EP0992364A2 - Matériau d'enregistrement sensible à la chaleur - Google Patents

Matériau d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP0992364A2
EP0992364A2 EP99307934A EP99307934A EP0992364A2 EP 0992364 A2 EP0992364 A2 EP 0992364A2 EP 99307934 A EP99307934 A EP 99307934A EP 99307934 A EP99307934 A EP 99307934A EP 0992364 A2 EP0992364 A2 EP 0992364A2
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EP
European Patent Office
Prior art keywords
heat
intermediate layer
sensitive recording
recording material
material according
Prior art date
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Granted
Application number
EP99307934A
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German (de)
English (en)
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EP0992364A3 (fr
EP0992364B1 (fr
Inventor
Masayuki Iwasaki
Hirofumi Mitsuo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of EP0992364A3 publication Critical patent/EP0992364A3/fr
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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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Definitions

  • the present invention relates to a heat-sensitive recording material. More particularly, the present invention relates to a heat-sensitive recording material comprising intermediate layers between a support and a heat-sensitive color developing layer thereof, which heat-sensitive recording material is excellent in color developing density.
  • Recording materials using electron donative colorless dyes and electron acceptive compounds as color developing components are well known in the form of pressure-sensitive paper, heat-sensitive paper, photosensitive pressure-sensitive paper, conductive heat-sensitive recording paper, and heat-sensitive transfer paper. Examples of such recording materials are described in detail, for example, in GB Patent No. 2,140,449, US Patent Nos. 4,480,052 and 4,436,920, Japanese Patent Application Publication (JP-B) No. 60-23992, Japanese Patent Application Laid-Open (JP-A) Nos. 57-179836, 60-123556, and 60-123557.
  • heat-sensitive recording for example, heat-sensitive recording materials using electron donating dye precursors and electron acceptive compounds are disclosed in JP-B Nos. 45-14039 and 43-4160.
  • An object of the present invention is to provide a heat-sensitive recording material which has high color developing density and is excellent in dot reproducibility.
  • the present invention provides a heat-sensitive recording material comprising a support having formed thereon at least one heat-sensitive color developing layer comprising an electron donative colorless dye and an electron acceptive compound, wherein a first intermediate layer and a second intermediate layer are sequentially laminated between the support and the heat-sensitive color developing layer, the first intermediate layer and the second intermediate layer comprise an inorganic pigment and a binder as main components, Oken type smoothness of the first intermediate layer is not less than 700 seconds, and density of the second intermediate layer on the first intermediate layer is not more than 1.0.
  • Fig. 1 is a vertical sectional view of a construction of an Oken type smoothness tester.
  • Intermediate layers of the present invention comprise a first intermediate layer formed on a support and a second intermediate layer laminated on the first intermediate layer.
  • Main components of the first intermediate layer are an inorganic pigment and a binder
  • main components of the second intermediate layer are an inorganic pigment and a binder.
  • the inorganic pigment contained in these first and second intermediate layers include, for example, kaolin, calcined kaolin, talc, agalmatolite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, and the like.
  • a desirable mean particle diameter of these inorganic pigments is 0.1-5 ⁇ m, preferably 0.5-3 ⁇ m.
  • the inorganic pigment contained in the second intermediate layer particularly desirably is an inorganic pigment having an oil absorption of 70 ml/100 g or more by a measuring method defined by JIS-5101.
  • An inorganic pigment having an oil absorption of 70 ml/100 g or less may be used in combination with the inorganic pigment having an oil absorption of 70 ml/100 g or more so far as the effect of the present invention is not impaired.
  • a water soluble polymer such as a starch derivative, polyvinyl alcohol and styrene-maleic anhydride, and a hydrophobic polymer emulsion such as styrene-butadiene latex and acrylic resin emulsion, and the like can be used.
  • the mixing ratio of the inorganic pigment and the binder in the first intermediate layer preferably is that, for 100 parts by weight of the inorganic pigment, the binder is 3-30 parts by weight, preferably 5-20 parts by weight.
  • the mixing ratio of the inorganic pigment and the binder in the second intermediate layer may be same as that of the first intermediate layer.
  • the first intermediate layer is formed by coating a coating solution obtained by adding together the inorganic pigment and the binder and additionally adding as required, a dispersing agent, a wax, a thickener, a surfactant, an ultraviolet ray absorbing agent, an antioxidant, a water-and-oil-repellent agent, organic hollow particles, and the like.
  • the first intermediate layer is formed by coating the solution on the support by a blade-coating method, free-fall-curtain method, air-knife coater method or the like, with the blade-coating method being more desirable than the other methods.
  • a preferable amount coated of the first intermediate layer is 3-30 g/m 2 , desirably 5-15 g/m 2 in solid weight.
