US2999035A - Heat sensitive reproduction sheet, method of making and method of using - Google Patents

Heat sensitive reproduction sheet, method of making and method of using Download PDF

Info

Publication number
US2999035A
US2999035A US797009A US79700959A US2999035A US 2999035 A US2999035 A US 2999035A US 797009 A US797009 A US 797009A US 79700959 A US79700959 A US 79700959A US 2999035 A US2999035 A US 2999035A
Authority
US
United States
Prior art keywords
heat sensitive
heat
acid
heavy metal
lead
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US797009A
Other languages
English (en)
Inventor
Sahler Wilhelm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Keuffel and Esser Co
Original Assignee
Keuffel and Esser Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Keuffel and Esser Co filed Critical Keuffel and Esser Co
Application granted granted Critical
Publication of US2999035A publication Critical patent/US2999035A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron

Definitions

  • I wTRANsPARENT BASE HG 2 /TRANSPARENT BASE REFLEX j I I I TIEAT SENSITIVE/COATING E4 E4 m MASTER PRINTED ON ONE IL L 1L OR BOTH sIDEs w w w MASTER PRINTED ON FIG.
  • This invention relates to heat sensitive materials for the reproduction of documents and the like. More particularly, the invention relates to heat sensitive materials of the type coated with a substance which upon exposure to sufficient heat undergoes a chemical change which involves a color change.
  • Heat sensitive materials for reproduction purposes are in use which are coated with a heat sensitive layer including two reactants which at normal room temperatures do not come into reactive relationship with each other, but
  • the said organic residues represented by R comprise alkyl, aralkyl and aryl, which may be substituted by at least one carboxylic, carboxylic ester, alkoxy, or dithiocarbamic acid group,
  • the nitrogen atom of the dithiocarbamic acid may together with the residues R and R form a ring, such as a piperidine or pyrrolidine ring, which may be substituted by lower alkyl residues.
  • dithiocarbamates suitable for the heat sensitive reproduction coatings provided by the invention is described in the literature.
  • Those heavy metal salts of the dithiocarbamic acids that are not yet known are prepared in analogous manner to the dithiocarbamic acid salts for which instructions are already available.
  • the preparation of the heat sensitive heavy metal salts of the dithiocarbamic acid in question can be prepared in organic solvents, in aqueous solution or in suspension. Two mols of the primary or secondary amine (which in the interest of a reduced reaction temperature are in solution) are permitted to react with one mol of carbon disulphide. After the reaction mixture has cooled, but before the salt (which is formed with the exsuch as lower alkyl, e.g. methyl, ethyl, propyl, or butyl radicals.
  • Heavy metal salts suitable for the heat sensitive substance according to the invention are, for example, salts of lead, mercury, tin, bismuth, cadmium, silver, thallium and bivalent iron.
  • the compounds are colorless to pale yellow.
  • Other heavy metal salts such as those of univalent copper, cobalt, and nickel are more deeply colored and therefore of less practical importance for application in the present invention.
  • the heavy metals of the b-sub-groups or of the transition group (VIII) of the table having an atomic number of at least 26 and at most 83 and being in the lower valence state, e.g. from 1 to 3, are used.
  • the heat sensitive heaw metal salts of the N-substituted dithiocarbamic acids in question comprise such of the general formula R1 S R I l 0 M wherein:
  • R stands for hydrogen or a lower alkyl radical
  • R and R may join to form a ring which may be substituted with a lower alkyl radical
  • M stands for a heavy metal having an atomic number of at least 26 and at most 83 and belonging to the sub group b or the transition group VIII of the periodic table and having a valence state from 1 to 3, and
  • X stands for an integer equal to the valence of the heavy metal.
  • lower alkyl radicals are such as methyl, ethyl, propyl, butyl, isobutyl, pentyl radicals.
  • a solution of a salt of the heavy metal in question is added, e.g. heavy metal chloride or acetate.
  • the heavy metal salt of the dithiocarbamic acid is immediately precipitated.
  • the alkali or ammonium salts of the dithiocarbam-i'c acids in question can first be formed and the heavy metal salt of the dithiocarbamate precipitated thereafter by the addition of a heavy metal salt in organic solvents or aqueous solution.
  • Formulae 1-13 are examples of dithiocarbamatesuse ful in the present invention and are shown on the attached sheets.
  • the heavy metal salt of a dithiocarbamate is applied to a suitable base material in the form of a coating including a suitable binding agent which may be a cellulose 1 tate; a polyamide or a silicone resin.
