EP0338808B1 - Résine alkyl salicylate pour papier de copiage sans carbone et son utilisation pour former des images - Google Patents

Résine alkyl salicylate pour papier de copiage sans carbone et son utilisation pour former des images Download PDF

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Publication number
EP0338808B1
EP0338808B1 EP89303890A EP89303890A EP0338808B1 EP 0338808 B1 EP0338808 B1 EP 0338808B1 EP 89303890 A EP89303890 A EP 89303890A EP 89303890 A EP89303890 A EP 89303890A EP 0338808 B1 EP0338808 B1 EP 0338808B1
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Prior art keywords
acid
alkyl
group
salicylic acid
substituted
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EP0338808A2 (fr
EP0338808A3 (en
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Karl M. Brinkman
David R. Hanley
John L. Sullivan
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SI Group Inc
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Schenectady International Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • 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

Definitions

  • the present invention relates to phenol/aldehyde condensation products useful in the development of colored images from colorless dyes.
  • the condensation products are especially useful in the imaging process described in United States Patent 4,440,846 in which images are produced by a light imaging process, and in carbonless copy paper systems.
  • United States Patent 4,440,846 discloses an imaging system in which images are formed by image-wise exposure of a photosensitive encapsulate containing a chromogenic material to actinic radiation and rupture of the capsules in the presence of a developer whereby a patterned reaction of the chromogenic material and developer is obtained which produces a contrasting image.
  • United States Patent 4,440,846 discloses an imaging system basically having: a substrate, a chromogenic material, a photosensitive composition, a coating containing said chromogenic material and said photosensitive composition on one surface of the substrate, and a developer material which is capable of reacting with the chromogenic material to form a visible image, wherein said photosensitive composition is encapsulated in a pressure rupturable capsule as an internal phase.
  • the term "encapsulated” refers to both so-called resin dispersion or open phase systems in which the internal phase containing the photosensitive composition and optionally the chromogenic material is dispersed as droplets throughout a dispersing medium and systems in which the capsule is formed with a discrete capsular wall, the latter encapsulation typically being in the form of microcapsules.
  • "Pressure rupturable capsules” are, accordingly, considered by U.S. Patent 4,440,846 to exist in either of these "encapsulated” systems.
  • the capsules are described as being “pressure rupturable” other means than pressure may be used to rupture them.
  • images are formed by exposing the coated composition containing the chromogenic material and the encapsulated photosensitive composition to actinic radiation and rupturing the capsules in the presence of a developer.
  • the invention system is designed such that when these steps are carried out, the image-forming reaction between the chromogenic material and the developer discriminately occurs in the exposed or unexposed areas and produces a detectable or latent image. This is accomplished image-wise by photochemically controlling the access between the chromogenic material and the developer such that a patterned reaction occurs.
  • image-wise it is meant that the reaction between the chromogenic material and the developer occur according to the exposure such that a positive or negative image is obtained.
  • the image may be formed by a change in color or a difference in contrast.
  • chromogenic material is encapsulated with the photosensitive composition.
  • the photosensitive composition can be described as having a viscosity which changes upon exposure to actinic radiation such that upon exposure there is a change in the viscosity of the internal phase in the exposed areas which image-wise determines whether the chromogenic material is accessible to the developer.
  • the photosensitive composition may be a radiation curable composition which, upon exposure to light, increases in viscosity and immobilizes the chromogenic material, thereby preventing it from reacting with the developer material entirely or in proportion to the tonal depth of the image in the exposed areas. (The term "curable" as used in U.S.
  • Patent 4,440,846 is not limited to materials which are cross-linked, but is open to materials which are simply polymerized.
  • the chromogenic material may be encapsulated with a substance which is depolymerized or otherwise decreased in molecular weight upon exposure, resulting in a decrease in molecular weight upon exposure, resulting in a decrease in viscosity which renders the chromogenic material mobile and accessible to the developer in the exposed areas upon capsule rupture.
  • U.S. Patent of Oda, 3,864,146 discloses a sheet of record material which is sensitized with a coating to produce color on contact with colorless chromogenic compounds.
  • Such coating comprises a binder in an amount sufficient to adhere the coating to the base sheet and a color reactant material.
  • the color material essentially comprises in combination:
  • R is hydroxyl, amino, amino substituted by at least one lower alkyl group having 1 to 5 carbon atoms, nitro or chlorine, which is substituted on one of the carbon atoms at the site adjacent to that of the carboxylic group on the aromatic ring, each X is substituted or unsubstituted group containing a monocyclic or bicyclic carbon ring formed with 6 or 10 carbon atoms, m is an integer of 1 or 2 and n is an integer of 1 to 3.
  • the aforementioned aromatic carboxylic acid derivatives do not provide practical color-forming reactant materials because of their very slight activity to the colorless chromogenic materials but they can be highly sensitive color-forming reactant materials when they are combined with certain metal ions or certain water-insoluble inorganic metallic compounds.
  • the color reactant material essentially comprises a mixture of the aromatic carboxylic acid derivatives described and one or more of oxides, hydroxides and carbonates of a metal selected from the group consisting of zinc, aluminum, calcium, magnesium, titanium, nickel, cobalt, manganese, iron, tin, chromium, copper and vanadium.
  • inorganic metallic compounds there may be included zinc oxide, aluminum oxide, calcium oxide, magnesium oxide, titanium oxide, zinc hydroxide, aluminum hydroxide, calcium hydroxide, zinc carbonate, calcium carbonate and magnesium hydroxide.
  • inorganic metallic compounds are water insoluble, per se, and exhibit no substantially color forming reaction even when brought into contact with the chromagenic materials.
  • the mixing ratio by weight of the aromatic carboxylic acid derivative or derivatives to the above mentioned inorganic metallic compound or compounds is selected within the range of 95:5 to 5:95.
  • 15 to 25 parts by weight of the aromatic carboxylic acid derivative may be mixed with 85 to 75 parts by weight of the inorganic compound described.
