EP0573085B1 - Matériau d'enregistrement photoconducteur ayant un système de liant durcissable sous l'influence de l'humidité - Google Patents

Matériau d'enregistrement photoconducteur ayant un système de liant durcissable sous l'influence de l'humidité Download PDF

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EP0573085B1
EP0573085B1 EP93201267A EP93201267A EP0573085B1 EP 0573085 B1 EP0573085 B1 EP 0573085B1 EP 93201267 A EP93201267 A EP 93201267A EP 93201267 A EP93201267 A EP 93201267A EP 0573085 B1 EP0573085 B1 EP 0573085B1
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recording material
group
photoconductive recording
hydrocarbon group
carbon atoms
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EP0573085A1 (fr
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David C/O Agfa-Gevaert N.V. Terrell
Stefaan c/o Agfa-Gevaert N.V. De Meutter
Harald C/O Agfa-Gevaert N.V. Blum
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity

Definitions

  • the present invention relates to photosensitive recording materials suitable for use in electrophotography.
  • photoconductive materials are used to form a latent electrostatic charge image that is developable with finely divided colouring material, called toner.
  • the developed image can then be permanently affixed to the photoconductive recording material, e.g. a photoconductive zinc oxide-binder layer, or transferred from the photoconductor layer, e.g. a selenium or selenium alloy layer, onto a receptor material, e.g. plain paper and fixed thereon.
  • the photoconductive recording material is reusable.
  • a photoconductor layer has to be used that rapidly loses its charge on photo-exposure and also rapidly regains its insulating state after the exposure to receive again a sufficiently high electrostatic charge for a next image formation.
  • the failure of a material to return completely to its relatively insulating state prior to succeeding charging/imaging steps is commonly known in the art as "fatigue".
  • the fatigue phenomenon has been used as a guide in the selection of commercially useful photoconductive materials, since the fatigue of the photoconductive layer limits the copying rates achievable.
  • a further important property which determines the suitability of a particular photoconductive material for electrophotographic copying is its photosensitivity, which must be sufficiently high for use in copying apparatuses operating with the fairly low intensity light reflected from the original.
  • Commercial usefulness also requires that the photoconductive layer has a spectral sensitivity that matches the spectral intensity distribution of the light source e.g. a laser or a lamp. This enables, in the case of a white light source, all the colours to be reproduced in balance.
  • active layer is meant a layer that plays a role in the formation of the electrostatic charge image.
  • Such a layer may be the layer responsible for charge carrier generation, charge carrier transport or both.
  • Such layers may have a homogeneous structure or heterogeneous structure.
  • Examples of active layers in said photoconductive recording material having a homogeneous structure are layers made of vacuum-deposited photoconductive selenium, doped silicon, selenium alloys and homogeneous photoconducting polymer coatings, e.g. of poly(N-vinylcarbazole) or polymeric binder(s) molecularly doped with an electron (negative charge carrier) transporting compound or a hole (positive charge carrier) transporting compound such as particular hydrazones, amines and heteroaromatic compounds sensitized by a dissolved dye, so that in said layers both charge carrier generation and charge carrier transport take place.
  • an electron (negative charge carrier) transporting compound or a hole (positive charge carrier) transporting compound such as particular hydrazones, amines and heteroaromatic compounds sensitized by a dissolved dye
  • Examples of active layers in said photoconductive recording material having a heterogeneous structure are layers of one or more photosensitive organic or inorganic charge generating pigment particles dispersed in a polymer binder or polymer binder mixture in the presence optionally of (a) molecularly dispersed charge transport compound(s), so that the recording layer may exhibit only charge carrier generation properties or both charge carrier generation and charge transport properties.
  • a charge generating and charge transporting layers are combined in contiguous relationship.
  • Layers which serve only for the charge transport of charge generated in an adjacent charge generating layer are e.g. plasma-deposited inorganic layers, photoconducting polymer layers, e.g. on the basis of poly(N-vinylcarbazole) or layers made of low molecular weight organic charge transporting compounds molecularly distributed in a polymer binder or binder mixture.
  • CGM's Useful charge carrier generating pigment materials belong to one of the following classes :
  • Organic charge carrier transporting substances may be either polymeric or non-polymeric materials.
  • Preferred non-polymeric materials for negative charge transport are :
  • CGL charge generating layer
  • CTL charge transport layer
  • One or more of the following phenomena can have a negative influence on the electro-optical properties of the photoconductive recording material :
  • Interfacial mixing between the CGL and the CTL can be avoided by using a CGL-binder or binders, which is/are insoluble in the solvent used for dissolving the CTL-binders in which CTM's exhibit optimum charge transport properties.
  • Hardening is considered here as a treatment which renders the binder of a charge generating layer of the photoconductive recording material insoluble in methylene chloride.
