EP0014826B1 - Element having reversible and fixed light-extinction effects which are variable with temperature - Google Patents
Element having reversible and fixed light-extinction effects which are variable with temperature Download PDFInfo
- Publication number
- EP0014826B1 EP0014826B1 EP80100111A EP80100111A EP0014826B1 EP 0014826 B1 EP0014826 B1 EP 0014826B1 EP 80100111 A EP80100111 A EP 80100111A EP 80100111 A EP80100111 A EP 80100111A EP 0014826 B1 EP0014826 B1 EP 0014826B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- ester
- amide
- ammonium salt
- acid
- 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
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- 238000012538 light obscuration Methods 0.000 title claims abstract description 24
- 230000002441 reversible effect Effects 0.000 title claims abstract description 6
- 230000000694 effects Effects 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 64
- 239000011159 matrix material Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 28
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- -1 halogen fatty acid Chemical class 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 3
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 3
- 229930195729 fatty acid Natural products 0.000 claims abstract description 3
- 239000000194 fatty acid Substances 0.000 claims abstract description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims abstract description 3
- 150000001337 aliphatic alkines Chemical class 0.000 claims abstract 2
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract 2
- 150000001926 cycloalkines Chemical class 0.000 claims abstract 2
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 230000004075 alteration Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 26
- 230000008569 process Effects 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000013500 data storage Methods 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000013021 overheating Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 230000002277 temperature effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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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
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/363—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a low molecular weight organic compound such as a fatty acid, e.g. for reversible recording
Definitions
- Example 10b and claim 9 of DE-A-2030652 relate to a body with reversible, fixed and temperature-variable light extinctions, the temperature behavior of which corresponds to that of the body according to the application.
- a substance pair consisting of two polymers dissolved in one another is used here, during which one substance of the substance pair according to the invention is low molecular weight and at least partially undissolved.
- US-A-3240932 describes a pair of substances consisting of a polymer matrix material and a more or less low-molecular substance for a body with likewise reversible, fixed and temperature-dependent light extinctions.
- the material pair in the desired areas is subjected to mechanical stress in order to generate maximum light absorbance, as a result of which the low-molecular substance crystallizes from its amorphous state and assumes an opaque character.
- the pair of substances is subjected to heating, through which the transparent amorphous state is restored. This is a different mechanism of action compared to the subject of the invention.
- US-A-3240932 also only mentions other low-molecular substances.
- EP-A-0000868 names substances of a pair of substances which can also be used in the pair of substances according to the application. However, these substances are selected and combined in the known pair of substances so that no fixed light extinctions are achieved. Rather, the change in light extinction achieved by changing the temperature disappears when the temperature falls below a certain initial temperature, so that only temporary recordings are possible here.
- the object underlying the invention was therefore to obtain new data storage and recording materials, the recorded data of which can be deleted in the simplest possible manner and which can then be used again for recording data.
- the bodies according to the invention with reversible, fixed and temperature-variable light extinctions consisting of a pair of substances (A and B), one substance (A) of which consists of at least one polymer and / or resin matrix material, and which when heated from the state maximum light absorbance from up to a temperature below a conversion temperature (T z) clear temperature (T 1) followed by cooling below a lower temperature value (T o) with increasing heating temperature (T) decreasing light absorbance and upon heating to a temperature between T 1 and T 2 and subsequent cooling under T o results in minimal light extinctions, whereby when heating above the transition temperature above T 1 (T z ) with subsequent cooling under T o maximum light extinction is obtained again, are characterized in that the other substance (B) of the pair of substances at least one organic low mole kular substance, which is at least partially obtained as a disperse insoluble phase in the substance (A) and an alkanol, alkanediol, hal
- the subject matter of the pair of substances in the subject matter of the invention is selected such that fixed light extinctions result with a temperature behavior that corresponds to that of DE-A-2030652.
- bodies When referring to bodies, they can have different shapes, such as sheets, blocks, films, tubes and the like, or they can take the form of a coating on another support, such as a transparent film.
- body is used here used in the broadest sense.
- the recording materials thus erased can be used again for data recordings, the recording process and erasing process being able to be repeated as often as desired.
- the heat required for image generation can be supplied in any way, preferably by means of finely bundled heat or light radiation or by contact heat from electrical conductor tracks.
- the images obtained on the recording materials according to the invention can be clearly recognized by the eye or read in the microscopic range using conventional photoelectronic devices. Data can be recorded using the analog method as well as the digital method.
- intermediate tones can also be produced with the subject matter of the invention, so that, with the appropriate temperature setting, photographic images with high resolution can be obtained.
- the recordings can be made in the positive process as well as in the negative process. If one starts from the state of minimal light extinction, ie from the maximally transparent state, one obtains opaque images, such as characters and the like, on the transparent base by heating above the transition temperature T 2 . These all have the maximum opacity that can be achieved. In order to achieve halftones or gray tones, in this positive process the image area of maximum opacity that is to be brightened must be heated to a temperature between T o and T 1 in a second process, a different brightening being achieved in this area depending on the heating temperature becomes. With the positive method, each recorded element can be completely erased by heating the area of these recorded elements to a temperature between T 1 and T 2 . The point to be corrected becomes completely transparent again. By then heating this point again to a temperature above T 2 , the correct recording element can then be inserted at the same point.
- a resolution of at least 300 to 400 lines per millimeter can be achieved, so that the method is suitable for any optical data recording, including the production of microfilms.
- the layer can be colored slightly, and then individual dots with a diameter of less than 0.003 mm can be recorded, the time required for the recording of a point being in the microsecond range, depending on the energy of the laser beam.
- the recordings can be deleted with the same laser beams, but by reducing the power.
- the dimensions of the body according to the invention can be chosen as desired.
- the preferred embodiment of these bodies consists of a transparent carrier film with a coating with the pair of substances A / B.
- the thickness of this coating can be varied as desired and for example, between about 10- 6 m and a few millimeters are. Coatings having a thickness between 10- 6 m and 10- 4 m are preferred.
- the material pairs A / B can also form self-supporting foils or films if one selects matrix materials which, together with the embedded organic low-molecular substances, are sufficiently mechanically stable so that they do not have to be supported on an additional carrier.
- T 1 and T 2 are preferably at least 5 ° C., particularly preferably 5 to 50, and particularly 5 to 15 ° C. If the distance from T 1 to T 2 is too large, the records have to be deleted using the negative method overheating, which can be disadvantageous for certain matrix materials or applications.
- the maximum opacity is necessarily restored when it cools down.
- maximum opacity, maximum transparency or an opaque intermediate tone depending on the temperature effect can be set there as desired.
- any intermediate tone can be subsequently adjusted to a temperature between T o and T 1 by heating the areas that have already been made opaque .
- the organic low-molecular substance (B) expediently has a refractive index at ambient temperature in the solid state which comes as close as possible to that of the matrix material (A), since maximum transparency is then achieved in the transparent state.
- the substance pair A / B can therefore be selected according to this criterion.
- the temperature T 2 corresponds essentially to the melting point of the organic, low-molecular substance (B). The latter can therefore be used as a further selection criterion.
- Material pairs A / B are preferably selected such that the organic low-molecular substance (B) in the solid state has two different state forms, such as, for. B. crystal forms, which have different refractive indices, which has a stable state at the clear temperature T 1 has a refractive index that comes as close as possible to that of the matrix material (A), while the other stable state has a refractive index that lies between this and that Melt the organic low molecular weight substance (B). In interaction with the matrix material (A), depending on the temperature pretreatment, corresponding state forms of the substance (B) appear.
- two different state forms such as, for. B. crystal forms, which have different refractive indices, which has a stable state at the clear temperature T 1 has a refractive index that comes as close as possible to that of the matrix material (A), while the other stable state has a refractive index that lies between this and that Melt the organic low molecular weight substance (B).
- the organic low molecular weight substance (B) is second in the matrix material (A), i.e. H. stored as a discrete phase, expediently finely distributed in the form of small to very small particles, such as droplets or crystallites.
- the degree of fine distribution of the organic substance in the matrix material can be adjusted depending on the desired effect and intended use.
- the organic substance (B) can be incorporated into the matrix material in various ways and can be finely distributed therein.
- One method consists in mixing and ge monomers and / or oligomers and / or prepolymers of the matrix material (A) with the organic substance (B) if necessary, add a hardener for the monomers, oligomers or prepolymers and polymerize this mixture to form and shape the matrix material.
- the organic substance (B) can be present in solution in the monomers, oligomers or prepolymers of the matrix material, provided that at any point during the polymerization an incompatibility or poor solubility or phase separation occurs, so that in the end point the matrix material and the organic substance are actually two separate phases are present, of which that organic substance (B) is the inner or disperse phase which is usually more or less finely dispersed in the matrix phase.
- Another method is to mix the organic substance (B) with a solution of the matrix material in an organic solvent and then to evaporate the solvent while shaping the matrix material.
- the organic substance can initially dissolve completely in the common solution when it is dissolved, but at some point in time when the solvent evaporates, it must precipitate out in a finely divided form as the second phase.
- Another method consists in melting the matrix material, then mixing or dispersing the organic substance (B) and finally cooling the matrix material with shaping after uniform mixing.
- the shaping can consist in polymerizing, hardening or solidifying the matrix material with the organic substance (B) finely divided therein by shaping the matrix material in conventional extruders with mouthpieces into foils or plates or other moldings or other conventional molding processes , such as film forming processes, or else polymerize the matrix material as a coating on another transparent body, such as a glass plate or transparent plastic film, or by coating the transparent body, such as a glass plate, by evaporation of the solvent or by solidification.
