US3020172A - Process of manufacture of temperaturesensitive recording paper - Google Patents
Process of manufacture of temperaturesensitive recording paper Download PDFInfo
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- US3020172A US3020172A US83840159A US3020172A US 3020172 A US3020172 A US 3020172A US 83840159 A US83840159 A US 83840159A US 3020172 A US3020172 A US 3020172A
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- polymerized
- paper base
- layer
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- organic
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- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000007788 liquid Substances 0.000 claims description 64
- 238000009835 boiling Methods 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 61
- 238000005245 sintering Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000003960 organic solvent Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 23
- 239000011247 coating layer Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- -1 HYDROXYL GROUPS Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 18
- 239000007800 oxidant agent Substances 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 230000001603 reducing effect Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000004965 peroxy acids Chemical class 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 7
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 6
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229940093499 ethyl acetate Drugs 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000005033 polyvinylidene chloride Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 241001422033 Thestylus Species 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940073584 methylene chloride Drugs 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical group OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241001233242 Lontra Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
Definitions
- a second method of producing the whitening is based on the formation of very many very small hollow spaces in the interior of the layer during the evaporation of the solvent. These hollow spaces are only formed when the solvent is evaporated sufiiciently rapidly before the solid constituents of the layer become coagulated. For this reason only very dilute solvents with a solid content up to approximately 6 percent by weight can be used, because.
- the solid highly polymerized constituents of the layer possess the property of tenaciously retaining the solvent.
- the layer does not otter any appreciable resistance tothe current of air. On continued drying the layer can break at the troughs of the'waves, or in any casethethickness of the layer is not uniform.
- the present. invention obviates these disadvantages and I is inert towards paper and in which the above-mentioned substance is insoluble, the higher boiling liquid being added in an amount such that the highly polymerized substance is not precipitated andfthe total mixture (C-l-A/B) has a'solid content of 6 to 20 percent by weight.
- a dark carrying paper P is then coated (step I in the accompanyingfiowsheet) with a layer of this mixture and first the low boiling solvent (B; step II)
- the process for 3,020,172 "Patented Feb. 6, 1962 2 and after this the higher boiling liquid (C; step 111) is evaporated.
- the highly, polymerized organic substance which forms the coating layer is dissolved in a low boiling point solvent, for example, acetone, methylacetate, tetrahydrofuran, dimethylacetal, or methylenechloride.
- a low boiling point solvent for example, acetone, methylacetate, tetrahydrofuran, dimethylacetal, or methylenechloride.
- the solvent is mainly evaporated, so that the substance which forms the coating layer is precipitated' as a finely divided light-colored precipitate in the organic liquid.
- the substance which forms the coating layer combines intimately with the surface of the carrying paper, an extremely good adherence being obtained.
- the whitening of the layer depends therefore on the precipitation of very small particles of solid deposited at random in an indifferent liquid.
- the time of evaporation of the solvent should be between l.8 and 24, preferably 2, that of the organic liquid, should be between 2.8 and 4, preferably 3,as compared withthat of diethylether which is taken to be equal to l.
- the indilierent organic liquid should have no chemical atiinity for the constituents of the carrying paper because experiments have shown that otherwise distortion and shrinking of the carrying paper occur, whereby the adherence of the temperature-sensitive layer considerably decreases.
- Substances which can be used with advantage are aliphatic hydrocarbons, for example, cyclohexane, hexane, heptane, benzine and the like.
- substances which form the coating layer all highly polymerized organic substances are suitable, provided they are soluble in the above-mentioned solvents and insoluble in the above-mentioned liquids and possess a satisfactory white shade or color and have, either in the pure form or in mixtures, a melting or sintering point which is between C. and 220 C.
- Suitable substances are for example cellulose esters, cellulose ethers, polystyrene, polyvinylacetate, ketone resins, derivatives'of colophony, phenol-formaldehyde resins, polyvinylchloride, polyvinylidenechloride, polymethacrylate, resins, etc.
- the concentration of the layer forming substance in the present process amounts to 6'to 20% and is preferably 10%, the solution has a viscosity which is comparablewith that of glycerine. Owing to this, the formation of waves and cracks on drying with air is prevented-and a layer of uniform thickness is formed.
- a mixture of high polymerizedsubstances may be used as the substance which forms the coating layer.
