US2505481A - Process of making pressure sensitive record material - Google Patents
Process of making pressure sensitive record material Download PDFInfo
- Publication number
- US2505481A US2505481A US63211A US6321148A US2505481A US 2505481 A US2505481 A US 2505481A US 63211 A US63211 A US 63211A US 6321148 A US6321148 A US 6321148A US 2505481 A US2505481 A US 2505481A
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- United States
- Prior art keywords
- reactants
- color
- forming
- record material
- pressure
- Prior art date
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- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 24
- 239000000376 reactant Substances 0.000 claims description 73
- 239000007787 solid Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 150000002484 inorganic compounds Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 44
- 239000005995 Aluminium silicate Substances 0.000 description 17
- 235000012211 aluminium silicate Nutrition 0.000 description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229920000609 methyl cellulose Polymers 0.000 description 10
- 239000001923 methylcellulose Substances 0.000 description 10
- 235000010981 methylcellulose Nutrition 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- -1 malachite green lactone Chemical class 0.000 description 9
- 229940107698 malachite green Drugs 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000005018 casein Substances 0.000 description 7
- 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 7
- 235000021240 caseins Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QUINKWASVQHVID-UHFFFAOYSA-N 3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=CC=C2C(=O)O1 QUINKWASVQHVID-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- 229940126639 Compound 33 Drugs 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- IXWIAFSBWGYQOE-UHFFFAOYSA-M aluminum;magnesium;oxygen(2-);silicon(4+);hydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] IXWIAFSBWGYQOE-UHFFFAOYSA-M 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 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
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910000386 magnesium trisilicate Inorganic materials 0.000 description 1
- 229940099273 magnesium trisilicate Drugs 0.000 description 1
- 235000019793 magnesium trisilicate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
Definitions
- This invention relates to improvements in process making a pressure-sensitive record material.
- This application is a division of the pending application of Barrett K. Green, Serial No. 784,939, filed November 8, 1947, for Process of making pressure-sensitive record material.
- the principal object of this invention is to provide a process of making a pressure-sensitive record material, on which a mark of distinctive color may be produced. by the mere application of localized pressure, and which is not subject to the disadvantages inherent in the pressuresensitive record material disclosed in United States Letters Patent No. 2,299,693, patented October 20, 1942, on the application filed by Barrett Green on February 23, 1940.
- the two reagents disclosed in this patent are gallic acid and rric ammonium sulphate, each dissolved in glycerine.
- reagents are ionized by the glycerine, which constitutes an ionizing medium, and the chemical reaction proceeds by interchange of ions when the two solutions are allowed. to mix, upon the rupture of the insulating medium.
- the reaction disclosed in that patent depends upon the presence of the reagents in an ionizing medium.
- any available ionizing medium is hygroscopic, with the result that the record material, made in accordance with this patent, is sensitive to an excess of moisture, and conditions of high humidity may cause the insulating medium to cease to be effective, with the result that the chemical reaction takes place without any application of localized pressure, and the record material is stained and discolored, so that it ceases to be useful.
- the principal object of the present invention is to provide a process of making a pressure-sensitive record material that is not subject to the defects and disadvantages of that disclosed in Patent No. 2,299,693, as indicated above.
- Another object of the present invention is to provide a process of making a record material upon which a mark of distinctive color may be produced, at the points of application of localized pressure thereto, by such mere application of localized pressure, and which will not become discolored or stained due to the effect of light, atmospheric conditions, or aging.
- Another object of this invention is to provide a process of making a pressure-sensitive record material in which the mark of distinctive color is produced by the chemical reaction of colorforming reactants, in the absence of any liquid ionizing medium therefor.
- a further object of this invention is to provide a process of making a pressure-sensitive record material in which a mark of distinctive color is produced by a reaction between solid particles of color-forming reactants.
