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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
• • 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
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof

Definitions

• This invention relates to record material of the kind in which dark-colored marks can be developed upon reactive contact with one or more colorless basic chromogenic materials (also called color formers).
• the invention finds particular application in thermally-responsive record material and systems, and in pressure-sensitive record material and systems (also called carbonless copying paper).
• Thermally-responsive record material typically consists of one or more substrate sheets, reels or rolls coated with color-forming materials comprising chromogenic material and acidic color developer material.
• Thermally-responsive record material systems are well known in the art, and are described in many patents, for example U.S. Patent Nos. 3,539,375; 3,674,535; 3,746,675; 4,151,748; 4,181,771; 4,246,318; and 4,470,057; to which reference can be made for additional information as desired.
• basic chromogenic material and acidic color developer material are contained in one or more coatings on a substrate which, when heated to a suitable temperature, melt, soften or sublime to permit said materials to react, thereby producing a colored mark by such reactive contact.
• Such systems have characteristic thermal responses, producing a color image of sufficient intensity upon selective thermal exposure.
• Pressure-sensitive carbonless copy paper of the transfer type typically consists of multiple cooperating superimposed plies in the form of sheets of paper which have coated, on one surface of one such ply, pressure-rupturable microcapsules containing a solution of one or more color formers (hereinafter referred to as a CB sheet) for transfer to a second ply carrying a coating comprising one or more color developers (hereinafter referred to as a CF sheet).
• a CB sheet pressure-rupturable microcapsules containing a solution of one or more color formers
• CF sheet color developers
• To the uncoated side of the CF sheet can also be applied pressure-rupturable microcapsules containing a solution of color formers resulting in a pressure-sensitive sheet which is coated on both the front and back sides (hereinafter referred to as a CFB sheet).
• the record material of the present invention utilises a phenol derivative as a color developer material.
• U.S. Patent No. 4,880,766 describes a series of known and new developer compositions including addition products of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon; a zinc modified addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon; mixtures of an acidic polymer and an organic carboxylic acid or metal salt thereof; polyvalent metalized carboxy-denatured terpentine phenol resins; and mixtures containing a certain weight percent phenolic group, divalent zinc and an aromatic carboxylate component.
• JP-A-62263086 discloses a thermal recording paper comprising a chromogenic material, a color developer and a Bisphenol A or Bisphenol S acryloyl, methacryloyl or alkyl derivative of a specified general formula. Of the Bisphenol A derivatives, only acryloyl and methacryloyl derivatives are individualized.
• US-A-4688058 discloses a thermal recording material comprising a chromogenic material, a color developer of specified general formula and a sensitizer of specified general formula.
• the general formula of the color developer includes alkoxy derivatives of Bisphenol A, but no such derivatives are individualized.
• JP-A-60165290 discloses a thermal recording sheet comprising a chromogenic material and, as a color developer, a generally-defined aralkyloxy derivative of Bisphenol A.
• a color developer a generally-defined aralkyloxy derivative of Bisphenol A.
• 2-(4-hydroxyphenyl)-2-(4-phenethyloxyphenyl) propane and 2-(4-hydroxyphenyl)-2-(4-benzyloxyphenyl) propane are individualized.
• the present invention seeks to provide record materials which give improved thermal response, or faster or more intense imaging.
• a record material comprising a substrate and a color developer material, characterized in that the color developer material comprises a substituted phenol of the formula wherein:
• R 4 and R 5 are not hydrogen simultaneously. It is preferred that R 1 and R 2 are each independently hydrogen or halogen. Of the halogens for R 1 or R 2 , chlorine and bromine are more preferred. Up to two chlorines or bromines on each phenyl, or hydrogen substitution, thereof is preferred. The methoxyphenylalkylphenols are preferred.
• Particularly preferred color developer materials within the above general formula and preferences are those which in which each of R 1 and R 2 is independently hydrogen or halogen and R 3 is C 1 -C 4 alkyl, preferably methyl.
• developers of the invention are typically coated on a substrate to provide either a conventional CF for pressure sensitive record materials, or coated on a substrate together with a chromogenic compound to yield a thermally sensitive record material having improved thermal response, or faster or more intense imaging.
• methoxyphenylalkylphenols other alkoxyphenylalkylphenols are useful.
• the methoxy group can be optionally replaced with ethoxy, propoxy, isopropoxy, isobutoxy, tertbutoxy, sec-butoxy, i.e. the alkoxy group can be from one to four carbons with methoxy being preferred.