  • Oken type smoothness of the first intermediate layer formed by a blade-coating method or the like is required to be not less than 700 seconds, desirably not less than 800 seconds, and more desirably not less than 900 seconds.
  • the smoothness of the layer is too low so that the smoothness of the first intermediate layer negatively influences smoothness of the second intermediate layer, and smoothness of a heat-sensitive color developing layer formed on the second intermediate layer tends be reduced, and thus uniformity of color developing density (dot reproducibility) decreases. Therefore, it is not preferable.
  • the Oken type smoothness is measured using a pressure type smoothness-and-air-permeability tester, manufactured by Kumagai Riki-Kogyo Co., Ltd., which is used in smoothness tests for paper and paperboard.
  • the pressure type smoothness-and-air-permeability tester consists of a measuring section 1, an air compressor 2, a pressure reducing valve 3, a filter 4, a regulating valve 5, a water column type air pressure governor 6 (height of the water column: 500 mm), a measurment air inlet orifice 7 (0.3 ⁇ ⁇ 50 mm), a water column manometer 8, and a scale plate 9.
  • the air pressure is regulated to be 5-7 kg/cm 2 at the air compressor 2, to be about 1 kg/cm 2 at the pressure reducing valve 3, and to be about 0.1 kg/cm 2 at the regulating valve 5.
  • the water column type air pressure governor 6 comprises a tank (inner diameter: 100 mm, height: 700 mm) and an air chamber having an opening at 500 mm under the water surface. The air is regulated again at this air pressure governor 6, then passes through the orifice 7 and reaches the measuring section.
  • test strips having a size of 60 ⁇ 60 mm square or more, which are clean and have no problems such as folds or creases, are prepared.
  • the test strips are left for four hours under conditions in which the temperature is 20 °C and the relative humidity is 65 %, and thereafter, are measured under the same environmental conditions.
  • Measurement of the smoothness is performed as follows: fill the water column type air pressure governor 6 with air having a pressure regulated to be about 0.1 kg/cm 2 ; adjust the tester so that the water column manometer 8 indicates 500 mm on the scale when a weight 10 having a pressure plate 11 made of rubber attached thereto is placed on a smoothness measuring head 13, and the water column manometer 8 indicates 0 mm on the scale when the weight 10 is removed; place a test strip 12 on the measuring head 13 with a measurement surface of the test strip 12 facing downward, then, apply a fixed load by a lever; read a value indicated by the water column manometer 8 ten seconds after the start of the measurement. This is repeated ten times. An average of the ten values obtained thereby is the value for Oken type smoothness in the present application.
  • the second intermediate layer laminated on the first intermediate layer is also formed by coating a coating solution obtained by adding together the inorganic pigment and the binder and additionally adding as required, a dispersing agent, a wax, a thickener, a surfactant, an ultraviolet ray absorbing agent, an antioxidant, a water-and-oil-repellent agent, organic hollow particles, and the like.
  • the second intermediate layer is formed by coating the solution on the first intermediate layer on the support by a blade-coating method, free-fall-curtain method, air-knife coater method or the like, with the free-fall-curtain method being more desirable than the other methods.
  • a preferable amount coated of the second intermediate layer is 3-20 g/m 2 , desirably 4-10 g/m 2 in solid weight. Density of the second intermediate layer is required to be not more than 1.0, desirably not more than 0.85, and more desirably, not more than 0.70.
  • density of the second intermediate layer is over 1.0, because image density tends to be insufficient. This phenomenon is caused because thermal energy obtained from a thermal head or the like does not effectively affect on a heat-sensitive recording layer during image formation.
  • the heat-sensitive color developing layer formed on these intermediate layers comprises an electron donative colorless dye and an electron acceptive compound as heat-sensitive color developing components.
  • a plurality of heat-sensitive color developing layers comprising a diazonium salt compound and a coupler may be provided as required on the heat-sensitive color developing layer comprising an electron donative colorless dye and an electron acceptive compound.
  • a heat-sensitive recording layer comprising the electron donative colorless dye and an acidic material as heat-sensitive color developing components
  • one of the components melts with heating and then both react with each other to develop a color.
  • a third meltable component (generally a low-melting-point organic material) may also be added to the heat-sensitive recording layer as required.
  • Examples of the electron donative colorless dye include a triarylmethane-based compound, a diphenylmethane-based compound, a thiazine-based compound, a xanthene-based compound, a spiropyrane-based compound and the like, and a triarylmethane-based compound and a xanthene-based compound are especially useful due to their high color developing density.
  • a portion thereof may be exemplified by 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (namely, crystal violet lactone), 3,3-bis(p-dimethylamino)phthalide, 3-(p-dimethylaminophenyl)-3-(1,3-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3-(o-methyl-p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 4,4'-bis(dimethylamino)benzhydrinbenzyl ether, N-halophenylleucoauramine, N-2,4,5-trichlorophenylleucoauramine, rhodamine-B-anilinolactam, rhodamine(p-nitroanilino)lactam