- the present invention contemplates a process of making a pressure-sensitive record material including the forming on a supporting member a film-like deposit of solid particles of a plurality of adsorption color-forming reactants disposed in contiguity with each other, such reactants being so selected that they react, in the absence of a liquid ionizing medium for the reactants, to form a distinctive color when brought into contact with each other, and a solid insulating medium insulating said reactants from colorforming reaction contact with each other.
- the insulating medium Upon application of localized pressure to the record material, as by drawing a stylus across it, the insulating medium is ruptured at the points of application of said localized pressure, and such rupture permits color-forming reaction contact between the reactants at such points, in the absence of any liquid ionizing medium for said reactants.
- the result is that a mark of distinctive color is produced by the mere application of localized pressure.
- the color reaction employed is of the, so-called, adsorption type wherein an inorganic compound causes a color change in an organic compound coming into adsorption contact therewith.
- the organic material is an electron donor aromatic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron acceptor-donor solid surface chemical reaction, giving ita distinctive color
- the inorganic material is a material which is an acid relative to the organic material so as to be an electron acceptor when in adsorption contact therewith. Both materials are in fine particle form in order to furnish a large reactant surface area per unit area of the record material which enhances the depth of color per unit area of the record material.
- solid particles of a plurality of color-forming reactants are interspersed in a solid insulating medium, which insulates the particles from colorforming reaction contact with each other.
- the rupture of this solid insulating medium by the application of localized pressure permits the solid particles of color-forming reactants to react with each other, at the points of application of such pressure, to produce the mark of distinctive color.
- solid particles. of one of thecolor-forming reactants are carried by and dispersed in a solid insulating-medium, to which a coating of solid particles of another color-forming reactant is applied.
- this pressure-sensitive recordmaterial includes a base web, such as a fibrous web. of paper or the like, to which the coatingof fsolid insulating medium and the colorforming reactants is applied.
- the insulating medium is a pressure-rupturable filrnderiveol from an organic film-forming hydrophilic colloid substance.
- One embodiment of this invention produces a material comprising a base web of paper or the likiebhavin g applied thereto a coating including casein ,or methyl cellulose as the solid insulating medium and solid particles of two color-forming rea ctantsj namely, kaolin and the compound 3,3; bis(p-dimethylaminophenyl) phthalide, also knownas'Pmalachite green lactone, having the structure
- This record material is normally white or light in color, and, upon application of localized pressure'th er eto, as by drawing a stylus thereover, a mark of dark'blue-green color is produced at the points of application of such pressure.
- the solid insulating medium in this record material serves to insulate the solid particles of kaolin and malachite green lactone from color-forming reaction contact with each other, and this insulating medium is ruptured, at the points of application of localized pressure, to permit such colorformin reaction contact, resulting in the mark of distinctive color.
- This pressure-sensitive record material is not affected substantially by atmospheric moisture and remains stable over long periods of time.
- the solid insulating medium may be casein or methyl cellulose, but other organic film-forming hydrophilic colloid materials such as gelatin, starch, polyvinyl alcohol or animal glue may be used instead.
- Attapulgite (Attapulgus clay), pyrophyllite, talc, bentonite, halloysite, calcium sulphate, magnesium trisilicate, zinc sulphide, and calcium fluoride are inorganic materials, any one of which may be substituted for the kaolin as one of the color-forming reactants. When any of these materials are substituted for the kaolin, the resulting record material will be white or light in color, and a dark blue-green mark will appear thereon as the re sult of the application'of localized pressure.
- a slurry of kaolin and water was prepared including fifty parts by weight of kaolin to fifty parts by weight of water, and a minor proportion, such as 0.3% by weight, of a suitable dispersing agent, such as sodium metaphosphate, was added to facilitate the dispersion of the particles of kaolin through the slurry and to reduce its viscosity.
- a 20% by weight solution of casein in water was formed by, first, disper ing the casein in cold water by stirring for fifteen minutes at room temperature, and, then heating up to 60 degrees centigrade.