  • a suitable binding agent which may be a cellulose 1 tate; a polyamide or a silicone resin.
  • Suitable base materials for the reproduction coatings of the-present invention are sheets and films of transparent materials, e.g. glass, naturally transparent paper, cellulose hydrate film, transparent plastic film, such as those made of polyvinyl chloride, cellulose acetate, poly-. ethylene terephthalate, and other substances in the form of films or sheets and capable of being permeated by light rays. 1
  • a reflex process in which the material provided with the heat sensitive coating is placed with its coated side against the master or original to be copied, which may have printing or writing on one or both sides. Radi ant heat is applied through the back of the heat sensitive material, for example by means of an infra-red lamp. The more intense the source of energy, the sharper is the image and the shorter the radiation time required. In the heat sensitive coating there is formed a direct, deeply colored mirror-image of the master which can be read correctly through the back of the transparent support.
  • the duration of heat action for the production of satisfactory heat images which will be sharp and rich in contrast cannot be generally specified. This must be established from case to case. It is dependent on a number of factors such as the type and intensity of the source of energy as well as its distance from the master, the type of base material and the composition of the heat sensitive coating.
  • the heat sensitive materials of the present invention can also be used to form images by means of a heated stylus or a heated stamp applied to the heat sensitive coating.
  • FIG. 1 illustrates the heat sensitive material including a coating of fine particles of a heavy metal salt of dithiocarbamic acid in a binder supported on a transparent base.
  • FIG. 2 illustrates the reflex method of printing in which the heat rays indicated by arrows pass, through the transparent base and the heat sensitive coating and are reflected in differing proportion in accordance with the image on the surface of the master in contact with the heat sensitive coating regardless of whether the master is printed on one or both sides to produce the image on the heat sensitive material.
  • FIG. 3 illustrates contact printing with the heat sensitive coating of the material being in contact with the image free surface of the master.
  • FIG. 4 illustrates heat rays passing through a master printed on one side with such printed side of the master in contact with the transparent base and the heat sensitive coating on the opposite surface.
  • FIG. 5 illustrates contact printing with the master printed on one side and that side in contact with the heat sensitive coating and the heat rays passing through the master.
  • FIG. 6 illustrates the heat rays passing through the master which is printed on one side with such printed side adjacent the source of heat rays and the printing free side in contact with the transparent base and the heat sensitive coating on the opposite surface.
  • FIG. 7 illustrates forming images by means of a heated stylus or stamp in contact with the heat sensitive coating.
  • the heat sensitivity of the heavy metal salts of the dithiocarbamic acids according to the present invention can be improved by adding to the heat sensitive coating amine salts or ammonium salts of readily heat-decomposible acids, i.e. acids whose mole cules are readily split or decomposed by the action of heat.
  • Reproduction coatings modified in this way re quire less heat for the formation of the colored image.
  • the practical significance of this is that the temperature at which color change takes place is lower than in the case of coatings containing the dithiocarbamates of heavy metals. Without any such amine salt or ammonium salt of an acid.
  • Amine salts and ammonium salts that have proved particularly suitable are those of carbonic acid, carbamic acid, trichloroacetic acid, and tribromoacetic acid, cyanoacetic acid, acetoacetic acid, acetone dicarboxylic acid, mono or dichloromalonic acid and mono or dibrornomalonic acid.
  • Acid amides such as acetamide and benzamide and also symmetrically substituted diarylguanidines, such as N,N'-diphenyl-guanidine and derivatives thereof substituted in the nucleus, can also be used for a similar purpose.
  • Free amines and guanidines with asymmetric or aliphatic substitution can also he used if the heat sensitive coating composition is to be used soon after its preparation.