- a suitable melting point for the mixture which is adapted tosuit the requirements of the recording apparatus, can be obtained.
- low melting point waxes or resins and softeners the melting point of the layer can be adjusted as desired.
- the whitening of the layer can be accelerated by removing the solvent by meansof a current of air at a temperature of about 35 C. instead of with a current of cold air.
- the higher boiling organic liquid can be evaporated by a current of hot air, the temperature of which is below the melting temperature of the solid constituents forming the coating layer. Therefore a current of air at a temperature of 20 to 40 C., pref erably 35 C., is first directed on to the layer until this appears white and after this a current of air at a temperature of 40 to 100 C., preferably 75 C., is directed on the layer until the higher boiling liquid is completely evaporated.
- An advantageous process in accordance with the invention is, for example, to use polyisobutylene as the highly polymerized substance and pentane, hexane or benzine as the lower boiling solvent, and ethylacetate or methylethylketone as the higher boiling organic liquid.
- the first precaution enables the thickness of the temperature-sensitive layer to be reduced without detracting from the degree of whiteness.
- an optical brightener which has the property of causing a grey surface to appear white.
- a temperature-sensitive layer made by the process described cannot be made thinner than 15' to 1 Without the dark background appearing through it.
- the thickness of the layer can be reduced to 5 1 while maintaining the necessary degree of whiteness. with a layer having a thickness of a is reduced by about three times.
- Optical brighteners are known in the textile industry. They are frequently used in order to cause textiles which have frequently been washed and have a grey appearance to appear white again.
- derivatives of benzthiazole, stilbene and triazine see British Patent No. 683,895, Swiss Patent No. 275,140 and Belgian Patent No. 540,323 which are known in commerce under the registered trademark Blankophor of Wegriken B. yer A.G., and are used as optical brighteners.
- the second additional precaution is based on the idea of producing the heat necessary for making the layer transparent by exothermic chemical reaction in the layer itself, the stylus requiring only to be heated to the reaction temperature at the place of contact.
- Suitable reactions which evolve the necessary heat are oxidation and neutralization processes.
- the nearest part of the layer melts, which part contains in addition to the highly polymerized organic substance, the peroxy acid (or an inorganic peroxy acid) and a reducing amine R'NH (or a suitable inorganic compound) and in The time of response as compared "3 some cases also an optical brightener.
- the reactions which then take place are substantially as follows:
- the time of response of the layer can be considerably varied.
- concentrations however, must not be so high that spontaneous reactions occur.
- Example 1 16.5 g. of celluloseaceto-butyrate and 0.8 g. of phthalic acid dicyclohexylester are dissolved in 120 g. of acetone. 80 g. of cyclohexane are then added with stirring. This mixture is applied in a thickness of 0.05 mm. to a black carrying paper by means of rollers, and is blown for 10 seconds with air at a temperature of 35 C. and then for 10 seconds with air at C. The layer obtained responds at a temperature of about 120 C.
- Example 2 11 g. of celluloseaceto-butyrate and 11 g. of ethyl cellulose are dissolved in 100 g. of tetrahydro furan and then 100 g. of benzine having a. boiling range of to C. are added while stirring. The further treatment is the same as in Example 1. The white layer obtained responds at a temperature of approximately C.
- Example 3 20 g. of polystyrene and 2.2 g. of a ketone res-in (made from cyclohexanone and methylcyclohexanone) are dissolved in 120 g. of methylacetate. Then 80 g. of heptane are added while stirring. The application and drying of the coating takes place as in Example 1. The layer obtained responds at a temperature of about 100 C.
- Example 4 22 g. of polyisobutylene (molecular weight about 200,000) are dissolved in 110 g. of hexane. 90 g. of ethylacetate are then added with stirring. The further treatment takes place as in Example 1. The layer obtained responds at a temperature of about C.
- Example 5 5
- Example 6 14 g. of celluloseaceto-butyrate, 0.7 g. of phthalic aciddicyclohexylester, 1.6 g. of nionoperoxyphthalic acid and 1 g. of meta-aminophenol are dissolved in 120 g. of acetone. Then 80 g. of 'cyclohexane are added with stirring. The further treatment is the same as in Example 1.
- the layer obtained has a time of response of only 0.25 milliseconds on contact with a stylus heated to 220 C.