- all known molding processes can be used, since the matrix material is polymer or resin materials, the shape of which is known to the person skilled in the art.
- the matrix materials can be thermoplastic or thermosetting plastics, natural or synthetic resins, they can harden into elastomers or rigid bodies.
- a wide variety of substance classes can be used as matrix materials, the special selection being based on the one hand on the refractive index and on the other hand on the physical properties required for a specific purpose. They should be as mechanically stable and film-forming as possible.
- suitable matrix materials are, for example, polyesters, polyamides, polystyrene, polyacrylates and. Polymethacrylates and silicone resins.
- the polyesters the high molecular weight linear saturated polyesters are particularly suitable, especially those with molecular weights of 10,000 to 20,000.
- vinylidene chloride copolymers such as polyvinylidene chloride-acrylonitrile copolymers, polyvinyl chloride, vinyl chloride, vinyl acetate and vinyl chloride-vinyl acetate copolymers and / or polyester.
- matrix materials are polymers made from 91% by weight vinyl chloride, 3% by weight vinyl acetate and 6% by weight vinyl alcohol, from 83% by weight vinyl chloride, 16% by weight vinyl acetate and 1% by weight maleic acid or from 90% by weight vinyl chloride , 5% by weight of polyvinyl acetate and 5% by weight of vinyl alcohol, vinyl chloride-acrylate copolymers, terpolymers with free carboxyl groups and polymers of 83% by weight of vinyl chloride, 16% by weight of vinyl acetate and 1% by weight of diacarboxylic acid.
- organic substance (B) is selected from 1: 3 to 1:16, preferably from 1: to 1:12, so that 3 to 16, preferably 6 to 12 parts by weight Matrix material come on a part by weight of the organic substance (B).
- Particularly useful organic substances (B) are those with at least one heteroatom, especially oxygen, nitrogen, sulfur and / or halogen, in the molecule.
- the halogen atoms in the halogen-substituted compounds of substance (B) are expediently chlorine or bromine, especially chlorine.
- the halogen compounds expediently contain one or two halogen substituents. Those compounds which have at least one straight-chain aliphatic group, expediently having 10 to 30 carbon atoms, have proven to be particularly favorable as organic substance (B).
- the aryl group is preferably phenyl or substituted phenyl.
- Low molecular weight in the case of substances (B) preferably means molecular weights of 100 to 700, preferably 300 to 500. It is advantageous to use substances (B) which, in the phase change from solid to liquid or vice versa, have a volume jump of at least 5%, preferably from 5 to 15% show.
- dyes, brighteners, UV or IR absorbers can be added to the respective material pairs A / B. If laser beams are used for data recording, it is possible to match the dye or the wavelength of the laser to one another in such a way that the highest possible thermal energy is supplied at a given resonance frequency. Suitable wetting agents and leveling aids can also be added to the substance mixtures, as are used, for example, in the coating industry to achieve better adhesion and surface smoothness.
- component A can consist of one or more polymers or resins and component B can consist of one or more organic low-molecular substances.
- the bodies according to the invention can advantageously be used as erasable record carriers. These can be used in various areas of application, such as data storage, decorative purposes, advertising purposes and others.
- thermofunctional layer produced in this way is opaque / white after cooling to room temperature and shows a fixed transparency when heated to 72 ° C and subsequent cooling, which can only be converted to the opaque state again by heating to temperatures above 77 ° C.
- Fig. 2 shows the dependence of the light absorbance on the temperature for this material.
- thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 63 ° C and then cooled, which can only be converted to the opaque state again by heating to temperatures above 74'C.
- any number of levels between the maximum and minimum extinction values can be reached corresponding to temperatures between 40 and 63 ° C.
- Fig. 3 shows the dependence of the light absorbance on the temperature for this material.
- thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 68 ° C and then cooled, which can only be converted to the opaque state again by heating to temperatures above 70 ° C.
- Fig. 4 shows the dependence of the light absorbance on the temperature for this material.
- a part of docosanoic acid is dissolved in 6 parts by weight of a 20% strength solution of a polyester based on a mixture of aromatic and non-aromatic dicarboxylic acids and aliphatic diols (Dynapol L 206 polyester from Dynamit Nobel) in trichlorethylene.
- This solution is applied with the aid of a wire knife to a 0.075 mm thick film of polyterephthalic acid glycol ester in such a way that a layer thickness of 0.02 mm results after evaporation of the solvent.
- thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 72 ° C and then cooled to temperatures below 72 ° C, which can only be converted to the opaque state again by heating to temperatures above 77 ° C.
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- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
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Abstract
Description
Es ist üblich, Informationen aller Art einschliesslich Daten, Bildern, Schriftzeichen, Mustern usw., auf transparenten Trägern aufzuzeichen, um sie optisch sichtbar zu speichern und entweder kopieren oder projizieren zu können. Auf diese Weise werden beispielsweise Mikrofilme und dergleichen gewonnen. Die Aufzeichnung erfolgt bekanntermassen mit Hilfe einer lichtempfindlichen Schicht auf optimalem Wege, wobei das Aufzeichnungsverfahren ein Entwickeln und Fixieren der aufzuzeichnenden Informationen einschliesst.It is common to record all types of information, including data, images, characters, patterns, etc., on transparent media in order to save them in an optically visible manner and to be able to either copy or project them. In this way, microfilms and the like are obtained, for example. As is known, the recording is carried out in an optimal way with the aid of a light-sensitive layer, the recording method including developing and fixing the information to be recorded.
Vielfach sind solchermassen aufgezeichnete Informationen geheim oder sollen wenigstens nicht in fremde Hände gelangen. Wenn soche Informationsträger nicht mehr benötigt werden, müssen sie daher sorgfältig vernichtet werden, wofür vielfach ein Zerkleinern nicht ausreicht, da etwa bei Mikrofilmen die Schrift so klein ist, dass die beim Zerkleinern erhaltenen Stücke noch unerwünschte zusammenhängende Informationen beinhalten. Es ist daher in solchen Fällen erforderlich, auf chemischem Wege die Schicht zu zerstören, was arbeitsaufwendig und durch Verwendung von Chemikalienlösungen unangenehm ist, besonders wenn grössere Mengen an Aufzeichnungsträgern vernichtet werden sollen. Ausserdem sind solche bekannten Aufzeichnungsträger, auf denen die Informationen gelöscht wurden, nicht wieder verwendbar.In many cases, information recorded in this way is secret or at least should not get into someone else's hands. If such information carriers are no longer required, they must therefore be carefully destroyed, for which shredding is often not sufficient, since, for microfilms, for example, the writing is so small that the pieces obtained during shredding still contain unwanted, coherent information. In such cases, it is therefore necessary to chemically destroy the layer, which is labor-intensive and unpleasant due to the use of chemical solutions, especially if large amounts of recording media are to be destroyed. In addition, such known recording media on which the information has been deleted cannot be reused.
Beispeil 10b und Anspruch 9 der DE-A-2030652 betreffen einen Körper mit reversiblen, fixierten und temperaturveränderlichen Lichtextinktionen, dessen Temperaturverhalten dem der anmeldungsgemässen Körper entspricht. Jedoch findet hier ein Stoffpaar aus zwei ineinander gelösten Polymeren Anwendung, während der eine Stoff des erfindungsgemässen Stoffpaares niedermolekular und zumindest teilweise ungelöst ist.Example 10b and claim 9 of DE-A-2030652 relate to a body with reversible, fixed and temperature-variable light extinctions, the temperature behavior of which corresponds to that of the body according to the application. However, a substance pair consisting of two polymers dissolved in one another is used here, during which one substance of the substance pair according to the invention is low molecular weight and at least partially undissolved.
Die US-A-3240932 beschreibt zwar für einen Körper mit gleichfalls reversiblen, fixierten und temperaturabhängigen Lichtextinktionen ein Stoffpaar aus einem polymeren Matrixmaterial und einer mehr oder weniger niedermolekularen Substanz. Hier wird jedoch zur Erzeugung maximaler Lichtextinktion das Stoffpaar in den gewünschten Bereichen einer mechanischen Belastung ausgesetzt, wodurch der niedermolekulare Stoff aus seinem amorphen Zustand kristallisiert und opaken Charakter annimmt. Zur Beseitigung dieses Zustandes wird das Stoffpaar einer Erwärmung unterzogen, durch die der durchsichtige amorphe Zustand wiederhergestellt wird. Dies ist im Vergleich zum Erfindungsgegenstand ein anderer Wirkmechanismus. Auch nennt die US-A-3240932 nur andere niedermolekulare Stoffe.US-A-3240932 describes a pair of substances consisting of a polymer matrix material and a more or less low-molecular substance for a body with likewise reversible, fixed and temperature-dependent light extinctions. Here, however, the material pair in the desired areas is subjected to mechanical stress in order to generate maximum light absorbance, as a result of which the low-molecular substance crystallizes from its amorphous state and assumes an opaque character. In order to eliminate this state, the pair of substances is subjected to heating, through which the transparent amorphous state is restored. This is a different mechanism of action compared to the subject of the invention. US-A-3240932 also only mentions other low-molecular substances.