  • the images obtained keep well. If they are required to be protected from any further influence of high temperatures, they can be subjected to a fixing process to convert the amine and ammonia salts of the readily heatdecomposable acids into heat-resistant salts. The images will then remain unafiected by temperatures up to over 150 C. It has been discovered that the fixing can be effected by an acid treatment. In general it is suflicient for a coating which has been subjected to heat to form an image to be exposed to the fumes of volatile acids. Examples' of suitable acids are hydrochloric acid, acetic acid and formic acid. Fixing is also elfected it one of the acids mentioned is rubbed or sprayed on the coated side of the finished heat copy. After drying, the copy is re sistant to the effect of heat within the limits mentioned above.
  • Lead benzyldithiocarbamate (Formula 1) is prepared by dissolving 53.3 g. of benzyl amine in 700 cc. of methanol and adding with stirring 19 g. of carbon disulphide. to normal, 48 g. of lead acetate dissolved in 100 cc. of water are stirred into the reaction mixture at about 2530 C.
  • the lead benzyldithiocarbamate precipitates, is separated by suction, washed consecutively with water, methanol and ether and dried in the air. white substance are obtained.
  • the product decomposes with black coloration if it is placed for one second ona plate (melting bed) heated to 211 C.
  • suspension A 100 g. of the lead benzyldithiocarbamate are suspended in 500 cc. of methylene chloride and ground for two hours in a ball mill. 250 cc. of a 5% solution of ethyl cellulose in methylene chloride are then mixed into the suspension to form suspension A.
  • Suspensions A and B are then thoroughly mixed together. The mixture is applied to naturally transparent paper and dried in moderate heat.
  • the coated transparent paper is placed with its coated side against the master to be copied, e.g. a sheet printed on both sides, and subjected to the action of a powerful infra-red lamp in such manner that the radiation passes through the noncoated side of the heat-sensitive reproduction paper.
  • the heat is heavily absorbed in the printed parts of the master to raise the temperature in the heat sensitive coating adjacent thereto which sets ofi the decomposition reaction in the parts of the heat sensitive coating in contact with the printing.
  • Direct mirror-image reproductions of the master are obtained in brown black, which can be read as correct images through the back of the transparent paper.
  • the copy obtained may be made resistant to further heat action, it is placed in a fume chamber over strong acetic acid at room temperature for three hours.
  • the ammonium salt is dissolved in 1000 cc. of methanol and the resultant solution is run into 1000 cc. of normal aqueous lead acetate solution containing additionally 60 g. of glacial acetic acid, cooling being maintained by the addition of pieces of ice.
  • the precipitated lead salt is separated by suction filtration, suspended in methanol and again separated by suction. It is then suspended in ether, again separated by suction and washed
  • the pure white product is dried in the -air. The substance decomposes within a second with black,
  • Suspensions A and B are-mixed and to the mixture are 7 added 60 cc. of a solution of ethyl cellulose in carbon tetrachloride, 40 cc. of a solution of 0.6 g. of a ketone resin, e.g. Kunststoffharz AW 2 of Badische Anilin and Soda-Fabrik, in 40 cc. of ethylene perchloride and 75 cc. of pure ethylene perchoride.
  • a ketone resin e.g. Kunststoffharz AW 2 of Badische Anilin and Soda-Fabrik
  • This mixture is applied to transparent paper in a thin layer and dried. If the coated transparent paper is placed in contact with a master in accordance with the instructions given in Example 1 and subjected to the action of radiant heat, a brown-black image of the master is formed.
  • Mercury-N-benzyl-dithiocarbamate corresponding to Formula 2 is prepared by mixing 10.7 g. of benylamine with 50 cc. of methanol, and adding 6 cc. of carbon disulphide with cooling and following with a solution of 14 g. of mercury-H-chloride in 50 cc. of methanol with thorough stirring.
  • the precipitated colorless mercury salt is purified with methanol and ether and dried in the air, as described in Example 4.
  • the pale yellowish product melts with decomposition (black coloration) within one second if put on a metal plate (melting bed) heated to 166 C.
  • Lead-3-methoxypropyl-dithiocarbamate corresponding to Formula 7 is prepared from 3-n1ethoxypropylamine1 in a manner analogous to that described in Example 1. It melts with decomposition (black coloration) if it is placed for one second on a plate (melting bed) heated at 130 C.
  • Suspension A.-27 g. of the product are ground in 200 cc. of carbon tetrachloride in a ball mill.
  • Suspension B.-12 g. of 1,6-diaminohexane are dissolved in a mixture consisting of 200 cc. of a 3% solution of ethyl cellulose in carbon tetrachloride and 600 cc. of pure carbon tetrachloride; dry carbon dioxide is then introduced until saturation is reached.
  • the resultant product is an extremely finely divided suspension of 1,6- diaminohexane carbamate corresponding to Formula 14.
