WO2002078970A1 - Materiau d'enregistrement thermosensible - Google Patents

Materiau d'enregistrement thermosensible Download PDF

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Publication number
WO2002078970A1
WO2002078970A1 PCT/EP2002/003309 EP0203309W WO02078970A1 WO 2002078970 A1 WO2002078970 A1 WO 2002078970A1 EP 0203309 W EP0203309 W EP 0203309W WO 02078970 A1 WO02078970 A1 WO 02078970A1
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Prior art keywords
group
alkyl
methyl
substituted
hydroxy
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PCT/EP2002/003309
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English (en)
Inventor
Mohammed Asad Amin
Kenneth Alfred Boardman
Robert Montgomery O'neil
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Ciba Specialty Chemicals Holding Inc.
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Publication of WO2002078970A1 publication Critical patent/WO2002078970A1/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
    • B41M5/30—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
    • B41M5/3375—Non-macromolecular compounds
    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds

Definitions

  • This invention relates to a heat-sensitive recording material, typically in the form of sheets coated with chromogenic material (colour formers) and colour developer materials.
  • the present invention relates to a heat-sensitive recording material with excellent thermal sensitivity and image stability characteristics.
  • Heat-sensitive recording materials are produced by applying to a support a colourless or light-coloured chromogenic substance and a colour developer, which reacts with the chromogenic substance upon heating to produce an image.
  • supports include paper, synthetic paper, plastic film or sheet.
  • a heating element such as a thermal print head is brought into contact with the recording material, reaction occurs between the colour former and colour developer to produce an image, thereby forming a record.
  • Particularly desirable characteristics of the record layer of the heat sensitive recording material include good thermal sensitivity, low tendency for premature image development, and good resistance to the effects of light, heat, humidity, oils, plasticisers and water.
  • EP-A 104, 353 discloses a composition comprising a colour forming fluoran compound, an acidic substance, for example, a phenolic compound such as 4,4'-isopropylidene diphenol (bis phenol A) and a benzenesulfonamide compound.
  • This composition comprises as colour former, at least one compound of formula (1 ), as colour developer, at least one benzene sulfonamide compound of formula (2) and as stabiliser, at least one compound of formula (3A) or (3B)
  • R 1 is hydrogen or a Ci - C 6 alkyl group
  • R 2 is a CrC 6 alkyl or alkoxyalkyl group, a cyclohexyl or phenyl group which may be substituted by C*rC alkyl, CrC -alkoxy or di(C C 4 alkyl)amino or R 1 and R 2 may be joined together to form with the nitrogen to which they are bound a heterocyclic ring
  • R 3 is hydrogen, a C C 4 alkyl or alkoxy group
  • R 4 is hydrogen, a halogen, a trifluoromethyl group or a C C 4 alkyl group
  • R 5 is hydrogen, a C C 5 alkyl group, an acetylamino group or a halogen atom
  • R 6 is a hydrogen atom, a C 1 -C 5 alkyl group, a cycloalkyl group or a phenyl group which may be substituted by C r C 4 alkyl
  • C C 12 alkyl stands for methyl, ethyl, n-, i-propyl, n-, i-, sec,- or tert.-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, preferably C* ⁇ -C 6 alkyl such as methyl, ethyl, n-, i-propyl, n-, i-, sec,- or tert.-butyl, n-pentyl, n-hexyl, more preferably C C 5 alkyl such as methyl, ethyl, n-, i-propyl, n-, i-, sec,- or tert.-butyl, n-pentyl, and most preferred C C alky
  • C C 4 alkoxy stands for methoxy, ethoxy, n-, i-propoxy, n-butoxy.
  • Cycloalkyl group stands for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably for C 5 -C 8 cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.
  • Halogen is to be understood as meaning fluorine, chlorine, bromine, iodine, in particular chlorine.
  • R 1 and R 2 or R 6 and R 7 together with the nitrogen atom to which they are bonded form a heterocyclic ring this can be a 5-, 6- or 7-membered ring, especially a pyrrolidine, piperidine, morpholine or piperazine ring.