  • a part of the inorganic metallic compound may be replaced by other inorganic pigments such as kaolin, clay and talc.
  • U.S. Patent 3,723,156 relates to record material sheets bearing a coating of an oil-soluble metal salt and an oil-soluble phenol-formaldehyde novolak resin as a combination co-reactant for colorless, chromogenic dye-precursor materials to develop a useful color therein.
  • oil-soluble phenol-formaldehyde novolak resins preferably those derived from the condensation of a para-substituted phenol with formaldehyde, had long been used, with great commercial success, in making acid-reactant record material sheets capable of developing color in oil solutions of base-reactant colorless, chromogenic dye-precursor materials.
  • Such resins and the use of them had been disclosed in U.S.
  • the metal salts found useful for use with oil-soluble phenol-formaldehyde resins in pressure-sensitive copy-papers of the "NCR Paper” type according to that patent include the oil-soluble salts of aluminum (III), barium (II), cadmium (II), calcium (II), cerium (III), cesium (I), cobalt (II), copper (III), indium (III), iron (II), and lead (II), magnesium (II), manganese (II), molybdenum (V), nickel (II), sodium (I), strontium (II), tin (II), titanium (IV), vanadium (IV), zinc (II), and zirconium (IV).
  • oil-soluble metal resinates tested and found useful therein were found useful therein inasmuch as they include metals from Periodic Groups I-A and B, II-A and B, III-A and B, IV-A and B, V-B, VI-B, VII-B, and VIII.
  • Eligible ions of the useful metal salts according to U.S. Patent 3,723,156 include acetylacetonate, hexafluoroacetylacetonate, benzoate, naphthenate, salicylate, 2-ethylhexanoate, abietate, oleate, and palmitate.
  • the candidate anion should confer on the metal salt ready solubility in the oily solvents used as the core-material encapsulated chromogenic inks in carbonless copy-papers.
  • oils in use are hydrocarbons such as paraffin oils, aromatic oils such as xylene and alkylated biphenyls, high molecular weight esters such as dioctyl adipate and dioctyl phthalate, halocarbons such as trichlorobiphenyl, and aromatic ethers such as diphenyl oxide.
  • hydrocarbons such as paraffin oils, aromatic oils such as xylene and alkylated biphenyls, high molecular weight esters such as dioctyl adipate and dioctyl phthalate, halocarbons such as trichlorobiphenyl, and aromatic ethers such as diphenyl oxide.
  • the metal modified resins of U.S. Patent 3,723,156 were said to have been designed to operate and to have operated well in developing oily dye-precursor inks of the type described.
  • the oily vehicle preferred therein was one of low volatility, such as chlorinated or alkylated biphenyl, which leaves an essentially wet print on the paper surface rather than a more volatile one such as xylene that readily evaporates to leave a dry print.
  • the enhancement of print intensity by the metal modified resins of this invention was said to be considerably greater in wet prints than in dry prints. Rapid and substantial solubility was required to give satisfactory print speed in use.
  • the metal salt anion should have a carbon content of at least four carbon atoms and preferably six or more carbon atoms. Metal salts of anions of less than four carbon atoms will operate to enhance color intensity and/or fade resistance provided they are still oil-soluble.
  • zinc (II) was preferred. All of the cited metal ions were said to improve the fade resistance of the developed prints. In addition to improved fade resistance, print intensity was markedly improved over known-art sheets by the preferred zinc (II) and furthermore, print intensity was improved or at least comparable to good commercial quality known-art sheets in sheets containing aluminum (III), cerium (III), cobalt (II), iron (II), iron (III), indium (III), manganese (II), and tin (II).
  • U.S. Patent 4,372,583 discloses a pressure-sensitive chromogenic copy system comprising a transfer sheet having on at least one surface thereof a color developer capable of reacting with a chromogen to form a color image, said color developer comprising an oligomeric aromatic carboxylic acid.
  • the patent also relates to transfer sheets utilizing said oligomeric compounds and to the compounds and method of making them as more fully described below.
  • the aromatic carboxylic acid used by that patent can be any polymerizable substituted or unsubstituted salicyclic, benzoic, or naphthoic acid. It was preferred to use compounds which do not contain substituents of a size or location on the compound so as to create steric hindrances and thereby retard or even prevent polymerization.
  • suitable acids are salicylic acid; acetyl salicylic acid; disalicylic acid; mono-and di-C1-C8 alkyl substituted salicylic acids (such as methyl salicylic acid and 3,5-di-tertiary butyl salicylic acid); the corresponding benzoic and naphthoic acids; 2-nitro benzoic acid; 2-amino naphthoic acid; and the thio compounds disclosed in co-pending U.S. patent application Serial No. 173,254, entitled “Chromogenic Copy System", filed on August 17, 1981, now United States Patent 4,303,719.
  • salicylic acid compounds particularly salicylic acid, 3,5-di-tertiary butyl salicylic acid, 3-octyl salicylic acid, 5-octyl salicylic acid, 3-tertiary butyl salicylic acid, and 5-tertiary butyl salicylic acid and the invention will be particularly described in connection therewith.
  • the resultant oligomer can be used as such or as the corresponding metal salts. These are formed by reacting the acidic oligomer with zinc, aluminum, monovalent alkali metal compounds, or other known metallic compounds conventionally used to form salts of acids used as color developers in carbonless copy systems.
  • U.S. Patent 3,772,052 discloses a color developer that is the metal compound of a polymer of an aldehyde or acetylene and an aromatic carboxylic acid having at least one hydroxyl group which is a product produced by the reaction of an alkali metal salt of the polymer of an aldehyde or acetylene and an aromatic carboxylic acid having at least one hydroxyl group with a water-soluble metal salt in a solvent in which both reagents are soluble.
  • the ratio of the alkali metal salt and water-soluble metal salt is not limited particularly, but a molar ratio of 1 to 1 is preferred.
  • Preparation of the alkali metal salt of the polymer used in the above-mentioned reaction can be carried out in a known manner, for example, by reacting the above-mentioned polymer with an alkali metal hydroxide or carbonate.