- the pressure-sensitive record material described above having methyl cellulose as the solid insulating medium and kaolin and malachite green lactone as the color-forming reactants, was successfully made by the following method: A solution was prepared by dissolving about 5 parts by weight of methyl cellulose in about 50 parts by weight of Water, which solution was divided into two equal parts" To one portion of this methyl cellulose solution, the slurry of kaolin and water prepared as described above was added, in the ratio by weight of kaolin to methyl cellulose of 40 to 1, and thoroughly *7 mixed. The other portion of themethyl-cellulose solution was rendered alkaline by, the addi.
- such coating should weigh about .0023 pound per square foot or" surface and should have a thickness of the order of from .0005 to .001 inch.
- the thickness of the coating varies, of course, with the treatment to which to record material is subjected in finishing.
- the solid particles of kaolin in this record material may be of about the order of ten microns in diameter, although considerable variation in particle size is possible without any ill effects.
- Particle size of the malachite green lactone is largely determined by the method of application of that ingredient.
- the particles of the reactant may be as large as ten microns in diameter and frequently are much smaller.
- a pressure-sensitive record material including the forming on a supporting member a film-like deposit of solid particles of a plurality of adsorption color-forming reactants disposed in contiguity with each other and a solid insulating medium, derived from an organic film-forming hydrophilic colloid substance, insulating said reactant particles from color-forming reaction with each other, at least one of said reactants being an inorganic compound and at least another of said reactants being an organic compound adsorbable therewith, said reactants being so selected as to react, in the absence of a liquid ionizing medium for the reactants, to form a distinctive color when brought into contact with each other, one of said colorforming reactants being the compound 3,3 bis(pdimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the organic reactant so as to be an electron acceptor when in adsorption contact with said organic
- the process of making a pressure-sensitive record material including the steps of coating a supporting member with a film of solid insulating material, derived from an organic film-forming hydrophilic colloid substance, having particles of a first color-forming solid reactant dispersed therein, and depositing on said film particles of a second color-forming solid reactant, one of said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with it and said reactants being so selected as to form a distinctive color when brought into contact with each other, and said solid insulating material being such as to insulate the reactants from color-forming reaction contact with each other, the second color-forming reactant being the compound 3,3 bis(p-dimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the second reactant so as to be an electron acceptor when in adsorption contact with said second reactant.
- the process of making a pressure-sensitive record material including the step of forming on a supporting member a film of a solid insulating medium, derived from a film-forming hydrophilic colloid substance, having interspersed therein solid particles of a plurality of color forming reactants, disposed in contiguity but insulated from color-forming reaction contact by such medium, at least one of the reactants being an inorganic compound and at least another of the reactants being an organic compound adsorbable with it, said reactants being so selected as to react in the absence of an ionizing medium to form a distinctive color when brought into contact with each other, one of the color-forming reactants being the compound 3,3 bis (p-dimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the organic reactant so as to be an electron acceptor when in adsorption contact with said organic reactant.