  • the piperazine ring may be substituted, for example by alkyl, at the nitrogen atom that is not bonded to the phenyl or alkyl radical.
  • R 1 is preferably a CrC 6 alkyl group, especially CrC -alkyl.
  • R 2 is preferably a C C 6 alkyl group, C C 4 alkoxy-CrC alkyl group, a cyclohexyl group or a phenyl group or a 4-methylphenyl group.
  • R 3 are hydrogen or methyl.
  • R 4 is preferably hydrogen, trifluoromethyl or C ⁇ -C 4 alkyl.
  • R 5 is preferably hydrogen or methyl.
  • R 6 is preferably hydrogen and R 7 is preferably a phenyl group which is unsubstituted or substituted by methyl, methoxy or especially by hydroxy.
  • R 8 and R 10 are preferably identical and are each hydrogen or C r C 4 alkyl and R 9 and R 11 are also preferably identical and are preferably each tert.-butyl, cyclohexyl or tert.-octyl.
  • X is sulfur, a SO 2 group or a CH 2 group.
  • R 13 is preferably C* ⁇ -C 12 alkyl and R 12 is preferably tert.-butyl, cyclohexyl or tert.-octyl.
  • Preferred colour formers of formula (1) include but are not limited to: 3-dimethylamino-6- methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl- 7-(3-trifluoromethyIanilino) fluoran, 3-diethylamino-6-methyl-7-(2-chloroanilino) fluoran, 3- diethylamino-6-methyl-7-(4-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-(2- fluoroanilino) fluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-diethylamino-6-methyl-7- (3-methylanilino) fluoran, 3-diethylamino-6-methyI-7-(4-methylanilino) fluoran, 3- diethylamino-6-ethoxye
  • Particularly preferred colour formers of formula (1 ) are 3-diethylamino-6-methyl-7- anilinofluoran, 3-diethylamino-6-methyl-7-(3-trifluoromethylanilino) fluoran, 3-diethylamino-6- methyI-7-(3-methylanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofIuoran, 3- dipentylamino-6-methyl-7-anilinofIuoran, 3-(N-methyl-N-propylamino)-6-methyl-7- anilinofluoran, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-p- toluidino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran and 3-(
  • Examples of colour developers of formula (2) include but are not limited to : N-(2- chIorophenyl)-4-methylbenzenesulfonamide, N-(4-chlorophenyl)- 4- methylbenzenesulfonamide, N-(4-methylphenyl)- 4-methylbenzenesulfonamide, N-(4- hydroxyphenyl)-2-methylbenzenesulfonamide, N-(3-hydroxyphenyl)-4- methylbenzenesulfonamide, N-(3-hydroxyphenyl)benzenesulfonamide, N-(4- hydroxyphenyl)-4- methylbenzenesulfonamide, N-(4-hydroxyphenyl) benzenesulfonamide, N-(2-hydroxyphenyl)-4- methylbenzenesulfonamide, N-(2-hydroxyphenyl) benzenesulfonamide, N-(4-sulfamoylphenyl)-
  • Preferred colour developers of formula (2) are N-(4-hydroxyphenyl)-4- methylbenzenesulfonamide, N-(4-hydroxyphenyl) benzenesulfonamide, N-(3- hydroxyphenyl)-4- methylbenzenesulfonamide, N-(3-hydroxyphenyl) benzenesulfonamide, N-(2-hydroxyphenyl)-4- methylbenzenesulfonamide, N-(2-hydroxyphenyl) benzenesulfonamide, N-(4-hydroxyphenyl)-2- methylbenzenesulfonamide, N-(4- methylphenyl)- 4-methylbenzenesulfonamide, N-(4-methoxyphenyl)- 4- methylbenzenesulfonamide, N-(2-methylphenyl)-benzenesulfonamide, N-(2- methoxyphenyl)-benzenesulfonamide and N-phenylbenzen
  • Examples of stabilisers of formulas (3A) or (3B) include but are not limited to : 2,2'- methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4 , -butylidene-bis(2-tert-butyl-5-methylphenol), 4,4'-thio-bis(2-tert-butyl-5-methylphenol), 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1 ,1 ,3-tris(2-methyl-4-hydroxy-5- cyclohexylphenyl) butane, bis (3-tert-butyl-4-hydroxy-6-methylphenyl) sulfone, 2,2'-thiobis(4- tert-octylphenol), 2,2'-thiobis(4-methylphenol), 2,2'-thiobis(4-eth
  • Preferred stabilisers of formulas (3A) or (3B) are 2,2'-methylene-bis(4-methyl-6-tert- butylphenol), 4,4'-butylidene-bis(2-tert-butyl-5-methyIphenol), 4,4'-thio-bis(2-tert-butyl-5- methylphenol), 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-tert-butyIphenyl) butane, 1 ,1 ,3-tris(2-methyl- 4-hydroxy-5-cyclohexylphenyl) butane and 2,2'-thiobis(4-tert-octylphenol).
