WO1981000084A1 - Process for preparing a thermochromic varnish,coating prepared therefrom and utilization thereof - Google Patents
Process for preparing a thermochromic varnish,coating prepared therefrom and utilization thereof Download PDFInfo
- Publication number
- WO1981000084A1 WO1981000084A1 PCT/CH1980/000039 CH8000039W WO8100084A1 WO 1981000084 A1 WO1981000084 A1 WO 1981000084A1 CH 8000039 W CH8000039 W CH 8000039W WO 8100084 A1 WO8100084 A1 WO 8100084A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- layer
- hardener
- thermochromic
- sulfur
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000576 coating method Methods 0.000 title abstract description 8
- 239000011248 coating agent Substances 0.000 title abstract description 5
- 239000002966 varnish Substances 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 15
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002427 irreversible effect Effects 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000002009 diols Chemical group 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 21
- 238000013459 approach Methods 0.000 claims description 18
- 239000004922 lacquer Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002845 discoloration Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims 2
- 239000006185 dispersion Substances 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- -1 sulphur ions Chemical class 0.000 abstract description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001449 anionic compounds Chemical class 0.000 abstract description 2
- 229910001412 inorganic anion Inorganic materials 0.000 abstract description 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 3
- 150000001412 amines Chemical class 0.000 abstract 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 5
- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHIJGQUZXXURRH-TYYBGVCCSA-N (e)-but-2-enedioic acid;nickel Chemical compound [Ni].OC(=O)\C=C\C(O)=O BHIJGQUZXXURRH-TYYBGVCCSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical compound [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- FYJVPALNHZOUGC-UHFFFAOYSA-N hexanedioic acid;iron Chemical compound [Fe].OC(=O)CCCCC(O)=O FYJVPALNHZOUGC-UHFFFAOYSA-N 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- MMUCNHNUAIJJRH-UHFFFAOYSA-N oxonickel hydrate Chemical compound [O].O.[Ni] MMUCNHNUAIJJRH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GVCGWXSZNUOTDW-UHFFFAOYSA-N sulfo cyanate Chemical compound OS(=O)(=O)OC#N GVCGWXSZNUOTDW-UHFFFAOYSA-N 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 108010089746 wobe Proteins 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
-
- 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
Definitions
- thermochromic lacquer Process for producing a thermochromic lacquer, layer produced from this lacquer and its use
- DE-AS 1 181 245 describes a multi-layer copy paper which consists at least of a carrier layer made of paper, a radiation-absorbing layer and a thermochromic layer.
- the thermochromic layer contains a thermoplastic substance, for example ethyl cellulose, as a film-forming agent together with a mixture of a heavy metal soap with butyl catechol or a water-soluble heavy metal salt with thiourea.
- the copy paper is intended for non-contact thermography with the aid of a radiation source, the radiation-absorbing layer permitting a reduction in the radiation energy.
- the present invention has for its object to provide a method for producing a thermochromic paint according to the preamble of claim 1, which is suitable for covering even non-porous, non-absorbent smooth surfaces. Another object is to produce optical contrasts on the thermochromic layers produced from this lacquer by heat transfer with contact by means of a heating head without soiling or damage.
- the batches which are suitable for their preparation should, if appropriate, be stable for a relatively long time before processing and the thermochromic layers produced from them should harden themselves at room temperature. Finally, these layers should have special properties which enable them to be used in new applications.
- thermochromic lacquers and layers produced therefrom if at least two batch-stable approaches are used which consist of mixtures which contain a contrast-forming constituent and a layer-forming agent compatible therewith.
- the first approach can, for example, consist of a finely divided heavy or noble metal compound dispersed in a resin-based solution and the second in a finely divided sulfur which is dispersed in a hardener for the resin-based and which releases sulfur in ionized form when heated above 70 C / Carbon covalent connection exist.
- the sulfur / carbon covalent compound can likewise be dispersed separately in a resin-based solution and the hardener can be used as a third, stable approach.
- the resin base can contain a prepolymer of methacrylic acid dissolved in an aromatic solvent or a compound containing epoxy groups which slowly and with only a moderate exothermic reaction to form an epoxy resin, in the first case a diol and in the second case an amine group-containing compound is used as a hardener.
- the heavy or noble metal compound is said to be a water- and solvent-insoluble oxide, a salt, or a compound with an inorganic anion or with a monocarboxylic acid with 2, 8, 10, 12, 14, 16, 18, 20, 22 or 28 carbon atoms or with a dicarboxylic acid such as fumaric acid or adipic acid from the metals bismuth, copper, silver, gold, mercury,
- a compound of the general formula can be used as the sulfur / carbon covalent compound
- thermochromic layers on smooth surfaces to be described later on plastic or metallized plastic, an intimate mixture of the approaches should be used, which can be applied in the screen printing process.
