Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/025—Applications of microcapsules not provided for in other subclasses
• • 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
  • B41M5/1246—Application of the layer, e.g. by printing
• • 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

Definitions

• This invention relates to improvements in process of making a pressure-sensitive record material. This application is a continuation in part of the pending applications of Barrett K.
• the principalobject of this invention is to ing: a-pressure-sensitive record material thatIis not subject to thesdefects anddisadvantages of that disclosed in Patent ,No.. 2,299,693, as indicated above.
• Another object of the present invention is to for Record material and coating for same, now provide vaprocess of making a record material abandoned; Serial No. 581,834, filed March 9, uponwhicha mark ,of,distinctive color may be 1945, for Coating for record material, now abanproduced, atthe points of application of localized 'doned; and SerialNo. 601,761,'filed June 2'7, 1945, pressure thereto, by such,,mere application of for Method of making pressure-sensitive marking localized pressure, and whichrwillnot become discolored ;orstained due ,tothe effect of light, atmospheric conditions, or aging.
• an insulating medium such as-gum dammar, having included therein interspersed droplets of aplurality of liquid reagents, which are chemically reactive to produce a distinctivecolor in the record materialatthe points of application of localized pressure thereto, such pressure rupturing the insulating medium to permit chemicalreaction between the two liquid reagents.
• the two reagents disclosed in :this patent are gallic acid and ferric 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 twosolutions are allowed to mix, upon the rupture of the insulatin medi- 11111.
• the reaction disclosed in that patent depends upon the presence of-thereagents 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 causethe insulating mediumto cease to be efiective, with the result that the chemical reaction takesplace 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 istosproVide a process ofmak- Av furtherobject of thisinvention is to provide aprocess ,ofxmaking a pressure-sensitive recordlmaterialflin which .a. mark .of-distinctive color is producedby a reaction betweensolid particles of color-forming reactants.
• a pressure-sensitive record material including ,the iforming on a supporting member a film-like deposit :of solid .partiEles :of a plurality of adsorption color-forming reactants disposed in contiguity witheach other, such reactants;beingvsogselected'thatsthey react, in the absence of a liquid ionizing medium forthe reactants, toiiorm a:distinctive:colcr whenbrought into adsorption contactzwith each other, and a solid insulating mediuminsulating saidreactants from color-forming reaction contact with each other.
• the insulating medium istruptured at the points ofzapplicationdofsaid localized pressure, and. such. rupture permits .coloreformmg reaction M 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 it a 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 the color-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 pressuresensitive record material includes a base web, such as a fibrous Web of paper or the like, to which the coating of solid insulating medium and the color-forming reactants is applied.
• the insulating medium is a pressure-rupturable film derived from an organic film-forming, hydrophilic col oid substance.
• the following embodiment of this invention constitutes the best mode of applying the prinoiple thereof contemplated up to the present time, and may be considered the preferred embodiment. It consists in a process for making a pressure-sensitive record material that comprises a base web, of paper or the like, to which is applied a coating including casein and solid particles of three color-forming reactants; namely, kaolin, the compound 3,3 bis (p-climethylaminophenyl) -6 dimethylamino phthalide,
• crystal violet lactone a referred to as crystal violet lactone and hav ing the structure and the compound tetramethylbenzidine, having the structure
• the casein constitutes the solid insulating medium, insulating one of the color-forming reactants-that is, kaolin-from color-forming reaction contact with the other color forming reactants-that is, crystal violet lactone and tetramethylbenzidine.
• This record material is normally white or bluish white in color, and, upon the application of localized pressure thereto, as by drawing a stylus thereover, a dark blue mark is produced at the points of application of such localized pressure.
• such coating weighs about .0023 pound per square foot or" surface and may 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 the 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 par ticle size is possible without any ill elfects.
• Particle size of the crystal violet lactone and the tetramethylbenzidine is largely determined by the method of application of those ingredients.
• ascent-i w particles of these reactants may be as large as ten microns in diameter and frequently are much smaller.
• Gelatin, methyl cellulose, starch, polyvinyl alcohol, and animal glue are representative organic hydrophilic colloid materials that may be substituted for casein as the solid insulating me: dium.
• Any of the following inorganic materials may be substituted for kaolin as one of the colorforming reactants: attapulgite (Attapulgus clay), pyrophyllite, talc, bentonite, halloysite, calcium sulphate, calcium citrate, magnesium trisilicate, zinc sulphide, Zirconium dioxide, calcium phosphate, barium sulphate, and calcium fluoride.
• the record material will be white in color, and application of localized pressure will produce a dark blue mark thereon, out this mark may fade upon continued exposure to light under conditions of high hu. midity.
• This pressure-sensitive record material is not substantially affected by the amount of atmospheric humidity ordinarily encountered, although the mark may fade somewhat if subjected to high humidity for a long-continued period of time.
