US3663258A - Heat-sensitive copy-sheet - Google Patents
Heat-sensitive copy-sheet Download PDFInfo
- Publication number
- US3663258A US3663258A US90120A US3663258DA US3663258A US 3663258 A US3663258 A US 3663258A US 90120 A US90120 A US 90120A US 3663258D A US3663258D A US 3663258DA US 3663258 A US3663258 A US 3663258A
- Authority
- US
- United States
- Prior art keywords
- sheet
- copy
- heat
- genacryl
- dye
- 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
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- ZJJSIXNQCAABKT-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine;2,2,2-trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl.CN(C)C(=N)N(C)C ZJJSIXNQCAABKT-UHFFFAOYSA-N 0.000 claims abstract description 7
- JQZWHMOVSQRYRN-UHFFFAOYSA-M n-(2-chloroethyl)-n-ethyl-3-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical group [Cl-].CC1=CC(N(CCCl)CC)=CC=C1C=CC1=[N+](C)C2=CC=CC=C2C1(C)C JQZWHMOVSQRYRN-UHFFFAOYSA-M 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- 229960004319 trichloroacetic acid Drugs 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LORKUZBPMQEQET-UHFFFAOYSA-M (2e)-1,3,3-trimethyl-2-[(2z)-2-(1-methyl-2-phenylindol-1-ium-3-ylidene)ethylidene]indole;chloride Chemical compound [Cl-].CC1(C)C2=CC=CC=C2N(C)\C1=C/C=C(C1=CC=CC=C1[N+]=1C)/C=1C1=CC=CC=C1 LORKUZBPMQEQET-UHFFFAOYSA-M 0.000 description 2
- ZOMLUNRKXJYKPD-UHFFFAOYSA-N 1,3,3-trimethyl-2-[2-(2-methylindol-3-ylidene)ethylidene]indole;hydrochloride Chemical compound [Cl-].C1=CC=C2C(C)(C)C(/C=C/C=3C4=CC=CC=C4NC=3C)=[N+](C)C2=C1 ZOMLUNRKXJYKPD-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—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
- B41M5/323—Organic colour formers, e.g. leuco dyes
Definitions
- This invention relates to heat-sensitive copy-sheet materials useful in the reproduction of graphic originals by the thermographic copying process involving brief exposure of the original to intense radiation while in heat-conductive contact with the copy-sheet.
- the invention relates to a novel method of making the copy-sheet.
- the invention relates to clear transparent copy-sheet materials from which color projection transparencies may be thermographically prepared.
- the copy-sheets of this invention are prepared from solutions containing a suitable dye as hereinafter defined together with tetramethylguanidine trichloroacetate and with sufficient trichloroacetic acid to provide a pH not higher than 3.
- An inert binder is included and the solution is coated on a suitable carrier or may be dried as a thin film on a temporary support and then stripped therefrom for use in absence of a carrier.
- Paper carriers are useful but clear transparent films, particularly heat-resistant films such as Mylar polyester films, are preferred.
- Polyvinyl acetate is a preferred example of an inert polymeric film-forming binder.
- Genacryl Blue 66G.F. (CI 42025) Genacryl Orange G (CI 48035) Genacryl Yellow SGF (CI 48065) Genacryl Yellow 30 (CI 48055) Genacryl Red 6B (CI 48020) Genacryl Orange R (CI 48040)
- the tetramethylguanidinium trichloroacetate, and sufficient trichloroacetic acid to give the required pH are dissolved together in a minimum quantity of water and the solution is then added to a solution of the dye and binder in a water-miscible organic solvent.
- the colored mixture is spread and dried, forming a colored dry film. Upon standing under normal room conditions for not longer than 24 hours, or in shorter times at moderately elevated temperatures, the film is found to be decolorized. It may then be made to become brilliantly colored by localized heating in the thermographic copying process.
- the thus developed images are permanent and project a colored image against a white background when the film is used as a projection transparency.
- the acidified salt solution is mixed into the dye and binder solution and the mixture is coated on two mil Mylar polyester film using a coating orifice of three mils, and allowed to dry.
- the coated film is magenta colored. It fades and becomes colorless within less than 24 hours, or may be decolorized by moderate heating for much shorter periods.
- thermographic copying machine in contact with a graphic original.
- the image areas become colored an intense but still transparent magenta; the background areas become colorless.
- the clear film obtained after 24 hours storage produces a similar copy.
- the amount of dye in the above formula may be reduced to as little as 0.005 gm. while still obtaining a projectable color image, and may be increased to as much as 0.5 gm. without causing the colorless coating to become light-diffusing. Within these ranges the amount of salt may also be varied so long as sufficient salt is present to cause conversion to the colored image while still avoiding light-diffusion.
- a heat-sensitive copy-sheet comprising a colorless dry film residue of a colored solution in a water-miscible volatile organic solvent of (a) an aqueous solution of tetramethylguanidinium trichloroacetate containing sufficient trichloracetic acid to provide a pH not higher than 3, (b) an inert film-forming binder, and (c) at least one dye from the class of Genacryl Blue 6G-GF, Genacryl Orange G, Genacryl Yellow SGF, Genacryl Yellow 36, Genacryl Red 6B and Genacryl Orange R.