Die EP-A-0000868 nennt zwar für einen Körper mit veränderlicher Lichtextinktion Stoffe eines Stoffpaares, die auch bei dem anmeldungsgemässen Stoffpaar Verwendung finden können. Doch werden diese Stoffe bei dem bekannten Stoffpaar so ausgewählt und kombiniert, dass keine fixierten Lichtextinktionen erzielt werden. Vielmehr verschwindet die durch Temperaturveränderung erzielte Veränderung der Lichtextinktion beim Unterschreiten einer bestimmten Ausgangstemperatur, so dass hier nur temporäre Aufzeichnungen möglich sind.For a body with variable light extinction, EP-A-0000868 names substances of a pair of substances which can also be used in the pair of substances according to the application. However, these substances are selected and combined in the known pair of substances so that no fixed light extinctions are achieved. Rather, the change in light extinction achieved by changing the temperature disappears when the temperature falls below a certain initial temperature, so that only temporary recordings are possible here.
Die der Erfindung zugrundeliegende Aufgabe bestand somit darin, neue Datenspeicherungs-und Aufzeichnungsmaterialien zu bekommen, deren aufgezeichnete Daten auf möglichst einfache Weise gelöscht werden können und die danach erneut zur Aufzeichnung von Daten verwendet werden können.The object underlying the invention was therefore to obtain new data storage and recording materials, the recorded data of which can be deleted in the simplest possible manner and which can then be used again for recording data.
Die erfindungsgemässen Körper mit reversiblen, fixierten und temperaturveränderlichen Lichtextinktionen, insbesondere zur Verwendung als löschbarer Aufzeichnungsträger, bestehend aus einem Stoffpaar (A und B), dessen einer Stoff (A) aus wenigstens einem Polymer- und/oder Harzmatrixmaterial besteht und das beim Erwärmen vom Zustand maximaler Lichtextinktion aus bis zu einer unter einer Umwandlungstemperatur (Tz) liegenden Klartemperatur (T1) und anschliessendem Abkühlen unter einen unteren Temperaturwert (To) mit steigender Erwärmungstemperatur (T) kleiner werdende Lichtextinktion und beim Erwärmen auf eine Temperatur zwischen T1 und T2 und anschliessendem Abkühlen unter To minimale Lichtextinktionen ergibt, wobei beim Erwärmen über die oberhalb T1 liegende Umwandlungstemperatur (Tz) mit anschliessendem Abkühlen unter To erneut maximale Lichtextinktion erhalten wird, sind dadurch gekennzeichnet, dass der andere Stoff (B) des Stoffpaares wenigstens eine organische niedermolekulare Substanz ist, die zumindest teilweise als disperse unlösliche Phase im Stoff (A) erhalten und ein Alkanol, Alkandiol, Halogenalkanol oder -alkandiol, Alkylamin, Alkan, Alken, Alkin, Halogenalkan, -alken oder -alkin, Cycloalkan, -alken oder -alkin, eine gesättigte oder ungesättigte Mono- oder Dicarbonsäure oder ein Ester oder ein Amid oder Ammoniumsalz derselben, eine gesättigte oder ungesättigte Halogenfettsäure oder ein Ester, ein Amid oder Ammoniumsalz derselben, eine Arylcarbonsäure oder ein Ester, ein Amid oder Ammoniumsalz derselben, eine Halogenarylcarbonsäure oder ein Ester, ein Amid oder ein Ammoniumsalz derselben, ein Thioalkohol, eine Thiocarbonsäure oder ein Ester, ein Amid oder Ammoniumsalz derselben oder ein Carbonsäureester eines Thioalkohols oder Gemische dieser Verbindungen, deren jede 10 bis 60, vorzugsweise 10 bis 38, besonders 10 bis 30 Kohlenstoffatome besitzt, wobei in den Estern die Alkoholgruppe ihrerseits gesättigt oder ungesättigt und/oder halogensubstituiert sein kann, ist.The bodies according to the invention with reversible, fixed and temperature-variable light extinctions, in particular for use as an erasable record carrier, consisting of a pair of substances (A and B), one substance (A) of which consists of at least one polymer and / or resin matrix material, and which when heated from the state maximum light absorbance from up to a temperature below a conversion temperature (T z) clear temperature (T 1) followed by cooling below a lower temperature value (T o) with increasing heating temperature (T) decreasing light absorbance and upon heating to a temperature between T 1 and T 2 and subsequent cooling under T o results in minimal light extinctions, whereby when heating above the transition temperature above T 1 (T z ) with subsequent cooling under T o maximum light extinction is obtained again, are characterized in that the other substance (B) of the pair of substances at least one organic low mole kular substance, which is at least partially obtained as a disperse insoluble phase in the substance (A) and an alkanol, alkanediol, haloalkanol or -alkanediol, alkylamine, alkane, alkene, alkyne, haloalkane, -alken or -alkyne, cycloalkane, -alkene or - alkyne, a saturated or unsaturated mono- or dicarboxylic acid or an ester or an amide or ammonium salt thereof, a saturated or unsaturated halogen fatty acid or an ester, an amide or ammonium salt thereof, an arylcarboxylic acid or an ester, an amide or ammonium salt thereof, a haloarylcarboxylic acid or an ester, an amide or an ammonium salt thereof, a thioalcohol, a thiocarboxylic acid or an ester, an amide or ammonium salt thereof or a carboxylic acid ester of a thioalcohol or mixtures of these compounds, each having 10 to 60, preferably 10 to 38, especially 10 to 30 carbon atoms has, the alcohol group in turn being saturated or unsaturated and / or halogen substituted in the esters can be, is.
Gegenüber der EP-A-0000868 sind beim Erfindungsgegenstand die betreffenden Stoffe des Stoffpaares so ausgewählt, dass sich fixierte Lichtextinktionen ergeben mit einem Temperaturverhalten, das dem der DE-A-2030652 entspricht.Compared to EP-A-0000868, the subject matter of the pair of substances in the subject matter of the invention is selected such that fixed light extinctions result with a temperature behavior that corresponds to that of DE-A-2030652.
Wenn hier von Körpern die Rede ist, so können diese unterschiedliche Form besitzen, wie etwa als Platten, Blöcke, Filme, Rohre und dergleichen, oder sie können die Form eines Überzuges auf einem anderen Träger, wie einer transparenten Folie haben. Der Begriff «Körper» wird hier also im weitesten Sinne verwendet.When referring to bodies, they can have different shapes, such as sheets, blocks, films, tubes and the like, or they can take the form of a coating on another support, such as a transparent film. The term "body" is used here used in the broadest sense.
Wenn hier von Informationen, Daten oder Aufzeichnungen die Rede ist, sollen auch diese Begriffe im weitesten Sinne verstanden werden, wie als Zahlen, Buchstaben, Bilder, Muster zu dekorativen Zwecken oder dergleichen.When information, data or records are mentioned here, these terms should also be understood in the broadest sense, such as numbers, letters, images, patterns for decorative purposes or the like.
Mit dem Erfindungsgegenstand wurde überraschenderweise gefunden, dass es erfindungsgemäss möglich ist, durch einfache Wärmeentwicklung ohne Nachbehandlung und ohne chemische Nassverfahren Aufzeichnungen zu erzeugen, d. h. auch ohne Entwicklungsverfahren und Fixierverfahren, wie sie bei lichtempfindlichen Schichten erforderlich sind. Besonders überraschend ist es, dass die durch Wärme erzeugten Aufzeichnungen ebenfalls ausschliesslich durch Wärmeeinwirkung gelöscht werden können, ohne dass chemische Verfahren oder Nassbehandlungen erforderlich wären.It has surprisingly been found with the subject matter of the invention that it is possible according to the invention to generate records by simple heat development without aftertreatment and without chemical wet processes, i. H. even without the development and fixing processes that are required for light-sensitive layers. It is particularly surprising that the recordings generated by heat can also be deleted exclusively by the action of heat, without the need for chemical processes or wet treatments.
Weiterhin ist es überraschend, dass die so gelöschten Aufzeichnungsmaterialien erneut für Datenaufzeichnungen verwendet werden können, wobei der Aufzeichnungsvorgang und Löschvorgang beliebig oft wiederholt werden kann.Furthermore, it is surprising that the recording materials thus erased can be used again for data recordings, the recording process and erasing process being able to be repeated as often as desired.
Die für die Bilderzeugung benötigte Wärme kann auf beliebige Weise zugeführt werden, vorzugsweise mittels fein gebündelter Wärme- oder Lichtstrahlung oder durch Kontaktwärme aus elektrischen Leiterbahnen. Je feiner die Wärmestrahlenbündelung ist und die Abmessungen der Leiterbahnen sind, desto schärfere Aufzeichnungen lassen sich erhalten. Mit Laserstrahlen bekommt man ein hohes Auflösungsvermögen in der Grössenordnung von 10-6 m. Dieses hohe .Auflösungsvermögen führt zu einer scharfen Bildwiedergabe.The heat required for image generation can be supplied in any way, preferably by means of finely bundled heat or light radiation or by contact heat from electrical conductor tracks. The finer the heat radiation bundle and the dimensions of the conductor tracks, the sharper the recordings can be obtained. With laser beams, you get a high resolving power in the order of 10- 6 m. This high resolution leads to sharp image reproduction.
Die auf den Aufzeichnungsmaterialien nach der Erfindung erhaltenen Bilder lassen sich mit dem Auge deutlich erkennen oder mit üblichen photoelektronischen Geräten im mikroskopischen Bereich ablesen. Es sind Datenaufzeichnungen nach dem Analogverfahren wie auch nach dem Digitalverfahren möglich.The images obtained on the recording materials according to the invention can be clearly recognized by the eye or read in the microscopic range using conventional photoelectronic devices. Data can be recorded using the analog method as well as the digital method.
Erstaunlicherweise kann man mit dem Erfindungsgegenstand auch Zwischentöne erzeugen, so dass man bei entsprechender Temperatureinstellung photographieartige Abbildungen mit hohem Auflösungsvermögen erhalten kann.Surprisingly, intermediate tones can also be produced with the subject matter of the invention, so that, with the appropriate temperature setting, photographic images with high resolution can be obtained.
