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
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
• • 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
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/337—Additives; Binders
  • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
• • 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
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
  • B41M5/3275—Fluoran compounds
• • 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
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania

Definitions

• the invention relates to a heat-sensitive recording material which has superior resistance to the effects of light, climate and oils and has better optical readability in the near infrared range.
• a heat-sensitive recording sheet is generally prepared by applying a coating composition to the surface of a support such as paper, synthetic paper, film, plastic, etc., which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained and Addition of a binder, filler, sensitizer, lubricant and other auxiliaries. Under the influence of heat from the thermal spring, thermal head, thermal stamp, laser beam, etc., an instantaneous chemical conversion takes place, which leads to the recording.
• a coating composition to the surface of a support such as paper, synthetic paper, film, plastic, etc.
• heat sensitive recording sheets include use in technical recording equipment, computer terminal printers, facsimile machine printers, ticket machines, bar code printer printers and the like. Recently, much higher and more diverse requirements have been placed on recording devices, which is why a high quality of the recording sheet is required.
• the rapid recording of the heat-sensitive recording sheet is said to have a clear high-density recording image even with little heat input, and it is also said to have superior resistance to the effects of light, climate and oils, that is, good durability.
• heat-sensitive recording sheets are used for heat-sensitive notes in which the color formation is restricted to the visible range. Therefore, when using a semiconductor laser as a bar code scanner of POS systems, etc., they were unsuitable for reading in the near infrared range.
• JA-OS 59-199757 and JA-OS 60-22681 have proposed heat-sensitive recording sheets in which a known color developing agent (acidic clay, phenolic resin, hydroxybenzoic acid ester, bisphenol-A) and a fluoranleuco dye are combined with superior color formation in the near IR range are.
• a known color developing agent acidic clay, phenolic resin, hydroxybenzoic acid ester, bisphenol-A
• fluoranleuco dye are combined with superior color formation in the near IR range are.
• JA-OS 62-243652, JA-OS 62-243653 and JA-OS 62-257970 describe heat-sensitive recording sheets in which a known color developing agent and a divinyl compound are combined with superior near-infrared color formation.
• the invention has for its object to provide a heat-sensitive recording material which is improved in the resistance to the action of light, climate and oils, and in the optical readability in the near infrared range, especially in bar code recordings.
• the dyes of the following general formula (IV) are preferred: wherein R1, R2, R3, R4, R5, R7, R8, R9, T1, T2, T3 and R4 have the meaning given above.
• R1, R2, R3, R4, R5, R7, R8, R9, T1, T2, T3 and R4 have the meaning given above.
• an alkyl group preferably has 1-8 carbon atoms and a cycloalkyl group 5-8 ring atoms.
• Aryl is preferably phenyl and naphthyl.
• fluorine leuco dyes is not particularly limited; you can use the following, for example: 2-methyl-6-p- (p-dimethylaminophenyl) aminoaniline fluoran, 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, p-nitro-6-p- (p-di ethylaminophenyl) amino-anilinofluoran, 2- Amino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-diethylamino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-phenyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-benzyl-6-p - (p-phenyl) aminoaniline flu
• a C1-C12 alkyl group and a C1-C12 alkoxy group can be a straight or branched radical.
• Typical examples of an alkyl group with 1-12 carbon atoms and an alkoxy group with 1-12 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl -, hexyl, octyl, nonyl, dodecyl, methoxy, ethoxy, tert-butoxy group and the like.
• Typical examples of a C3-C10 cycloalkyl group are a cyclohexyl, 2-ethylcyclohexyl, p-tert-butylcyclohexyl group and the like.
• Halogen-substituted zinc benzoate derivatives which can be used according to the invention are colorless substances with high melting points and can be prepared by reacting a halogen-substituted sodium benzoate derivative with zinc sulfate.
• the stabilizer that can be used according to the invention is selected from several organic carboxylic acid metal salts.
• Benzoic acid zinc salts with 1 - 2 halogen atoms on the benzene ring show greater resistance to light, oils and climatic influences than organic carboxylic acids and their polyvalent metal salts.
• Halogen-substituted zinc benzoate derivatives which can be used according to the invention are, for example:
• Preferred examples of the organic color developing agent which can be used according to the invention are bisphenol A types, 4-hydroxybenzoic acid esters, 4-hydroxyphthalic diesters, phthalic acid monoesters, bis (hydroxyphenyl) sulfides, 4-hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di- [2- (hydroxyphenyl) -2-propyl] benzene, 4-hydroxybenzoyloxybenzoic acid ester, bisphenolsulfones, etc.
• suitable compounds of this type are as follows:
• the above color developing agents can be used either alone or in combination.