  • Suspensions A and B are intimately mixed and applied to transparent paper. This heat sensitive reproduction paper gives black images when subjected to the process described in Example 1.
  • Suspension B Lead N-phenylethyldithiocarbamate corresponding to Formula 4 (melting point 170 C., with decomposition within 1 second) is prepared from phenylethylamine in a manner analogous to that described in Example 1. 3 g. of this compound are likewise finely suspended in 25 cc. of benzene by means of a ball mill.
  • Suspension C.-2 g. of the benzylamine salt of monochloroacetic acid are finely suspended in 20 cc. of benzene.
  • Suspensions A, B and C are mixed and 50 cc. of a 5% solution of polyvinylcarbazole in benzene and 100 cc. of pure benzene are added to the mixture.
  • the product thus obtained is applied in a thin coating to a glass plate and dried. Black-brown images are obtained if this reproduction material is treated in the manner described in Example 1.
  • Tin benzyl dithiocarbainate corresponding to Formula 3 is prepared as follows: 10.7 g. of benzylamine are mixed with 50 cc. of methanol; 6 cc. of carbon disulphide are added with stirring and as soon as the benzyl amine salt of benzyldithiocarbamic acid begins to precipitate, 9.5 g. of tin-II-chloride dissolved in 50 cc. of water are added to the reaction mixture with cooling. The pale yellowish tin salt of benzyl-dithiocarbamic acid is separated by suction filtration and washed with methanol and ether. The product is then dried in the air. The pale yellowish product decomposes Without melting if it is put for 1 second on a plate (melting bed) heated to 178 C.
  • Lead-N-(carboxymethyl)-dithiocarbamate corresponding to Formula 9 is prepared by the solution of 22.3 g. of glycocoll hydrochloride in 20 cc. of water and the addition with external cooling of 35 g. potassium hydroxide dissolved in 30 cc. of water. The alkaline solution is then shaken with 15.2 g. of carbon disulphide until the greater part of the carbon disulphide is dissolved. Potassium chloride is precipitated and is filtered off. The filtrate is freed from any remaining carbon disulphide by ether extraction. From the solution of the dipotassium salt of dithiocarbamic acetic acid the di-lead salt is precipitated by careful addition of a solution of 76 g.
  • Lead-1,4-diamino-butane-bis-dithiocarbamate corresponding to Formula 8 is obtained if 8.4 g. of 14 diaminobutane are dissolved in 50 cc. of methanol and 12 cc. of carbon disulphide are added to the solution with stirring and external cooling and the mixture is then quickly poured into 50 cc. of a cooled normal lead acetate solution.
  • Colorless lead salt corresponding to Formula 8 precipitates out and is separated by suction, washed consecutively with water, a little methanol and ether and dried in the air. The product decomposes without melting if it is put for one second on a plate (melting bed) heated to 131 C.
  • the lead salt is separated by suction, suspended in methanol, thoroughly mixed therein, again separated by suction, Washed with ether and dried in the air.
  • the colorless product decomposes with black coloration if it is placed for one second on a plate (melting bed) heated to 254 C.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including at least one heavy metal salt of an N-substituted amino-dithioformic acid of the general formula R is selected from the group consisting of hydrogen and a lower alkyl residue,
  • R stands for an organic residue selected from the group consisting of alkyl, aryl, aralkyl, substituted alkyl, substituted arytl, and substituted aralkyl radicals, and wherein R and R may join to form a ring which may be substituted by lower alkyl residues,
  • M is a heavy metal selected from the group consisting of metals of the b-sub-groups and the transition group VIII of the periodic table having an atomic number of at least 26 and at most 83, and
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including a binding agent and at least one heavy metal salt of an N-substituted aminodithioforrnic acid of the general formula R is selected from the group consisting of hydrogen and a lower alkyl residue,
  • R stands for an organic residue selected from the group consisting of alkyl, aryl, aralkyl, substituted alkyl, substituted 'aryl, and substituted aralkyl radicals, and wherein R and R may join to form a ring which ma be substituted by lower alkyl residues,
  • M is a heavy metal selected from the group consisting of metals of the b-sub groups and the transition group VIII of the periodic table having an atomic number of at least 26 and at most 83, and
  • X is an integer equal to the valence of the heavy metal.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including a binding agent selected from the group consisting of cellulose derivatives, polyvinyl compounds, polyamides and silicone resins and at least one heavy metal salt on an N-substituted aminodithioformic acid of the general formula wherein R is selected from the group consisting of hydrogen and 4.