Abstract
A coating composition containing a dye, such for example as Genacryl Orange, and tetramethylguanidine trichloroacetate in a solution of inert binder at a pH not higher than 3 is applied to a carrier sheet to form a colored coating which on brief standing becomes colorless and heat-sensitive.
Description
Unite States atem 1151 3,663,258 Wiese Jr. et al. 1 Ma 16 1972 a 9 [541 HEAT-SENSITIVE COPY-SHEET 3,293,061 12/1966 Lawton ..1 17/368 3,413,138 11/1968 Georgalas. 17/368 {721 g fgg Damn 3,473,945 10/1969 Futaki ..117/36.8 3,483,013 12/1969 Berg et al.. 17/362 [73] Assignee: Minnesota Mining and Manufacturing 3,573,958 6/1971 Small .11 17/368 p y Paul, Minn 3,594,208 7/1971 Wiese et al. ..1 17/369 [22] Filed: Nov. 16, 1970 Primary Examiner-Murray Katz 1 1 1 1 90,120 Att0rney -Kinney, Alexander, Sell, Steldt& Delahunt [52] U.S. Cl. ..1l7/36.8,117/l38.8 F, 117/155 UA ABSTRACT [51] Int. Cl ..B4lm 5/22 A coatin g composmon contammg a dye, such for example as [58] F1eld ofSearch ..1 17/369, 36.8, 36.2 Genacryl Orange and tetramethylguanidine trichlemacetate in a solution ofinert binder at a pH not higher than 3 is applied [56] References cued to a carrier sheet to form a colored coating which on brief UNITED STATES PATENTS standing becomes colorless and heat-sensitive.
3,166,583 l/1965 Martin et al. ..1 17/36.8 4 Claims, N0 Drawings HEAT-SENSITIVE COPY-SHEET This invention relates to heat-sensitive copy-sheet materials useful in the reproduction of graphic originals by the thermographic copying process involving brief exposure of the original to intense radiation while in heat-conductive contact with the copy-sheet. In one important aspect the invention relates to a novel method of making the copy-sheet. In another aspect the invention relates to clear transparent copy-sheet materials from which color projection transparencies may be thermographically prepared.
The copy-sheets of this invention are prepared from solutions containing a suitable dye as hereinafter defined together with tetramethylguanidine trichloroacetate and with sufficient trichloroacetic acid to provide a pH not higher than 3. An inert binder is included and the solution is coated on a suitable carrier or may be dried as a thin film on a temporary support and then stripped therefrom for use in absence of a carrier. Paper carriers are useful but clear transparent films, particularly heat-resistant films such as Mylar polyester films, are preferred. Polyvinyl acetate is a preferred example of an inert polymeric film-forming binder.
The following dyes have been found particularly effective in copy-sheets made in accordance with this invention:
Genacryl Blue 66G.F. (CI 42025) Genacryl Orange G (CI 48035) Genacryl Yellow SGF (CI 48065) Genacryl Yellow 30 (CI 48055) Genacryl Red 6B (CI 48020) Genacryl Orange R (CI 48040) The tetramethylguanidinium trichloroacetate, and sufficient trichloroacetic acid to give the required pH, are dissolved together in a minimum quantity of water and the solution is then added to a solution of the dye and binder in a water-miscible organic solvent. The colored mixture is spread and dried, forming a colored dry film. Upon standing under normal room conditions for not longer than 24 hours, or in shorter times at moderately elevated temperatures, the film is found to be decolorized. It may then be made to become brilliantly colored by localized heating in the thermographic copying process. The thus developed images are permanent and project a colored image against a white background when the film is used as a projection transparency.
Surprisingly, all attempts to decolorize the solution prior to coating and drying, e.g., by heating or by prolonged storage, result in a film product which remains colored on prolonged storage and therefore is not subsequently capable of forming a useful contrasty colored image by thermographic copying methods.
In a specific Example, 0.050 gm. of tetramethyl-guanidinium trichloroacetate is dissolved in 0.1 ml. of water and approximately one-tenth drop of dilute aqueous trichloroacetic acid is added to bring the pH of the solution to 3 as determined with p Hydrion" (pH 1-5) indicator paper. Separately, 0.075 gm. of Genacryl Red 68 (CI 48020) is mixed with 5 gm. of a 10 percent solution of Gelva V-IOO" polyvinyl acetate in methylethyl ketone. The acidified salt solution is mixed into the dye and binder solution and the mixture is coated on two mil Mylar polyester film using a coating orifice of three mils, and allowed to dry. The coated film is magenta colored. It fades and becomes colorless within less than 24 hours, or may be decolorized by moderate heating for much shorter periods.
The film as initially produced and while still colored is passed through a thermographic copying machine in contact witha graphic original. The image areas become colored an intense but still transparent magenta; the background areas become colorless. The clear film obtained after 24 hours storage produces a similar copy.
