US3149991A - Heat developable paper - Google Patents
Heat developable paper Download PDFInfo
- Publication number
- US3149991A US3149991A US164594A US16459462A US3149991A US 3149991 A US3149991 A US 3149991A US 164594 A US164594 A US 164594A US 16459462 A US16459462 A US 16459462A US 3149991 A US3149991 A US 3149991A
- Authority
- US
- United States
- Prior art keywords
- amine
- keto compound
- dye
- adduct
- sheet
- 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
Links
Images
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
- B41M5/26—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/165—Thermal imaging composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
- Y10T428/31841—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31844—Of natural gum, rosin, natural oil or lac
- Y10T428/31848—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
Definitions
- This invention relates to heat marking processes and provides a novel heat sensitive sheet useful for copying and recording uses, and characterized by the ability to form a mark of contrasting color when heated to an activation temperature in the range of 50 to 150 C.
- Sheets of this type are commonly employed in thermographic copying processes, in which a sheet is placed next to a graphic original and is exposed with the original to infrared radiation which causes selective heating of the dark areas of the original suflicient to form a copy thereof on the copy sheet. A more detailed description of this process is set forth in US. Patent No. 2,740,896.
- the sheets of this invention may also be used in recording devices in which marking is accomplished by means of a heated stylus.
- materials which are reactive to form a dye are incorporated in the sheet in intimate association.
- These materials include an organic keto compound, that is a ketone or aldehyde, and a primary or secondary amine.
- Numerous well known dyes are formed from precursor materials of this type; those useful in this invention are those which will react to form a dye when mixed together at temperatures below 150 C.
- both precursors are present in the sheet, with the amine being present as a component of a solid stable co-crystal adduct formed by combining the amine with a bisphenol.
- Adducts of this type are described in US. Patent No. 2,829, 175, and also in the co-pending application of William R. Lawton and Eugene F. Lopez, Serial No. 840,514, filed September 17, 1959, now US. Patent No. 3,104,979, assigned to the assignee of this application.
- the organic keto compound should be lightly colored solid and non-hygroscopic, and otherwise stable at normal conditions of temperature and humidity, that is, those conditions one might expect to encounter in actual conditions of storage, shipment, and use.
- keto compounds have been found to be effective in compositions of the present invention. Representative of these compounds and particularly useful are the ketones and aldehydes of monoand polynuclear aromatic compounds, and quinoid compounds.
- the cocrystal adduct should be similarly stable, and lightly colored, and should in addition be dissociable to yield the amine component at the desired activation tem perature in the range of 50-150 C.
- the particular amine and bisphenol are accordingly to be selected with reference to these criteria on the basis of known, or readily ascertainable, characteristics of the materials of this type.
- the keto compound and the co-crystal adduct are dispersed separately or together in a binder solution and applied as one or more coatings to a paper or other base by conventional techniques.
- the keto compound may be dissolved in the binder solution, but if so, the solvent should not be one that attacks the co-crystal adduct to bring about premature color reaction.
- the relative proportions of the two components should be such as to provide mutual reaction, with a total concentration sufficient to produce a distinct contrasting color mark when the sheet is heated. These quantities are generally not critical and may be determined by routine experimentation.
- Example 1 A co-crystal adduct is first formed by combining:
- a second dispersion is prepared consisting of:
- This mixture is similarly charged in a ball mill and milled overnight at 40 F.
- the two dispersions are now mixed in the ratios of 11.0 parts of the TCBA/EEA dispersion to 13.5 parts of the 2,S-dichloronaphthoquinone dispersion, and the resulting mixture is coated on a 25-pound per ream (500 sheets, 24 inches by 36 inches) glassine at a dry-coating weight of 4.0 pounds per ream.
- the resulting coated sheet provides satisfactory reproductions when employed as a thermographic copy in a Minnesota Mining and Manufacturing Company Thermo-Fax Secretary Model 17H copying machine on the range of the machine settings of 1-7.