- the process of making a pressure-sensitive iatoeg iei record material including the steps of forming a dispersion of solid particles of a first-color-forming reactant in a solution of a solid insulating medium derived from an organic film-forming hydrophilic colloid substance, forming a dispel sion of solid particles of a secondcolor-forming reactant in a solution of said insulating medium, mixing said dispersions, coating a base web with the mixture of said dispersions, and evaporating the solvent therefrom, leaving on the base web Ia coating of solid-insulating mediumhaving said solidreactant-particles interspersed therein, one of said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with'it and said reactants being so selecte'd as to' react in the absence of an ionizing medium-to form a distinctive color when brought into adsorption contact with each other, the second color-forming reactant being the compound 33 bis (p-di
- the processof making a pressure-sensitive record material including the steps of forming a dispersion of solid particles of a first color-form ing reactant in a solution of a solid insulating medium derived from an organic film-forming hydrophilic' colloid substance, forming a dispersion of solid particles of a secondcolOr-forming 8 reactantin a solution of saidlinsulating medium; mixing said dispersions, coating a base web with the mixture of said dispersions and evaporating the solvent therefrom, leaving on the base web a coating of solid insulating medium having said solid reactant particles interspersed therein, one of' said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with it and said reactants being so selected as to react in the absence of an ionizing medium to form a distinctive color when brought into adsorption contact with each other, the dispersion of the solid particles of the second color-forming reactant being formed by precipitation thereof by the neutralization of an acidified solution of said reactant
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Description
patented Apr. 25, 1959 PROCESS OF MAKING PRESSURE SENSITIVE RECORD MATERIAL Barrett K. Green, Dayton, Ohio, assignor to The National Cash Register Company,
Dayton,
Ohio, a corporation of Maryland No Drawing. Original application November 8,
1947, Serial No. 784,939. Divided and this application December 2, 1948, Serial No. 63,211
11 Claims.
This invention relates to improvements in process making a pressure-sensitive record material. This application is a division of the pending application of Barrett K. Green, Serial No. 784,939, filed November 8, 1947, for Process of making pressure-sensitive record material.
The principal object of this invention is to provide a process of making a pressure-sensitive record material, on which a mark of distinctive color may be produced. by the mere application of localized pressure, and which is not subject to the disadvantages inherent in the pressuresensitive record material disclosed in United States Letters Patent No. 2,299,693, patented October 20, 1942, on the application filed by Barrett Green on February 23, 1940. That patent discloses a pressure-sensitive record material including the combination of an insulating medium, a rupturable solid material such as gum dammar, having included therein interspersed droplets of a plurality of liquid reagents, which are chemically reactive to produce a distinctive color in the record material :at the points of application of localized pressure thereto, such pressure rup=- turing the insulating medium to permit chemical reaction between the two liquid reagents. The two reagents disclosed in this patent are gallic acid and rric ammonium sulphate, each dissolved in glycerine. These reagents are ionized by the glycerine, which constitutes an ionizing medium, and the chemical reaction proceeds by interchange of ions when the two solutions are allowed. to mix, upon the rupture of the insulating medium. The reaction disclosed in that patent depends upon the presence of the reagents in an ionizing medium. However, any available ionizing medium is hygroscopic, with the result that the record material, made in accordance with this patent, is sensitive to an excess of moisture, and conditions of high humidity may cause the insulating medium to cease to be effective, with the result that the chemical reaction takes place without any application of localized pressure, and the record material is stained and discolored, so that it ceases to be useful.
As stated above, the principal object of the present invention is to provide a process of making a pressure-sensitive record material that is not subject to the defects and disadvantages of that disclosed in Patent No. 2,299,693, as indicated above.
Another object of the present invention is to provide a process of making a record material upon which a mark of distinctive color may be produced, at the points of application of localized pressure thereto, by such mere application of localized pressure, and which will not become discolored or stained due to the effect of light, atmospheric conditions, or aging.
In short, it is the object of this invention to provide a process of making a pressure-sensitive record material in which the mark of distinctive color will be produced only at the points of application of localized pressure, and at no other points, and under no other conditions.
Another object of this invention is to provide a process of making a pressure-sensitive record material in which the mark of distinctive color is produced by the chemical reaction of colorforming reactants, in the absence of any liquid ionizing medium therefor.
A further object of this invention is to provide a process of making a pressure-sensitive record material in which a mark of distinctive color is produced by a reaction between solid particles of color-forming reactants.
Further objects, and objects relating to details and economies of operation, will definitely appear from the detailed description to follow. The objects of this invention have been attained by the several embodiments thereof described in detail in the following specification. This invention is clearly defined and pointed out in the appended claims.