• the fluoranleuco dye according to the invention can be used to further improve the optical readability in the near infrared range in combination with at least one substance from the group of the fluorene leuco dyes, divinylphthalide derivatives [in addition to those of the general formula (II)], sulfonylmethane derivatives, etc.
• the divinyl compounds according to the invention can of course also be used in combination with at least one substance from the group of the fluorene leuco dyes, fluoranleuco dyes [in addition to those of the general formula (I)], sulfonylmethane derivatives, etc.
• Preferred fluorene leuco dyes are the following near infrared absorbing leuco dyes of the general formula (VII): wherein R21, R22, R23, R24, R25 and R26 are the same or different and each represents a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C3-C8 alkoxyalkyl group, a C3-C9 unsaturated alkyl group, one Tetrahydrofurfuryl group, a tetrahydropyran-2-methyl group, an alkyl group which can be substituted by a halogen atom, a C1-C4 alkyl group and / or a C1-C4 alkoxy group, an aryl group which by a halogen atom, a C1-C4 alkyl group and / or a C1-C4 alkoxy group can be substituted, or a C2-C8 alkyl group
• the selection of the leuco dye of the formula (VII) used according to the invention is not subject to any particular restrictions; you can use the following, for example: 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′ - (6′-dimethylamino) phthalide and 3,6-bis (diethylamino) fluorene-9-spiro-3 ′ - (6 ′ -diethylamino) -phthalide.
• Preferred divinylphthalide derivatives are the following leuco dyes of the general formula (VIII) which absorb in the near infrared range: wherein R27, R28, R29 and R30 are the same or different and each have a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C3-C8 alkoxyalkyl group, a halogen atom, an aryl group, which is replaced by a halogen atom, a C1-C4- Alkyl group and / or a C1-C4-alkoxy group may be substituted, or a C1-C8-alkyl group which may be substituted by a halogen atom, a C1-C4-alkyl group and / or a C1-C4-alkoxy group; R27 and R28 or R29 and R30 optionally together or with an adjacent benzene ring a heterocyclic Can form a ring; and R31 and
• Preferred sulfonylmethane derivatives are the following leuco dyes of the general formula (IX) which absorb in the near infrared range: wherein R41, R42, R43 and R44 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group; R45 and R46 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted one Represent phenyl group; and R47 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group.
• R41, R42, R43 and R44 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group
• R45 and R46 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted one Represent phenyl group
• R47 represents a substituted or un
• sulfonylmethane derivatives which can be used according to the invention is not subject to any particular restrictions, for example the following can be used: Bis- (p-dimethylaminostyryl) -p-methylphenylsulfonylmethane, Bis- (p-diethylaminostyryl) -p-methylphenylmethane, Bis (p-dimethylaminostyryl) benzenesulfonylmethane.
• a sensitizer can be added to the color development layer according to the invention.
• Typical examples of such sensitizers are fatty acid amides, such as stearic acid amide, palmitic acid amide, etc., ethylene bisamide, montan wax, polyethylene wax, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzylbiphenyl, phenylnaphthoxynyl carbonate, 1,4-phenyl-1-phthalyl-1,4-phthalate -naphthoic acid phenyl ester etc.
• Binders according to the invention are, for example, completely saponified polyvinyl alcohol, degree of polymerization: 200-1900, partially saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose styrene, methyl cellulose acid, carboxy Copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene, copolymers of the above compounds, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin and coumarone resin.
• These high molecular weight Binders can be used after being dissolved in a solvent such
• the type and amount of the organic color developing agent according to the invention, the basic colorless chromogenic dye, the other additives which are determined depending on the desired effect and the suitability for recording purposes are not restricted.
• the heat-sensitive material according to the invention is produced by applying the coating composition to a base material such as paper, synthetic paper, film, plastic, etc.
• the organic color developing agent according to the invention, iron salt of a saturated higher fatty acid, the basic colorless chromogenic dye and optionally the other additives are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, attritor, sand grinder, etc., or by means of a suitable emulsifying machine .
• a grinding device such as a ball mill, attritor, sand grinder, etc.
• Various additives are added to produce the coating composition of the invention.
• the additives which can be used according to the invention are, for example, the following: fillers; Release agents for preventing sheet sticking, such as metal salts of fatty acids; lubricant for mottling prevention such as fatty acid amide, ethylene bisamide, montan wax, polyethylene wax, etc .; Dispersants such as sodium dioctylsulfosuccinic acid, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, sodium alginate, etc .; UV absorbers of the benzophenone and triazole series; Anti-foaming agents; Fluorescent dyes; water repellant, etc.
• both inorganic and organic fillers which are used in the paper processing industry can be used as the fillers according to the invention.
• the fillers according to the invention are alumina, talc, silicon dioxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, kaolin, titanium dioxide, zinc oxide, calcium carbonate, aluminum oxide, urea-formaldehyde resin, polystyrene resin, phenolic resin, etc.