  • Additional stabilisers may also be used in the heat sensitive recording materials of the invention. These include but are not limited to : bis (3,5-dibromo-4-hydroxyphenyl) sulfone, 2,2'-methylene bis (4,6-di-tert-butylphenyl) phosphate and alkali metal, ammonium and polyvalent metal salts thereof, 4-benzyloxy-4'-(2-methylglycidyloxy) diphenyl sulfone, 4,4'- diglycidyloxydiphenyl sulfone, 1 ,4-diglycidyloxybenzene, 4-[ ⁇ -(hydroxymethyl)benzyloxy]-4- hydroxydiphenyl sulfone, metal salts of p-nitrobenzoic acid, metal salts of phthalic acid mono benzyl ester, metal salts of cinnamic acid and mixtures thereof.
  • the heat sensitive recording material of the invention can contain a sensitiser.
  • sensitisers are stearamide, methylol stearamide, methylene bis (stearamide), p-benzylbiphenyl, m-terphenylford 4-methoxybiphenyl, dibenzyl oxalate, di(4- methylbenzyl) oxalate, di(4-chloro-benzyl) oxalate, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, 1 ,2-diphenoxyethane, 1 ,2-bis(4-methylphenoxy) ethane, ethylene glycol bis (m-tolyl ether), 1 ,2-(diphenoxymethyl) benzene, diphenyl sulphone, 4,4'-dimethylbiphenyl, phenyl-1 -hydroxy-2-naphthoate, 4-methylphenyl biphenyl
  • Preferred sensitisers are p-benzylbiphenyl, 2-benzyloxynaphthalene, m-terphenyl, dibenzyl oxalate, di(4-methylbenzyl) oxalate, dibenzyl terephthalate, 1 ,2-diphenoxyethane, 1 ,2-bis(4- methylphenoxy) ethane, ethylene glycol bis (m-tolyl ether), 1 ,2-(diphenoxymethyl) benzene, 4-methylphenyl biphenyl ether and 1 ,2-bis(3,4-dimethylphenyl) ethane.
  • the heat sensitive recording material of the invention can be prepared according to conventional methods.
  • the colour forming compound, colour developer, stabiliser and, if desired, the sensitiser are ground separately in water or a suitable dispersing medium, such as aqueous polyvinyl alcohol, to form an aqueous or other dispersion.
  • a suitable dispersing medium such as aqueous polyvinyl alcohol
  • binders used for the heat sensitive recording material include polyvinyl alcohol (fully and partially hydrolysed), carboxy, amide, sulfonic and butyral modified polyvinyl alcohols, derivatives of cellulose such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose, copolymer of styrene-maleic anhydride, copolymer of styrene-butadiene, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyamide resin and mixtures thereof.
  • Exemplary fillers which can be used include calcium carbonate, precipitated calcium carbonate, clay, calcined clay, aluminium hydroxide, talc, titanium dioxide, zinc oxide, silica, polystyrene resin, urea-formaldehyde resin, hollow plastic pigment and mixtures thereof.
  • Representative lubricants for use in heat sensitive recording materials include stearamide, methylene bis stearamide, polyethylene, camauba wax, paraffin wax, zinc stearate or calcium stearate and mixtures thereof.
  • additives can also be employed, if necessary.