• These compounds include materials such as 4-[1-(4-ethoxyphenyl)-1,3-dimethylbutyl] phenol; 4-[1-ethyl-1-(4-ethoxyphenyl)propyl]phenol; 4-[1-(4-ethoxyphenyl)-1-methylpropyl]phenol: 4-[1-(4-ethoxyphenyl)cyclohexyl]phenol; 4-[1-(4-ethoxyphenyl)-3-methylbutyl]phenol; 4-[1-(3,5-dibromo-4-ethoxyphenyl)-1-methylethyl]2,6-dibromophenol; 4-[1-(4-isobutoxyphenyl)-1,3-dimethylbutyl]phenol, 4-[1-(4-propoxyphenyl)-1,3-dimethylbutyl] phenol; ; 4-[1-ethyl-1-(4-propoxyphenyl)propyl]phenol; 4-[1
• resulting materials are viscous oils at room temperature
• chlorination or bromination at R 1 or R 2 increases molecular weight and helps provide solid materials.
• the oils can be used when ground together with clays or other carriers.
• the methoxy versions are typically solids at room temperature and preferred in thermal record materials.
• Substituted phenols and alkoxyphenylalkylphenols for use in the invention are preparable as follows:
• Bisphenols also called biphenols
• the biphasic systems can consist of aqueous alkali and a water-immiscible solvent such as CH 2 Cl 2 or ethyl ether.
• the product is removed from further reaction by extraction into the solvent.
• Another method of synthesis is to treat the bisphenol with an alkylating agent in aqueous alkali; the product precipitates out of the aqueous alkali.
• 4-[1-(4-alkoxyphenyl)cyclohexyl]phenol can be illustrated with 4-[1-(4-methoxyphenyl)cyclohexyl]phenol, which can be prepared by a condensation reaction.
• Record systems using the alkoxyphenylalkylphenol developers of the invention have been found to have surprisingly improved image formation characteristics such as improved thermal response or faster image formation or more intense images in the record systems.
• a record system with an improved thermal response desirably produces an image upon application of a lower amount of energy making the system useful in facsimile equipment described as of higher sensitivity.
• the desired melting point of compounds of this type for thermal systems would be in a range of 60° to 150°C.
• Thermally-sensitive mark-forming systems are well known in the art and are described in many patents, for example U.S. Patent Nos. 3,539,375; 3,674,535; 3,746,675; 4,151,748; 4,181,771 and 4,245,318.
• basic chromogenic material and acidic color developer material are contained in a coating or coatings on a substrate which, when heated to a suitable temperature, melts or softens to permit said materials to react, thereby producing a colored mark.
• the record material according to this invention includes a substrate or support material which is generally in sheet form.
• sheets can be referred to as support members and are understood to also mean webs, ribbons, tapes, belts, films, cards and the like. Sheets denote articles having two large surface dimensions and a comparatively small thickness dimension. Paper is preferred.
• the substrate or support material can be opaque, transparent or translucent and could, itself, be colored or not. It can be a film including, for example, cellophane and synthetic polymeric sheets cast, extruded, or otherwise formed.
• the compounds of the invention are more preferably and most advantageously utilized in thermally-responsive systems.
• the components of the color-forming system (colorformer and developer of the invention) are in a substantially contiguous relationship and substantially homogeneously distributed throughout the active coated layer material deposited on the substrate.
• a coating composition is prepared which includes a fine dispersion of the components of the color-forming system, polymeric binder material, surface active agents and other additives in an aqueous coating medium.
• the composition can additionally contain inert pigments in the same or additional layers, such as clay, talc, aluminum hydroxide, calcined kaolin clay and calcium carbonate; synthetic pigments, such as urea-formaldehyde resin pigments; natural waxes such as Carnauba wax, synthetic waxes; lubricants such as zinc stearate; wetting agents; defoamers, sensitizers and antioxidants.
• Sensitizers for example, can include acetoacet-o-toluidine, phenyl-1-hydroxy-2-naphthoate, 1,2-diphenoxyethane, and p-benzylbiphenyl. These materials can be applied in one or more layers.
• the various components can be in the same layer or separated by placing various components in different layers.
• the chromogenic material for example, can be placed throughout an overcoat layer.
• the developer or sensitizers can be placed throughout a separate layer or layers, such as an underlayer. Preferred is one active layer with chromogen, developer and sensitizers.
• the color-forming system components are substantially insoluble in the dispersion vehicle (preferably water) and are ground to an individual average particle size of between about 1 ⁇ m to about 10 ⁇ m, preferably about 1-3 ⁇ m.
• the polymeric binder material is substantially vehicle soluble although latexes are also eligible in some instances.
• Preferred water soluble binders include polyvinyl alcohol, hydroxy ethylcellulose, methylcellulose, methylhydroxypropylcellulose, starch, modified starches, gelatin and the like.