- Example 7 2.6 mg. of. an optical brightener (Blankophor) are added to the solution obtained in Example 6.
- the layer is applied in the same way as in Example 1 and base. thickness of about 5 to 8p.
- the time or response is from 0.1 to 0.18 millisecond.
- Example 8 18 g. of polystyrene, 2 g. of a ketone resin (made from cyclohexanone and methylcyclohexanone), 0.65 g. of dibenzoylperoxide and 1.5g. of N-dimethyl-meta-aminophenol are dissolved in 120 g. of methylacetate. After addition of 80 g. of heptane the layer is applied to black paper as in Example 1.
- Example 9 1.5 mg. of optical brightener (Blankophor) are added to the mixture described in Example 8 and the mixture is applied to black paper in the manner described in Example 1, the layer having a thickness of to 8a. This has a time of response of 0.1 to 0.15 millisecond on contact with a stylus heated to 220 C.
- optical brightener Bitophor
- a process for manufacturing temperature-sensitive recording paper having a light-colored coating layer on a dark carrier paper base comprising admixing with the solution of a polymerized organic substance having a sintering point of from about 80 to 220 C. in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being added in such amounts to said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight; applying said resulting mixture on said paper base; heating the resulting layer of said mixture on said paper base to evaporate substantially exclusively said solvent therefrom, thereby forming a finely divided gray to white precipitate of said polymerized substance in said inert liquid on said paper base; and then heating further to
- said polymerized organic substance is selected from the group consisting of cellulose esters, cellulose ethers, polystyrene, polyvinylacetate, ketone resins, colophony derivatives, formaldehyde resins, polyvinylidene chloride, polyvinyl chloride, polymethacrylate, coumarone' resins and polyacetone, methylacetate, tetrahydrofuran, dimethylacetal and methylenechloride, and the higher boiling organic liquid is selected from the group consisting of cyclohexane, hexane, heptane and benzine.
- a process for manufacturing temperature-sensitive recording paper having a light-colored coating layer on a dark carrier paper base comprising admixing with the solution of a polymerized organic substance having a sintering point of from about 80 to 220 C. in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, an organicliquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being added in such amounts to said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight; applying said resulting mixture on said paper base; directing a current of air at a temperature of from about 20 to 40 C.
- a process for manufacturing temperature-sensitive recording paper having a light-colored coating layer on a dark carrier paper base comprising admixing with the solution of a polymerized organic substance having a sintering point of from about 80 to- 220 C. and an optical brightener in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, an organic liquidfree from hydroxyl groups which has a boiling pointabovc the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being added in such amounts to said solution that said polymerized material is not me cipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight; applying said resulting mixture on said paper base; heating the resulting layer of said mixture on said paper base to evaporate substantially exclusively said solvent therefrom, thereby forming a finely divided gray to White precipitate of said polymerized substance in said iner
- optical brightener is selected from the group consisting of benzthiazole Optical brighteners, stilbene optical brighteners and triazine optical brighteners.
- a process for manufacturing temperature-sensitive recording paper having a light-colored coating layer on a dark carrier paper base comprising admixing with the solution of a polymerized organic substance having a sintering point of from about to 220 C. in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, a reducing amine capable of reacting with said oxidizing agent at temperature above their melting points, with evolution of heat, and an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintexing point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being added in such amounts to said solution.
- said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight; applying said resulting mixture on said paper base; heating the resulting layer of said mixture on said paper base to evaporate substantially exclusively said solvent therefrom, thereby forming a finely divided gray to white precipitate of said polymerized substance in said inert liquid on said paper base; and then heating further to such temperature as to evaporate said inert liquid therefrom and forming a gray to white coating of said polymerized substance on said paper base.
- a process for manufacturing temperature-sensitive recording paper having a light-colored coating layer on a dark carrier paper base comprising admixing with the solution of a polymerized organic substance having a sintering point of from about 89 to 220 C., an optical brightener, and an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, and a re ducing amine capable of reacting with said oxidizing agent at a temperature above their melting points with evolution of heat in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, organic liquid free from bydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being added in such amounts to said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight; applying
- a coating bath for the manufacture of temperaturesensitive recording paper consisting essentially of a solution of a polymerized organic substance having a sintering point of from about 80 to 220 C. in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, and an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution. that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight.