- Such layers preferably have a thickness of 10 to 100 ⁇ m and they experience an irreversible local dark discoloration by contact with a heating element heated to a temperature of 140 to 200 C for a maximum of 10 to 300 milliseconds without any sticking of the layer to the heating element.
- An older protective right (CH patent application No. 9361 / 78-4) describes a card-shaped payment medium with optical markings which represent value units and which are arranged between two protective layers which are impervious to visible light and for gradual validation of the payment medium can be erased or changed by supplying thermal energy, at least part of the payment means having a thermochromic material.
- thermochromic layers can be coated by means of a cover layer containing the thermochromic material or itself contain the thermochromic material.
- the production of thermochromic layers for this purpose poses particular problems. Since the thermal energy to be used for deleting the optical markings and for producing the thermographic black coloring is often very limited, the careful coordination of the composition of the mixture of the lacquers required for producing such layers with the printing conditions and the layer thickness must be particularly important Attention should be paid. These dependencies are explained below using a drawing figure
- This figure shows areas in which the mochromic layers made of the thermochromic lacquers experience an irreversible blackening when they are touched by a heating head.
- the diagram shows the touch time in milliseconds on the horizontal and the temperature of the print head in C on the vertical. Four zones are delimited from bottom to top within a period of time between 10 and 300 milliseconds, a layer thickness of 10 to 100 .mu.m predetermined by a coating method using pressure being required for the thermochromic layers.
- Zones 1 and 2 are the so-called forbidden zones, which extend over the range from 0 to 140 ° C.
- the blackening temperature of the mochromic layer of zone 1 is in this range, the exothermic reaction of the mixture of the components used for their production is already so violent that a black color can already be observed when the layer hardens.
- the pot life of the mixtures for layers in the zones 1 and 2 is insufficient for the same reason.
- the temperature can reach up to 70 C in such layers. They are insufficiently thermostable.
- Zones 3 and 4 are in the range of the limits of the invention, within which at room temperature even for a long time Storage should not blacken the thermochromic layer.
- two-component resin systems are selected which, after mixing, produce an exothermic reaction which is limited to an increase in temperature to 40 ° C. and harden to a dust-dry state at room temperature after 30 to 60 minutes.
- Zone 3 extends over printhead temperatures of 150 + 10 C. It offers the best compromise between stability against unintentional blackening and the energy required for the desired blackening. These layers are therefore particularly suitable for the debitable card-shaped means of payment described in more detail in Examples 1 and 2.
- thermochromic layers of components with a relatively low exothermic effect are provided for the reaction. They show a higher heat stability. In contrast, a higher thermal energy expenditure is necessary for the intended blackening.
- thermochromic layers are suitable for card-shaped payment means with optical markings, which can be canceled by contact with a heating element and whose cancellation is indicated by local blackening of the thermochromic layer. They are produced from a varnish from two or three approaches which can be stored by themselves using the screen printing method.
- the heating energy of the heating element is used for these purposes 2 is limited to 150 to 400 mJ for an area of 8 mm and is also in the deletion of the markings and in the
- Dividing blackening process is in addition to the layer thickness
- the first batch consists of 10 parts by weight of a colorless prepolymer of methacrylic acid, 3 parts of pencilate in finely dispersed form with a particle size of at most 5 ⁇ m, which are finely dispersed together, for example in a ball mill.
- the second batch contains 25 parts by weight of a colorless prepolymer of methacrylic acid, which is finely dispersed together with 5 parts of thiobenzamide.
- the third approach consists of a hardener with at least one diol.
- a lacquer is produced from 130 parts by weight of the first batch, 25 parts of the second batch and 60 parts of the third batch in a three-roller mixer. Since in this case there is a sufficient proportion of hardener for a mixture with a contrast-forming constituent, a dispersed mixture of the thiobenzamide which is compatible with the hardener is also suitable as a second batch, with more prepolymer accordingly being present in the first batch.
- the mixture can be mixed with a diluent, for example with a mixture of toluene and xylene with a boiling point of 110 to 140 ° C. in proportions of up to 10% of the total mixture, in order to achieve a viscosity suitable for coating Winning lacquers. If desired, it is used with matting agents or other substances for - 7 -
- a heavy metal soap which is sparingly soluble in water and solvents can be used, which is able to form an irreversibly dark-colored metal sulfide compound with sulfur ions in the heat. Because very fine layers are to be applied, the price of the corresponding heavy metal portion does not play a significant role for the purpose described.