  • Examples of the electron acceptive compound include a phenol derivative, a salicylic acid derivative, hydroxybenzoate, and the like. Bisphenols and hydroxybenzoates are particularly preferred.
  • a portion thereof may be exemplified by 2,4'-dihydroxydiphenylsulfone, 2,2'-dihydroxydiphenylsulfone, 2,2-bis(p-hydroxyphenyl)propane (namely, bisphenol A), 2,2-bis(p-hydroxyphenyl)pentane, 2,2-bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(4'-hydroxy-3',5'-dichlorophenyl)propane, 1,1-(p-hydroxyphenyl)cyclohexane, 1,1-(p-hydroxyphenyl)propane, 1,1-(p-hydroxyphenyl)pentane, 1,1-(p-hydroxyphenyl)-2-ethylhexane, 3,5-di( ⁇ -methylbenzyl)salicylic acid and polyvalent metal salts thereof, 3,5-di(tert-butyl)salicylic acid and polyvalent metal salt
  • the low-melting-point organic compounds are called sensitizers because color developing reactions start at lower temperatures with addition of these low-melting-point organic compounds.
  • a known material can be used, for example, benzyl p-benzyloxybenzoate, ⁇ -naphthylbenzyl ether, ⁇ -naphthylbenzyl ether, phenyl ⁇ -naphtoate, phenyl ⁇ -hydroxy- ⁇ -naphtoate, ⁇ -naphtol-(p-chlorobenzyl)ether, 1,4-butane diol phenyl ether, 1,4- butane diol-p-methylphenyl ether, 1,4-butane diol-p-ethylphenyl ether, 1,4-butane diol-m-methylphenylether, 1-phenoxy-2-(p-tolyloxy)ethane, 1-phenoxy-2-(p-e)
  • a heat-sensitive color developing layer comprising a diazonium salt compound and a coupler which develops color by reacting with the diazonium salt compound under heat
  • the reaction between the diazonium salt compound and the coupler takes place due to heating.
  • a dye is thus formed and color develops.
  • the color image can be fixed by light exposure after the above development. This is because the light exposure decomposes unreacted diazonium salt in the heat-sensitive color developing layer. Thus, a reheating processing will not result in color development in the light-fixed layer.
  • Diazonium salt compounds are compounds represented by the formula Ar-N 2 + X- (in which Ar represents an aromatic ring, N 2 + represents a diazonium group, and X- represents an acid anion), and the maximum absorption wavelengths of these are controlled depending on types and positions of the substituents in the Ar portion.
  • diazonium salt compound used in the present invention examples include 4-(N-(2-(2,4-di-tert-amylphenoxy)butyryl)piperazino)benzene diazonium, 4-dioctylaminobenzene diazonium, 4-(N-(2-ethylhexanoyl) piperazino)benzene diazonium, 4-dihexylamino-2-hexyloxybenzene diazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino-2-octyloxybenzene diazonium, 2,5-dibutoxy-4-morpholinobenzene diazonium, 2,5-octoxy-4-morpholinobenzene diazonium, 2,5-dibutoxy-4-(N-(2-ethylhexanoyl)piperazin
  • salts of hexafluorophosphoric acid salts of tetrafluoroboric acid, salts of 1,5-naphthalenesulfonic acid and the like can be useful.
  • Examples of the coupler which develops color by reacting under heat with above-described diazonium salt used in the present invention include resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyloxypropylamide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetacetoanilide, benzoylacetanilide,
  • examples of the basic material include compounds which cause decomposition and the like under heat to release an alkaline material.
  • Representative examples thereof include nitrogen-containing compounds such as an organic ammonium salt, organic amine, amide, urea and thiourea and derivatives thereof, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines, and the like.
  • a protective layer can be provided on these heat-sensitive color developing layers as required.
  • the protective layer can comprise organic or inorganic powder, a binder, a surfactant, a thermally fusible material, and the like.
  • the powder include inorganic powder such as kaolin, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica and the like, and organic powder such as urea-formalin resin, stylen/methacrylic acid copolymer, polystyrene, and the like.
  • polyvinyl alcohol As a binder in the protective layer, polyvinyl alcohol, carboxy modified polyvinyl alcohol, vinyl acetate- acrylic amide copolymer, silicon modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelatins, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, a polyacrylic amide derivative, polyvinyl pyrolidone, and latex such as styrene-butadiene gum latex, acrylonitrile-butadiene gum latex, methyl acrylate-butadiene gum latex, vinyl acetate emulsion, and the like can be used.
  • cross-linking agent examples include water soluble primary condensates such as N-methylolurea, N-methylolmelamine and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid, borax and colloidal silica, and polyamide epichlorohydrine.
  • the protective layer may further comprise a known ultraviolet ray absorbing agent or a precursor thereof.
  • the support in the present invention a conventional known support can be used.
  • the support include woodfree paper, neutral paper, acidic paper, regenerated paper, coated paper, polyolefine resin laminated paper, synthetic paper, polyester film, cellulose derivative film such as cellulose triacetate film and the like, polystyrene film, polyolefine film such as polypropylene film and polyethylene film, and the like.
  • the coating solution for the intermediate layers was coated in a dry coating amount of 10 g/m 2 using a brade coating method onto a woodfree paper having a basic weight of 50 g/m 2 , then was dried in an oven and subjected to a calender treatment.