- said polymerized organic substance is selected from the 8 group consisting of cellulose esters, cellulose ethcrs, polystyrene, polyvinylacetate, ketone resins, colophony derivatives, formaldehyde resins, polyvinylidene chloride, polyvinyl chloride, polymethacrylate, coumarone resins and polyisobutylene.
- the low boiling solvent is selected from the group consisting of acetone, methylacetate, tetrahydrofuran, dimethylacetal and methylcnechloride
- the higher boiling organic liquid is selected from the group consisting of cyclohexane, hexane, heptane and benzine.
- the low boiling solvent is selected from the group consisting of pentane and hexane
- the higher boiling organic liquid is selected from the group consisting of ethylacetate and methyl ethyl ketone
- the polymerized organic substance is polyisobutylene
- a coating bath for the manufacture of temperaturesensitive recording paper consisting essentially of a solu tion of a polymerized organic substance having a sintering point of from about to 220 C. and an optical brightener in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, and an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by Weight.
- a coating bath for the manufacture of temperaturescnsitive recording paper consisting essentially of a solution of a polymerized organic substance having a sistering point of from about 80 to 220 C., an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, and a reducing amine capable of reacting with said oxidizing agent at a temperature above their melting points with evolution of heat in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, and an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by Weight.
- a coating bath for the manufacture of temperaturesensitive recording paper consisting essentially of a solution of a polymerized organic substance having a sintering point of from about 80 to 220 C., an optical brightener, and an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, and a reducing amine capable of reacting with said oxidizing agent at a temperature above their melting points with evolution of heat in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, and an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight.
- a temperature-sensitive recording paper consisting essentially of a dark carrier paper base and a coating thereon of a finely divided gray to white precipitate of a polymerized organic substance having a sintering point of from about 80 to 220 C.; said coating having a thickness of at least about 10 to 15 microns, and being 9 formed from a layer of a mixture of the solution of said polymerized organic substance in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, with an organic liquid tree from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight, in which layer said polymerized substance has first been precipitated by evaporation substantially only of said solvent, and
- a temperatureeeusitive recording paper consisting essentially of a dark earlier paper base and a coating thereon of a finely divided gray to white precipitate of a polymerized organic substance having a siutering point of from about 80 to 220 C. and being selected from the group consisting of cellulose esters, cellulose ethers, polystyrene, polyvinylacetate, ketone resins, colophony derivatives, formaldehyde resins, polyvinylidene chloride, polyvinyl chloride, polymethacrylate, coumarone resins and polyisobutylene; said coating having a thickness of at least about 10 to 15 microns, and being formed from a layer of a mixture of the solution of said polymerized organic substance in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, with an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which
- a temperature-sensitive recording paper consisting essentially of a dark carrier paper base and a coating thereon of a finely divided gray towhite precipitate of a polymerized organic substance having a sintering point of from about 80 to 220 C. and an optical brightener; said coating having a thickness of at least about microns, and being formed from a layer of a mixture of the solution of said polymerized organic substance in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, with an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said Organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material in insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that the solids content of the resulting mixture is from about 6 to 20% by weight, in which layer said polymerized substance has first been precipitated by evaporation substantially only of said solvent
- a temperaturesensitive recording paper consisting essentially of a dark carrier paper base and a coating thereon of a finely divided gray to white precipitate of a polymerized organic substance having a sintering point of from about 80 to 220 C., an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, and a reducing amine capable of reacting with said oxidizing agent at a temperature above their melting points with evolution of heat; said coating having a thickness of at least about 10 to 15 microns, and being formed from a layerof a mixture of the solution of said polymerized organic substance in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, with an organic liquid free from hydroxyl groups which has a boiling point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material
- a temperature-sensitive recording paper consisting essentially of a dark carrier paper base and a coating thereon of a finely divided gray to white precipitate of a polymerized organic substance having a sintering point of from about 80 to 220 C., an optical brightener, an oxidizing agent selected from the group consisting of acid peroxides and peroxyacids, and a reducing amine cature above their melting points with.