  • Illustrative of the polymer of an aldehyde and an aromatic carboxylic acid having at least one hydroxyl group used in U.S. Patent 3,772,052 are a salicylic acid-aldehyde polymer, a p-hydroxybenzoic acid-aldehyde polymer, a 2,6-dihydroxybenzoic acid-aldehyde polymer and a salicylic acid-acetylene polymer.
  • the polymer applicable to U.S. Patent 3,772,052 is a polymer of an aldehyde and an aromatic carboxylic acid having at least one hydroxyl group, while metal compounds of phenol-aldehyde polymers mentioned in Japanese Patent No. 511,757, phenol-acetylene polymers, maleic acid-rosin resins and partly or extensively hydrolyzed styrene-maleic anhydride polymers were said to have no developing capacity.
  • the aromatic carboxylic acid used in U.S. Patent 3,772,052 is a compound having at least one carboxyl group per aromatic nucleus and includes, for example, benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-indobenzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, p-isopropyl-benz
  • metal salts used in U.S. Patent 3,772,052 are metals of Group Ib of the Periodic Table such as copper and silver, Group IIa such as magnesium and calcium, Group IIb such as zinc, cadmium and mercury, Group IIb such as aluminum and gallium, Group IVa such as tin and lead, Group IVb such as chromium and molybdenum, Group VIIb such as manganese and Group VII such as cobalt and nickel.
  • salts of zinc, tin, aluminum and nickel are preferably used.
  • U.S. Patent 3,874,895 discloses using a color developer containing, as necessary constituents, an acidic polymer and an organic carboxylic acid or a metal salt thereof.
  • organic carboxylic acids used in that patent include organic compounds having at least one carboxyl group, and include aliphatic carboxylic acids and aromatic carboxylic acids. Most preferred of such acids were those having a maximum of three carboxyl groups and from about 5 to about 20 carbon atoms.
  • aromatic carboxylic acids were especially preferred as they were said to provide excellent effects and, in particular, aromatic carboxylic acids having at least one hydroxy group were preferred with those having from one to three hydroxyl groups being most preferred.
  • any organic carboxylic acid exhibits an improved effect as compared to the use of acidic polymer alone, and aliphatic carboxylic acids or metal salts thereof, in particular, the monobasic acids and dibasic acids thereof were said to be excellent from the viewpoint of film quality. Monobasic acids were most preferred, however.
  • the aromatic carboxylic acid was preferably from the benzene series, especially salicylic acid derivatives which preferably have at least one alkyl group having more than 3 carbon atoms, or at least one aryl group or a cyclohexyl group, or is substituted with a combination of such groups.
  • organic carboxylic acids used in U.S. Patent 3,874,895
  • metals forming a metal salt with the organic carboxylic acids included sodium, lithium, potassium, magnesium, calcium, zinc, cadmium, aluminum, tin, lead, chromium, manganese, cobalt, nickel, and the like.
  • the patent stated that there is no overly critical aspect to the selection of the exact metal used, i.e., substantially all metal salts are useful.
  • U.S. Patent 3,896,255 disclosed that when a coating solution containing a metal compound of aromatic carboxylic acid was prepared, not only was the viscosity of the coating solution increased but metal compound was formed in the form of particles, so that the color development power and the film surface strength of the final color developer layer were often insufficient, and that improvements can be attained by incorporating a surface active agent in a color developer coating solution containing a metal component of an aromatic carboxylic acid.
  • the aromatic carboxylic acid of U.S. Patent 3,896,255 was preferably represented by the formula: wherein R may be the same or different and represents a hydrogen atom, a hydroxy group, a halogen atom such as chlorine, a nitro group, an alkyl group having 1 to 10 carbon atoms (preferably 3 to 6 carbon atoms) of which total carbon atoms are less than 13, an aryl group such as phenyl group, an arylamino group such as anilino group, and an alicyclic group such as hexyl group, m is an integer of 0 to 7 and n is an integer of 0 to 5, and the aromatic carboxylic acid may be dimerized through the substituent R as a methylene group.
  • More preferable compounds were those represented by the formula: wherein R, m and n are as defined above.
  • aromatic carboxylic acids in U.S. Patent 3,896,255 were benzoic acid, o-, m- or p-chlorobenzoic acid, o-, m- or p-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, p-t-butyl benzoic acid, N-phenyl anthranilic acid, 4-methyl-3-nitro-benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3,5-dinitrosalicylic acid, 5-t-butyl salicylic acid, 3-phenylsalicylic acid, 3-methyl-5-butyl salicylic acid, 3,5-di-t-butyl salicylic acid, 3,5-diamyl salicylic acid, 3-cyclohexyl salicylic acid, 5-cyclohexyl salicylic acid, 3-methyl-5-iso
  • aromatic carboxylic acids having at least one hydroxyl group were said to be especially effective and those having a hydroxy group in the o-position, i.e., the aromatic carboxylic acids represented by the following formulae, were most effective.
  • R, m and n are as defined above.
  • metals which form the metal compound of the aromatic carboxylic acid used in U.S. Patent 3,896,255 there can be mentioned metals of Group IB of the Periodic Table as, e.g., copper and silver; metals of Group II A as, e.g., magnesium and calcium; metals of Group II B, e.g., zinc, cadmium and mercury; metals of Group III B, e.g., aluminum and gallium; metals of Group IV A, e.g., tin and lead; metals of Group VI A, e.g., chromium and molybdenum; metals of Group VII B, e.g., manganese; and metals of Group VIII such as cobalt and nickel.
  • zinc, tin, aluminum and nickel were said to be especially effective.
  • U.S. Patent 3,924,027 discloses a sensitized sheet for use in a pressure sensitive copy system, having a coating comprising an acceptor, the acceptor being a particulate mixture of (a) an organic acid substance selected from the group consisting of aromatic carboxylic acids and polyvalent metal salts thereof, and (b) an organic high molecular weight compound.