  • additives are for example fluorescent whitening agents and ultraviolet absorbers.
  • the ultraviolet absorbers may be employed in either the thermosensitive colouring layer or in a protective layer, and if desired, may be used in microencapsulated form in the protective layer.
  • ultraviolet absorbers that may be used in the invention include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate and like salicylic acid type ultraviolet absorbers ; 2,4-Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4- methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- methoxy-5-sulfobenzophenone and like benzophenone type ultraviolet absorbers ; 2-Ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-dipheny!acrylate and like cyanoacrylate type ultraviolet absorbers ;
  • 2-(2'-Hydroxyphenyl) benzotriazole 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(2'- hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3,5'-di-tert-butylphenyl) benzotriazole, 2-(2'-hydroxy-3,5'-di-tert-butylphenyl) benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'- hydroxy-3,5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3,5'-di-tert- butylphenyl)-5-tert-butylbenzotriazole, 2-(2'-hydroxy-3,5'-di-tert-amylphen
  • the coating composition so obtained can be applied to a suitable substrate such as paper, plastic sheet and resin coated paper, and used as the heat sensitive recording material.
  • a suitable substrate such as paper, plastic sheet and resin coated paper
  • the system of the invention can be employed for other end use applications using colour forming materials, for example, a temperature indicating material.
  • the quantity of the coating is usually in the range of 2 to 10 g/m 2 , most often in the range 4 to 8g/m 2 .
  • thermosensitive colouring layer can in addition contain a protective layer and, if desired, an undercoat layer.
  • the undercoat layer may be interposed between the substrate and the thermosensitive colouring layer.
  • the protective layer usually comprises a water-soluble resin in order to protect the thermosensitive colouring layer. If desired, the protective layer may contain water-soluble resins in combination with water-insoluble resins.
  • resins conventional resins can be employed.
  • polyvinyl alcohol starch and starch derivatives
  • cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose
  • sodium polyacrylate polyvinyl pyrrolidone
  • polyacrylamide/acrylic acid ester copolymers acrylamide/acrylic acid ester/methacrylic acid copolymers
  • alkali metal salts of styrene/maleic anhydride copolymers alkali metal salts of isobutylene/maleic anhydride copolymers
  • polyacrylamide sodium alginate; gelatin; casein; water-soluble polyesters and carboxyl modified polyvinyl alcohols.
  • the protective layer may also contain a water-resisting agent such as a polyamide resin, polyamide-epichlorohydrin resin, melamine-formaldehyde resin, polyfunctional aziridine, formaldehyde, glyoxal, or chromium alum.
  • a water-resisting agent such as a polyamide resin, polyamide-epichlorohydrin resin, melamine-formaldehyde resin, polyfunctional aziridine, formaldehyde, glyoxal, or chromium alum.
  • the protective layer may contain fillers, such as finely-divided inorganic powders, e.g. calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium or silica, or a finely- divided organic powder, e.g., a urea-formaldehyde resin, a styrene/methacrylic acid copolymer or polystyrene.
  • fillers such as finely-divided inorganic powders, e.g. calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium or silica, or a finely- divided organic powder, e.g., a urea-formaldehyde resin, a styrene/methacrylic acid copolymer or polystyren
  • the undercoat layer usually contains as its main components a binder resin and a filler.
  • binder resins for use in the undercoat layer are: polyvinyl alcohol; starch and starch derivatives; cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose; sodium polyacrylate; polyvinyl pyrrolidone; polyacrylamide/acrylic acid ester copolymers; acrylamide/acrylic acid ester/methacrylic acid copolymers; alkali metal salts of styrene/maleic anhydride copolymers; alkali metal salts of isobutylene/maleic anhydride copolymers; polyacrylamide; sodium alginate; gelatin; casein; water-soluble polymers such as water-soluble polyesters and carboxyl-group-modified polyvinyl alcohols; polyvinyl acetate; polyurethanes; styrene/butadiene copolymers
  • fillers for use in the undercoat layer are: finely-divided inorganic powders, e.g. calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium, silica or calcined clay (eg Ansilex, Engelhard Corp.), and finely-divided organic powders of, e.g., urea-formaldehyde resins, styrene/methacrylic acid copolymers and polystyrene.