• Eligible latex material include polyacrylates, styrene-butadiene-rubber latexes, polyvinylacetates, polystyrene, and the like.
• Eligible chromogenic compounds such as the phthalide, leucauramine, spiropyran and fluoran compounds
• examples of the compounds include Crystal Violet Lactone (3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, U.S. Patent No. Re. 23,024); phenyl-, indol-, pyrrol-, and carbazol-substituted phthalides (for example, in U.S. Patent Nos.
• Patent 4,510,513 also known as 3-dibutylamino-6-methyl-7-anilino-fluoran; 3-dibutylamino-7-(2-chloroanilino)fluoran; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-3,5'6-t ris(dimethylamino)spiro[9H-fluorene-9,1'(3'H)-isobenzofu ran]-3'-one; 7-(1-ethyl-2-methylindol-3-yl)-7-(4-diethylamino-2-ethox yphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one (U.S.
• Patent No. 4,246,318 3-diethylamino-7-(2-chloroanilino)fluoran
• U.S. Patent No. 3,920,510 3-(N-methylcyclohexylamino)-6-methyl-7-anilinofluoran
• eligible acidic developer material which can be used in a mixture in thermal record systems along with the novel developers of the invention, include the compounds listed in U.S. Patent No. 3,539,375 as phenolic reactive material, particularly the monophenols and diphenols.
• Eligible acidic developer material also includes, without being considered as limiting, the following compounds which may be used individually or in mixtures: 4,4'-isopropylidenediphenol (Bisphenol A); p-hydroxybenzaldehyde; p-hydroxybenzophenone; p-hydroxypropiophenone; 2,4-dihydroxybenzophenone; 1,1-bis(4-hydroxyphenyl)cyclohexane;salicyanilide; 4-hydroxy-2-methylacetophenone; 2-acetylbenzoic acid; m-hydroxyacetanilide; p-hydroxyacetanilide; 2,4-dihydroxyacetophenone; 4-hydroxy-4'-methylbenzophenone; 4,4'-dihydroxybenzophenone; 2,2-bis(4
• phenolic developer compounds Preferred among these are the phenolic developer compounds. More preferred among the phenol compounds are 4,4'-isopropylidenediphenol, ethyl-4,4-bis (4-hydroxyphenyl)pentanoate, n-propyl-4,4-bis(4-hydroxyphenyl)pentanoate, isopropyl-4,4-bis(4-hydroxyphenyl) pentanoate, methyl-4,4-bis(4-hydroxyphenyl)pentanoate, 2,2-bis (4-hydroxyphenyl)-4-methylpentane, p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl) cyclohexane, and benzyl-p-hydroxybenzoate. Acid compounds of other kind and types are eligible.
• Pressure-sensitive mark-forming systems provide a marking system of disposing on and/or within sheet support material unreacted mark-forming components and a liquid solvent in which one or both of the mark-forming components is soluble, said liquid solvent being present in such form that it is maintained isolated by a pressure-rupturable barrier from at least one of the mark-forming components until application of pressure causes a breach of the barrier in the area delineated by the pressure pattern.
• the mark-forming components are thereby brought into reactive contact, producing a distinctive mark.
• color former material can include solid particles of color former alone or particles comprising color former dispersed or dissolved in resin.
• the developer composition can be utilized in either a transfer carbonless copy paper system as disclosed hereinbefore or in a self-contained carbonless copy paper system such as disclosed in U.S. Patent Nos. 2,730,457 and 4,167,346. Many of both types of carbonless copy paper systems are exemplified in U.S. Patent No. 3,672,935.
• a coated back (CB) sheet and a coated front (CF) sheet is constructed.
• the coating of the CB sheet can comprise the color developer material and microcapsules containing a liquid solvent for the color former material coated on the CF sheet.
• the coating of the CB additionally preferably contains protective stilt material such as uncooked starch particles as disclosed in British Patents Nos. 1232347 and 1252858.
• acidic developer material may be employed in the coating of the second support, such as, for example, clays; treated clays (U.S. Patent Nos. 3,622,364 and 3,753,761); aromatic carboxylic acids such as salicylic acid; derivatives of aromatic carboxylic acids and metal salts thereof (U.S. Patent No, 4,022,936); phenolic developers (U.S. Patent Nos. 3,244,550 and 4,573,063); acidic polymeric material such as phenol-formaldehyde polymers, etc. (U.S. Patent Nos. 3,455,721 and 3,672,935); and metal-modified phenolic resins (U.S. Patent Nos. 3,732,120; 3,737,410; 4,165,102; 4,165,103; 4,166,644 and 4,188,456).