  • An aromatic carboxylic acid to be used for this purpose is represented by the formula I, wherein R1, R2, R3 and R4 each represents hydrogen, halogen or a hydroxyl, amino, carboxyl, carbamoyl, N-substituted carbamoyl, alkyl, cycloalkyl, alkoxyl, aryloxy, aralkyl or alkylaryl group, and any adjacent pair or R1 to R6 can, together with the carbon atoms to which they are attached, complete a ring.
  • Compounds of formula I wherein R1 or R5 is a hydroxyl group are especially important in embodiments of the invention as mentioned in detail hereinafter.
  • aromatic carboxylic acids of formula I wherein R1 and R6 are not a hydroxyl group include benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, p-t-butylbenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, tetrachlorobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-carboxybiphenol, p-oxybenzoic acid, paramethoxybenzoic acid, p-butoxybenzoic acid, p-octoxybenzoic acid, gallic acid, anthranilic acid, phthalic acid monoamide, phthalic acid monoanilide, 3-tert-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3-
  • Aromatic carboxylic acids of formula I wherein R1 or R6 is a hydroxyl group are defined by formula II, wherein R4 to R6 are as defined in R1 to R4 of formula I.
  • carboxylic acids examples include salicylic acid, o-cresotinic acid, p-cresotinic acid, 3-ethylsalicylic acid, 4-ethylsalicylic acid, 3-isopropylsalicylic acid, 4-isopropylsalicylic acid, 5-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 5-tert-butylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3-phenylsalicylic acid, 5-phenylsalicylic acid, 3-benzylsalicylic acid, 5-tert-octylsalicylic acid, 3-( ⁇ -methylbenzyl) salicylic acid, 5-( ⁇ -methylbenzyl) salicylic acid, 5-nonyl salicylic acid, 5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 5-chlorosalicylic acid
  • R4 and R6 are halogen, alkyl, cycloalkyl, aryl, aralkyl or alkylaryl can be easily derived in commercial scales from phenols, alkylphenols, arylphenols or halogenated phenols.
  • aromatic carboxylic acids examples include 3,5-dichlorosalicylic acid, 3-chloro-5-tert-butylsalicylic acid, 3-chloro-5-tert-amylsalicylic acid, 3-chloro-5-tert-octylsalicylic acid, 3-chloro-5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3,5-dimethylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3-methyl-5-cyclohexylsalicylic acid, 3-methyl-5-tert-octylsalicylic acid, 3-methyl-5-( ⁇ -methylbenzyl) salicylic acid, 3-methyl-5-nonylsalicylic acid, 3-methyl-5-( ⁇ , ⁇ -dimethylbenzyl salicylic acid, 3,5-diisopropylsalicylic acid, 3,5-di-sec-butylsalicylic acid, 3-tert-butyl-5-chloro
  • the aromatic carboxylic acid used in that patent includes, for example, benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-iodo-benzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, p-isopropyl-benzoic acid, 2,5-dinitrobenzoic acid, 3,4-dinitrobenzoic acid,
  • Group Ib metals such as copper, silver, etc.
  • Group IIa metals such as magnesium, calcium, etc.
  • Group IIb metals such as zinc, cadmium, mercury, etc.
  • Group IIIb metals such as aluminum, gallium, etc.
  • Group IVb metals such as tin, lead
  • those salts wherein zinc, tin, aluminum or nickel is used are especially effective.
  • they are used in the form of the inorganic salts thereof such as chloride, sulfate, nitrate, etc., or in the form of the organic salts thereof such as oxalate, acetate, etc.
  • These metal salts or alkali metal salts of the aromatic carboxylic acid exhibit almost no color-developing ability when used separately, but when their reaction product is coated onto a support, the metal salts of the carboxylic acids show excellent color developing ability.
  • U.S. Patent 4,134,847 discloses a color developer which is obtained by the process which comprises heating a mixture of at least one aromatic carboxylic acid, at least one water-insoluble organic polymer and at least one oxide or carbonate of a polyvalent metal in the presence of water to melt at least one of aromatic carboxylic acid and said polymer and to make the mixture into a homogeneous mass.
  • the organic carboxylic acid useful in that patent is represented by the following formula I except for the compounds having a heteroaromatic ring.
  • R1, R2, R3, R4 and R5 each represents hydrogen, halogen or a hydroxyl, amino, carboxyl, carbamoyl, N-substituted carbamoyl, alkyl, cycloalkyl, alkoxyl, aryl, aryloxy, aralkyl or alkylaryl group, and any adjacent pair of R1 to R5 can complete a ring such as naphthalene ring.
  • Compounds of formula I wherein R1 or R5 is a hydroxyl group are especially important in embodiments of the invention as mentioned in detail hereinafter.
  • aromatic carboxylic acids of formula I wherein R1 and R5 are not a hydroxyl group include benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, p-tert-butylbenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, p-oxybenzoic acid, p-butoxybenzoic acid, p-octoxybenzoic acid, gallic acid, anthranilic acid, phthalic acid monoamide, 3-tert-butyl-t-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 3-( ⁇ -methylbenzyl)-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxy
  • Aromatic carboxylic acids of formula I wherein R1 or R5 is a hydroxyl group are defined by formula II, wherein R6 to R9 are as defined in R1 to R5 of formula I.
  • carboxylic acids examples include salicylic acid, o-cresotinic acid, p-cresotinic acid, 3-ethylsalicylic acid, 4-ethylsalicylic acid, 3-isopropylsalicylic acid, 4-isopropylsalicylic acid, 5-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 5-tert-butylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3-phenylsalicylic acid, 5-phenylsalicylic acid, 3-benzyl-salicylic acid, 5-tert-octylsalicylic acid, 3-( ⁇ -methylbenzyl) salicylic acid, 5-( ⁇ -methylbenzyl) salicylic acid, 5-nonylsalicylic acid, 5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 5-chlorosalicylic
  • R6 and R8 are halogen, alkyl, cycloalkyl, aryl, aralkyl or alkylaryl can be easily derived in commercial scales from phenols, alkylphenols, arylphenols or halogenated phenols.