Die Aufzeichnungen können im Positivverfahren wie auch im Negativverfahren erfolgen. Geht man von dem Zustand minimaler Lichtextinktion, d. h. vom maximal transparenten Zustand aus, so bekommt man durch Erhitzen über die Umwandlungstemperatur T2 auf dem transparenten Grund opake Abbildungen, wie Schriftzeichen und dergleichen. Diese besitzen alle die maximal erreichbare Opazität. Um Halbtöne bzw. Grautöne zu erzielen, muss bei diesem Positivverfahren der Bildbereich maximaler Opazität, der aufgehellt werden soll, in einem zweiten Vorgang auf eine Temperatur zwischen To und T1 erwärmt werden, wobei je nach der Erwärmungstemperatur in diesem Bereich eine unterschiedliche Aufhellung erreicht wird. Beim Positivverfahren kann man jedes aufgezeichnete Element vollständig löschen, indem man den Bereich dieser aufgezeichneten Elemente auf eine Temperatur zwischen T1 und T2 erwärmt. Dabei wird die zu korrigierende Stelle wieder vollständig transparent. Durch anschliessendes erneutes Erwärmen dieser Stelle auf eine Temperatur oberhalb T2 lässt sich dann an der gleichen Stelle das richtige Aufzeichnungselement einfügen.The recordings can be made in the positive process as well as in the negative process. If one starts from the state of minimal light extinction, ie from the maximally transparent state, one obtains opaque images, such as characters and the like, on the transparent base by heating above the transition temperature T 2 . These all have the maximum opacity that can be achieved. In order to achieve halftones or gray tones, in this positive process the image area of maximum opacity that is to be brightened must be heated to a temperature between T o and T 1 in a second process, a different brightening being achieved in this area depending on the heating temperature becomes. With the positive method, each recorded element can be completely erased by heating the area of these recorded elements to a temperature between T 1 and T 2 . The point to be corrected becomes completely transparent again. By then heating this point again to a temperature above T 2 , the correct recording element can then be inserted at the same point.
Beim Negativverfahren geht man von dem Zustand maximaler Opazität bzw. maximaler Lichtextinktion aus. Erwärmt man auf eine Temperatur im Bereich zwischen To und T1, bekommt man je nach der Erwärmungstemperatur beliebige Grautöne zwischen dem Zustand maximaler Opazität und dem Zustand maximaler Transparenz. Diese Grautöne können beim Negativverfahren in einem Arbeitsgang erzielt werden.In the negative process, the state of maximum opacity or maximum light extinction is assumed. If you heat to a temperature in the range between T o and T 1 , depending on the heating temperature, you get any gray tones between the state of maximum opacity and the state of maximum transparency. These shades of gray can be achieved in one step in the negative process.
Unabhängig davon, ob man nach dem Negativverfahren oder nach dem Positivverfahren arbeitet, kann man ein Auflösungsvermögen von mindestens 300 bis 400 Linien pro Millimeter erzielen, so dass das Verfahren für jegliche optische Datenaufzeichnung, etwa auch für die Herstellung von Mikrofilmen, geeignet ist. Zur besseren Absorption von Laserstrahlen kann die Schicht schwach eingefärbt werden, und es lassen sich dann einzelne Punkte mit einem Durchmesser von weniger als 0,003 mm aufzeichnen, wobei die für die Aufzeichnung eines Punktes erforderliche Zeit je nach Energie des Laserstrahles im Mikrosekundenbereich liegt. Mit den gleichen Laserstrahlen, jedoch durch Reduktion der Leistung, lassen sich die Aufzeichnungen wieder löschen.Regardless of whether you use the negative method or the positive method, a resolution of at least 300 to 400 lines per millimeter can be achieved, so that the method is suitable for any optical data recording, including the production of microfilms. For better absorption of laser beams, the layer can be colored slightly, and then individual dots with a diameter of less than 0.003 mm can be recorded, the time required for the recording of a point being in the microsecond range, depending on the energy of the laser beam. The recordings can be deleted with the same laser beams, but by reducing the power.
Die Abmessungen der erfindungsgemässen Körper können beliebig gewählt werden. Die bevorzugte Ausbildung dieser Körper besteht in einer transparenten Trägerfolie mit einer Beschichtung mit dem Stoffpaar A/B. Die Dicke dieser Beschichtung kann beliebig variiert werden und beispielsweise zwischen etwa 10-6 m und einigen Millimetern liegen. Beschichtungen mit einer Dikke zwischen 10-6 m und 10-4 m sind bevorzugt. Selbstverständlich können die Stoffpaare A/B auch selbsttragende Folien oder Filme bilden, wenn man Matrixmaterialien auswählt, die zusammen mit den eingelagerten organischen niedermolekularen Substanzen ausreichend mechanisch stabil sind, um nicht auf einem zusätzlichen Träger abgestützt werden zu müssen.The dimensions of the body according to the invention can be chosen as desired. The preferred embodiment of these bodies consists of a transparent carrier film with a coating with the pair of substances A / B. The thickness of this coating can be varied as desired and for example, between about 10- 6 m and a few millimeters are. Coatings having a thickness between 10- 6 m and 10- 4 m are preferred. Of course, the material pairs A / B can also form self-supporting foils or films if one selects matrix materials which, together with the embedded organic low-molecular substances, are sufficiently mechanically stable so that they do not have to be supported on an additional carrier.
In der Zeichnung bedeutet
- Fig.1 eine graphische Darstellung eines typischen Kurvenverlaufes der Abhängigkeit der Lichtextinktion von der Erwärmungstemperatur bei einem Stoffpaar (A/B) nach der Erfindung,
- Fig. 2 die entsprechende Kurve für das konkrete Stoffpaar des Beispiels 1,
- Fig. 3 die entsprechende Kurve für das konkrete Stoffpaar des Beispiels 2 und
- Fig. 4 die entsprechende Kurve für das konkrete Stoffpaar des Beispiels 3.
- 1 shows a graphical representation of a typical curve profile of the dependence of the light extinction on the heating temperature for a pair of substances (A / B) according to the invention,
- 2 shows the corresponding curve for the specific material pair of example 1,
- Fig. 3 shows the corresponding curve for the specific material pair of Example 2 and
- 4 shows the corresponding curve for the specific material pair of example 3.
Anhand der Fig. 1 lässt sich das Verhalten der erfindungsgemäss zu verwendenden Stoffpaare von Matrixmaterial A und niedermolekularer organischer Substanz B erläutern. Wenn man die Lichtextinktion gegen die Erwärmungstemperatur aufträgt, so kann man unterschiedliche Kurvenverläufe bei den erfindungsgemässen Stoffpaaren bekommen, doch gehorchen diese Kurvenverläufe alle den eingangs aufgezeigten Prinzipien.The behavior of the substance pairs of matrix material A and low molecular weight organic substance B to be used according to the invention can be explained with reference to FIG. 1. If you compare the light absorbance with the heating temperature applies, you can get different curves for the material pairs according to the invention, but these curves obey all of the principles outlined above.
Nimmt man einen Körper aus einem Stoffpaar A/B nach der Erfindung im Zustand maximaler Opazität und erwärmt diesen Körper von einer Temperatur To aus, und geht man dabei nicht über die Temperatur Ti, so hellt sich die Opazität je nach Temperatursteigerung mehr und mehr auf, d. h. der Körper wird an den erwärmten Stellen lichtdurchlässiger, d. h. transparenter. Beim Abkühlen bis auf die Temperatur To oder darunter bleibt dieser Trübungszwischenwert zwischen maximaler Opazität und maximaler Transparenz erhalten oder im wesentlichen erhalten. Auf diese Weise gelingt es, bei den Aufzeichnungen erfindungsgemäss Halbtöne oder Grautöne zu erzeugen.If one takes a body from a pair of substances A / B according to the invention in the state of maximum opacity and heats this body from a temperature T o , and if one does not go beyond the temperature T i , the opacity brightens more and more depending on the temperature increase on, ie the body becomes more translucent, ie more transparent, in the heated areas. When cooling to the temperature T o or below, this intermediate haze value between maximum opacity and maximum transparency is retained or essentially retained. In this way it is possible to produce halftones or gray tones according to the invention in the recordings.
Erwärmt man jedoch über T1 hinaus bis höchstens T2, so stellt sich beim Abkühlen des Körpers auf die Temperatur To oder darunter stets maximale Transparenz oder minimale Lichtextinktion ein.However, if one heats beyond T 1 to at most T 2 , then when the body cools down to the temperature T o or below, there is always maximum transparency or minimal light extinction.
Man braucht also, um zu maximaler Transparenz zu kommen, nicht auf einen scharfen Temperaturwert zu erwärmen, sondern es genügt, an den transparent zu machenden Stellen auf eine Temperatur irgendwo zwischen T1 und T2 zu erhitzen. Je grösser dieser Temperaturabstand zwischen T1 und T2 ist, desto leichter lässt sich die maximale Lichtdurchlässigkeit ohne Gefahr von Zwischenwerten oder Rückkehr zur maximalen Opazität erreichen. Vorzugsweise beträgt der Abstand zwischen T1 und T2 mindestens 5°C, besonders bevorzugt 5 bis 50, und besonders 5 bis 15° C. Wenn der Abstand von T1 zu T2 zu gross ist, muss man im Negativverfahren beim Löschen der Aufzeichnungen zu hoch erhitzen, was bei bestimmten Matrixmaterialien oder Anwendungen von Nachteil sein kann.In order to achieve maximum transparency, one does not need to heat up to a sharp temperature value, but it is sufficient to heat up to a temperature somewhere between T 1 and T 2 at the points to be made transparent. The greater this temperature difference between T 1 and T 2 , the easier it is to achieve maximum light transmission without the risk of intermediate values or a return to maximum opacity. The distance between T 1 and T 2 is preferably at least 5 ° C., particularly preferably 5 to 50, and particularly 5 to 15 ° C. If the distance from T 1 to T 2 is too large, the records have to be deleted using the negative method overheating, which can be disadvantageous for certain matrix materials or applications.