  • finely-divided inorganic powders e.g. calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium, silica or calcined clay (eg Ansilex, Engelhard Corp.)
  • finely-divided organic powders e.g., urea-formal
  • the undercoat layer may contain a water-resisting agent. Examples of such agents are given above.
  • Another embodiment of the present invention relates to a composition, consiting essentially of a colour forming compound of formula
  • R 1 is hydrogen or a C-i - C 6 alkyl group
  • R 2 is a C-rC 6 alkyl or alkoxyalkyl group, a cyclohexyl or phenyl group which may be substituted by CrC 4 alkyl, C C 4 -alkoxy or di(C C 4 alkyl)amino or R 1 and R 2 may be joined together to form with the nitrogen a heterocyclic ring
  • R 3 is hydrogen, a C r C 4 alkyl or alkoxy group
  • R 4 is hydrogen, a halogen, a trifluoromethyl group or a C C alkyl group, at least one colour developing compound of formula
  • R 5 is hydrogen, a CrC 5 alkyl group, an acetylamino group or a halogen atom
  • R 6 is a hydrogen atom, a C C 5 alkyl group, a cycloalkyl group or a phenyl group which may be substituted by C* ⁇ -C 4 alkyl, CrC 4 -alkoxy, hydroxy or a halogen atom
  • R 7 is a C C 5 alkyl group, a cycloalkyl group or a phenyl group which may be substituted by C r C alkyl, C C 4 - alkoxy, hydroxy or a halogen atom, or R 6 and R 7 may be linked together to form with N a saturated ring, and at least one stabiliser of formula (3A) or (3B) or
  • R 8 , R 9 , R 10 and R 11 are independently, a C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl group, a phenyl group which may be substituted by C ⁇ -C alkyl, C C -alkoxy, hydroxy or a halogen atom, an unsubstituted benzyl group or a benzyl group which is substituted by C ⁇ -C alkyl, or a ⁇ , ⁇ - dimethyl benzyl group, X is an oxygen atom, a sulfur atom, a -SO 2 - group, a CH 2 group or a group CH-Y in which Y is C C 12 alkyl; R 12 is a C C 12 alkyl or C 5 -C 8 cycloalkyl and R 13 is C ⁇ - C 12 alkyl or a phenyl group which may be substituted d-C 4 alkyl, C C 4 -alkoxy, or a halogen atom
  • a further embodiment relates to the use of this inventive composition for the manufacture of a heat-sensitive colored image-forming layer for the manufacture of heat-sensitive recording material.
  • Example 1 This illustrates the preparation of a typical commercial heat-sensitive recording material comprising 3-dibutylamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and 2-benzyloxynaphthalene as sensitiser.
  • Dispersions A1 , B1 and C1 are prepared by grinding the compositions shown below in an attritor until average particle sizes of about 1 ⁇ are attained.
  • a thermal coating mixture is then prepared by combining together the following components: parts Dispersion A1 66.5
  • Zinc stearate (33% aqueous dispersion) 15.0
  • Ciba®TINOPAL® ABP-X fluorescent whitening agent
  • This coating mixture is applied at a coatweight of about 5.0 g/m 2 to a base paper weighing 50 g/m 2 and then dried.
  • the resulting sheet is calendered by means of a laboratory calender to produce the recording sheet .
  • Example 2 This illustrates the preparation of a heat-sensitive recording material comprising 3-dibutyIamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and N-(4-hdroxyphenyl)-4-methyibenzenesulfonamide as co-developer.
  • Dispersion B2 is prepared by grinding the composition shown below in an attritor until an average particle size of about 1 ⁇ is attained.
  • a thermal coating mixture is then prepared by combining together the following components:
  • Zinc stearate (33% aqueous dispersion) 15.0
  • Ciba ⁇ TINOPALI® ABP-X fluorescent whitening agent
  • This coating mixture is applied at a coatweight of about 5.0 g/m 2 to a base paper weighing 5 500 gg//mm 22 aanndd tthheenn ddrriieedd.