  • aromatic carboxylic acids examples include 3,5-dichlorosalicylic acid, 3-chloro-5-tert-butylsalicylic acid, 3-chloro-5-tert-amylsalicylic acid, 3-chloro-5-tert-octylsalicylic acid, 3-chloro-5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3,5-dimethylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3-methyl-5-cyclohexylsalicylic acid, 3-methyl-5-tert-octylsalicylic acid, 3-methyl-5-( ⁇ -methyl-benzyl) salicylic acid, 3-methyl-5-nonylsalicylic acid, 3-methyl-5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3,5-diisopropylsalicylic acid, 3,5-sec-butylsalicylic acid, 3-tert-butyl-5-chloro
  • Aromatic carboxylic acids of formula II in which R7 or R9 is alkyl or phenyl can be derived from, for example, metacresol, metapropylphenol, metaphenylphenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol and 3,5-xylenol.
  • carboxylic acids examples include 3,4-dimethylsalicylic acid, 4,5-dimethylsalicylic acid, 4,6-dimethylsalicylic acid, 4-methyl-5-isopropylsalicylic acid, 4-methyl-5-sec-butylsalicylic acid, 4-methyl-5-tert-butylsalicylic acid, 4-methyl-5-tert-amylsalicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 4-methyl-5-benzyl-salicylic acid, 4-methyl-5-tert-octylsalicylic acid, 4-methyl-5-( ⁇ -methylbenzyl) salicylic acid, 4-methyl-5-nonylsalicylic acid, 4-methyl-5-( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3,6-dimethylsalicylic acid, 3-tert-butyl-6-methylsalicylic acid, 3-tert-amyl-6-methylsalicylic acid, 3-cyclohex
  • Aromatic carboxylic acids derived from, for example, bisphenol A, 4,4′-dihydroxycyclohexylidenebiphenyl, 4,4′-dihydroxymethylenebiphenyl and 2,2′-dihydroxydiphenyloxide are regarded as condensates of salicyclic acid.
  • carboxylic acids examples include 5-(4′-hydroxybenzyl) salicylic acid, 5-(3′-carboxy-4′-hydroxybenzyl) salicylic acid (methylene-bissalicylic acid, 3-tert-butyl-5-(3′,5′-di-tert-butyl-4-hydroxybenzyl) salicylic acid, 3-( ⁇ , ⁇ -dimethylbenzyl)-5- ⁇ 3′,5′-di( ⁇ , ⁇ -dimethylbenzyl)-4′-hydroxybenzyl ⁇ salicylic acid, 3-tert-butyl-5-( ⁇ , ⁇ -dimethyl-3′,5′-di-tert-butyl-4′-hydroxy-benzyl) salicylic acid, 5-( ⁇ , ⁇ -dimethyl-3′-carboxy-4′-hydroxybenzyl) salicylic acid, 5-( ⁇ , ⁇ -dimethyl-4′-hydroxybenzyl) salicylic acid, 3-(2′-hydroxyphenoxy) salicylic acid, 3-(2′-hydroxy
  • the organic polymers which U.S. Patent 4,134,847 discloses for mixture with these acids include polymers of ⁇ -methyl styrene.
  • U.S. Patent 4,199,619 discloses use of organic acceptors including various aromatic carboxylic acids such as benzoic acid, p-tert-butyl-benzoic acid, 4-methyl-3-nitro benzoic acid, salicylic acid, 3-phenyl salicylic acid, 3-cyclohexyl salicylic acid, 3-tert-butyl-5-methyl salicyclic acid, 3,5,-di-tert-butyl salicylic acid, 3-methyl-5-benzyl salicylic acid, 3-phenyl-5-( ⁇ , ⁇ -dimethylbenzyl ⁇ salicylic acid, 3-cyclohexyl-5- ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3-( ⁇ , ⁇ -dimethylbenzyl-5-methyl salicylic acid, 3,5-dicyclohexyl salicylic acid, 3,5-di(
  • U.S. Patent 4,219,219 discloses the use of (i) developers comprising a polyvalent metal salt of a substituted salicylic acid represented by the following general formula (I) or (II) and (ii) developers comprising a polyvalent metal salt of a substituted salicylic acid represented by the following general formula (I) or (II) and one or more oxides, hydroxides, carbonates or carboxylic acid salts of zinc, aluminum, titanium, silicon, boron, magnesium and calcium or inorganic pigments such as activated clay, kaolin talc and the like: wherein R represents a hydrogen atom an alkyl group, an aralkyl group or an aryl group, R1 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group and Ar and Ar′ which may be the same or different, each represents an aryl group.
  • U.S. Patent 4,234,212 discloses a recording sheet coated with a color developer obtained from a dispersion containing a melamine resin and/or a urea resin, a polyvalent metal salt of an aromatic carboxylic acid and a water-soluble polymer containing hydroxyl groups.