Erwärmt man den erfindungsgemässen Körper auf die Temperatur T2 oder darüber, so stellt sich beim Abkühlen zwingend wieder die maximale Opazität ein.If the body according to the invention is heated to the temperature T 2 or above, the maximum opacity is necessarily restored when it cools down.
Je nach Temperatureinstellung auf den betreffenden Stellen des erfindungsgemässen Körpers lässt sich dort also frei nach Wahl maximale Opazität, maximale Transparenz oder ein von der Temperatureinwirkung abhängiger opaker Zwischenton einstellen.Depending on the temperature setting on the relevant areas of the body according to the invention, maximum opacity, maximum transparency or an opaque intermediate tone depending on the temperature effect can be set there as desired.
Verwendet man im Gegensatz zu dem oben beschriebenen Negativverfahren ein Positivverfahren und geht von einem erfindungsgemässen Körper im Zustand maximaler Transparenz aus, so bleibt diese Transparenz bis zur Umwandlungstemperatur T2 nach dem Abkühlen auf dem maximalen Ausgangswert. Erst bei Erreichen der Temperatur T2 oder einer darüberliegenden Temperatur wird der Körper beim Abkühlen opak und erreicht die maximale Opazität.If, in contrast to the negative method described above, a positive method is used and the body according to the invention is in the state of maximum transparency, this transparency remains at the maximum initial value up to the transition temperature T 2 after cooling. Only when the temperature T 2 or a temperature above it is reached does the body become opaque when it cools down and reaches the maximum opacity.
Ausgehend vom transparenten Zustand lassen sich also keine Zwischentöne erreichen, sondern nur maximale Transparenz und maximale Opazität, doch lässt sich, wie oben dargelegt, durch ein zweites Erwärmen der bereits opak gemachten Stellen auf eine Temperatur zwischen To und T1 jeder beliebige Zwischenton nachträglich einstellen.Starting from the transparent state, no intermediate tones can be achieved, but only maximum transparency and maximum opacity, but, as explained above, any intermediate tone can be subsequently adjusted to a temperature between T o and T 1 by heating the areas that have already been made opaque .
Die Fig. 2 bis 4 zeigen konkrete Ausführungsbeispiele für Stoffpaare gemäss den Ausführungsbeispielen 1 bis 3.2 to 4 show concrete exemplary embodiments for material pairs according to exemplary embodiments 1 to 3.
Aufgrund der obigen technischen Lehre ist es dem Fachmann also möglich, anhand einiger Routineversuche jene Stoffpaare auszuwählen, die unter den Erfindungsgegenstand fallen. Hierzu braucht er lediglich von dem Stoffpaar, das durch Dispergieren der Substanz B in dem Matrixmaterial A erhalten wurde, ein Diagramm der Lichtextinktion in Abhängigkeit von der Temperatur oder der Lichtdurchlässigkeit in Abhängigkeit von der Temperatur anzufertigen, was letzteres mit handelsüblichen Apparaturen und automatischen Aufzeichnern möglich ist. Wenn die dabei erhaltene Kurve den oben geschilderten Verlauf mit einer Umwandlungstemperatur T2 und einer Klartemperatur T1 zeigt, entspricht das Stoffpaar zwingend dem Erfindungsgegenstand.On the basis of the above technical teaching, it is therefore possible for a person skilled in the art to select those substance pairs which fall under the subject matter of the invention on the basis of a few routine tests. To do this, he only needs to make a diagram of the light absorbance as a function of temperature or the light transmittance as a function of temperature from the pair of substances obtained by dispersing substance B in the matrix material A, the latter being possible with commercially available apparatus and automatic recorders . If the curve obtained thereby shows the course described above with a transition temperature T 2 and a clear temperature T 1 , the pair of substances necessarily corresponds to the subject of the invention.
Zweckmässig besitzt die organische niedermolekulare Substanz (B) bei Umgebungstemperatur im festen Zustand einen Brechungsindex, der dem des Matrixmaterials (A) möglichst nahekommt, da dann im transparenten Zustand maximale Transparenz erreicht wird. Das Stoffpaar A/B kann also nach diesem Kriterium ausgewählt werden.The organic low-molecular substance (B) expediently has a refractive index at ambient temperature in the solid state which comes as close as possible to that of the matrix material (A), since maximum transparency is then achieved in the transparent state. The substance pair A / B can therefore be selected according to this criterion.
Die Temperatur T2 stimmt im wesentlichen mit dem Schmelzpunkt der organischen, niedermolekularen Substanz (B) überein. Deshalb kann letzterer als weiteres Auswahlkriterium herangezogen werden.The temperature T 2 corresponds essentially to the melting point of the organic, low-molecular substance (B). The latter can therefore be used as a further selection criterion.
Bevorzugt werden Stoffpaare A/B so ausgewählt, dass die organische niedermolekulare Substanz (B) im festen Zustand zwei unterschiedliche Zustandsformen, wie z. B. Kristallformen, besitzt, die unterschiedliche Brechungsindices haben, wobei die eine stabile Zustandsform bei der Klartemperatur T1 einen Brechungsindex hat, der dem des Matrixmaterials (A) möglichst nahekommt, während die andere stabile Zustandsform einen Brechungsindex hat, der zwischen diesem und dem der Schmelze der organischen niedermolekularen Substanz (B) liegt. Im Zusammenspiel mit dem Matrixmaterial (A) stellen sich in Abhängigkeit der Temperaturvorbehandlung entsprechende Zustandsformen der Substanz (B) ein.Material pairs A / B are preferably selected such that the organic low-molecular substance (B) in the solid state has two different state forms, such as, for. B. crystal forms, which have different refractive indices, which has a stable state at the clear temperature T 1 has a refractive index that comes as close as possible to that of the matrix material (A), while the other stable state has a refractive index that lies between this and that Melt the organic low molecular weight substance (B). In interaction with the matrix material (A), depending on the temperature pretreatment, corresponding state forms of the substance (B) appear.
Die organische niedermolekulare Substanz (B) ist in dem Matrixmaterial (A) als zweite, d. h. als diskrete Phase eingelagert, und zwar zweckmässig fein verteilt in der Form kleiner bis kleinster Teilchen, wie als Tröpfchen bzw. Kristallite. Der Grad der Feinverteilung der organischen Substanz in dem Matrixmaterial kann je nach dem erwünschten Effekt und Verwendungszweck eingestellt werden.The organic low molecular weight substance (B) is second in the matrix material (A), i.e. H. stored as a discrete phase, expediently finely distributed in the form of small to very small particles, such as droplets or crystallites. The degree of fine distribution of the organic substance in the matrix material can be adjusted depending on the desired effect and intended use.
Die organische Substanz (B) kann in das Matrixmaterial in unterschiedlicher Weise eingearbeitet und darin fein verteilt werden. Eine Methode besteht darin, Monomere und/oder Oligomere und/ oder Vorpolymere des Matrixmaterials (A) mit der organischen Substanz (B) zu vermischen und gegebenenfalls einen Härter für die Monomeren, Oligomeren oder Vorpolymeren zuzusetzen und dieses Gemisch unter Ausbildung und Formgebung des Matrixmaterials auszupolymerisieren. Dabei kann die organische Substanz (B) in den Monomeren, Oligomeren oder Vorpolymeren des Matrixmaterials durchaus gelöst vorliegen, sofern zu irgendeinem Zeitpunkt während der Polymerisation eine Unverträglichkeit bzw. Schwerlöslichkeit bzw. Phasentrennung auftritt, so dass dann im Endpunkt tatsächlich Matrixmaterial und organische Substanz als zwei getrennte Phasen vorliegen, von denen diejenige organische Substanz (B) die innere oder disperse Phase ist, die in der Matrixphase gewöhnlich mehr oder weniger feinteilig dispergiert ist.The organic substance (B) can be incorporated into the matrix material in various ways and can be finely distributed therein. One method consists in mixing and ge monomers and / or oligomers and / or prepolymers of the matrix material (A) with the organic substance (B) if necessary, add a hardener for the monomers, oligomers or prepolymers and polymerize this mixture to form and shape the matrix material. The organic substance (B) can be present in solution in the monomers, oligomers or prepolymers of the matrix material, provided that at any point during the polymerization an incompatibility or poor solubility or phase separation occurs, so that in the end point the matrix material and the organic substance are actually two separate phases are present, of which that organic substance (B) is the inner or disperse phase which is usually more or less finely dispersed in the matrix phase.