  • TThhee rreessuullttiinngg sshheeet is calendered by means of a laboratory calender to produce the recording sheet.
  • Example 3 This illustrates the preparation of a heat-sensitive recording material according to the present invention comprising 3-dibutylamino-6-methyl-7-anilinofIuoran as colour former, N-(4-hydroxyphenyl)-4-methylbenzenesulfonamide as colour developer, 4,4'- thiobis(2-tert-butyl-5-methylphenol) as stabiliser and 2-benzyloxynaphthalene as sensitiser.
  • Dispersion D1 is prepared by grinding the composition shown below in an attritor until an average particle size of about 1 ⁇ is attained.
  • a thermal coating mixture is then prepared by combining together the following components:
  • Zinc stearate (33% aqueous dispersion) 15.0
  • Ciba®TINOPAL® ABP-X fluorescent whitening agent
  • This coating mixture is applied at a coatweight of about 5.0 g/m 2 to a base paper weighing 50 g/m 2 and then dried.
  • the resulting sheet is calendered by means of a laboratory calender to produce the recording sheet.
  • Example 4 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion D1 , 1 ,1 ,3-tris(2-methyl-4-hydroxy-5- cyclohexylphenyl) butane is substituted for 4,4'-thiobis(2-tert-butyl-5-methylphenol).
  • Example 5 A heat sensitive recording material is prepared in the same manner as in Example 1 except that in the preparation of dispersion A1 , 3-diethylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran.
  • Example 6 A heat sensitive recording material is prepared in the same manner as in Example 2 except that in the preparation of dispersion A1 , 3-diethylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran.
  • Example 7 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion A1 , 3-diethylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran.
  • Example 8 A heat sensitive recording material is prepared in the same manner as in Example 4 except that in the preparation of dispersion A1 ) 3-diethylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran.
  • Example 9 A heat sensitive recording material is prepared in the same manner as in Example 1 , except that in the preparation of dispersion A1 , 3-(N-ethyl-N-isoamylamino)-6- methyl-7-anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran and in the preparation of dispersion C1 , p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 10 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion A1 , 3-(N-ethyl-N-isoamylamino)-6- methyl-7-anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran and in the preparation of dispersion C1 , p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 11 A heat sensitive recording material is prepared in the same manner as in Example 1 except that in the preparation of dispersion A1 , 3-dipentylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-aniIinofluoran and in the preparation of dispersion C1 , p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 12 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion A1 , 3-dipentylamino-6-methyl-7- anilinofluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran and in the preparation of dispersion C1, p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 13 A heat sensitive recording material is prepared in the same manner as in Example 1 except that in the preparation of dispersion A1 , 3-diethylamino-6-methyl-7-(3- methylanilino) fluoran is substituted for 3-dibutylamino-6-methyl-7-aniIinofluoran and in the preparation of dispersion C1, p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 14 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion A1 , 3-diethylamino-6-methyl-7-(3- methylanilino) fluoran is substituted for 3-dibutylamino-6-methyl-7-anilinofluoran and in the preparation of dispersion C1 , p-benzylbiphenyl is substituted for 2-benzyloxynaphthalene.
  • Example 15 A heat sensitive recording material is prepared in the same manner as in Example 1 except that in the preparation of dispersion C1 , ethylene glycol bis (m-tolyl ether) is substituted for 2-benzyloxynaphthalene.
  • Example 16 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion C1 , ethylene glycol bis (m- tolyl ether) is substituted for 2-benzyloxynaphthalene.
  • Example 17 A heat sensitive recording material is prepared in the same manner as in Example 3 except that in the preparation of dispersion C1 , ethylene glycol bis (m-tolyl ether) is substituted for 2-benzyloxynaphthalene and in the preparation of dispersion D1 4,4'- butylidene bis(2-tert-butyl-5-methylphenol) is substituted for 4,4'-thio bis(2-tert-butyl-5- methylphenol).
  • the dynamic thermal sensitivity of each heat sensitive recording material is measured using an Atlantek Thermal Response Tester (Model 200).
  • the imaged recording material is stored for 24 hr at 60°C / 70% relative humidity.