  • Suitable polyvalent metal salts of aromatic carboxylic acids which can be employed include those polyvalent metal salts of aromatic carboxylic acids represented by the following general formula (I): wherein R1, R2, R3, R4 and R5, which may be the same or different, each may have up to 18 carbon atoms and represents, for example, a hydrogen atom, a halogen atom (e.g., a chlorine atom or a bromine atom), a hydroxy group, an amino group, an alkylamino group (e.g., an alkylamino group substituted with one or two alkyl groups containing 1 to 12 carbon atoms, such as a methylamino group, an ethylamino group, an isobutylamino group, an octylamino group, a dodecylamino group, a diethylamino group, a dibutylamino group, a di-2-ethylhexylamino group, an N-eth
  • aromatic carboxylic acids represented by the general formula (I) include 2,4-dichlorobenzoic acid, p-isopropylbenzoic acid, 2,5-dinitrobenzoic acid, p-t-butylbenzoic acid, N-phenylanthranilic acid, 4-methyl-3-nitrobenzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3,5-dinitrosalicylic acid, 5-t-butyl-salicylic acid, 3-phenylsalicylic acid, 3-methyl-5-t-butylsalicylic acid, 3,5-di-t-amylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3-methyl-5-isoamylsalicylic acid, 5-isoamylsalicylic acid, 3,5-di-sec-butylsalicylic acid, 5-nonylsalicylic acid, 2-hydroxy
  • aromatic carboxylic acids represented by the general formula (I) include 3,5-di( ⁇ -methyl-benzyl)salicylic acid, 3-( ⁇ -methylbenzyl)-5- ⁇ , ⁇ -dimethyl-benzyl)salicylic acid, 3-(4′- ⁇ -dimethylbenzyl)phenyl-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid, 3,5-di-t-butylsalicylic acid, 3,5-di-5-octylsalicylic acid, 3-cyclo-hexyl-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid, 3-phenyl-5-( ⁇ , ⁇ -dimethylbenzyl)-salicylic acid, 3,5-di( ⁇ , ⁇ -dimethylbenzyl)-salicylic acid and so on.
  • Suitable polyvalent metals forming salts with the above-described aromatic carboxylic acids which are disclosed in U.S. Patent 4,234,212 are, for example, magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, silver, cadmium, indium, tin, antimony, barium, tungsten, lead, bismuth and so on.
  • especially effective polyvalent metals include zinc, tin, aluminum, magnesium, calcium and the like. The most preferred polyvalent metal is zinc.
  • a specific binder is employed in preparing a coating solution containing a color developer.
  • the binder is selected depending upon the strength of the film which the binder forms, the dispersibility of the color developer to be employed into the binder, and the extent of influence of the binder upon the color development capability of the color developer.
  • suitable water-soluble polymers which can be used as binders include water-soluble binders where crystals and cross-linking are not present and containing hydroxyl groups, carboxyl groups, sulfo groups, or salts thereof, for example, natural macromolecular compounds such as proteins (e.g., gelatin, albumin, casein, etc.), starches (e.g., cereal starch, ⁇ -starch, oxidized starch, etherified starch, esterified starch, etc.), celluloses (e.g., carboxymethyl cellulose, hydroxymethyl cellulose, etc.), saccharides (e.g., agar, sodium alginate, carboxymethyl starch, gum arabic, etc.) and the like, and water-soluble, synthetic high polymers, such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, maleic acid copolymers and the like.
  • PVA polyvinyl alcohol
  • PVA polyvinyl
  • Suitable latex binders disclosed by U.S. Patent 4,234,212 include styrene-butadiene latex (SBR), acrylonitrile-butadiene latex, acrylic acid type latexes, vinyl acetate type latexes, methylmethacrylate-butadiene latex, and the carboxy denatured latexes thereof.
  • SBR styrene-butadiene latex
  • acrylic acid type latexes acrylic acid type latexes
  • vinyl acetate type latexes vinyl acetate type latexes
  • methylmethacrylate-butadiene latex methylmethacrylate-butadiene latex
  • U.S. Patent 4,374,671 discloses a process for producing a color developer in which zinc oxide is combined with at least one acid selected from the group consisting of salicylic acid and nuclear substituted salicylic acids and at least one metal silicate as an inorganic pigment.
  • Patent 4,374,671 can be represented by the following general formula: wherein R1 and R2 represents hydrogen, chlorine, a saturated and unsaturated alkyl group having 1 to 15 carbon atoms, a phenyl group, a cyclohexyl group, a phenyl alkyl group having 7 to 21 carbon atoms, an alkyl1 phenyl alkyl2 group wherein the alkyl1 and alkyl2 groups have 1 to 15 carbon atoms, a 1-hydroxy-2-carboxy benzyl group and a 4-hydroxy-3-carboxy benzyl group.
  • the nuclear substituted salicylic acid includes, for example, 5-tert-butylsalicylic acid, 3-phenylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-isopropylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-tert-amylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, 3-methyl-5-isoamylsalicylic acid, 5-isoamylsalicylic acid, 3,5-di-sec-butylsalicylic acid, 5-laurylsalicylic acid, 3-methyl-5-laurylsalicylic acid, 3-methylsalicylic acid, 2-4-cresotonic acid, 2,5-cresotonic acid, 2,3-cresotonic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 6-hydroxysalicylic
  • EP-A- 194601 discloses a developer in a carbonless copying system which is produced by the interaction of a salicylic acid, an alkyl-substituted phenol, and an aldehyde which is reacted with a metal source.
  • phenol/aldehyde condensation products useful in the development of colored images from colorless dye are produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source.
  • the phenol/aldehyde condensation product is synthesized by combining and then heating the alkyl-substituted salicylic acid, the alkyl-substituted phenol, the aldehyde, the metal source and water. After the reaction has occurred, the mixture is cooled and then filtered to obtain the phenol/aldehyde condensation product.
  • the developers of the present invention are particularly useful in a photosensitive imaging system in which images are formed by image-wise reaction of one or more chromogenic materials with the developer, and in carbonless copy paper systems.
  • the presently disclosed developers are produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source to form a phenol/aldehyde condensation product.
  • the alkyl-substituted salicylic acid is preferably substituted with at least one alkyl group containing three or more carbon atoms.
  • the alkyl group contains at least four carbon atoms, especially four to twelve carbon atoms.
  • Particularly useful are salicylic acids of the formula: where R is an alkyl group containing from four to twelve carbon atoms.
  • the group R is octyl or nonyl, especially tertiary -octyl (derived from di-isobutene) and nonyl (derived from propylene trimer).
  • the group R may also be a dodecyl group.
  • the currently preferred materials use the nonyl group.
  • the alkylphenol component preferably contains at least one alkyl group containing at least three carbon atoms, especially four to twelve carbon atoms.
  • the phenols are phenols substituted in the para -position with an alkyl group containing four to twelve carbon atoms, particularly tertiary -butyl, tertiary -octyl, nonyl (derived from propylene trimer) and dodecyl.