- Satisfactory copy sheets may be formed in the manner described in Example 1 by substituting for the 2,5-dichloronaphthoquinone, in comparable molar ratios with the amine of the co-crystal adduct, ketone derivatives of related aromatic and quinoid compounds, such as 1,4- naphthoquinone; Z-amino-1,4-naphthoquinone; tetrachlorobenzoquinone; Z-methyl-1,4-naphthoquinone; l-nitroanthraquinone; 1,5-dinitroanthraquinone; l-nitro, 2-carboxy-anthraquinone; 9,10-dihydro-9-oxyanthracene.
- ketone derivatives of related aromatic and quinoid compounds such as 1,4- naphthoquinone; Z-amino-1,4-naphthoquinone; tetrachlorobenzoquinone
- Example 1 Further satisfactory copy sheets may be prepared by substituting for the TCBA/EEA of Example 1 a co-crystal adduct of any primary or secondary amine selected from the class consisting of hydrazine, alkyl amines, cycloalkyl amines, aryl amines, alkanol amines, aralkyl amines and heterocyclic amines.
- a co-crystal adduct of any primary or secondary amine selected from the class consisting of hydrazine, alkyl amines, cycloalkyl amines, aryl amines, alkanol amines, aralkyl amines and heterocyclic amines.
- Example 2 In a preferred embodiment of the present invention the keto compound is selected from the group of aromatic ketones bearing the typical polynuclear indane structure,
- keto compound and the co-crystal adduct formed from tetrachlorobisphenol A and hexanediamine are applied to the carrier sheet as dispersions in successive coating layers.
- composition in the first layer consists of:
- the sheet When dried, the sheet is very well suited for conventional thermographic copy processes.
- Additional copy sheets may be prepared in the manner described in Example 2 by employing other indane ketones such as indane-1,2,3-trione; indarie-LZ-dione; indane-1,3- dione; bis-indane-1,3-dione; Z-hydroxy-indane-1,3-dione; bis-2-hydroxy-indane-1,3-dione; 2-phenyl-indane-1,3-dione.
- indane ketones such as indane-1,2,3-trione; indarie-LZ-dione; indane-1,3- dione; bis-indane-1,3-dione; Z-hydroxy-indane-1,3-dione; bis-2-hydroxy-indane-1,3-dione; 2-phenyl-indane-1,3-dione.
- indane ketones such as indane-1,2,3-trione; indarie-LZ-dione; indane-1,3
- Example 2 It will be observed in Example 2 that the resin binder of the first layer is insoluble in the solvent of the second layer, and that thereby two distinct layers are formed without intermingling. Best results are obtained from two incompatible resins in this manner, but satisfactory results can be obtained when compatible resins, or the same resin, are employed in both layers.
- Example 3 Various aromatic aldehydes may be employed as the keto compound in the preparation of copy sheets of the present invention. The following is a typical example.
- a base sheet as previously described is coated with a 10% solution of 2,4-dinitrobenzaldehyde in ethyl alcohol at a rate sufficient to deposit about 1-2 pounds per ream of the aldehyde.
- this layer is topcoated to about 3 pounds per ream from a dispersion consisting of:
- Tetrachlorobisphenol A/diethanolamine co-crystals prepared from tetrachlorobisphenol A and the amine in the manner described in Example 1 15
- Pliolite VT vinyl toluene/butadiene resin
- VM & P Naphtha 50 The previously noted substitutions of various co-crystal adducts may be employed with respect to Example 3 as well and, in addition, other keto compounds may be used, such as 3,S-dinitrosalicylaldehyde; 3,5-dichlorosalicylaldehyde; 5-chl0rosalicylaldehyde; o-nitrocinnamaldehyde; 5-chlorovanillin; S-nitrovanillin; 5-'nitrosalicylaldehyde.
- the sheets described in the foregoing examples have activation temperatures in the range of 50 C. to 150 C., as determined by placing the sheet against a heated surface for 1 second, and measuring the lowest temperature at which a visibly distinct color change occurs in the heated area.
- the accompanying drawing illustrates schematically a heat-sensitive sheet corresponding to this invention.
- the sheet is represented as being in cross-section.