  • a heat sensitive material-for the reproduction of imagm comprising a base material in sheet form coated with a heat sensitive layer including at least one heat sensitive substance selected from the group consisting of amine salts and ammonium salts of readily heat-decom- 11 posable acids and heavy metal salts of N-substituted amino-dithioformic acids of the general formula R is selected from the group consisting of hydrogen and a lower alkyl residue,
  • R stands for an organic residue selected from the group consisting of alkyl, aryl, ara'lkyl, substituted alkyl, substituted aryl, and substituted aralkyl radicals, and wherein R and R may join to form a ring which may be substituted by lower alkyl residues,
  • M is a heavy metal selected from the group consisting of metals of the b-sub-groups and the transition group VIII of the periodic table having an atomic number of at least 26 and at most 83, and
  • X is an integer equal to the valence of the heavy metal.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including at least one binding agent and at least one heat sensitive substance selected from the group consisting of amine salts and ammonium salts of readily heat-decomposable acids, and a heavy metal salt of N-substituted amino-dithioformic acids of the general formula wherein R is selected from the group consisting of hydrogen and a lower 'alkyl residue,
  • R stands for an organic residue selected from the group consisting of 'alkyl, aryl, aralkyl, substituted alkyl, substituted aryl, and substituted aralkyl radicals, and wherein R and R may join to form a ring which may be substituted by lower alkyl residues,
  • M is a heavy metal selected from the group consisting of metals of the b-sub-groups and the transition group VIII of the periodic table having an atomic number of at least 26 and at most 83, and
  • X is an integer equal to the valence of the heavy metal.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including lead benzyldithiocarbamate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including lead-N-(w-phenyln-pentyl)-dithiocarbamate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated 12 with a heat sensitive layer including lead-N-(carbethoxymethyl) dithiocarbarnate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including lead benzylhydryldithiocarbamate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including lead-diphenylmethyldithiocarbamate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including mercury-N-benzyldithiocarbamate.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet formed coated with a heat sensitive layer including lead benzyldithiocarbamate and 1,6-diamino-hexane.
  • a heat sensitive material for the reproduction of images comprising a base material in sheet form coated with a heat sensitive layer including lead benzylhydryldithiocarbamate and N,N-diphenyl-guanidine.
  • a process for the manufacture of a heat sensitive reproduction material which comprises applying to a support a coating consisting of an N-substituted heavy metal dithiocarbamate, the heavy metal being selected from the group consisting of the heavy metals of the b-sub-groups and the transition group VIII of the periodic table having an atomic number of at least 26 and at most 83, and at least one heat sensitive substance selected from the group consisting of salts of amines and ammonium salts of readily heat-decomposable acids.
  • a process for the manufacture of reproductions which comprises subjecting the heat sensitive material claimed in claim 1 to heat diiferentially in correspondence with the desired image by placing the heat sensitive material and a master one upon the other and exposing the combined material from one side to radiant heat without subjecting to immediate heat radiation the surface carrying the heat sensitive layer.
  • a process for the manufacture of reproductions claimed in claim 15 which comprises contacting the heat sensitive material with a heated surface.
  • a process as claimed in claim 15 which comprises the step of fixing the image formed by subjecting the material to heat by exposing the material to the action of a volatile acid.
  • a process as claimed in claim 15 which comprises the step of fixing the image formed by subjecting the material to heat by exposing the material to the action of vapors of volatile acids selected from the group consisting of formic acid, acetic acid, and hydrochloric acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Color Printing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US797009A 1958-03-08 1959-03-04 Heat sensitive reproduction sheet, method of making and method of using Expired - Lifetime US2999035A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK34266A DE1100464B (de) 1958-03-08 1958-03-08 Kopierschichten zur Herstellung von Bildern durch Einwirkung von Waerme