In general, the present invention contemplates a process of making a pressure-sensitive record material including the forming on a supporting member a film-like deposit of solid particles of a plurality of adsorption color-forming reactants disposed in contiguity with each other, such reactants being so selected that they react, in the absence of a liquid ionizing medium for the reactants, to form a distinctive color when brought into contact with each other, and a solid insulating medium insulating said reactants from colorforming reaction contact with each other. Upon application of localized pressure to the record material, as by drawing a stylus across it, the insulating medium is ruptured at the points of application of said localized pressure, and such rupture permits color-forming reaction contact between the reactants at such points, in the absence of any liquid ionizing medium for said reactants. The result is that a mark of distinctive color is produced by the mere application of localized pressure.
The color reaction employed is of the, so-called, adsorption type wherein an inorganic compound causes a color change in an organic compound coming into adsorption contact therewith.
Of the reactant materials employed the organic material is an electron donor aromatic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron acceptor-donor solid surface chemical reaction, giving ita distinctive color, and the inorganic material is a material which is an acid relative to the organic material so as to be an electron acceptor when in adsorption contact therewith. Both materials are in fine particle form in order to furnish a large reactant surface area per unit area of the record material which enhances the depth of color per unit area of the record material.
According to one embodiment of the invention, solid particles of a plurality of color-forming reactants are interspersed in a solid insulating medium, which insulates the particles from colorforming reaction contact with each other. The rupture of this solid insulating medium by the application of localized pressure permits the solid particles of color-forming reactants to react with each other, at the points of application of such pressure, to produce the mark of distinctive color. meaning to another form of this invention, solid particles. of one of thecolor-forming reactants are carried by and dispersed in a solid insulating-medium, to which a coating of solid particles of another color-forming reactant is applied. In this casefthe application of localized pressure ruptulresjthe solid insulating medium, at the pointsof application of such pressure, and brings about color-forming reaction contact between thei solid particles of color-forming reactants at suchpoints, thus producingthe mark of distinctive -co1or. Preferably, this pressure-sensitive recordmaterial includes a base web, such as a fibrous web. of paper or the like, to which the coatingof fsolid insulating medium and the colorforming reactants is applied.
The insulating medium is a pressure-rupturable filrnderiveol from an organic film-forming hydrophilic colloid substance.
Since it is difficult to show precisely the spatial relationship between the solid particles of colorfor fning reactants, the solid insulating medium, an d the base web, it is preferred not to attempt to illustrate any embodiment of this invention by drawings.
Inithe following examples, there will be describedembodiments of this invention, by means offwhich-the objects of the invention have been successfully attained.
' One embodiment of this invention produces a material comprising a base web of paper or the likiebhavin g applied thereto a coating including casein ,or methyl cellulose as the solid insulating medium and solid particles of two color-forming rea ctantsj namely, kaolin and the compound 3,3; bis(p-dimethylaminophenyl) phthalide, also knownas'Pmalachite green lactone, having the structure This record material is normally white or light in color, and, upon application of localized pressure'th er eto, as by drawing a stylus thereover, a mark of dark'blue-green color is produced at the points of application of such pressure. The solid insulating medium in this record material serves to insulate the solid particles of kaolin and malachite green lactone from color-forming reaction contact with each other, and this insulating medium is ruptured, at the points of application of localized pressure, to permit such colorformin reaction contact, resulting in the mark of distinctive color. This pressure-sensitive record material is not affected substantially by atmospheric moisture and remains stable over long periods of time. According to this embodiment of the invention, the solid insulating medium may be casein or methyl cellulose, but other organic film-forming hydrophilic colloid materials such as gelatin, starch, polyvinyl alcohol or animal glue may be used instead. Attapulgite (Attapulgus clay), pyrophyllite, talc, bentonite, halloysite, calcium sulphate, magnesium trisilicate, zinc sulphide, and calcium fluoride are inorganic materials, any one of which may be substituted for the kaolin as one of the color-forming reactants. When any of these materials are substituted for the kaolin, the resulting record material will be white or light in color, and a dark blue-green mark will appear thereon as the re sult of the application'of localized pressure.