  • Oken type smoothness of the coated surface thereof was 800 seconds. (Measuring time of Oken type smoothness was 10 seconds.)
  • the same coating solution for the intermediate layers was coated in a dry coating amount of 10 g/m 2 on the coated surface of the first intermediate layer by a free-fall-curtain method, then was dried in an oven and subjected to a calender treatment.
  • Density of the coating of the second intermediate layer was 0.67.
  • the following surfactant was added to the coating solution for the intermediate layers: coating solution for the intermediate layers 100 parts 30% sodium dodecylbenzene sulfate aqueous solution 1 part [Coating of a heat-sensitive color developing layer]
  • coating solution for the intermediate layers 100 parts 30% sodium dodecylbenzene sulfate aqueous solution 1 part [Coating of a heat-sensitive color developing layer]
  • These were mixed and milled by a ball mill to obtain a mean particle diameter of 0.6 ⁇ m, thus preparing solution B.
  • Preparation of solution C 2,4'-dihydroxydiphenylsulfone 20 parts 10% polyvinyl alcohol aqueous solution 20 parts water 50 parts
  • a coating solution for the heat-sensitive recording layer was obtained by mixing and stirring 10 parts of 30% zinc stearate dispersed solution into the mixture of solutions A, B and C after mixing and stirring them.
  • This coating solution for the heat-sensitive recording layer was coated on the intermediate-layer-side of the woodfree paper, previously coated with the first and the second intermediate layers, in dry coating amount of 5 g/m 2 by a hand-coating bar method, then was dried in an oven and subjected to a calender treatment.
  • the heat-sensitive recording layer was coated.
  • This coating solution for the protective layer was coated on the previously obtained heat-sensitive recording layer in a dry coating amount of 2 g/m 2 by a hand-coating bar method, thus obtaining a heat-sensitive recording paper.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that the second intermediate layer was coated by an air-knife method. Density of the second intermediate layer was 0.96 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that the first intermediate layer was coated by a free-fall-curtain method and the second intermediate layer was coated by a blade-coating method. Oken type smoothness of the first intermediate layer was 650 seconds, and density of the second intermediate layer was 1.05 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that both of the first and the second intermediate layers were coated by a blade-coating method. Oken type smoothness of the first intermediate layer was 800 seconds, and density of the second intermediate layer was 1.04 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that both of the first and the second intermediate layers were coated by a free-fall-curtain method. Oken type smoothness of the first intermediate layer was 650 seconds, and density of the second intermediate layer was 0.94 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that the first intermediate layer was coated with a blade-coating method in a dry coating amount of 20 g/m 2 , and the second intermediate layer was not provided. Oken type smoothness of the intermediate layer was 850 seconds, and density thereof was 1.03 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that the first intermediate layer was coated with a free-fall-curtain method in a dry coating amount of 20 g/m 2 , and the second intermediate layer was not provided. Oken type smoothness of the intermediate layer was 680 seconds, and density thereof was 0.68 at that time.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that a protective layer was not provided.
  • a heat-sensitive recording paper was obtained in the same way as Comparative Example 3, except that kaolin (oil absorption, 37 ml/100 g) was used in the first intermediate layer instead of calcined kaolin. Oken type smoothness of the first intermediate layer was 950 seconds, and density of the second intermediate layer was 0.68.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that kaolin (oil absorption, 37 ml/100 g) was used in the second intermediate layer instead of calcined kaolin. Oken type smoothness of the first intermediate layer was 800 seconds, and density of the second intermediate layer was 0.90.
  • a heat-sensitive recording paper was obtained in the same way as Example 1, except that the amount of 48% SBR latex (SN-307 manufactured by Sumitomo Chemical Co., Ltd.) in the second intermediate layer was increased to 60 parts. Density of the second intermediate layer was 1.03.
  • a bar code pattern produced by CODESOFT manufactured by Nippon Brady K. K. was printed using a Zebra printer 140 XiII at a set energy level of +20, then reproducibility of the bar code portion was observed and sensory evaluation was performed.
  • Example 1 Recording Density Chemical Resistance Plasticizer Resistance Blurring Thickening Example 1 1.20 ⁇ 1.14 ⁇ ⁇ Example 2 1.16 ⁇ 1.15 ⁇ ⁇ Comp. Ex. 1 1.07 ⁇ 1.06 ⁇ ⁇ Comp. Ex. 2 1.06 ⁇ 1.04 ⁇ ⁇ Comp. Ex. 3 1.08 ⁇ 1.05 ⁇ ⁇ Comp. Ex. 4 1.07 ⁇ 1.06 ⁇ ⁇ Comp. Ex. 5 1.06 ⁇ 1.05 ⁇ ⁇ Example 3 1.35 ⁇ 0.15 ⁇ ⁇ Example 4 1.29 ⁇ 1.15 ⁇ ⁇ Comp. Ex. 6 1.05 ⁇ 1.03 ⁇ ⁇ Example 5 1.12 ⁇ 1.10 ⁇ ⁇ *Blurring and thickening are those of bar codes.
  • a heat-sensitive recording material can be provided which has high recording density and is excellent in dot reproducibility.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP19990307934 1998-10-09 1999-10-08 Matériau d'enregistrement sensible à la chaleur Expired - Lifetime EP0992364B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP28757098 1998-10-09
JP28757098A JP3739947B2 (ja) 1998-10-09 1998-10-09 感熱記録材料及びその製造方法