Publications (1)

Publication Number Publication Date
US2999035A true US2999035A (en) 1961-09-05

Family

ID=7219979

Family Applications (1)

Application Number Title Priority Date Filing Date
US797009A Expired - Lifetime US2999035A (en) 1958-03-08 1959-03-04 Heat sensitive reproduction sheet, method of making and method of using

Country Status (7)

Country Link
US (1) US2999035A (en))
BE (1) BE576280A (en))
CH (1) CH379537A (en))
DE (1) DE1100464B (en))
FR (1) FR1231069A (en))
GB (1) GB910511A (en))
NL (2) NL98320C (en))

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111423A (en) * 1960-05-16 1963-11-19 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3157526A (en) * 1962-04-17 1964-11-17 Bemis Bro Bag Co Thermo-sensitive copy sheet and method of making
US3178306A (en) * 1962-04-12 1965-04-13 Orchard Paper Company Thermographic copying sheet and heat sensitive composition
US3223838A (en) * 1962-10-16 1965-12-14 Konishiroku Photo Ind Method for the preparation of relief images by the use of a heat-sensitive sheet
US3234381A (en) * 1962-01-02 1966-02-08 Ibm Method for information handling by the exposure of stretched rubber to a thermal pattern
US3238047A (en) * 1960-11-21 1966-03-01 Itek Corp Data processing media
US3250636A (en) * 1963-01-02 1966-05-10 Xerox Corp Method and apparatus for image reproduction with the use of a reusable heat demagnetizable ferromagnetic imaging layer
US3260613A (en) * 1963-03-15 1966-07-12 Interchem Corp Heat-sensitive sheet for thermographic copying
US3288627A (en) * 1965-08-05 1966-11-29 Addressograph Multigraph Heat-sensitive diazotype material coated sheet
US3301697A (en) * 1960-12-02 1967-01-31 Robert B Russell Thermographic transfer sheet having a support of a paper and plastic coating and the method of use
US3405265A (en) * 1964-12-04 1968-10-08 Gevaert Photo Prod Nv Thermographic copying method and apparatus having means for uniformly pre-heating the copy sheet
US3505093A (en) * 1967-12-01 1970-04-07 Minnesota Mining & Mfg Heat-sensitive copy-sheet containing bis(triphenylphosphine)borohydridocopper (i)
US3513021A (en) * 1966-08-24 1970-05-19 Minnesota Mining & Mfg Electromagnetic-sensitive recording medium
US3537872A (en) * 1963-02-26 1970-11-03 Hisako Kishida Thermographic process
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur
US4061836A (en) * 1976-04-13 1977-12-06 Bard Laboratories, Inc. Thermographic recording system
US4061831A (en) * 1976-04-13 1977-12-06 Bard Laboratories, Inc. Thermal recording system
US4460676A (en) * 1980-02-21 1984-07-17 Fabel Warren M Non-impact single and multi-ply printing method and apparatus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1880449A (en) * 1930-08-07 1932-10-04 Eastman Kodak Co Tropochromic coating
US2626494A (en) * 1950-04-13 1953-01-27 Pak Rapid Inc Packaging machine
US2663656A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1880449A (en) * 1930-08-07 1932-10-04 Eastman Kodak Co Tropochromic coating
US2626494A (en) * 1950-04-13 1953-01-27 Pak Rapid Inc Packaging machine
US2663656A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111423A (en) * 1960-05-16 1963-11-19 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3238047A (en) * 1960-11-21 1966-03-01 Itek Corp Data processing media
US3301697A (en) * 1960-12-02 1967-01-31 Robert B Russell Thermographic transfer sheet having a support of a paper and plastic coating and the method of use
US3234381A (en) * 1962-01-02 1966-02-08 Ibm Method for information handling by the exposure of stretched rubber to a thermal pattern
US3178306A (en) * 1962-04-12 1965-04-13 Orchard Paper Company Thermographic copying sheet and heat sensitive composition
US3157526A (en) * 1962-04-17 1964-11-17 Bemis Bro Bag Co Thermo-sensitive copy sheet and method of making
US3223838A (en) * 1962-10-16 1965-12-14 Konishiroku Photo Ind Method for the preparation of relief images by the use of a heat-sensitive sheet
US3250636A (en) * 1963-01-02 1966-05-10 Xerox Corp Method and apparatus for image reproduction with the use of a reusable heat demagnetizable ferromagnetic imaging layer
US3537872A (en) * 1963-02-26 1970-11-03 Hisako Kishida Thermographic process
US3260613A (en) * 1963-03-15 1966-07-12 Interchem Corp Heat-sensitive sheet for thermographic copying
US3405265A (en) * 1964-12-04 1968-10-08 Gevaert Photo Prod Nv Thermographic copying method and apparatus having means for uniformly pre-heating the copy sheet
US3288627A (en) * 1965-08-05 1966-11-29 Addressograph Multigraph Heat-sensitive diazotype material coated sheet
US3513021A (en) * 1966-08-24 1970-05-19 Minnesota Mining & Mfg Electromagnetic-sensitive recording medium
US3505093A (en) * 1967-12-01 1970-04-07 Minnesota Mining & Mfg Heat-sensitive copy-sheet containing bis(triphenylphosphine)borohydridocopper (i)
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur
US4061836A (en) * 1976-04-13 1977-12-06 Bard Laboratories, Inc. Thermographic recording system
US4061831A (en) * 1976-04-13 1977-12-06 Bard Laboratories, Inc. Thermal recording system
US4460676A (en) * 1980-02-21 1984-07-17 Fabel Warren M Non-impact single and multi-ply printing method and apparatus