- binder materials such as chlorinated rubber, polyvinyl acetal, acrylic ester polymer, polyvinyl acetate, polyvinyl ethyl ether, polyvinyl methylol resin.
- Other ingredients may also be included in the coating such as anti-tack agents, anti-finger printing agents, and anti-static agents, and bases other than glassine, e.g. regenerated cellulose, cellulose esters, other forms of paper and plastic materials may also be used if desired.
- a heat sensitive sheet adapted for dry heat marking processe, stable and lightly colored under normal conditions and responsive to heating to an activation temperature in the range of 50 C. C. by changing visibly and irreversibly to a contrasting color through the formation of a dye
- said sheet including a solid stable lightly colored non-hygroscopic keto compound selected from the group consisting of ketones and aldehydes of monoand polynuclear aromatic compounds and quinoid compounds, and a solid stable crystalline co-crystal adduct of a bisphenol and an amine selected from the group consisting of primary and secondary amines and hydrazine, said amine and keto compound being dye precursors which when combined are reactive at a temperature of less than 150 C. to form said dye, said adduct having a dissociation temperature between 5 0 C. and 150 C. at which said amine is released for reaction with said keto compound.
- a heat sensitive sheet adapted for dry heat marking processes, stable and lightly colored under normal conditions and responsive to heating to an activation temperature in the range of 50 C.150 C. by changing visibly and irreversibly to a contrasting color through the formation of a dye
- said sheet including a solid stable lightly colored non-hygroscopic keto compound selected from the group consisting of ketones and aldehydes of monoand poly-nuclear aromatic compounds, and quinoid compounds, and a solid stable crystalline co-crystal adduct of a bisphenol and an amine, said amine and keto compound being dye precursors which when combined are reactive at a temperature of less than 150 C. to form said dye, said adduct having a dissociation temperature between 50 C. and 150 C. at which said amine is released for reaction with said keto compound, said keto compound and said adduct each being dispersed as intimately associated particles in a binder resin, and forming therewith a heat sensitive coating on said sheet.
- a heat sensitive sheet adapted for dry heat marking processes, stable and lightly colored under normal conditions and responsive to heating to an activation temperature in the range of 50 C.150 C. by changing visibly and irreversibly to a contrasting color through the formation of a dye
- said sheet including a solid stable lightly colored non-hygroscopic keto compound selected from the group consisting of ketones and aldehydes of monoand poly-nuclear aromatic compounds, and quinoid compounds, and a solid stable crystalline cocrystal adduct of a bisphenol and an amine, said amine and keto compound being dye precursors which when combined are reactive at a temperture of less than 150 C. to form said dye, said adduct having a dissociation temperature between 50 C. and 150 C.
- said keto compound being dispersed in a binder resin and forming therewith a first layer
- said adduct being dispersed in a binder resin and forming therewith a second layer adjacent to said first layer.
Landscapes
- Chemical & Material Sciences (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)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE626634D BE626634A (de) | 1962-01-05 | ||
NL287455D NL287455A (de) | 1962-01-05 | ||
US164594A US3149991A (en) | 1962-01-05 | 1962-01-05 | Heat developable paper |
CH1526562A CH411950A (fr) | 1962-01-05 | 1962-12-28 | Feuille pour le marquage à sec par la chaleur |
DEN22557A DE1214252B (de) | 1962-01-05 | 1962-12-31 | Waermeempfindliches Kopiermaterial |
GB48988/62A GB1000987A (en) | 1962-01-05 | 1962-12-31 | Heat sensitive sheets |
FR920220A FR1346578A (fr) | 1962-01-05 | 1963-01-02 | Papier développable par la chaleur |