Another embodiment of the invention for making the record material described above consists of the following method: A slurry of kaolin and water was prepared including fifty parts by weight of kaolin to fifty parts by weight of water, and a minor proportion, such as 0.3% by weight, of a suitable dispersing agent, such as sodium metaphosphate, was added to facilitate the dispersion of the particles of kaolin through the slurry and to reduce its viscosity. A 20% by weight solution of casein in water was formed by, first, disper ing the casein in cold water by stirring for fifteen minutes at room temperature, and, then heating up to 60 degrees centigrade. Five parts of a 28% ammonium hydroxide solution were then added to the hot casein solution, which was stirred for about fifteen minutes and allowed to cool to room temperature. The kaolin slurry and the alkaline caseinsolution were then thoroughly mixed in the ratio by Weight of kaolin to casein of 10 to 1, and blended, and it was found desirable to add a small percentage of tributyl phosphate in alcohol, or other antifoaming agent, at this stage. This mixture of the kaolin slurry and the casein solution was then applied as a coating to the paper, dried thereon, and then cal ndered or treated in any desired way to give the proper surface finish. A solution in toluene of about 3% by weight of malachite green lactone was then applied to the coated side of the paper. The excess of this solution was removed and the treated paper dried to evaporate the'toluene, after which it was ready for use.
According to another embodiment of the invention, the pressure-sensitive record material described above, having methyl cellulose as the solid insulating medium and kaolin and malachite green lactone as the color-forming reactants, was successfully made by the following method: A solution was prepared by dissolving about 5 parts by weight of methyl cellulose in about 50 parts by weight of Water, which solution was divided into two equal parts" To one portion of this methyl cellulose solution, the slurry of kaolin and water prepared as described above was added, in the ratio by weight of kaolin to methyl cellulose of 40 to 1, and thoroughly *7 mixed. The other portion of themethyl-cellulose solution was rendered alkaline by, the addi. tion of ammonium hydroxide solution, to an eX- tent sufficient to precipitate the malachite green lactone from the acid solution thereof mixed with this portion. 6 grams of malachite green lactone were dissolved in 50 cc. of 3.7% hydrochloric acid solution, and this acid solution was mixed with the ammoniacal portion of the methyl cellulose solution, in such proportions that the ratio by weight of kaolin to malachite green lactone in the coating will be about 100 to 3, the mixture being neutral or slightly alkaline, so that the malachite green lactone is precipitated therein. The two portions of the methyl cellulose solution were then thoroughly mixed and applied as a coating to the paper, which coating was dried in the usual manner.
When these ingredients, in either embodiment, are applied to the paper as a coating thereon, such coating should weigh about .0023 pound per square foot or" surface and should have a thickness of the order of from .0005 to .001 inch. The thickness of the coating varies, of course, with the treatment to which to record material is subjected in finishing. The solid particles of kaolin in this record material may be of about the order of ten microns in diameter, although considerable variation in particle size is possible without any ill effects. Particle size of the malachite green lactone is largely determined by the method of application of that ingredient. The particles of the reactant may be as large as ten microns in diameter and frequently are much smaller.
The pressure-sensitive record materials disclosed herein are not claimed in this application but are disclosed and claimed in the pending application of Barrett K. Green, Serial No. 784,938, filed November 8, 1947, for Pressuresensitive record material, and in a division thereof, Serial No. 59,422 filed November 10, 1948.
It is understood that the process of making a pressure-sensitive record material described herein is susceptible of considerable variation without departing from the spirit of the invention.