Also Published As

Publication number Publication date
GB910511A (en) 1962-11-14
DE1100464B (de) 1961-02-23
NL98320C (en))
NL236864A (en))
FR1231069A (fr) 1960-09-26
CH379537A (de) 1964-07-15
BE576280A (en))

Similar Documents

Publication Publication Date Title
US2999035A (en) Heat sensitive reproduction sheet, method of making and method of using
US3220846A (en) Use of salts of readily decarboxylated acids in thermography, photography, photothermography and thermophotography
ZA847940B (en) Light-sensitive compounds possessing trichloromethyl groups,a process for their production and lightsensitive mixtures containing these compounds
DE1547935A1 (de) Verfahren zum Fixieren eines bildmaessig belichteten Aufzeichnungsmaterials
DE2228258C3 (de) Strahlungsempfindliches photographisches Aufzeichnungsmaterial
DE2415603A1 (de) Waermeempfindliche materialien und ihre verwendung in aufzeichnungsverfahren
DE2403100A1 (de) Aufzeichnungsverfahren mit photolytischer und/oder thermolytischer erzeugung von aminoverbindungen
DE1522385C3 (de) Lichtempflindliche Materialien
EP0031956A1 (de) Lichtempfindliches Aufzeichnungsmaterial
US3679415A (en) Diazotype photographic elements having extended exposure latitude with specific u-v absorber
US3409438A (en) Photosensitive heat developable copysheet
DE1117387B (de) Verfahren zur Herstellung von Vervielfaeltigungen mit Einkomponenten-Diazotypieschichten
DE2000623C3 (de) Photographisches Verfahren zur Herstellung von Bildern
US2326782A (en) Photosensitive material
DE2609565C2 (de) Aufzeichnungsverfahren zur Erzeugung eines positiven Bildes
US3752671A (en) Material containing photosensitive halo azido naphthalenes
DE2043355C3 (de) Elektrophotographisches Aufzeichungs material
US3097297A (en) Heat sensitive coating
DE1231552B (de) Verfahren zur Herstellung einer Zwischenkopier-vorlage
DE2123829C3 (de) Photoleitfähiges Gemisch mit einer Photoleiter-Bindemittel-Mischung, die einen Schwefel enthaltenden Photoleiter enthält
US2456514A (en) Diazotype light-sensitive materials
US3699130A (en) Halo azido naphthalenes
CA1080967A (en) Copying or recording processes, using phenols
DE1962391C2 (de) Benzoldiazoniumverbindungen und deren Verwendung
US3758303A (en) Photographic imaging of material containing halo azido naphthalenes