  • the currently preferred materials use the tertiary -octyl group.
  • the aldehyde is preferably formaldehyde, although the formaldehyde may be supplied, for example, from paraformaldehyde or a similar source of formaldehyde.
  • the preferred metal source is zinc oxide.
  • the phenol/aldehyde condensation product may be synthesized by combining and heating the alkyl-substituted salicylic acid, the alkyl-substituted phenol, the aldehyde, the metal source and water.
  • the following is a general example of a suitable manufacturing process:
  • dodecylphenol was carboxylated to provide a raw material suitable for use in the aldehyde condensation reactions of the present invention.
  • the carboxylation procedure took place at the same time, temperature and pressure parameters described above.
  • the product, dodecylsalicylic acid had an acid number of 163 to 184 and a conversion of 85 to 96%.
  • the aldehyde condensation reactions of the present invention produced a product which was in both dispersed and solid form.
  • the final dispersion product was a white, smooth, slightly viscous liquid.
  • the product had a pH of 5.4 to 6.4, a viscosity of 20 to 1300 centipoise, non-volatiles of 50 to 60%, and a Tg of 45 to 65.
  • the performance of the obtained phenol/aldehyde condensation products in developing colored images from colorless dyes was evaluated by performing carbonless copy paper testing on samples of the products in both dispersed and solid form.
  • the samples were first combined with other components of a water-based coated front (CF) sheet coating formulation.
  • the formulation was then coated on a sheet of paper.
  • test coating formulation was typical of the CF formulations used by the carbonless copy paper industry. All resins were in the dispersed form. Other components of the coating formulation were in slurry form.
  • the CF coating formulation was prepared in the following manner:
  • the amount of resin dispersion to be added to the coating slurry was calculated as 2.5 grams divided by the resin's active resin content. This amount of resin dispersion was added to 23.9 grams of slurry. Water was then added to bring the total solution weight to 83.3 grams. After sufficient agitation, the slurry was ready for coating.
  • the slurry was drawn down on a sheet of paper to create a coated front sheet according to the following procedure: Using a pipette, a bead of slurry was drawn along a #14 Meyer Rod across the paper to be coated. The paper was then drawn smoothly from under the rod, coating the paper. The coated samples were dried for a minimum of twenty minutes and were then ready for carbonless copy paper testing.
  • Carbonless copy paper testing on the coated samples included calender intensity, 3-day oven aging at 140°C and 5-day lightbox aging.
  • a coated front sheet and a coated back sheet were placed face to face and passed through the nip of a two roll calender to create an image.
  • a BNL-2 Opacimeter sold by Technidyne Corp. was used to determine image intensity and the speed of image development (print speed).
  • Image intensity was expressed as the ratio of the reflectance from the imaged area to the reflectance from a white standard: The coated samples were calendered and the imaged surface read in one spot with the opacimeter at intervals of 20, 40 and 50 seconds. One minute and one hour readings were taken in five spots and reported as averages. Image intensity was measured on a scale of 1 to 100, with the lower numbers being the more intense values.
  • HRJ-4002 produced the best results as an industrial standard in carbonless copy paper testing.
  • the calender intensity values of Table 1 show that in every case, the presently disclosed dispersions performed better in calender intensity testing that did HRJ-4002.
  • the resins performed at least as well as HRJ-4002, with PTBP+DSA resin performing slightly better than HRJ-4002.
  • This test measured the degree to which exposure of an unimaged CF sheet of carbonless paper to an elevated temperature affected its ability to develop an image.
  • Unimaged samples were aged in an oven for three days at 140°C. After oven aging was complete, the samples were imaged by calendering with a coated back (CB) sheet and tested for print speed and image intensity with an opacimeter. Measurements were taken at 20, 40 and 50 second intervals after calendering. One minute and 1 hour readings were taken five times each at different spots of the sample and reported as an average of the five individual measurements. These intensity measurements at various time intervals were compared with intensity measurements of freshly coated samples taken at identical time intervals. The loss of image intensity after oven aging was reported as a decline in image performance after heat aging. The results are summarized in Table 2.
  • Imaged samples were tested for image intensity on the opacimeter for use as a baseline. These imaged samples were then subjected to five days in a fluorescent lightbox as specified according to the ASTM F 767-82 test method. Intensity values were again determined with the opacimeter. The magnitude of the difference between initial intensity values and image intensity after lightbox exposure was taken as the measure of the degree of image fade. These results are shown in Table 3.
  • Carbonless copy paper testing was performed on the obtained products with nonylsalicylic acid contents of 30, 40, 50 and 75 percent of the total phenols content. Testing consisted of calender intensity measurements, oven aging, lightbox aging, YI 313 measurements and color shift determinations. The same general procedures described in Examples 4 through 6 above (with the specific parameters given in Tables 4 through 6) were used in calender intensity testing, oven aging and lightbox aging.
  • YI 313 The YI 313 method was used to measure background yellowing and report it as a numerical value or "yellowness index.”
  • a Hunter Colorquest Spectrophotometer was used to measure the reflectance spectrum of a sample of freshly coated CF paper. Then, by means of computer software, the "yellowness index", or YI 313 value, was calculated according to the formula specified in ASTM's YI 313 method.
  • the sample was then placed in a lightbox containing fluorescent bulbs of the type described in ASTM's test method F 767 - 82.
  • the sample was exposed to the fluorescent light for five days, then removed from the lightbox.
  • the yellowness index or YI 313 value was again measured using the Hunter Colorquest Spectrophotometer.
  • the difference in the YI 313 value of the test CF sheet before and after lightbox exposure was taken as the measure of the degree of yellowing of the unimaged coating when exposed to light.
  • Color shift was also determined using a Hunter Colorquest Spectrophotometer. The results of this test are from the L, a, and b scales based on the opponent-colors theory of color visions. Color shift testing requires a baseline and was performed on imaged samples. After baseline values were determined, the samples were subjected to lightbox aging, according to standard methods described above. New L, a, and b values were determined after lightbox aging and changes in color, as expressed by changes in the L, a, b values, were noted.