Eine andere Methode besteht darin, die organische Substanz (B) mit einer Lösung des Matrixmaterials in einem organischen Lösungsmittel zu vermischen und anschliessend das Lösungsmittel unter Formgebung des Matrixmaterials zu verdampfen. Auch hier kann zunächst beim Auflösen die organische Substanz sich vollständig in der gemeinsamen Lösung auflösen, muss aber beim Verdampfen des Lösungsmittels zu irgendeinem Zeitpunkt in feinteiliger Form als zweite Phase ausfallen. Selbstverständlich ist es auch möglich, die Substanzen so auszuwählen, dass die organische Substanz (B) sich überhaupt nicht vollständig in der Lösung des Matrixmaterials auflöst, sondern stets als zweite Phase darin dispergiert bleibt, wobei dafür Sorge getragen werden muss, dass man eine feinteilige Dispergierung etwa in der Form von kleinen Tröpfchen oder Kristalliten bekommt, etwa durch wirksame Rühreinrichtungen, Ultraschall oder wirksame Zerkleinerung des Feststoffes.Another method is to mix the organic substance (B) with a solution of the matrix material in an organic solvent and then to evaporate the solvent while shaping the matrix material. Here, too, the organic substance can initially dissolve completely in the common solution when it is dissolved, but at some point in time when the solvent evaporates, it must precipitate out in a finely divided form as the second phase. Of course, it is also possible to select the substances in such a way that the organic substance (B) does not completely dissolve in the solution of the matrix material at all, but always remains dispersed therein as a second phase, care being taken to ensure that there is a fine dispersion in the form of small droplets or crystallites, for example by means of effective stirring devices, ultrasound or effective comminution of the solid.
Eine weitere Methode besteht darin, das Matrixmaterial zu schmelzen, sodann die organische Substanz (B) zuzumischen oder zu dispergieren und abschliessend nach gleichmässigem Durchmischen das Matrixmaterial unter Formgebung abzukühlen.Another method consists in melting the matrix material, then mixing or dispersing the organic substance (B) and finally cooling the matrix material with shaping after uniform mixing.
Die Formgebung kann darin bestehen, dass man das Matrixmaterial mit der darin feinverteilten organischen Substanz (B) in einer Form polymerisieren, aushärten oder erstarren lässt, indem man das Matrixmaterial in üblichen Extrudern mit Mundstücken zu Folien oder Platten oder anderen Formlingen verformt oder andere übliche Formverfahren, wie Folienformverfahren, anwendet oder aber das Matrixmaterial als Beschichtung auf einem anderen transparenten Körper, wie einer Glasplatte oder transparenten Kunststoffolie, auspolymerisieren oder durch Verdampfen des Lösungsmittels oder durch Erstarren eine Beschichtung dieses transparenten Körpers, wie einer Glasplatte, bilden lässt. Grundsätzlich sind alle bekannten Formverfahren anwendbar, da es sich bei dem Matrixmaterial um Polymer- oder Harzmaterialien handelt, deren Formgebung dem Fachmann bekannt ist.The shaping can consist in polymerizing, hardening or solidifying the matrix material with the organic substance (B) finely divided therein by shaping the matrix material in conventional extruders with mouthpieces into foils or plates or other moldings or other conventional molding processes , such as film forming processes, or else polymerize the matrix material as a coating on another transparent body, such as a glass plate or transparent plastic film, or by coating the transparent body, such as a glass plate, by evaporation of the solvent or by solidification. In principle, all known molding processes can be used, since the matrix material is polymer or resin materials, the shape of which is known to the person skilled in the art.
Die Matrixmaterialien können thermoplastische oder duroplastische Kunststoffe, natürliche oder synthetische Harze sein, sie können zu Elastomeren oder starren Körpern härten.The matrix materials can be thermoplastic or thermosetting plastics, natural or synthetic resins, they can harden into elastomers or rigid bodies.
Als Matrixmaterialien können die unterschiedlichsten Stoffklassen verwendet werden, wobei sich die spezielle Auswahl einerseits nach dem Brechungsindex und andererseits nach den für einen speziellen Verwendungszweck benötigten physikalischen Eigenschaften richtet. Sie sollen möglichst mechanisch stabil und filmbildend sein. Beispiele geeigneter Matrixmaterialien sind etwa Polyester, Polyamide, Polystyrol, Polyacrylate und . Polymethacrylate sowie Siliconharze. Unter den Polyestern sind besonders die hochmolekularen linearen gesättigten Polyester, besonders solche mit Molekulargewichten von 10000 bis 20000 geeignet. Besonders brauchbar als Matrixmaterial sind Vinylidenchlorid-Copolymere, wie Polyvinylidenchlorid-Acrylnitrii-Copolymere, Polyvinylchlorid, Vinylchlorid-, Vinylacetat- und Vinylchlorid-Vinylacetat-Copolymere und/oder Polyester. Spezielle Beispiele von Matrixmaterialien sind Polymere aus 91 Gewichts-% Vinylchlorid, 3 Gewichts- % Vinylacetat und 6 Gewichts-% Vinylalkohol, aus 83 Gewichts-% Vinylchlorid, 16 Gewichts-% Vinylacetat und 1 Gewichts-% Maleinsäure oder aus 90 Gewichts-% Vinylchlorid, 5 Gewichts-% Polyvinylacetat und 5 Gewichts-% Vinylalkohol, Vinylchlorid-Acrylat-Copolymere, Terpolymerisate mit freien Carboxylgruppen und Polymere aus 83 Gewichts-% Vinylchlorid, 16 Gewichts-% Vinylacetat und 1 Gewichts-% Diacarbonsäure. Handelsnamen solcher Polymere sind Vinylite VAGH, VMCC und VROH (Union Carbide), Vinnol E 5/48A, E 15/ 40A und H 15/45M (Wacker-Chemie) und Vilit MC 39 (Chemische Werke Hüls AG). Günstigerweise verwendet man Matrixmaterialien (A), die Weissbruch zeigen.A wide variety of substance classes can be used as matrix materials, the special selection being based on the one hand on the refractive index and on the other hand on the physical properties required for a specific purpose. They should be as mechanically stable and film-forming as possible. Examples of suitable matrix materials are, for example, polyesters, polyamides, polystyrene, polyacrylates and. Polymethacrylates and silicone resins. Among the polyesters, the high molecular weight linear saturated polyesters are particularly suitable, especially those with molecular weights of 10,000 to 20,000. Particularly useful as matrix material are vinylidene chloride copolymers, such as polyvinylidene chloride-acrylonitrile copolymers, polyvinyl chloride, vinyl chloride, vinyl acetate and vinyl chloride-vinyl acetate copolymers and / or polyester. Specific examples of matrix materials are polymers made from 91% by weight vinyl chloride, 3% by weight vinyl acetate and 6% by weight vinyl alcohol, from 83% by weight vinyl chloride, 16% by weight vinyl acetate and 1% by weight maleic acid or from 90% by weight vinyl chloride , 5% by weight of polyvinyl acetate and 5% by weight of vinyl alcohol, vinyl chloride-acrylate copolymers, terpolymers with free carboxyl groups and polymers of 83% by weight of vinyl chloride, 16% by weight of vinyl acetate and 1% by weight of diacarboxylic acid. Trade names of such polymers are Vinylite VAGH, VMCC and VROH (Union Carbide), Vinnol E 5 / 48A,
Es ist günstig, das Gewichtsverhältnis von organischer Substanz (B) zu Matrixmaterial (A) im Bereich von 1 : 3 bis 1:16, vorzugsweise von 1 : bis 1:12 zu halten, so dass 3 bis 16, vorzugsweise 6 bis 12 Gewichtsteile Matrixmaterial auf ein Gewichtsteil der organischen Substanz (B) kommen. Besonders brauchbare organische Substanzen (B) sind solche mit wenigstens einem Heteroatom, besonders Sauerstoff, Stickstoff, Schwefel und/ oder Halogen, im Molekül.It is favorable to keep the weight ratio of organic substance (B) to matrix material (A) in the range from 1: 3 to 1:16, preferably from 1: to 1:12, so that 3 to 16, preferably 6 to 12 parts by weight Matrix material come on a part by weight of the organic substance (B). Particularly useful organic substances (B) are those with at least one heteroatom, especially oxygen, nitrogen, sulfur and / or halogen, in the molecule.
Die Halogenatome sind in den halogensubstituierten Verbindungen der Substanz (B) zweckmässig Chlor oder Brom, besonders Chlor. Zweckmässig enthalten die Halogenverbindungen einen oder zwei Halogensubstituenten. Als besonders günstig erwiesen sich solche Verbindungen als organische Substanz (B), die wenigstens eine geradkettige aliphatische Gruppe, zweckmässig mit 10 bis 30 Kohlenstoffatomen, enthalten. In den Arylverbindungen ist die Arylgruppe vorzugsweise Phenyl oder substituiertes Phenyl.The halogen atoms in the halogen-substituted compounds of substance (B) are expediently chlorine or bromine, especially chlorine. The halogen compounds expediently contain one or two halogen substituents. Those compounds which have at least one straight-chain aliphatic group, expediently having 10 to 30 carbon atoms, have proven to be particularly favorable as organic substance (B). In the aryl compounds, the aryl group is preferably phenyl or substituted phenyl.
Niedermolekular bedeutet bei den Substanzen (B) vorzugsweise Molekulargewichte von 100 bis 700, vorzugsweise 300 bis 500. Zweckmässig benutzt man solche Substanzen (B), die bei der Phasenveränderung von fest nach flüssig oder umgekehrt einen Volumensprung von wenigstens 5%, vorzugsweise von 5 bis 15% zeigen.Low molecular weight in the case of substances (B) preferably means molecular weights of 100 to 700, preferably 300 to 500. It is advantageous to use substances (B) which, in the phase change from solid to liquid or vice versa, have a volume jump of at least 5%, preferably from 5 to 15% show.