AT8363A AT247716B (de) | 1962-01-05 | 1963-01-04 | Wärmeempfindliches Blattmaterial |
ES283951A ES283951A1 (es) | 1962-01-05 | 1963-01-05 | Perfeccionamientos en hojas sensibles al calor preparadas para el relevado y desarrollo de señales gráficas por procedimientos térmicos |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US164594A US3149991A (en) | 1962-01-05 | 1962-01-05 | Heat developable paper |
Publications (1)
Publication Number | Publication Date |
---|---|
US3149991A true US3149991A (en) | 1964-09-22 |
Family
ID=22595190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US164594A Expired - Lifetime US3149991A (en) | 1962-01-05 | 1962-01-05 | Heat developable paper |
Country Status (8)
Country | Link |
---|---|
US (1) | US3149991A (de) |
AT (1) | AT247716B (de) |
BE (1) | BE626634A (de) |
CH (1) | CH411950A (de) |
DE (1) | DE1214252B (de) |
ES (1) | ES283951A1 (de) |
GB (1) | GB1000987A (de) |
NL (1) | NL287455A (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3293061A (en) * | 1963-11-21 | 1966-12-20 | Man Res Lab Inc | Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet |
US4097288A (en) * | 1977-02-25 | 1978-06-27 | Lawton William R | Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone |
US4111703A (en) * | 1977-02-25 | 1978-09-05 | Graphic Controls Corporation | Heat-sensitive coating composition with 4-aromatic and hydroxy substituted piperidine derivative and cyclic polyketo compound |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2663656A (en) * | 1952-05-15 | 1953-12-22 | Minnesota Mining & Mfg | Heat-sensitive copying paper |
US2899334A (en) * | 1958-05-19 | 1959-08-11 | Heat-sensitive layer | |
US2967785A (en) * | 1959-08-14 | 1961-01-10 | Eastman Kodak Co | Thermographic copying material |
US2995466A (en) * | 1959-08-07 | 1961-08-08 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US3024362A (en) * | 1958-08-09 | 1962-03-06 | Kalle Ag | Heat sensitive reproduction material and mbthod of using same |
US3076707A (en) * | 1959-04-22 | 1963-02-05 | Nashua Corp | Heat developable copy sheet and compositions useful therefor |
-
0
- NL NL287455D patent/NL287455A/xx unknown
- BE BE626634D patent/BE626634A/xx unknown
-
1962
- 1962-01-05 US US164594A patent/US3149991A/en not_active Expired - Lifetime
- 1962-12-28 CH CH1526562A patent/CH411950A/fr unknown
- 1962-12-31 GB GB48988/62A patent/GB1000987A/en not_active Expired
- 1962-12-31 DE DEN22557A patent/DE1214252B/de active Pending
-
1963
- 1963-01-04 AT AT8363A patent/AT247716B/de active
- 1963-01-05 ES ES283951A patent/ES283951A1/es not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2663656A (en) * | 1952-05-15 | 1953-12-22 | Minnesota Mining & Mfg | Heat-sensitive copying paper |
US2899334A (en) * | 1958-05-19 | 1959-08-11 | Heat-sensitive layer | |
US3024362A (en) * | 1958-08-09 | 1962-03-06 | Kalle Ag | Heat sensitive reproduction material and mbthod of using same |
US3076707A (en) * | 1959-04-22 | 1963-02-05 | Nashua Corp | Heat developable copy sheet and compositions useful therefor |
US2995466A (en) * | 1959-08-07 | 1961-08-08 | Minnesota Mining & Mfg | Heat-sensitive copy-sheet |
US2967785A (en) * | 1959-08-14 | 1961-01-10 | Eastman Kodak Co | Thermographic copying material |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3293061A (en) * | 1963-11-21 | 1966-12-20 | Man Res Lab Inc | Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet |
US4097288A (en) * | 1977-02-25 | 1978-06-27 | Lawton William R | Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone |
US4111703A (en) * | 1977-02-25 | 1978-09-05 | Graphic Controls Corporation | Heat-sensitive coating composition with 4-aromatic and hydroxy substituted piperidine derivative and cyclic polyketo compound |
Also Published As
Publication number | Publication date |
---|---|
ES283951A1 (es) | 1963-03-16 |
BE626634A (de) | 1900-01-01 |
AT247716B (de) | 1966-06-27 |
CH411950A (fr) | 1966-04-30 |
NL287455A (de) | 1900-01-01 |
GB1000987A (en) | 1965-08-11 |
DE1214252B (de) | 1966-04-14 |
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