399A (en) * | 1950-11-06 | 1959-09-01 | Ncr Co | Filled paper |
US3049468A (en) * | 1957-12-23 | 1962-08-14 | Ici Ltd | Manufacture of coloured paper |
-
1964
- 1964-08-12 GB GB3292564A patent/GB1082293A/en not_active Expired
- 1964-08-26 US US39232964 patent/US3330722A/en not_active Expired - Lifetime
- 1964-09-21 NL NL6410989A patent/NL6410989A/xx unknown
- 1964-09-29 BE BE653728D patent/BE653728A/xx unknown
- 1964-10-16 DE DE19641471717 patent/DE1471717B2/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2663653A (en) * | 1948-03-17 | 1953-12-22 | Standard Register Co | Manifold sheet and process of making same |
US2902399A (en) * | 1950-11-06 | 1959-09-01 | Ncr Co | Filled paper |
US2654673A (en) * | 1951-10-20 | 1953-10-06 | Ncr Co | Colorless printing fluid |
US3049468A (en) * | 1957-12-23 | 1962-08-14 | Ici Ltd | Manufacture of coloured paper |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3753761A (en) * | 1968-11-12 | 1973-08-21 | Mizusawa Industrial Chem | Pressure sensitive recording paper |
US3864146A (en) * | 1971-06-16 | 1975-02-04 | Kanzaki Paper Mfg Co Ltd | Sensitized record sheet material |
US3933578A (en) * | 1973-05-30 | 1976-01-20 | Fuji Photo Film Co., Ltd. | Method of recovering pressure sensitive copying paper waste paper |
US3963852A (en) * | 1973-08-04 | 1976-06-15 | Moore Business Forms, Inc. | Clay-coated record material of improved image durability |
DE2731418A1 (en) * | 1977-07-12 | 1979-01-18 | Feldmuehle Ag | COLOR-REACTIVE RECORDING MATERIAL AND METHOD OF ITS MANUFACTURING |
US4458922A (en) * | 1980-06-12 | 1984-07-10 | The Wiggins Teape Group Limited | Record material carrying a color developer composition |
US4435004A (en) | 1980-06-13 | 1984-03-06 | The Wiggins Teape Group Limited | Record material carrying a color developer composition |
US4462616A (en) * | 1981-12-04 | 1984-07-31 | The Wiggins Teape Group Limited | Record material |
US4509065A (en) * | 1981-12-04 | 1985-04-02 | The Wiggins Teape Group Limited | Record material |
US5209947A (en) * | 1989-12-16 | 1993-05-11 | The Wiggins Teape Group Limited | Process for the production of record material |
US5304242A (en) * | 1991-05-16 | 1994-04-19 | The Wiggins Teape Group Limited | Color developer composition |
US5880063A (en) * | 1995-05-22 | 1999-03-09 | Wallace Computer Services, Inc. | Method of improving coverage of chromogenic reaction product |
Also Published As
Publication number | Publication date |
---|---|
DE1471717B2 (en) | 1971-07-15 |
GB1082293A (en) | 1967-09-06 |
BE653728A (en) | 1965-01-18 |
NL6410989A (en) | 1965-05-03 |
DE1471717A1 (en) | 1968-12-19 |
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