- a monocarboxylic acid with 2, 8, 10, 14, 16, 18, 20, 22 or 28 carbon atoms or a dicarboxylic acid such as
- Fumaric acid or adipic acid can be used. Oxides of these metals or salts of noble metals which form dark-colored sulfides are also suitable.
- the heavy metal soap must be finely dispersed and should have a particle size of less than 5 m. It can also act as a dispersant.
- Thiourea is of limited use as a sulfur / carbon covalent compound, since it is partially converted into sulfocyanate in the heat and reacts with certain heavy metal compounds even at room temperature. For this reason it is difficult to dose. After all, it is water and alcohol soluble.
- Thiobenzamide is ideal, especially because it is available in a very fine form with particle sizes of approximately 10 ⁇ m.
- the binder system should only contain solvents which have a boiling point of at least 110 ° C.
- the layer thickness should be 10 to 100 ⁇ m with an optimum at 15 ⁇ m.
- the thermochromic layer is already hardening at room temperature and it is heat-resistant, even up to 130 C with a very short heat load
- thermochromic layer is briefly touched, preferably with a heating head heated to 150 + 10 C (zone 3 of the diagram) with a contact area of 2 x 4 mm.
- a heating energy of only about 300 mJ must be used to destroy the marking and blacken the thermochromic layer.
- the sulfur / carbon covalent compound initially cleaves sulfide ions.
- the sulfide ions then combine with the heavy metal ions to form a heavy metal sulfide that is black in color.
- These sulfides are very stable chemical compounds.
- the binder helps to create sharp, non-leaking prints. Furthermore, this binder combination prevents the heating head used for printing from sticking to the thermographic layer. The heating heads therefore remain clean and the layers smooth.
- thermochromic layers produced according to this example are intended for the same purposes and for the same temperatures of the heating head as those according to example 1.
- the first approach contains as a metal compound a part by weight of finely divided basic bismuth nitrate and a part of a slowly hardening and low exothermic glycidyl ether.
- the second approach contains two parts of the glycidyl ether and one part of thiobenzamide. Both batches are individually finely dispersed in a dispersing device.
- the third approach is formed by a diamine cold hardener which forms an insoluble epoxy resin with the glycidyl ether.
- thermochromic layer formed by means of a lacquer from the same parts of the three batches as in Example 1 in the screen printing process.
- the properties of the thermochromic layer produced in this way are analogous to those of Example 1. They can also be used for plastic check cards, credit cards, identification cards or access cards.
- the first batch consists of 10 parts by weight of the prepolymer of methacrylic acid used in the first example, 2 parts of iron adipate and 1 part of iron octoate, which are treated up to a particle size of at most 5 ⁇ m in a ball mill and dispersed together.
- the second batch is formed by dispersing 10 parts of the prepolymer used in the first component with 3 parts of N, N'-diphenylthiourea.
- the same hardener as in Example 1 is used.
- the lacquer used for the layer formation is produced from 13 parts each of the first and second batch, from 6 parts of the third batch and optionally from up to 10% of the solvent mixture used in Example 1 in a dispersing device. It can be applied in the same way as that of Example 1. It can also be produced without or with the addition of a suitable aromatic diluent by means of a doctor blade or in the form of a varnish by spraying in layer thicknesses of less than 100 ⁇ m. In this way, printable coatings can be produced on smooth metal or plastic surfaces, on housings of electrical or telephone apparatuses, albums and book covers by supplying heat.
- the thermochromic layers according to this example fall under zone 3 or 4 of the diagram with regard to their thermal behavior.
- the first batch consists of 10 parts of the prepolymer according to Example 1 and 3 parts of copper laurate.
- the second batch contains 3 parts of prepolymer and 1 part of phenylthiourea.
- the third approach is formed by the hardener described in Example 1. The batches 1 and 2 are separately finely dispersed.
- the layer-forming lacquer consists of 15 parts of the first, 4 parts of the second and third batch and up to 10 diluents.
- layers are formed from a first batch with 10 parts by weight of prepolymer, 2 parts of nickel fumarate and 1 part of nickel oxide hydrate, a second batch with 10 parts of prepolymer and 3.8 parts of N-allylthiocarbamide (thiosinamine) and with the same hardener as above, by dispersing 13 parts of the first, 7 parts of the second and 3.5 parts of the third batch together.
- the layers of this lacquer show a thermal behavior according to the lowest part of zone 3 of the diagram. There is one for the darkness
- Milliseconds and a temperature of 210 C of the heating element require a heating energy of 210 mJ.