• clays such as, for example, clays; treated clays (U.S. Patent Nos. 3,622,364 and 3,753,761); aromatic carboxylic acids such as salicylic acid;
• microcapsules for use in the coating of the CB sheet can be prepared by any of several processes well known in the disclosed art in such as 2,800,457; 3,533,958; 3,755,190; from gelatin as disclosed in U.S. Patent Nos. 3,800,457 and 3,041,289; or, more preferably, from urea-formaldehyde resin and/or melamine-formaldehyde resin as disclosed in U.S. Patent Nos. 4,001,140; 4,081,376; 4,089,802; 4,100,103; 4,105,823; 4,444,699; or 4,552,811.
• the liquid solvent employed in the microcapsules can be any material which has sufficient solubility for the color former material, which is liquid within the temperature range at which carbonless copy paper is normally used and which does not suppress or otherwise adversely affect the color-forming reaction.
• eligible liquids include, but are not limited to, those solvents conventionally used for carbonless copy paper, including ethyldiphenylmethane (U.S. Patent No. 3,996,406); benzylxylenes (U.S. Patent No. 4,130,299); alkyl biphenyls such as propylbiphenyl (U.S. Patent Nos. 3,627,581) and butylbiphenyl (U.S. Patent No.
• dialkyl phthalates in which the alkyl groups thereof have from 4 to 13 carbon atoms, e.g. dibutyl phthalate, dioctylphthalate, dinonyl phthalate and ditridecylphthalate; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (U.S. Patent No. 4,027,065); C 10 -C 14 alkyl benzenes such as dodecyl benzene; alkyl or aralkyl benzoates such as benzyl benzoate; alkylated naphthalenes such as dipropylnaphthalene (U.S. Patent No. 3,806,463); partially hydrogenated terphenyls; high boiling straight or branched chain hydrocarbons; and mixtures of the above.
• the color developing potential of the compounds is tested for thermal systems by heating an equal amount of chromogenic compound and test developer on a glass slide and observing the color produced, Table 1. Some of the compounds were also tested in coatings on paper. Separate dispersions, Table 2, of chromogenic material and developer were made and mixed at various ratios. Additional materials such as filler, lubricant and sensitizer were added, Table 3. The thermal response of the coatings was tested by contacting a heated metal block for 5 seconds and reading the color product with a MacBeth densitometer, Table 4. The coatings were also tested on a laboratory test printer, Table 5.
• Tables 4 and 5 show that the compounds of the invention, examples 1 thru 4, are equal to or better than two common developer compounds, controls 1 and 2.
• the data for examples 5 thru 12 shows the improved thermal response obtained with a mixture of the invention compounds and the commercial compounds.
• the data for examples 14 thru 19 demonstrates improved thermal response obtained with a commercial sensitizing agent.
• Example 13 serves as a control. Examples 20-25 describe more preferred combinations.
• sensitizer can alternatively be acetoacet-o-toluidine or phenyl-1-hydroxy-2-naphthoate.
• B-3 Phenol, 4-[1- N-102/Acetone (4-methoxyphenyl)-1,3-dimethylbutyl]- Black 2.
• B-3 Bu N-102/Acetone Black 3.
• Dimethylsulfate (7ml, 0.075 mole) was dissolved in ethyl ether (350ml).
• NaOH(6.0g, 0.15 mole) was dissolved in water (350 ml).
• 1,1-Bis(4-hydroxyphenyl) cyclohexane (13.4g, 0.05 mole) was added to the NaOH solution. Not all of the 1,1-Bis(4-hydroxy-phenyl)cyclohexane dissolved in the aqueous NaOH. Then the two mixtures were stirred together at room temperature for 18.5 hours. The ethyl ether layer was separated. The H 2 O layer was washed with ethyl ether.

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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)
• Photoreceptors In Electrophotography (AREA)
• Color Printing (AREA)
• Thermal Transfer Or Thermal Recording In General (AREA)
• Medicines Containing Plant Substances (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1991
  • 1991-11-27 CA CA002056267A patent/CA2056267A1/en not_active Abandoned
• 1992
  • 1992-01-15 AT AT92300349T patent/ATE153919T1/de not_active IP Right Cessation
  • 1992-01-15 ES ES92300349T patent/ES2102454T3/es not_active Expired - Lifetime
  • 1992-01-15 EP EP92300349A patent/EP0497465B1/en not_active Expired - Lifetime
  • 1992-01-15 DE DE69220098T patent/DE69220098T2/de not_active Expired - Fee Related
  • 1992-01-29 FI FI920403A patent/FI102598B/fi active IP Right Grant
  • 1992-01-31 JP JP4042348A patent/JPH04310792A/ja active Pending

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