• a cover layer e.g. be applied from a polymer.
• the reason for the superior optical readability of the heat-sensitive recording sheet according to the invention in the near infrared range is probably the following:
• the colored image of the recording sheet when using conventional, electron-donating color developing agents do not take up any light in the near infrared range.
• the fluoranleuco dyes of the general formula (I) according to the invention or the divinyl compounds of the general formula (II) according to the invention absorb during color development in the heat-melting reaction in the presence of an electron acceptor particularly strong in the near infrared range (especially in the range of 700 - 1500 nm).
• a heat sensitive recording sheet consists of a basic colorless dye as an electron donor and an organic acidic substance, e.g. a phenolic compound, aromatic carboxylic acid, organic sulfonic acid, etc.
• the heat-melting reaction is a kind of acid-base reaction based on electron donation and uptake, thereby forming a metastable charge transfer complex, which leads to the colored image .
• each of the halogen atoms is bonded directly to a benzene nucleus and, because of its strong electron attraction, leads to a decrease in the electron density on the metal via the mediation of the ⁇ electrons of the benzene ring.
• zinc is a transition metal atom with an empty d-orbital and, in contrast to other polyvalent metals (magnesium, aluminum, calcium, titanium, manganese, tin and nickel), takes up electrons more easily.
• the halogen-substituted zinc benzoate derivative therefore leads to the strengthening of the chemical bond between an organic color developing agent and the fluoranleuco dye according to the invention or the divinyl compound according to the invention. Therefore, it is believed that the chemical bond even under the influence of light, heat Moisture etc. is not dissolved for a long time, so that the recording image is very stable and the optical readability in the near infrared region is not reduced.
• the reason for the better thermal responsiveness is based on the fact that halogen-substituted zinc benzoate derivatives have a superior color development ability and, because of their synergism with another color development agent, lead to an increase in color development sensitivity.
• Stabilizer (see Table I) 4.0 parts 10% aqueous solution of polyvinyl alcohol 9.2 parts Water 5.2 parts
• a heat-sensitive coating composition is obtained:
• Solution A (dye dispersion) 9.2 parts
• Solution B (color developing agent dispersion) 36.0 parts
• Solution C (stabilizer dispersion) 18.4 parts Kaolin clay (50% aqueous dispersion) 12.0 parts.
• This coating composition was applied in a coating amount of 6.0 g / m 2 on a base paper with a weight of 50 g / m 2, dried and supercalendered in order to achieve a smoothness of 200-600 s.
• a heat sensitive recording sheet was obtained.
• Solution A (dye dispersion 1) 4.6 parts Solution D (dye dispersion 2) 4.6 parts Solution C (stabilizer dispersion) 18.4 parts Solution B (color developing agent dispersion) 36.0 parts Kaolin clay (50% aqueous dispersion) 12.0 parts
• This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 s.
• a heat sensitive recording sheet was obtained.
• a heat-sensitive recording sheet was obtained in the same manner as in Example 1, except that Solution C was not used.
• Color developing agent (see Table III) 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 parts
• Stabilizer (see Table III) 4.0 parts 10% aqueous solution of polyvinyl alcohol 9.2 parts Water 5.2 parts
• the solutions of the above compositions were individually milled in a attritor to a particle size of 1 ⁇ m.
• the solutions were mixed together in the following proportions; a heat-sensitive coating composition is obtained.
• Solution A (dye dispersion) 9.2 parts
• Solution B (color developing agent dispersion) 36.0 parts
• Solution C (stabilizer dispersion) 18.4 parts Kaolin clay (50% aqueous dispersion) 12.0 parts
• This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 s.
• a heat sensitive recording sheet was obtained.
• a heat-sensitive recording sheet was obtained in the same manner as in Example 3, except that Solution C was not used.
• Example 3 10th 4,4'-isopropylidenediphenol Z-salt of p-chlorobenzoic acid 3,3-bis [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide 1.50 1.19 11 4,4'-isopropylidenediphenol Zinc salt of m-chlorobenzoic acid 3,3-bis [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide 1.49 1.18 12 1,7-di (4-hydroxyphenylthio) 3,5-dioxaheptane Z

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Inorganic Chemistry (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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• 1988
  • 1988-08-19 US US07/234,463 patent/US4853362A/en not_active Expired - Fee Related
  • 1988-09-12 EP EP88114852A patent/EP0307836B1/fr not_active Expired - Lifetime
  • 1988-09-12 CA CA000577088A patent/CA1296896C/fr not_active Expired - Lifetime
  • 1988-09-12 DE DE8888114852T patent/DE3880599D1/de not_active Expired - Fee Related

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