- thermochromic layers according to Examples 3 to 5 have properties similar to those according to Example 1. They are transparent and, due to their small layer thickness of at most 100 ⁇ m, in the worst case they show a hardly noticeable discoloration due to the metal compound. They form a sharp, high-contrast mark on the heated areas. They are suitable especially good for coating small areas and for imitating hot stamped foils. The best results are achieved when both the weight ratio of prepolymer to hardener and the heavy metal compound to the sulfur / carbon covalent compound are stoichiometric.
- the thermochromic layers made from these compounds have very good mechanical and chemical resistance, wet strength and adhesive strength on various surfaces.
- thermochromic layers contain sulfur / carbon covalent compounds which only release sulfur ions in the heat and, in contrast to what is known as a binder, high-temperature-resistant two-component polymers. They are therefore particularly stable, abrasion-resistant and do not stick to the heating elements in the zones marked 3 and 4 in the diagram.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Paints Or Removers (AREA)
- Printing Methods (AREA)
- Credit Cards Or The Like (AREA)
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH5987/79 | 1979-06-27 | ||
CH598779A CH641200A5 (de) | 1979-06-27 | 1979-06-27 | Verfahren zur herstellung eines thermochromen lacks, aus diesem lack hergestellte schicht und deren verwendung. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1981000084A1 true WO1981000084A1 (en) | 1981-01-22 |
Family
ID=4302541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CH1980/000039 WO1981000084A1 (en) | 1979-06-27 | 1980-03-21 | Process for preparing a thermochromic varnish,coating prepared therefrom and utilization thereof |
Country Status (13)
Country | Link |
---|---|
US (1) | US4394407A (de) |
EP (1) | EP0030939B1 (de) |
JP (1) | JPS5915079B2 (de) |
AT (1) | AT384433B (de) |
BE (1) | BE884031A (de) |
CH (1) | CH641200A5 (de) |
DE (1) | DE2927094C2 (de) |
ES (1) | ES8105640A1 (de) |
GB (1) | GB2066977B (de) |
IT (1) | IT1131372B (de) |
NL (1) | NL8020078A (de) |
SE (1) | SE444537B (de) |
WO (1) | WO1981000084A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0351875A2 (de) * | 1988-07-22 | 1990-01-24 | Nippon Paper Industries Co., Ltd. | Masse zur Herstellung eines im nahen IR absorbierenden Materials und die Masse oder das Material enthaltender Formkörper |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60193594U (ja) * | 1984-05-31 | 1985-12-23 | 京セラ株式会社 | 自発光式標識 |
JPH0244560Y2 (de) * | 1987-04-03 | 1990-11-27 | ||
DE3932505C2 (de) | 1989-09-28 | 2001-03-15 | Gao Ges Automation Org | Datenträger mit einem optisch variablen Element |
US5997849A (en) * | 1993-12-29 | 1999-12-07 | Chromatic Technologies, Inc. | Thermochromic ink formulations, nail lacquer and methods of use |
US5591255A (en) * | 1993-12-29 | 1997-01-07 | Chromatic Technologies, Inc. | Thermochromic ink formulations, nail lacquer and methods of use |
AT404696B (de) * | 1994-03-16 | 1999-01-25 | Landis & Gyr Business Support | Informationsträger mit wärmeempfindlichen gitterstrukturen |
DE19801589C2 (de) * | 1998-01-17 | 2001-02-01 | Bundesdruckerei Gmbh | Verfahren zur fälschungssicheren Herstellung von Wert- und Sicherheitsdokumenten |
FI982837A (fi) * | 1998-12-30 | 2000-07-01 | Nokia Mobile Phones Ltd | Elektroninen laite, elektronisen laitteen kuori ja elektronisen laitte en kuoren valmistusmenetelmä |
DE19932240B4 (de) * | 1999-07-10 | 2005-09-01 | Bundesdruckerei Gmbh | Optisch variabel darstellbare/versteckbare Sicherheitselemente für Wert- und Sicherheitsdokumente |
US7172991B2 (en) * | 2001-10-11 | 2007-02-06 | Hewlett-Packard Development Company, L.P. | Integrated CD/DVD recording and labeling |