- said coating having a thickness of at least about 5 microns, and being formed from a layerof a mixture of the solution of said polymerized organic substance in an organic solvent therefor having a boiling point lower than the sintering point of said polymerized material, with an organic liquid free from hydroxyl groups which has a boil ing point above the boiling point of said organic solvent and below the sintering point of said polymeric material, which is inert'toward said paper base, and in which said polymerized material is insoluble, said liquid being contained in such amounts in said solution that said polymerized material is not precipitated therefrom, and that References Cited in the file of this patent UNITED STATES PATENTS 2,519,660 James jAug. 22, 1950 2,686,676 Rowe et al Aug. 17, 1954 2,739,909 Rosenthal Mar. 27, 1956 2,859,351 Clark et al. Nov. 4, 1958,
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH6401058A CH370954A (de) | 1958-09-16 | 1958-09-16 | Verfahren zur Herstellung temperaturempfindlicher Registrierpapiere |
CH7437459A CH377188A (de) | 1958-09-16 | 1959-06-12 | Verfahren zur Herstellung temperaturempfindlicher Registrierpapiere |
Publications (1)
Publication Number | Publication Date |
---|---|
US3020172A true US3020172A (en) | 1962-02-06 |
Family
ID=25737805
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US83840159 Expired - Lifetime US3020172A (en) | 1958-09-16 | 1959-09-08 | Process of manufacture of temperaturesensitive recording paper |
Country Status (6)
Country | Link |
---|---|
US (1) | US3020172A (en, 2012) |
CH (3) | CH370954A (en, 2012) |
DE (1) | DE1153612B (en, 2012) |
FR (1) | FR1242396A (en, 2012) |
GB (1) | GB868579A (en, 2012) |
NL (6) | NL99492C (en, 2012) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111421A (en) * | 1961-04-27 | 1963-11-19 | Columbia Ribbon & Carbon | Method for preparing pressure-sensitive duplicating elements |
US3145117A (en) * | 1959-11-08 | 1964-08-18 | Katchaisky Aharon | Process for production of pressure sensitive recording medium |
US3167443A (en) * | 1961-07-07 | 1965-01-26 | Interchem Corp | Pressure sensitive copying sheet |
US3180752A (en) * | 1961-11-06 | 1965-04-27 | Interchem Corp | Heat-sensitive copying sheets |
US3306763A (en) * | 1961-02-15 | 1967-02-28 | Oxford Paper Co | Method of making heat sensitive recording sheet |
US3320089A (en) * | 1964-03-09 | 1967-05-16 | Judson Bigelow Inc | Method of making blush coated recording sheet, coated sheet and coating composition |
US3511700A (en) * | 1964-10-21 | 1970-05-12 | Litton Business Systems Inc | Electro-sensitive marking blank |
US3620806A (en) * | 1968-05-17 | 1971-11-16 | Westvaco Corp | Blushed polystyrene coating on paper |
US3869305A (en) * | 1971-08-10 | 1975-03-04 | Aluminum Co Of America | Method for producing an opaque coating |
US3915726A (en) * | 1973-11-14 | 1975-10-28 | Ppg Industries Inc | Production of void containing polymer films using an emulsified, high boiling non-solvent |
US3928260A (en) * | 1973-10-29 | 1975-12-23 | Aluminum Co Of America | Opaque white coating composition comprising essentially cellulose ester/cross-linking agent/catalyst/solvent and organic liquid |
US4296179A (en) * | 1974-06-24 | 1981-10-20 | Wardwell Charles R | Frangible bonding using blush lacquer |
CN117468268A (zh) * | 2023-12-27 | 2024-01-30 | 湖南大道新材料有限公司 | 一种阻水纸袋及其制备方法与应用 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2007347A1 (en, 2012) * | 1968-03-23 | 1970-01-09 | Feldmuehle Ag | |
GB2252838A (en) * | 1991-02-12 | 1992-08-19 | Scimat Ltd | Heat- or pressure-sensitive recording medium |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2519660A (en) * | 1947-09-06 | 1950-08-22 | Little Inc A | Recording material |
US2686676A (en) * | 1949-04-08 | 1954-08-17 | Dictaphone Corp | Recording progress indicator for magnetic records |