What is claimed is:
l. The process of making a pressure-sensitive record material including the forming on a supporting member a film-like deposit of solid particles of a plurality of adsorption color-forming reactants disposed in contiguity with each other and a solid insulating medium, derived from an organic film-forming hydrophilic colloid substance, insulating said reactant particles from color-forming reaction with each other, at least one of said reactants being an inorganic compound and at least another of said reactants being an organic compound adsorbable therewith, said reactants being so selected as to react, in the absence of a liquid ionizing medium for the reactants, to form a distinctive color when brought into contact with each other, one of said colorforming reactants being the compound 3,3 bis(pdimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the organic reactant so as to be an electron acceptor when in adsorption contact with said organic reactant.
2. The process of making a pressure-sensitive record material including the steps of coating a supporting member with a film of solid insulating material, derived from an organic film-forming hydrophilic colloid substance, having particles of a first color-forming solid reactant dispersed therein, and depositing on said film particles of a second color-forming solid reactant, one of said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with it and said reactants being so selected as to form a distinctive color when brought into contact with each other, and said solid insulating material being such as to insulate the reactants from color-forming reaction contact with each other, the second color-forming reactant being the compound 3,3 bis(p-dimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the second reactant so as to be an electron acceptor when in adsorption contact with said second reactant.
3. The process of making a pressure-sensitive record material including the step of forming on a supporting member a film of a solid insulating medium, derived from a film-forming hydrophilic colloid substance, having interspersed therein solid particles of a plurality of color forming reactants, disposed in contiguity but insulated from color-forming reaction contact by such medium, at least one of the reactants being an inorganic compound and at least another of the reactants being an organic compound adsorbable with it, said reactants being so selected as to react in the absence of an ionizing medium to form a distinctive color when brought into contact with each other, one of the color-forming reactants being the compound 3,3 bis (p-dimethylaminophenyl) phthalide, having the structure and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the organic reactant so as to be an electron acceptor when in adsorption contact with said organic reactant.
4. The process of claim 3 in which the inorganic color-forming reactants is kaolin.
5. The process of claim 4 in which the solid insulating medium is methyl cellulose.
6. The process of making a pressure-sensitive iatoeg iei record material including the steps of forming a dispersion of solid particles of a first-color-forming reactant in a solution of a solid insulating medium derived from an organic film-forming hydrophilic colloid substance, forming a dispel sion of solid particles of a secondcolor-forming reactant in a solution of said insulating medium, mixing said dispersions, coating a base web with the mixture of said dispersions, and evaporating the solvent therefrom, leaving on the base web Ia coating of solid-insulating mediumhaving said solidreactant-particles interspersed therein, one of said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with'it and said reactants being so selecte'd as to' react in the absence of an ionizing medium-to form a distinctive color when brought into adsorption contact with each other, the second color-forming reactant being the compound 33 bis (p-dimethylaminophenyl)' phthalide, having the structure 113) :N' N 0 H) 2 and the inorganic reactant being in fine particle form providing a large adsorbent surface area and which is an acid relative to the organic reactant so as'to be ail-electron acceptor when in adsorption contact with saidorganic reactant.
'7. The process of claim 6 in which the inorganic color-forming reactant is kaolin.