Zur Verbesserung der optischen Eigenschaften, wie zur Erhöhung der optischen Absorption in einem bestimmten Wellenlängenbereich oder zur Erhöhung des Kontrastes gegenüber der Umgebung, kann man den jeweiligen Stoffpaaren A/B Farbstoffe, Aufheller, UV- oder IR-Absorber zusetzen. Im Falle der Verwendung von Laserstrahlen zur Datenaufzeichnung ist es möglich, den Farbstoff bzw. die Wellenlänge des Lasers so aufeinander abzustimmen, dass bei einer gegebenen Resonanzfrequenz eine möglichst hohe Wärmeenergie zugeführt wird. Auch können den Stoffgemischen geeignete Netzmittel und Verlaufshilfsmittel zugesetzt werden, wie sie beispielsweise in der Lackindustrie zur Erzielung besserer Haftung und Oberflächenglattheit benutzt werden.To improve the optical properties, such as to increase the optical absorption in a certain wavelength range or to increase the contrast with the surroundings, dyes, brighteners, UV or IR absorbers can be added to the respective material pairs A / B. If laser beams are used for data recording, it is possible to match the dye or the wavelength of the laser to one another in such a way that the highest possible thermal energy is supplied at a given resonance frequency. Suitable wetting agents and leveling aids can also be added to the substance mixtures, as are used, for example, in the coating industry to achieve better adhesion and surface smoothness.
Wenn oben von Stoffpaaren (A/B) die Rede ist, bedeutet dies selbstverständlich, dass die Komponenten A aus einem oder mehreren Polymeren oder Harzen und die Komponente B aus einer oder mehreren organischen niedermolekularen Substanzen bestehen kann.Of course, when material pairs (A / B) are mentioned above, this means that component A can consist of one or more polymers or resins and component B can consist of one or more organic low-molecular substances.
Aufgrung der besonderen überraschenden Eigenschaften lassen sich die erfindungsgemässen Körper mit Vorteil als löschbare Aufzeichnungsträger verwenden. Diese können auf den verschiedenen Anwendungsgebieten eingesetzt werden, wie zur Datenspeicherung, zu Dekorationszwekken, zu Werbezwecken und anderem.Due to the special surprising properties, the bodies according to the invention can advantageously be used as erasable record carriers. These can be used in various areas of application, such as data storage, decorative purposes, advertising purposes and others.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung.The following examples serve to further explain the invention.
10 Gewichtsteile eines hochmolekularen linearen Copolyesters auf der Basis aromatischer Dicarbonsäuren und aliphatischer Diole (Polyester Dynapol L 206 der Firma Dynamit Nobel) werden bei ca. 160°C aufgeschmolzen. Zu dieser Schmelze wird ein Teil Docosansäure zugemischt und die Schmelze in einer 0,01 mm dicken Schicht auf eine Glasplatte aufgebracht.10 parts by weight of a high molecular weight linear copolyester based on aromatic dicarboxylic acids and aliphatic diols (polyester Dynapol L 206 from Dynamit Nobel) are melted at approx. 160 ° C. A portion of docosanic acid is mixed into this melt and the melt is applied in a 0.01 mm thick layer to a glass plate.
Die so erzeugte thermofunktionelle Schicht ist nach dem Abkühlen auf Zimmertemperatur opak/ weiss und zeigt beim Erwärmen auf 72°C und anschliessender Abkühlung eine fixierte Transparenz, die erst wieder durch erneute Erwärmung auf Temperaturen über 77°C in den opaken Zustand überführt werden kann.The thermofunctional layer produced in this way is opaque / white after cooling to room temperature and shows a fixed transparency when heated to 72 ° C and subsequent cooling, which can only be converted to the opaque state again by heating to temperatures above 77 ° C.
Fig. 2 zeigt die Abhängigkeit der Lichtextinktion von der Temperatur für dieses Material.Fig. 2 shows the dependence of the light absorbance on the temperature for this material.
Zu 6 Gewichtsteilen einer 30%igen Lösung eines Copolymeren aus Vinylidenchlorid und Acrylnitril (Saran F 310 der Firma Dow Chemicals & Co.) in Tetrahydrofuran werden 6 Gewichtsteile einer 5%igen Lösung von Docosansäure in Tetrahydrofuran gemischt.6 parts by weight of a 5% solution of docosanoic acid in tetrahydrofuran are mixed into 6 parts by weight of a 30% solution of a copolymer of vinylidene chloride and acrylonitrile (Saran F 310 from Dow Chemicals & Co.) in tetrahydrofuran.
Zur Verbesserung der Verlaufseigenschaften werden 0,2% einer 16%igen Lösung von FC 430 (Fluorad Netzmittel der 3M Company) in Tetrahydrofuran zugemischt. Diese Mischung wird derart auf eine 0,050 mm dicke Folie aus Polyterephthalsäureglycolester aufgebracht, dass nach dem Verdampfen des Lösungsmittels ein Schichtdicke von 0,01 mm resultiert. Die so erzeugte thermofunktionelle Schicht ist opak/weiss und zeigt beim Erwärmen auf 63°C und anschliessender Abkühlung eine fixierte Transparenz, die erst wieder durch erneute Erwärmung auf Temperaturen über 74'C in den opaken Zustand überführt werden kann.To improve the leveling properties, 0.2% of a 16% solution of FC 430 (Fluorad wetting agent from 3M Company) in tetrahydrofuran is added. This mixture is applied to a 0.050 mm thick film of polyterephthalic acid glycol ester in such a way that a layer thickness of 0.01 mm results after evaporation of the solvent. The thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 63 ° C and then cooled, which can only be converted to the opaque state again by heating to temperatures above 74'C.
Darüberhinaus lassen sich bei entsprechender Temperatursteuerung beliebig viele Stufen zwischen Maximal- und Minimalwert der Extinktion entsprechend Temperaturen zwischen 40 und 63°C erreichen.In addition, with appropriate temperature control, any number of levels between the maximum and minimum extinction values can be reached corresponding to temperatures between 40 and 63 ° C.
Fig. 3 zeigt die Abhängigkeit der Lichtextinktion von der Temperatur für dieses Material.Fig. 3 shows the dependence of the light absorbance on the temperature for this material.
Zu 6 Gewichtsteilen einer 30%igen Lösung eines Vinylchlorid-Vinylacetat-Copolymers (Vilit AS 47 der Firma Chemische Werke Hüls AG) in Methylisobutylketon werden 6 Gewichtsteile einer 10%igen Lösung von Docosanol in Tatrahydrofuran gemischt. Diese Lösung wird derart auf eine 0,075 mm dicke Folie aus Polyterephthalsäureglycolester aufgebracht, dass nach dem Verdampfen des Lösungsmittels eine Schichtdicke von ca. 0,01 mm resultiert. Die so erzeugte thermofunktionelle Schicht ist opak/weiss und zeigt beim Erwärmen auf 68°C und anschliessender Abkühlung eine fixierte Transparenz, die erst wieder durch erneute Erwärmung auf Temperaturen über 70°C in den opaken Zustand überführt werden kann.6 parts by weight of a 10% solution of docosanol in tatrahydrofuran are mixed with 6 parts by weight of a 30% solution of a vinyl chloride-vinyl acetate copolymer (Vilit AS 47 from Chemische Werke Huls AG) in methyl isobutyl ketone. This solution is applied to a 0.075 mm thick film of polyterephthalic acid glycol ester in such a way that a layer thickness of approximately 0.01 mm results after evaporation of the solvent. The thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 68 ° C and then cooled, which can only be converted to the opaque state again by heating to temperatures above 70 ° C.
Fig. 4 zeigt die Abhängigkeit der Lichtextinktion von der Temperatur für dieses Material.Fig. 4 shows the dependence of the light absorbance on the temperature for this material.
In 6 Gewichtsteilen einer 20%igen Lösung eines Polyesters auf der Basis eines Gemisches aromatischer und nichtaromatischer Dicarbonsäuren und aliphatischer Diole (Polyester Dynapol L 206 der Firma Dynamit Nobel) in Trichloräthylen wird ein Teil Docosansäure gelöst. Diese Lösung wird mit Hilfe eines Drahtrakels derart auf eine 0,075 mm dicke Folie aus Polyterephthalsäureglycolester aufgebracht, dass nach dem Verdampfen des Lösungsmittels eine Schichtdicke von 0,02 mm resultiert.A part of docosanoic acid is dissolved in 6 parts by weight of a 20% strength solution of a polyester based on a mixture of aromatic and non-aromatic dicarboxylic acids and aliphatic diols (Dynapol L 206 polyester from Dynamit Nobel) in trichlorethylene. This solution is applied with the aid of a wire knife to a 0.075 mm thick film of polyterephthalic acid glycol ester in such a way that a layer thickness of 0.02 mm results after evaporation of the solvent.