  • the colour densities of the imaged and un-imaged section of the recording material are measured using a MacBeth densitometer before and after the test.
  • the imaged recording material is contacted with a strip of PVC (phthalate ester plasticiser content 20 -25%) under 100g cm "2 pressure for 24 hours / 50° C.
  • the colour density of the imaged section of the recording material is measured using a MacBeth densitometer before and after the test.
  • the imaged recording material is coated with a thin layer of cottonseed oil using a gravure printer and stored for 24 hours / 40° C.
  • the colour density of the imaged section of the recording material is measured using a MacBeth densitometer before and after the test.
  • the recording material comprising of an imaged and un-imaged section, is exposed to fluorescent tubes emitting artificial sunlight (approximately 1200 Lux) for 120 hours.
  • the colour densities of the imaged and un-imaged sections of the recording material are measured using a MacBeth densitometer before and after the test.
  • the imaged recording material is immersed in de-ionised water for 3 hours at 20 C.
  • the colour density of the imaged section of the recording material is measured using a MacBeth densitometer before and after the test.
  • the results of the above evaluations are illustrated in Table 1 and are rated in the following way:
  • Example 3 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 1) containing 3-dibutylamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and 2-benzyloxynaphthalene as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity and hydrothermal resistance.
  • a standard thermal paper composition (Example 1) containing 3-dibutylamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and 2-benzyloxynaphthalene as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity and hydrothermal resistance.
  • it exhibits superior plasticiser, oil, light and water fastness properties. It is only slightly inferior with respect to background stability to light.
  • Example 4 (composition according to the invention) performs similarly to Example 1 with respect to initial intensity and hydrothermal resistance. It exhibits superior background whiteness, background whiteness after ageing, background hydrothermal stability, plasticiser, oil, light and water fastness properties. It is only slightly inferior with respect to dynamic sensitivity.
  • Example 2 contains 3-dibutylamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and N-(4-hdroxyphenyl)-4-methylbenzenesulfonamide as co-developer and exhibits superior performance in certain resistance tests compared with either Examples 3 or 4.
  • this composition is unsuitable for use as a heat sensitive recording material due to its markedly inferior dynamic sensitivity and its highly undesirable tendency to adhere to the thermal print head during recording.
  • Example 7 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 5) containing 3-diethylamino-6-methyl-7-anilinofluoran as colour former, bis phenol A as colour developer and 2-benzyloxynaphthalene as sensitiser with respect to initial intensity, dynamic sensitivity, hydrothermal resistance and light fastness background stability. It exhibits superior background whiteness, background whiteness after ageing, plasticiser, oil, light and water fastness properties.
  • Example 8 (composition according to the invention) performs similarly to Example 5 with respect to initial intensity, hydrothermal resistance, plasticiser and water resistance. It exhibits superior background whiteness, background whiteness after ageing, background hydrothermal resistance, oil and light fastness resistance. It is only slightly inferior with respect to dynamic sensitivity.
  • Example 6 contains 3-diethylamino-6-methyl-7-anilinofIuoran as colour former, bis phenol A as colour developer and N-(4-hydroxyphenyl)-4-methylbenzenesulfonamide as co- developer and exhibits superior performance in certain resistance tests compared with either Examples 7 or 8.
  • this composition is unsuitable for use as a heat sensitive recording material due to its markedly inferior dynamic sensitivity, its inferior background whiteness after ageing, its poor background hydrothermal stability and its highly undesirable tendency to adhere to the thermal print head during recording.
  • Example 10 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 9) containing 3-(N-ethyl-N-isoamylamino)-6-methyl-7- anilinofluoran as colour former, bis phenol A as colour developer and p-benzylbiphenyl as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity, hydrothermal resistance and water fastness. It exhibits superior plasticiser, oil and light fastness properties. It is only slightly inferior in background light properties.
  • Example 12 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 11) containing 3-dipentylamino-6-methyl-7- anilinofluoran as colour former, bis phenol A as colour developer and p-benzylbiphenyl as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity and hydrothermal resistance. It exhibits superior plasticiser, oil, light and water fastness properties. It is only slightly inferior in background hydrothermal stability and background light stability.