8. The process'of claim 7 in which the" solid insulating medium is methyl cellulose.
9. The processof making a pressure-sensitive record material including the steps of forming a dispersion of solid particles of a first color-form ing reactant in a solution of a solid insulating medium derived from an organic film-forming hydrophilic' colloid substance, forming a dispersion of solid particles of a secondcolOr-forming 8 reactantin a solution of saidlinsulating medium; mixing said dispersions, coating a base web with the mixture of said dispersions and evaporating the solvent therefrom, leaving on the base web a coating of solid insulating medium having said solid reactant particles interspersed therein, one of' said reactants being an inorganic compound and the other of said reactants being an organic compound adsorbable with it and said reactants being so selected as to react in the absence of an ionizing medium to form a distinctive color when brought into adsorption contact with each other, the dispersion of the solid particles of the second color-forming reactant being formed by precipitation thereof by the neutralization of an acidified solution of said reactant in the insulating medium, said particles being made of the compound 3,3 bis(p-dimethylaminophenyl) 6-di methylamino phthalide, having the structure REFERENCES CITED The followingreferences are of record in the file of this patent:
FOREIGN PATENTS Country Date Great Britain Jan. 4, 1943 Number
Claims (1)
1. THE PROCESS OF MAKING A PRESSURE-SENSITIVE RECORD MATERIAL INCLUDING THE FORMING ON A SUPPORTING MEMBER A FILM-LIKE DEPOSIT OF SOLID PARTICLES OF A PLURALITY OF ADSORPTION COLOR-FORMING REACTANTS DISPOSED IN CONTIGUITY WITH EACH OTHER AND A SOLID INSULATING MEDIUM, DERIVED FROM AN ORGANIC FILM-FORMING HYDROPHILIC COLLOID SUBSTANCE, INSULATING SAID REACTANT PARTICLES FROM COLOR-FORMING REACTION WITH EACH OTHER, AT LEAST ONE OF SAID REACTANTS BEING AN INORGANIC COMPOUND AND AT LEAST ANOTHER OF SAID REACTANTS BEING AN ORGANIC COMPOUND ADSORBABLE THEREWITH, SAID REACTANTS BEING SO SELECTED AS TO REACT, IN THE ABSENCE OF A LIQUID IONIZING MEDIUM FOR THE REACTANTS, TO FORM A DISTINCTIVE COLOR WHEN BROUGHT INTO CONTACT WITH EACH OTHER, ONE OF SAID COLORFORMING REACTANTS BEING THE COMPOUND 3,3 BIS(PDIMETHYLAMINOPHENYL) PHTHALIDE, HAVING THE STRUCTURE
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63211A US2505481A (en) | 1944-01-31 | 1948-12-02 | Process of making pressure sensitive record material |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52057344A | 1944-01-31 | 1944-01-31 | |
| US58183445A | 1945-03-09 | 1945-03-09 | |
| US60176145A | 1945-06-27 | 1945-06-27 | |
| US784939A US2505471A (en) | 1944-01-31 | 1947-11-08 | Process of making pressure sensitive record material |
| US63211A US2505481A (en) | 1944-01-31 | 1948-12-02 | Process of making pressure sensitive record material |
| US714657XA | 1951-08-31 | 1951-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2505481A true US2505481A (en) | 1950-04-25 |
Family
ID=31721908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US63211A Expired - Lifetime US2505481A (en) | 1944-01-31 | 1948-12-02 | Process of making pressure sensitive record material |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2505481A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618573A (en) * | 1944-01-31 | 1952-11-18 | Ncr Co | Process of making pressure sensitive record material |
| US2695245A (en) * | 1950-01-18 | 1954-11-23 | Ncr Co | Process of recording by decoloring |
| US2730457A (en) * | 1953-06-30 | 1956-01-10 | Ncr Co | Pressure responsive record materials |
| US4348234A (en) * | 1979-03-20 | 1982-09-07 | Ciba-Geigy Corporation | Coating compositions for the production of a recording material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB550332A (en) * | 1941-06-30 | 1943-01-04 | Josef Groak | Improvements in or relating to transfer copying materials |
-
1948
- 1948-12-02 US US63211A patent/US2505481A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB550332A (en) * | 1941-06-30 | 1943-01-04 | Josef Groak | Improvements in or relating to transfer copying materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618573A (en) * | 1944-01-31 | 1952-11-18 | Ncr Co | Process of making pressure sensitive record material |
| US2695245A (en) * | 1950-01-18 | 1954-11-23 | Ncr Co | Process of recording by decoloring |
| US2730457A (en) * | 1953-06-30 | 1956-01-10 | Ncr Co | Pressure responsive record materials |
| US4348234A (en) * | 1979-03-20 | 1982-09-07 | Ciba-Geigy Corporation | Coating compositions for the production of a recording material |
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