Die so erzeugte thermofunktionelle Schicht ist opak/weiss und zeigt beim Erwärmen auf 72°C und anschliessender Abkühlung auf Temperaturen unter 72°C eine fixierte Transparenz, die erst wieder durch erneute Erwärmung auf Temperaturen über 77°C in den opaken Zustand überführt werden kann.The thermofunctional layer produced in this way is opaque / white and shows a fixed transparency when heated to 72 ° C and then cooled to temperatures below 72 ° C, which can only be converted to the opaque state again by heating to temperatures above 77 ° C.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80100111T ATE8025T1 (en) | 1979-02-24 | 1980-01-10 | BODY WITH REVERSIBLE FIXED AND TEMPERATURE CHANGING LIGHT EXTINCTION. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792907352 DE2907352A1 (en) | 1979-02-24 | 1979-02-24 | BODY WITH REVERSIBLE, FIXABLE AND TEMPERATURE VARIABLE LIGHT TEXT INK |
| DE2907352 | 1979-02-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0014826A2 EP0014826A2 (en) | 1980-09-03 |
| EP0014826A3 EP0014826A3 (en) | 1981-07-22 |
| EP0014826B1 true EP0014826B1 (en) | 1984-06-20 |
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ID=6063887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80100111A Expired EP0014826B1 (en) | 1979-02-24 | 1980-01-10 | Element having reversible and fixed light-extinction effects which are variable with temperature |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0014826B1 (en) |
| JP (1) | JPS55154198A (en) |
| AT (1) | ATE8025T1 (en) |
| AU (1) | AU532554B2 (en) |
| BR (1) | BR8001060A (en) |
| CA (1) | CA1142357A (en) |
| DD (1) | DD149189A5 (en) |
| DE (2) | DE2907352A1 (en) |
| ES (1) | ES8200272A1 (en) |
| IL (1) | IL59376A (en) |
| NO (1) | NO800352L (en) |
| ZA (1) | ZA80990B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177063A2 (en) * | 1984-10-05 | 1986-04-09 | Röhm GmbH | Process for producing optically readable information |
| FR2578546A1 (en) * | 1985-03-07 | 1986-09-12 | Central Glass Co Ltd | MULTI-COMPONENT RESIN COMPOSITION, WHOSE LIGHT TRANSMITTANCE IS VARIABLE WITH TEMPERATURE |
| DE3726015A1 (en) * | 1986-08-05 | 1988-02-11 | Ricoh Kk | REVERSIBLE HEAT SENSITIVE RECORDING MATERIALS |
| EP0302374A2 (en) * | 1987-08-05 | 1989-02-08 | Hoechst Aktiengesellschaft | Dispersion, reversible bistable dispersion layer prepared therefrom and its use |
| JPH023858U (en) * | 1989-02-14 | 1990-01-11 | ||
| EP0405054A1 (en) * | 1989-06-30 | 1991-01-02 | Telenorma Gmbh | Portable data carrier with optical display area |
| WO1991000585A1 (en) * | 1989-06-30 | 1991-01-10 | Telenorma Gmbh | Device for displaying changing information |
| EP0506085A1 (en) * | 1991-03-28 | 1992-09-30 | Matsushita Electric Industrial Co., Ltd. | A reversible thermosensitive recording material and a recording medium using the same |
| JPH0524349A (en) * | 1991-12-19 | 1993-02-02 | Ricoh Co Ltd | Heat-sensitive image recording and erasing method |
| EP0567012A2 (en) * | 1992-04-20 | 1993-10-27 | Tomoegawa Paper Co. Ltd. | Reversible heat-sensitive recording medium |
| DE4439097A1 (en) * | 1994-11-02 | 1996-05-09 | Orga Kartensysteme Gmbh | Memory chip or magnetic strip card |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE473772C (en) * | 1926-08-07 | 1929-04-02 | Telefunken Gmbh | Arrangement for light control, especially for the purposes of picture telegraphy |
| US3240932A (en) * | 1962-10-31 | 1966-03-15 | Ibm | Reversible printing method |
| FR1465453A (en) * | 1964-10-02 | 1967-01-13 | Keuffel & Esser Co | Recording method and medium |
| US3496355A (en) * | 1966-01-13 | 1970-02-17 | Keuffel & Esser Co | Imaging method wherein a latent heat image is developed by the uniform application of mechanical force |
| DE2030652A1 (en) * | 1969-06-24 | 1971-04-22 | Ncr Co | Display device |
| FR2335347A1 (en) * | 1977-01-18 | 1977-07-15 | Agfa Gevaert | Thermosensitive opaque copying sheets - including a layer of styrene or methyl methacrylate copolymer with a plasticising monomer |
| EP0000868A1 (en) * | 1977-08-25 | 1979-03-07 | Firma Wolfgang Dabisch | Body with reversibly changeable temperature dependent extinction of light and method for the manufacture of this body |
-
1979
- 1979-02-24 DE DE19792907352 patent/DE2907352A1/en not_active Withdrawn
-
1980
- 1980-01-10 DE DE8080100111T patent/DE3068278D1/en not_active Expired
- 1980-01-10 AT AT80100111T patent/ATE8025T1/en not_active IP Right Cessation
- 1980-01-10 EP EP80100111A patent/EP0014826B1/en not_active Expired
- 1980-02-11 NO NO800352A patent/NO800352L/en unknown
- 1980-02-13 IL IL59376A patent/IL59376A/en not_active IP Right Cessation
- 1980-02-21 ZA ZA00800990A patent/ZA80990B/en unknown
- 1980-02-21 DD DD80219196A patent/DD149189A5/en unknown
- 1980-02-22 AU AU55831/80A patent/AU532554B2/en not_active Ceased
- 1980-02-22 BR BR8001060A patent/BR8001060A/en unknown
- 1980-02-22 CA CA000346304A patent/CA1142357A/en not_active Expired
- 1980-02-22 JP JP2068580A patent/JPS55154198A/en active Pending
- 1980-02-22 ES ES488878A patent/ES8200272A1/en not_active Expired
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE473772C (en) * | 1926-08-07 | 1929-04-02 | Telefunken Gmbh | Arrangement for light control, especially for the purposes of picture telegraphy |
| US3240932A (en) * | 1962-10-31 | 1966-03-15 | Ibm | Reversible printing method |
| FR1465453A (en) * | 1964-10-02 | 1967-01-13 | Keuffel & Esser Co | Recording method and medium |
| US3496355A (en) * | 1966-01-13 | 1970-02-17 | Keuffel & Esser Co | Imaging method wherein a latent heat image is developed by the uniform application of mechanical force |
| DE2030652A1 (en) * | 1969-06-24 | 1971-04-22 | Ncr Co | Display device |
| FR2335347A1 (en) * | 1977-01-18 | 1977-07-15 | Agfa Gevaert | Thermosensitive opaque copying sheets - including a layer of styrene or methyl methacrylate copolymer with a plasticising monomer |
| EP0000868A1 (en) * | 1977-08-25 | 1979-03-07 | Firma Wolfgang Dabisch | Body with reversibly changeable temperature dependent extinction of light and method for the manufacture of this body |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177063A2 (en) * | 1984-10-05 | 1986-04-09 | Röhm GmbH | Process for producing optically readable information |
| EP0177063A3 (en) * | 1984-10-05 | 1988-11-23 | Rohm Gmbh | Process for producing optically readable information |
| FR2578546A1 (en) * | 1985-03-07 | 1986-09-12 | Central Glass Co Ltd | MULTI-COMPONENT RESIN COMPOSITION, WHOSE LIGHT TRANSMITTANCE IS VARIABLE WITH TEMPERATURE |
| DE3726015A1 (en) * | 1986-08-05 | 1988-02-11 | Ricoh Kk | REVERSIBLE HEAT SENSITIVE RECORDING MATERIALS |
| EP0302374A3 (en) * | 1987-08-05 | 1990-10-31 | Hoechst Aktiengesellschaft | Dispersion, reversible bistable dispersion sheet prepared therefrom and its use |
| EP0302374A2 (en) * | 1987-08-05 | 1989-02-08 | Hoechst Aktiengesellschaft | Dispersion, reversible bistable dispersion layer prepared therefrom and its use |
| JPH023858U (en) * | 1989-02-14 | 1990-01-11 | ||
| EP0405054A1 (en) * | 1989-06-30 | 1991-01-02 | Telenorma Gmbh | Portable data carrier with optical display area |
| WO1991000585A1 (en) * | 1989-06-30 | 1991-01-10 | Telenorma Gmbh | Device for displaying changing information |
| EP0506085A1 (en) * | 1991-03-28 | 1992-09-30 | Matsushita Electric Industrial Co., Ltd. | A reversible thermosensitive recording material and a recording medium using the same |
| JPH0524349A (en) * | 1991-12-19 | 1993-02-02 | Ricoh Co Ltd | Heat-sensitive image recording and erasing method |
| EP0567012A2 (en) * | 1992-04-20 | 1993-10-27 | Tomoegawa Paper Co. Ltd. | Reversible heat-sensitive recording medium |
| US5627126A (en) * | 1993-07-06 | 1997-05-06 | Ricoh Company, Ltd. | Reversible thermosensitive recording medium and method of producing the same |
| DE4439097A1 (en) * | 1994-11-02 | 1996-05-09 | Orga Kartensysteme Gmbh | Memory chip or magnetic strip card |
| WO1998017595A1 (en) * | 1996-10-17 | 1998-04-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing a thermooptical variable polymerized material, and use of same |
Also Published As
| Publication number | Publication date |
|---|---|
| IL59376A0 (en) | 1980-05-30 |
| IL59376A (en) | 1985-08-30 |
| ES488878A0 (en) | 1981-11-01 |
| JPS55154198A (en) | 1980-12-01 |
| AU5583180A (en) | 1980-09-04 |
| AU532554B2 (en) | 1983-10-06 |
| EP0014826A2 (en) | 1980-09-03 |
| EP0014826A3 (en) | 1981-07-22 |
| ES8200272A1 (en) | 1981-11-01 |
| CA1142357A (en) | 1983-03-08 |
| NO800352L (en) | 1980-08-25 |
| BR8001060A (en) | 1980-11-04 |
| ZA80990B (en) | 1981-03-25 |
| DE2907352A1 (en) | 1980-08-28 |
| DE3068278D1 (en) | 1984-07-26 |
| ATE8025T1 (en) | 1984-07-15 |
| DD149189A5 (en) | 1981-07-01 |
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