  • Example 14 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 13) containing 3-diethyIamino-6-methyl-7-(3- methylanilino) fluoran as colour former, bis phenol A as colour developer and p- benzylbiphenyl as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity and hydrothermal resistance. It exhibits superior plasticiser, oil, light and water fastness. It is only slightly inferior in background light stability.
  • Example 16 (composition according to the invention) performs similarly to a standard thermal paper composition (Example 15) containing 3-dibutyIamino-6-methyl-7- anilinofluora ⁇ as colour former, bis phenol A as colour developer and ethylene glycol bis (m- tolyl ether) as sensitiser with respect to initial intensity, background whiteness, background whiteness after ageing, dynamic sensitivity and hydrothermal resistance. It exhibits superior plasticiser, oil, light and water fastness properties. It is only slightly inferior in background light stability.
  • Example 17 performs similarly to a standard thermal paper composition (Example 15) with respect to initial intensity, plasticiser resistance and background light stability. It exhibits superior background whiteness, background whiteness after ageing, background hydrothermal stability, oil, light and water fastness. It is only slightly inferior in dynamic sensitivity and hydrothermal resistance.

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

Abstract

La présente invention se rapporte à un matériau d'enregistrement thermosensible comprenant au moins un composé chromogène, au moins un composé révélateur chromogène et au moins un stabilisant, à une composition essentiellement composée de la sélection de composés précitée et à l'utilisation de cette dernière.
PCT/EP2002/003309 2001-04-02 2002-03-25 Materiau d'enregistrement thermosensible WO2002078970A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01810329.1 2001-04-02
EP01810329 2001-04-02

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WO2002078970A1 true WO2002078970A1 (fr) 2002-10-10

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture
AU2014214937B2 (en) * 2013-02-06 2017-11-16 Fujifilm Hunt Chemicals Us, Inc. Chemical coating for a laser-markable material

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EP0104353A2 (fr) 1982-08-31 1984-04-04 Hodogaya Chemical Co., Ltd. Matériel d'enregistrement sensible à la chaleur
EP0252691A2 (fr) * 1986-07-10 1988-01-13 Kanzaki Paper Manufacturing Company Limited Matériel pour l'enregistrement photosensible
EP0503856A1 (fr) * 1991-03-11 1992-09-16 Oji Paper Company Limited Matériau d'enregistrement thermosensible
WO2000053426A1 (fr) * 1999-03-05 2000-09-14 Nippon Paper Industries Co., Ltd. Materiau d'enregistrement thermique
JP2000345067A (ja) 1999-06-03 2000-12-12 Mitsui Chemicals Inc 顕色剤組成物および感熱記録材料
WO2001016095A1 (fr) * 1999-08-31 2001-03-08 Mitsubishi Paper Mills Ltd. Compose recepteur d'electrons et materiau pour thermogravure

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Publication number Priority date Publication date Assignee Title
EP0104353A2 (fr) 1982-08-31 1984-04-04 Hodogaya Chemical Co., Ltd. Matériel d'enregistrement sensible à la chaleur
EP0252691A2 (fr) * 1986-07-10 1988-01-13 Kanzaki Paper Manufacturing Company Limited Matériel pour l'enregistrement photosensible
EP0503856A1 (fr) * 1991-03-11 1992-09-16 Oji Paper Company Limited Matériau d'enregistrement thermosensible
WO2000053426A1 (fr) * 1999-03-05 2000-09-14 Nippon Paper Industries Co., Ltd. Materiau d'enregistrement thermique
JP2000345067A (ja) 1999-06-03 2000-12-12 Mitsui Chemicals Inc 顕色剤組成物および感熱記録材料
WO2001016095A1 (fr) * 1999-08-31 2001-03-08 Mitsubishi Paper Mills Ltd. Compose recepteur d'electrons et materiau pour thermogravure

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
AU2014214937B2 (en) * 2013-02-06 2017-11-16 Fujifilm Hunt Chemicals Us, Inc. Chemical coating for a laser-markable material
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture

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