US20050196604A1 (en) * | 2004-03-05 | 2005-09-08 | Unifoil Corporation | Metallization process and product produced thereby |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1407481A (fr) * | 1964-01-16 | 1965-07-30 | Koreska Gmbh W | Matériau d'enregistrement sensible à la chaleur et procédé pour sa fabrication |
FR1421954A (fr) * | 1964-01-24 | 1965-12-17 | Ilford Ltd | Nouveaux composés triazéniques, leur préparation et leurs applications |
GB1029735A (en) * | 1963-03-28 | 1966-05-18 | Sun Chemical Corp | Heat-sensitive coating compositions |
FR2089372A5 (de) * | 1970-04-09 | 1972-01-07 | Eastman Kodak Co | |
DE2327135A1 (de) * | 1972-05-29 | 1973-12-20 | Mitsubishi Paper Mills Ltd | Waermeempfindliches aufzeichnungsmaterial |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1100050B (de) * | 1959-03-14 | 1961-02-23 | Kalle Ag | Waermeempfindliches Kopiermaterial |
BE631000A (de) * | 1962-04-12 | 1900-01-01 | ||
JPS494343B1 (de) * | 1970-12-17 | 1974-01-31 |
-
1979
- 1979-06-27 CH CH598779A patent/CH641200A5/de not_active IP Right Cessation
- 1979-07-04 DE DE2927094A patent/DE2927094C2/de not_active Expired
-
1980
- 1980-03-21 JP JP55500596A patent/JPS5915079B2/ja not_active Expired
- 1980-03-21 AT AT0904080A patent/AT384433B/de not_active IP Right Cessation
- 1980-03-21 US US06/233,783 patent/US4394407A/en not_active Expired - Fee Related
- 1980-03-21 WO PCT/CH1980/000039 patent/WO1981000084A1/de active IP Right Grant
- 1980-03-21 NL NL8020078A patent/NL8020078A/nl not_active Application Discontinuation
- 1980-03-21 GB GB8101279A patent/GB2066977B/en not_active Expired
- 1980-06-20 IT IT22899/80A patent/IT1131372B/it active
- 1980-06-26 BE BE0/201196A patent/BE884031A/fr not_active IP Right Cessation
- 1980-06-26 ES ES492802A patent/ES8105640A1/es not_active Expired
-
1981
- 1981-01-26 EP EP80900487A patent/EP0030939B1/de not_active Expired
- 1981-02-26 SE SE8101268A patent/SE444537B/sv not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1029735A (en) * | 1963-03-28 | 1966-05-18 | Sun Chemical Corp | Heat-sensitive coating compositions |
FR1407481A (fr) * | 1964-01-16 | 1965-07-30 | Koreska Gmbh W | Matériau d'enregistrement sensible à la chaleur et procédé pour sa fabrication |
FR1421954A (fr) * | 1964-01-24 | 1965-12-17 | Ilford Ltd | Nouveaux composés triazéniques, leur préparation et leurs applications |
FR2089372A5 (de) * | 1970-04-09 | 1972-01-07 | Eastman Kodak Co | |
DE2327135A1 (de) * | 1972-05-29 | 1973-12-20 | Mitsubishi Paper Mills Ltd | Waermeempfindliches aufzeichnungsmaterial |
Non-Patent Citations (1)
Title |
---|
Derwent Japanese Patents Report, Volume 5, Nr. 40, veroffentlicht im 1966, London (GB) Mitsubishi Paper Mills Ltd. "Thermophotographic sheets", siehe Teil 3, Seite 4, Spalte 2, letzter Abschnitt bis Seite 5, Spalte 1, Abschnitt 1, ubereinstimmend mit JP, B, 17191/66 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0351875A2 (de) * | 1988-07-22 | 1990-01-24 | Nippon Paper Industries Co., Ltd. | Masse zur Herstellung eines im nahen IR absorbierenden Materials und die Masse oder das Material enthaltender Formkörper |
EP0351875A3 (en) * | 1988-07-22 | 1990-09-26 | Jujo Paper Co., Ltd. | Composition for the preparation of a near ir absorbing material and molded articles containing this composition or this material |
Also Published As
Publication number | Publication date |
---|---|
BE884031A (fr) | 1980-10-16 |
GB2066977B (en) | 1983-07-13 |
DE2927094A1 (de) | 1981-01-08 |
JPS5915079B2 (ja) | 1984-04-07 |
NL8020078A (nl) | 1981-04-29 |
SE8101268L (sv) | 1981-02-26 |
IT1131372B (it) | 1986-06-18 |
JPS56500801A (de) | 1981-06-18 |
IT8022899A0 (it) | 1980-06-20 |
AT384433B (de) | 1987-11-10 |
EP0030939B1 (de) | 1984-04-18 |
US4394407A (en) | 1983-07-19 |
DE2927094C2 (de) | 1984-06-28 |
SE444537B (sv) | 1986-04-21 |
CH641200A5 (de) | 1984-02-15 |
GB2066977A (en) | 1981-07-15 |
EP0030939A1 (de) | 1981-07-01 |
ATA904080A (de) | 1987-04-15 |
ES492802A0 (es) | 1981-06-01 |
ES8105640A1 (es) | 1981-06-01 |
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