• this pressure-sensitive record material does not become stained or discolored by exposure to high humidity for-long periods or time, and retains its ability to respond to the application of localized pressure, and to produce the mark of distinctive color, under such conditions. Ehis is thought tobe due to the fact that the record material does not include any hygroscopic ionizing media. Consequently, the structure of the record material is not altered or modified due to the absorption of water from the atmosphere.
• a method constituting one embodiment of this invention that has been used successfully to make the pressure-sensitive record material described above is as follows: A slurry of kaolin and water was prepared including fifty parts by weight of lin throughout the slurry. The addition of this dispersing agent reduces the viscosity of the slurry considerably, thus facilitating its mixing and application, and also preventing the settling of the solid particles of kaolin. A 20% by weight solution of casein in water was formed by, first, dispersing the casein in cold water by stirring ior fifteen minutes atroom temperature and, then, heating upto degrees centigrade, Five parts by weight, of a 28% ammonium hydroxide, solue h tion-that is, one having a specific gravity of 25.9 31%., at
• casein solution containing the kaolin was passed through a homogenizer, or other means for mixing and thoroughly dispersing the particles of kaolin in the casein solution, and the two portions of casein solution, one containing the kaolin and the other containing the crystal violet lactone and the tetramethylbenzidine, were then mixed thoroughly and applied as a coating to the base web or paper. This coating-was then dried on the paper in the usual manner.
• the resulting record material had a light bluish-white color approaching White.
• gelatin is substituted for casein as the solid insulating medium
• the procedure described above is modified, in that the gelatin is first dissolved in water at a temperature above 40 degrees centigrade, and this gelatin solution is then divided into two equal parts, to one of which the slurry of kaolin and water is added as before.
• the other part of the gelatin solution is made sufficiently ammoniacal to neutralize and precipitate the crystal violet lactone and the tetramethylbenzidine when the hydrochloric acid solution of these ingredients is added thereto.
• These two portions of the gelatin solution are then mixed, and the mixture is applied as a coating to the paper and then dried.
• the gelatin solution should be kept at a temperature above 40 degrees centigrade throughout the entire procedure.
• methyl cellulose is used as the solid insulating medium in substitution for the casein
• a solution is prepared by dissolving about parts by weight of methyl cellulose (of any vscosity between 2000 and 4000 centipoises at 68 degrees Fahrenheit) in about 50 parts by weight of water, and this solution is divided into two equal parts.
• the slurry of kaolin and water is added, in the ratio of 40 parts by weight of kaolin to one part by weight of methyl cellulose, and mixed, as described in connection with the use of casein.
• the other portion of the methyl cellulose solution is rendered sufficiently ammoniacal to precipitate the crystal violet lactone and the tetramethylvbenzidine from the hydrochloric acid solution thereof, when the latter is added to and mixed with this portion of the methyl cellulose solution in such proportions that the ratio by Weight of ,kaolin to crystal violet lactone and tetramethylbenzidine in the coating will be 100 to 3.
• the two portions of the methyl cellulose solution are,
• Another embodiment of this invention produces a material comprising a base web of paper or the like having applied thereto a coating including casein or methyl cellulose as the solid insulating medium and solid particles of two color-forming reactants; namely, kaolin and the compound 3,3 bis (p-dimethylaminophenyl) phthalide, also known as malachite green lactone, having the structure
• This record material is normally white or light in color, and, upon application of localized pressure thereto, as by drawing a stylus thereover, a mark of dark blue-green color is produced at the points of application of such pressure.
• the process for making the novel record material with malachite green lactone is claimed in a divisional application Serial No. 63,211, filed December 2, 1948.
• Another embodiment of this invention proloses a material that comprises a base web of paper having applied thereto a coating including casein as the solid insulating medium and two color-forming reactants; namely, kaolin and the compound 2,4-bis [p-(p-dimethylaminophenylazo) anilinol G-hydroxy sym. triazine, having the structure
• the pressure-sensitive record material made using these ingredients is normally yellow in color, and the application of localized pressure thereto, as by drawing a stylus across the material, ruptures the solid insulating medium and permits the solid particles of kaolin and the organic color-forming reactant to come into color-forming reaction contact with each other, producing a dark blue mark at the points of application of such localized pressure.
• Another embodiment of this invention produces a pressure-sensitive record material including a base web of paper having applied thereto a coating including casein as the solid insulating medium and two color-forming reactants; namely, kaolin and the compound o-hydroxybenzalacetophenone, having the structure
• This record material comprises solid particles of kaolin and o-hydroxybenzalacetophenone insulated from color-forming reaction contact with each other by casein as the solid insulating medium.
• the record material is normally light yellow in color, and application of localized pressure thereto ruptures the insulating medium at the points of application of such pressure, permitting color-forming reaction contact between the particles at such points and producing a reddishyellow mark.
• Another embodiment of this invention produces a pressure-sensitive record material consisting of a web of paper having applied thereto a coating comprising casein as the solid insulat-- ing medium and two color-forming reactants; namely, kaolin and the compound bis (p-dimethylaminophenyl) methanol, also known as Mich! lers hydrol and having the structure