The amount of dye in the above formula may be reduced to as little as 0.005 gm. while still obtaining a projectable color image, and may be increased to as much as 0.5 gm. without causing the colorless coating to become light-diffusing. Within these ranges the amount of salt may also be varied so long as sufficient salt is present to cause conversion to the colored image while still avoiding light-diffusion.
What is claimed is as follows:
1. A heat-sensitive copy-sheet comprising a colorless dry film residue of a colored solution in a water-miscible volatile organic solvent of (a) an aqueous solution of tetramethylguanidinium trichloroacetate containing sufficient trichloracetic acid to provide a pH not higher than 3, (b) an inert film-forming binder, and (c) at least one dye from the class of Genacryl Blue 6G-GF, Genacryl Orange G, Genacryl Yellow SGF, Genacryl Yellow 36, Genacryl Red 6B and Genacryl Orange R.
2. Copy-sheet of claim 1 wherein the ratio of dye to tetramethylguanidinium trichloroacetate is about 3:2.
3. Copy-sheet of claim 2 wherein the dye is Genacryl Red 6B and the binder is polyvinyl acetate.
4. Copy-sheet of claim 1 wherein the ratio of binderzdyezsalt is about 20:3:2.
Claims (3)
- 2. Copy-sheet of claim 1 wherein the ratio of dye to tetramethylguanidinium trichloroacetate is about 3:2.
- 3. Copy-sheet of claim 2 wherein the dye is Genacryl Red 6B and the binder is polyvinyl acetate.
- 4. Copy-sheet of claim 1 wherein the ratio of binder:dye:salt is about 20:3:2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9012070A | 1970-11-16 | 1970-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3663258A true US3663258A (en) | 1972-05-16 |
Family
ID=22221414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US90120A Expired - Lifetime US3663258A (en) | 1970-11-16 | 1970-11-16 | Heat-sensitive copy-sheet |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3663258A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013074907A1 (en) | 2011-11-17 | 2013-05-23 | Air Products And Chemicals, Inc. | Processes, products, and compositions having tetraalkylguanidine salt of aromatic carboxylic acid |
| EP2725047A1 (en) | 2012-10-24 | 2014-04-30 | Air Products And Chemicals, Inc. | Delay action catalyst for improving the stability of polyurethane systems having halogen containing blowing agents |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166583A (en) * | 1962-05-01 | 1965-01-19 | Du Pont | Aralkylcy anoforms |
| 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 |
| US3413138A (en) * | 1965-10-13 | 1968-11-26 | Interchem Corp | Thermosensitive copy sheet |
| US3473945A (en) * | 1965-08-30 | 1969-10-21 | Mitsubishi Paper Mills Ltd | Coated thermosensitive copying sheet |
| US3483013A (en) * | 1966-10-28 | 1969-12-09 | Minnesota Mining & Mfg | Fade resistant sheet for making color projection transparency |
| US3573958A (en) * | 1968-05-31 | 1971-04-06 | Francis E Small | Heat sensitive recording sheet |
| US3594208A (en) * | 1969-06-16 | 1971-07-20 | Minnesota Mining & Mfg | Heat sensitive color projection transparency blank and method of making |
-
1970
- 1970-11-16 US US90120A patent/US3663258A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166583A (en) * | 1962-05-01 | 1965-01-19 | Du Pont | Aralkylcy anoforms |
| 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 |
| US3473945A (en) * | 1965-08-30 | 1969-10-21 | Mitsubishi Paper Mills Ltd | Coated thermosensitive copying sheet |
| US3413138A (en) * | 1965-10-13 | 1968-11-26 | Interchem Corp | Thermosensitive copy sheet |
| US3483013A (en) * | 1966-10-28 | 1969-12-09 | Minnesota Mining & Mfg | Fade resistant sheet for making color projection transparency |
| US3573958A (en) * | 1968-05-31 | 1971-04-06 | Francis E Small | Heat sensitive recording sheet |
| US3594208A (en) * | 1969-06-16 | 1971-07-20 | Minnesota Mining & Mfg | Heat sensitive color projection transparency blank and method of making |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013074907A1 (en) | 2011-11-17 | 2013-05-23 | Air Products And Chemicals, Inc. | Processes, products, and compositions having tetraalkylguanidine salt of aromatic carboxylic acid |
| US9765009B2 (en) | 2011-11-17 | 2017-09-19 | Evonik Degussa Gmbh | Processes, products, and compositions having tetraalkylguanidine salt of aromatic carboxylic acid |
| US10464876B2 (en) | 2011-11-17 | 2019-11-05 | Evonik Degussa Gmbh | Processes, products, and compositions having tetraalkylguanidine salt of aromatic carboxylic acid |
| EP2725047A1 (en) | 2012-10-24 | 2014-04-30 | Air Products And Chemicals, Inc. | Delay action catalyst for improving the stability of polyurethane systems having halogen containing blowing agents |
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