EP0030939A1 - Procede pour la preparation d'un vernis thermochromique, couche preparee a partir de ce vernis et son utilisation. - Google Patents

Procede pour la preparation d'un vernis thermochromique, couche preparee a partir de ce vernis et son utilisation.

Info

Publication number
EP0030939A1
EP0030939A1 EP80900487A EP80900487A EP0030939A1 EP 0030939 A1 EP0030939 A1 EP 0030939A1 EP 80900487 A EP80900487 A EP 80900487A EP 80900487 A EP80900487 A EP 80900487A EP 0030939 A1 EP0030939 A1 EP 0030939A1
Authority
EP
European Patent Office
Prior art keywords
compound
layer
sulfur
hardener
thermochromic
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.)
Granted
Application number
EP80900487A
Other languages
German (de)
English (en)
Other versions
EP0030939B1 (fr
Inventor
Eva Blazso
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.)
Siemens Building Technologies AG
Landis and Gyr AG
Original Assignee
Landis and Gyr AG
LGZ Landis and Gyr Zug AG
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 Landis and Gyr AG, LGZ Landis and Gyr Zug AG filed Critical Landis and Gyr AG
Publication of EP0030939A1 publication Critical patent/EP0030939A1/fr
Application granted granted Critical
Publication of EP0030939B1 publication Critical patent/EP0030939B1/fr
Expired legal-status Critical Current

Links

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)
  • Paints Or Removers (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Credit Cards Or The Like (AREA)
  • Printing Methods (AREA)

Abstract

Pour la preparation de vernis thermochromique, on utilise un melange approprie pour la serigraphie de deux ou trois composes entreposables. Le premier compose est un compose de metal lourd ou noble disperse dans une solution a base de resine. Le deuxieme compose est un compose covalent du soufre et du carbone, dispersable dans la solution a base de resine ou dans un durcisseur de resine et le troisieme compose est un durcisseur. La resine et le compose metallique sont dans des rapports stoechiometriques avec respectivement le durcisseur et le compose covalent du soufre et du carbone. Le compose metallique est un derive d'un oxyde, d'un anion inorganique ou d'un acide mono- ou dicarboxylique, formant avec les ions de soufre, des sulfures metalliques de couleur noire irreversible. La resine est un prepolymere d'acide methacrylique ou d'un ether glycidylique et le durcisseur est un diol ou une amine. La couche thermochromique a une epaisseur de 10 a 1000 (Alpha)m et subit une coloration noire irreversible et locale avec un element chauffant. Les couches de vernis sont utilisees sur des cartes de credit avec marquages optiques qui peuvent etre effaces thermiquement et dont l'effacement peut etre rendu visible par noircissement.
EP80900487A 1979-06-27 1981-01-26 Procede pour la preparation d'un vernis thermochromique, couche preparee a partir de ce vernis et son utilisation Expired EP0030939B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH598779A CH641200A5 (de) 1979-06-27 1979-06-27 Verfahren zur herstellung eines thermochromen lacks, aus diesem lack hergestellte schicht und deren verwendung.
CH5987/79 1979-06-27

Publications (2)

Publication Number Publication Date
EP0030939A1 true EP0030939A1 (fr) 1981-07-01
EP0030939B1 EP0030939B1 (fr) 1984-04-18

Family

ID=4302541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80900487A Expired EP0030939B1 (fr) 1979-06-27 1981-01-26 Procede pour la preparation d'un vernis thermochromique, couche preparee a partir de ce vernis et son utilisation

Country Status (13)

Country Link
US (1) US4394407A (fr)
EP (1) EP0030939B1 (fr)
JP (1) JPS5915079B2 (fr)
AT (1) AT384433B (fr)
BE (1) BE884031A (fr)
CH (1) CH641200A5 (fr)
DE (1) DE2927094C2 (fr)
ES (1) ES492802A0 (fr)
GB (1) GB2066977B (fr)
IT (1) IT1131372B (fr)
NL (1) NL8020078A (fr)
SE (1) SE444537B (fr)
WO (1) WO1981000084A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
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 (fr) * 1987-04-03 1990-11-27
JPH0781127B2 (ja) * 1988-07-22 1995-08-30 日本製紙株式会社 近赤外線吸収剤用組成物並に近赤外線吸収材料及びそれらを含有した成形体
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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1100050B (de) * 1959-03-14 1961-02-23 Kalle Ag Waermeempfindliches Kopiermaterial
BE631000A (fr) * 1962-04-12 1900-01-01
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
US3679426A (en) * 1970-04-09 1972-07-25 Eastman Kodak Co Photosensitive and thermosensitive elements,compositions and processes
JPS494343B1 (fr) * 1970-12-17 1974-01-31

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8100084A1 *

Also Published As

Publication number Publication date
JPS56500801A (fr) 1981-06-18
ES8105640A1 (es) 1981-06-01
WO1981000084A1 (fr) 1981-01-22
SE444537B (sv) 1986-04-21
BE884031A (fr) 1980-10-16
GB2066977B (en) 1983-07-13
SE8101268L (sv) 1981-02-26
JPS5915079B2 (ja) 1984-04-07
ES492802A0 (es) 1981-06-01
AT384433B (de) 1987-11-10
NL8020078A (nl) 1981-04-29
EP0030939B1 (fr) 1984-04-18
IT1131372B (it) 1986-06-18
IT8022899A0 (it) 1980-06-20
US4394407A (en) 1983-07-19
GB2066977A (en) 1981-07-15
CH641200A5 (de) 1984-02-15
DE2927094A1 (de) 1981-01-08
DE2927094C2 (de) 1984-06-28
ATA904080A (de) 1987-04-15

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