• casein forms the abuser
• the record material is normally white or light gray in color.
• Another embodiment of this invention produces a record material consisting of a web of paper having applied thereto a coating comprising casein as the solid insulating medium and two color-forming reactants; namely, kaolin and the compound bis (p-dimethylaminophenyl) ,methoxymethane, also known as (methyl ether of Michlers hydrol, having the structural formula
• the casein constitutes the solid medium insulating thesolid .particles of kaolin and bi methyl ether of .Michlerfs hydrol from color-forming reaction contact with each other, and, when this solid insulating ,medium is ruptured by the application of localized pressure, color-formingreaction contact between the particles .is ,permittedlat the points ,of application of such pressure, producing a .dark blue
• the material is normally whitabut application of localized pressure thereto, as vby drawing a styluszacross it, IEZOdllGGSgS, blue-green mark at the points of1 application of suchpr s ur duets the localized rupture of the insulatingme- -dium, permitting color-forming reaction contact between thereactant particles: at such points.
• Another embodiment .oithis invention produces ea pressureesensitive recordmateitial comprisinea web of paper hav ng apphed thereto a coating in- CHsHN- NHO H3
• This record material is normally white, but the a plication of localized pressure thereto ruptures the insulating medium, casein, at the points of application of such pressure, permitting coloriorming reaction contact between the solid particles of kaolin and the solid particles of the compound 3,3 bis (p-methylaminophenyl) ,phthalide, resulting in the production of a bright blue mark.
• Another embodimentlof this invention produces a pressure-sensitive record material consisting of a web of paper having applied thereto a coating consisting of casein as the solid insulating medium and solid particles of two color-forming reactants; namely, ikaolin and the compound 3,3 bis (p-ethylaminophenyl) phthalide, having the structural formula
• This record material is normally white, butthe application of localized pressure thereto ruptures the vsolid insulating medium at thepoints of application of such pressure, thus permitting colordimethylaminobenzohydr-yl) 5 dimethylamino benzoic acid, having the structural formula
• thecasein constitutes divisional application
• the solid insulating medium insulating the solid particles of kaolin and the compound 201,4 bis dimethylaminobenzohydryl) dimethylamino benzoic acid from color-forming reaction contact with each other.
• the record material is normally white, and the application of localized pressure thereto ruptures the solidinsulating medium at the points of application of such pressure, permitting color-forming reaction contact between the solid particles of the reactants, producing a dark blue mark.
• Another embodiment of this invention produces a record material consisting of a web of paper having applied thereto a coating including casein as the solid insulating medium and solid particles of two color-forming reactants; namely, kaolin and the compound 3,3 bis (p-di n-propylaminophenyl) phthalide, having the structural formula sure to this record material ruptures the insulating medium. and permits color-forming reaction contact between the solid particles of the two reactants, thus producing a blue-green mark at the points of application of such pressure.
• two color-forming reactants namely, kaolin and the compound 3,3 bis (p-di n-propylaminophenyl) phthalide
• Another embodiment of this invention produces a record material consisting oi. a web of paper having applied thereto a coating including casein as the solid insulating medium and solid particles of two color-forming reactants; namely, kaolin and the compound 4.-- (p-dimethylaminophenylazo) benzanilide, having the structural formula 0 tact between the solid particles of the reactants and thus producing the distinctive mark.
• a record material consisting oi. a web of paper having applied thereto a coating including casein as the solid insulating medium and solid particles of two color-forming reactants; namely, kaolin and the compound 4.-- (p-dimethylaminophenylazo) benzanilide, having the structural formula 0 tact between the solid particles of the reactants and thus producing the distinctive mark.
• the organic reactant being an electron donor aromatic organic compound having a double bond system which is convertible to a more highly polarized conjugated form upon taking part in an electron acceptordonor solid surface chemical reaction, giving it a distinctive color
• 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 record material including the steps of forming on a supporting member a film of solid insulating material having particles of a first colorforming inorganic reactant dispersed therein, and depositing on said film particles of a second organic color-forming reactant adsorbable on the first reactant particles, said reactants being so selected as to form a distinctive color when brought into adsorption contact with each other,
• said solid insulating material being derived from an organic film-forming hydrophilic colloid substance such as to insulate the reactants from color-forming reaction contact with each other the organic reactant being an electron donor aromatic organic 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 it a distinctive color, 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 second color-forming reactant is a mixture of the compound 3,3 bis (p-dimethylaminophenyl) -6 dimethylamino phthalide, having the structure and the compound tetramethylbenzidine, having the structure 12.
• the second color-forming reactant is the compound 3,3 bis (p-dimethylaminophenyD-6 dimethylamino phthalide, having the structure I Ha)2 BARRETT K. GREEN.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Color Printing (AREA)
• Paper (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Paints Or Removers (AREA)