US2739909A (en) * | 1950-06-29 | 1956-03-27 | Nashua Corp | Coated paper suitable for stylus inscription and method of making the same |
US2859351A (en) * | 1951-02-02 | 1958-11-04 | Minnesota Mining & Mfg | Method of making permanent facsimile copies |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2653126A (en) * | 1950-02-23 | 1953-09-22 | Rca Corp | Method of marking |
-
0
- NL NL261301D patent/NL261301A/xx unknown
- NL NL102588D patent/NL102588C/xx active
- NL NL102591D patent/NL102591C/xx active
- NL NL243343D patent/NL243343A/xx unknown
- NL NL262879D patent/NL262879A/xx unknown
- NL NL99492D patent/NL99492C/xx active
-
1958
- 1958-09-16 CH CH6401058A patent/CH370954A/de unknown
-
1959
- 1959-06-12 CH CH7437559A patent/CH377635A/de unknown
- 1959-06-12 CH CH7437459A patent/CH377188A/de unknown
- 1959-09-08 US US83840159 patent/US3020172A/en not_active Expired - Lifetime
- 1959-09-14 DE DEP27802A patent/DE1153612B/de active Pending
- 1959-09-15 FR FR805128A patent/FR1242396A/fr not_active Expired
- 1959-09-15 GB GB3145859A patent/GB868579A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2519660A (en) * | 1947-09-06 | 1950-08-22 | Little Inc A | Recording material |
US2686676A (en) * | 1949-04-08 | 1954-08-17 | Dictaphone Corp | Recording progress indicator for magnetic records |
US2739909A (en) * | 1950-06-29 | 1956-03-27 | Nashua Corp | Coated paper suitable for stylus inscription and method of making the same |
US2859351A (en) * | 1951-02-02 | 1958-11-04 | Minnesota Mining & Mfg | Method of making permanent facsimile copies |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3145117A (en) * | 1959-11-08 | 1964-08-18 | Katchaisky Aharon | Process for production of pressure sensitive recording medium |
US3306763A (en) * | 1961-02-15 | 1967-02-28 | Oxford Paper Co | Method of making heat sensitive recording sheet |
US3111421A (en) * | 1961-04-27 | 1963-11-19 | Columbia Ribbon & Carbon | Method for preparing pressure-sensitive duplicating elements |
US3167443A (en) * | 1961-07-07 | 1965-01-26 | Interchem Corp | Pressure sensitive copying sheet |
US3180752A (en) * | 1961-11-06 | 1965-04-27 | Interchem Corp | Heat-sensitive copying sheets |
US3320089A (en) * | 1964-03-09 | 1967-05-16 | Judson Bigelow Inc | Method of making blush coated recording sheet, coated sheet and coating composition |
US3511700A (en) * | 1964-10-21 | 1970-05-12 | Litton Business Systems Inc | Electro-sensitive marking blank |
US3620806A (en) * | 1968-05-17 | 1971-11-16 | Westvaco Corp | Blushed polystyrene coating on paper |
US3869305A (en) * | 1971-08-10 | 1975-03-04 | Aluminum Co Of America | Method for producing an opaque coating |
US3928260A (en) * | 1973-10-29 | 1975-12-23 | Aluminum Co Of America | Opaque white coating composition comprising essentially cellulose ester/cross-linking agent/catalyst/solvent and organic liquid |
US3915726A (en) * | 1973-11-14 | 1975-10-28 | Ppg Industries Inc | Production of void containing polymer films using an emulsified, high boiling non-solvent |
US4296179A (en) * | 1974-06-24 | 1981-10-20 | Wardwell Charles R | Frangible bonding using blush lacquer |
CN117468268A (zh) * | 2023-12-27 | 2024-01-30 | 湖南大道新材料有限公司 | 一种阻水纸袋及其制备方法与应用 |
CN117468268B (zh) * | 2023-12-27 | 2024-03-22 | 湖南大道新材料有限公司 | 一种阻水纸袋及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
DE1153612B (de) | 1963-08-29 |
GB868579A (en) | 1961-05-17 |
CH377635A (de) | 1964-05-15 |
NL262879A (en, 2012) | 1900-01-01 |
FR1242396A (fr) | 1960-09-30 |
NL261301A (en, 2012) | 1900-01-01 |
CH370954A (de) | 1963-07-31 |
NL99492C (en, 2012) | 1900-01-01 |
NL102591C (en, 2012) | 1900-01-01 |
NL243343A (en, 2012) | 1900-01-01 |
CH377188A (de) | 1964-04-30 |
NL102588C (en, 2012) | 1900-01-01 |
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