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EP0992364A2 true EP0992364A2 (fr) 2000-04-12
EP0992364A3 EP0992364A3 (fr) 2003-01-02
EP0992364B1 EP0992364B1 (fr) 2005-01-12

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JP (1) JP3739947B2 (fr)
DE (1) DE69923133T2 (fr)
ES (1) ES2237048T3 (fr)

Cited By (2)

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EP1918118A1 (fr) * 2005-08-25 2008-05-07 Oji Paper Company Limited Matériau d impression thermosensible et son procédé de production
WO2021192980A1 (fr) * 2020-03-23 2021-09-30 Ricoh Company, Ltd. Support d'enregistrement thermosensible et procédé de production de support d'enregistrement thermosensible

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Publication number Priority date Publication date Assignee Title
CN100413702C (zh) 2003-07-18 2008-08-27 日本制纸株式会社 热敏记录体
JP2006297845A (ja) * 2005-04-25 2006-11-02 Oji Paper Co Ltd 感熱記録体
CN115537040B (zh) * 2022-08-30 2023-09-15 江西广源化工有限责任公司 一种超细氢氧化镁及其制备方法和应用

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EP1918118A1 (fr) * 2005-08-25 2008-05-07 Oji Paper Company Limited Matériau d impression thermosensible et son procédé de production
EP1918118A4 (fr) * 2005-08-25 2009-12-30 Oji Paper Co Matériau d'impression thermosensible et son procédé de production
EP2223809A1 (fr) * 2005-08-25 2010-09-01 Oji Paper Co., Ltd. Procédé de production d'un matériau d'enregistrement thermosensible
WO2021192980A1 (fr) * 2020-03-23 2021-09-30 Ricoh Company, Ltd. Support d'enregistrement thermosensible et procédé de production de support d'enregistrement thermosensible
CN115315357A (zh) * 2020-03-23 2022-11-08 株式会社理光 热敏记录介质和产生热敏记录介质的方法

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ES2237048T3 (es) 2005-07-16
DE69923133T2 (de) 2005-06-16
DE69923133D1 (de) 2005-02-17
EP0992364B1 (fr) 2005-01-12

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