Priority Applications (31)

Applications Claiming Priority (5)

Publications (1)

Family

ID=31192441

Family Applications (1)

Country Status (6)

Cited By (15)

Families Citing this family (12)

Citations (4)

• 0
  • BE BE478120D patent/BE478120A/xx unknown
  • BE BE485588D patent/BE485588A/xx unknown
  • BE BE480326D patent/BE480326A/xx unknown
  • BE BE485589D patent/BE485589A/xx unknown
• 1946
  • 1946-03-01 GB GB6474/46A patent/GB629165A/en not_active Expired
  • 1946-03-07 FR FR923465D patent/FR923465A/fr not_active Expired
  • 1946-03-07 FR FR923467D patent/FR923467A/fr not_active Expired
• 1947
  • 1947-11-08 US US784939A patent/US2505471A/en not_active Expired - Lifetime
  • 1947-11-27 CH CH276723D patent/CH276723A/fr unknown
• 1948
  • 1948-01-06 CH CH277328D patent/CH277328A/fr unknown
  • 1948-09-22 GB GB24784/48A patent/GB656859A/en not_active Expired
  • 1948-10-26 CH CH291101D patent/CH291101A/fr unknown
  • 1948-10-27 CH CH291102D patent/CH291102A/fr unknown
  • 1948-11-05 FR FR59544D patent/FR59544E/fr not_active Expired
  • 1948-11-05 FR FR59543D patent/FR59543E/fr not_active Expired
• 1949
  • 1949-01-01 DE DEP29055D patent/DE878806C/de not_active Expired
  • 1949-01-01 DE DEP29058A patent/DE871604C/de not_active Expired
• 1952
  • 1952-07-18 FR FR63097D patent/FR63097E/fr not_active Expired
  • 1952-07-31 DE DEN5871A patent/DE932614C/de not_active Expired
  • 1952-08-25 GB GB21260/52A patent/GB714657A/en not_active Expired

Patent Citations (4)

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