  • Calender intensity measurements, oven aging, lightbox aging, YI 313 measurements and color shift determinations are carbonless copy paper test methods widely used by the industry. These tests are designed to measure what are considered to be some of the important attributes of carbonless copy paper, i.e., print speed, image intensity, and fading or color change due to the environment.
  • nonylsalicylic acid As is clear from the above data, varying the percentage of nonylsalicylic acid to total phenol content has little or no effect on the performance of the phenol/aldehyde condensation product, except for very high levels of nonylsalicylic acid (75% nonylsalicylic acid). 30 and 40% nonylsalicylic acid results are identical to 50% nonylsalicylic acid results in calender intensity, lightbox aging, and YI-313 measurements. Oven age testing indicates 40% nonylsalicylic acid is slightly better in performance than 50% nonylsalicylic acid.

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Claims (13)

  1. Système dans lequel des images sont formées sélectivement dans des parties d'une surface sous la forme d'une matière colorée par la réaction d'une ou plusieurs matières chromogènes incolores avec un agent développateur acide,
       amélioré en ce que l'agent développateur contient un produit de condensation phénol/aldéhyde formé par l'interaction d'un acide salicylique alkyle-substitué, d'un phénol alkyle-substitué et d'un aldéhyde, produit de condensation que l'on a fait réagir avec une source de métal.
  2. Système selon la revendication 1, dans lequel des images sont formées sélectivement dans des parties d'une surface sous la forme d'une matière colorée par la réaction d'une ou plusieurs matières chromogènes incolores avec un agent développateur acide,
       amélioré en ce que l'agent développateur contient un produit de condensation phénol/aldéhyde formé par un procédé dans lequel on combine à la fois un acide salicylique alkyle-substitué, un phénol alkyle-substitué, un aldéhyde et une source de métal que l'on fait réagir.
  3. Système selon la revendication 1, dans lequel des images sont formées sélectivement dans des parties d'une surface sous la forme d'une matière colorée par la réaction d'une ou plusieurs matières chromogènes incolores avec un agent développateur acide,
       amélioré en ce que l'agent développateur contient un produit de condensation phénol/aldéhyde formé par un procédé dans lequel on fait réagir un acide salicylique alkyle-substitué, un phénol alkyle-substitué et un aldéhyde pour former un produit de condensation et on fait ensuite réagir le produit avec une source de métal.
  4. Système selon une quelconque des revendications qui précèdent, dans lequel des images sont formées par l'exposition à un rayonnement actinique, à la manière d'une image, d'un produit photosensible encapsulé contenant une matière chromogène et par la rupture des capsules en présence d'un agent développateur avec obtention d'une réaction de la matière chromogène et de l'agent développateur selon des motifs avec production d'une image contrastée.
  5. Système selon une quelconque des revendications 1 à 3 dans lequel les images sont formées par l'application sélective d'une pression sur des microcapsules contenant un chromogène dans des parties de ladite surface, les microcapsules s'ouvrant en présence d'un agent développateur de couleur, libérant ainsi le chromogène qui réagit avec l'agent développateur de couleur pour former une image au point de pression.
  6. Système selon une quelconque des revendications qui précèdent, dans lequel l'acide salicylique alkyle-substitué est substitué par au moins un groupe alkyle contenant au moins trois atomes de carbone.
  7. Système selon la revendication 6, dans lequel l'acide salicylique alkyle-substitué a pour formule :
    Figure imgb0027
        dans laquelle R est un groupe alkyle contenant 4 à 12 atomes de carbone.
  8. Système selon la revendication 7, dans lequel R est un groupe octyle, de préférence un groupe tert-octyle, ou un groupe nonyle ou un groupe dodécyle.
  9. Système selon une quelconque des revendications qui précèdent, dans lequel le phénol alkyle-substitué est substitué par au moins un groupe alkyle contenant au moins trois atomes de carbone.
  10. Système selon la revendication 9, dans lequel le phénol alkyle-substitué est substitué en position para par un groupe alkyle contenant 4 à 12 atomes de carbone, choisi de préférence parmi le tert-butyle, les groupes tert-octyle, les groupes nonyle et les groupes dodécyle.
  11. Système selon une quelconque des revendications qui précèdent, dans lequel l'aldéhyde est le formaldéhyde.
  12. Système selon une quelconque des revendications qui précèdent, dans lequel la source de métal est de l'oxyde de zinc.
  13. Système dans lequel des images sont formées sélectivement dans des parties d'une surface sous la forme d'une matière colorée par la réaction d'une ou plusieurs matières chromogènes incolores avec un agent développateur acide,
       amélioré en ce que l'agent développateur contient un produit de condensation phénol/aldéhyde de formule :
    Figure imgb0028
        dans lequel R est tel que défini dans la revendication 7, R' est un groupe alkyle contenant au moins trois atomes de carbone et est, de préférence, un groupe alkyle tel que défini dans la revendication 10 et n est un entier égal à 1 ou plus.
EP89303890A 1988-04-20 1989-04-19 Résine alkyl salicylate pour papier de copiage sans carbone et son utilisation pour former des images Expired - Lifetime EP0338808B1 (fr)

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US4226962A (en) * 1977-09-06 1980-10-07 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
US4173684A (en) * 1977-09-06 1979-11-06 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
JPS5625493A (en) * 1979-08-08 1981-03-11 Fuji Photo Film Co Ltd Preparing recording material composition
US4440846A (en) * 1981-11-12 1984-04-03 Mead Corporation Photocopy sheet employing encapsulated radiation sensitive composition and imaging process
US4620874A (en) * 1984-06-28 1986-11-04 Btl Specialty Resins Corporation Metal modified phenolic resin color developers
US4612254A (en) * 1985-03-07 1986-09-16 Occidental Chemical Corporation Aromatic carboxylic acid and metal-modified phenolic resins and methods of preparation

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