  • Various hardenable binder systems have been proposed for CGL's for use with electron-transporting CTL's, for example : polyhydroxy compounds or resins hardened with polyisocyanates, polyepoxy compounds or resins hardened with poly NH-group containing compounds or resins and polyepoxy compounds or resins hardened with polyaminoamides.
  • the hardeners used acting as crosslinking agents are either highly toxic, induce dermatitis and are subject to moisture induced degradation, or undergo colouration and loss of activity due to oxidation as is the case of poly NH-group containing compounds or resins and polyaminoamides.
  • the hardenable binder systems often exhibit a limited potlife as a consequence of premature curing, whereby the CGM-binder dispersion becomes increasingly viscous and reproducible coating becomes impossible.
  • a photoconductive recording material containing a support and a charge generating layer (CGL) in contiguous relationship (contact) with a charge transporting layer (CTL) containing a n-charge transporting material (n-CTM), wherein the binder of said charge generating layer (CGL) is made insoluble in methylene chloride by crosslinking, and said binder is composed essentially of a binder composition hardened under the influence of moisture and prepared by mixing the following components (A) and (B) :
  • the photoconductive recording material according to the present invention has a charge generating layer (CGL) containing as the sole binder one or more resins obtained by mixing and moisture-hardening :
  • component (A) consists essentially of a copolymer of :
  • the binder product obtained in curing the above-defined binder composition with the aid of water results from the hydrolysis of the blocked amine moieties of component (B), whereby one hydroxyl group is formed per amino group (primary or secondary amino group).
  • These groups, especially said amino groups enter into rapid cross-linking reaction with the anhydride groups of copolymer (A).
  • the copolymer containing anhydride groups contains additionally epoxide groups as described in US-P 4,904,740, wherein the last mentioned groups also take part in a crosslinking reaction with free amino groups.
  • Preferred maleic anhydride copolymers for use according to the present invention contain styrene, methacrylate and/or acrylate units.
  • radical formers applied in the copolymerisation process are those suitable for reaction temperatures of 60 to 180 °C such as organic peroxides and other radical formers mentioned in US-P 4,975,493.
  • blocked amines are oxazolanes, e.g. those described in said US-P 4,975,493.
  • Blocked amines containing aldimine or ketimine groups for generating free amine with water are described in US-P 4,937,293.
  • Blocked amines containing hexahydropyrimidine, tetrahydropyrimidine, or tetrahydroimidazole moieties for generating free amino groups are described in US-P 4,970,270.
  • Blocked amines being amidacetal or amidaminal compounds are described in published European Patent Application 346669.
  • the blocked amines representing said component (B) have preferably a molecular weight of from 86 to 10,000, preferably from 250 to 4,000 and contain a statistical average of from 1 to 50, preferably 1 to 10, especially 2 to 4 structural units corresponding to at least one of the following general formulae (IV), (V), (VI), (VII), (VIII) and (IX): wherein :
  • General formula (IV) includes 5-membered tetrahydro-imidazole and 6-membered hexahydropyrimidine structural units.
  • General formula (V) includes 5-membered dihydro-imidazole and 6-membered tetrahydropyrimidine structural units.
  • General formulae (VI), (VII), (VIII) and (IX) relate respectively to oxazolane (VI), aldimine and ketimine (VII), bicyclic amide acetal (VIII) and bicyclic amide aminal (IX) structural units.
  • Suitable aldehydes or ketones for reaction with polyamines to prepare said blocked amines containing hexahydropyrimidine, tetrahydropyrimidine or tetrahydroimidazole units as described above correspond to the following general formula : wherein R 5 and R 6 have the same meaning as described above, and preferably having a molecular weight of from 72 to 200 for the ketones, and from 58 to 250 for the aldehydes.
  • the polyamines used for the preparation of the compounds containing hexahydropyridine or tetrahydroimidazole groups are in particular organic compounds containing at least 2 primary and/or secondary amino groups.
  • Suitable polyamines are, e.g. those corresponding to the following general formula : R 8 - NH - R 7 - NH - R 9 in which
  • Particularly preferred polyamines are those in which R 8 and R 9 (identical or different) stand for an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, n-pentyl or n-hexyl and at least one of the groups denoted by R 8 and R 9 is a group obtainable by the addition of an amine hydrogen atom to an olefinically unsaturated compound.
  • olefinically unsaturated compounds suitable for the preparation of such modified polyamines include derivatives of (methyl)acrylic acid such as the esters, amides or nitriles thereof or, e.g.
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene or vinyl toluene or, e.g. vinyl esters such as vinyl acetate, vinyl propionate or vinyl butyrate or, for example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether or mono- or diesters for fumaric acid, maleic acid or tetrahydrophthalic acid.
  • R 8 and/or R 9 may also stand for an aminoalkyl or hydroxyalkyl group containing, e.g. 2 to 4 carbon atoms.
  • Ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-and 1,3-butylene diamine and diethylene triamine are particularly useful.
  • the preferred compounds containing aldimine or ketimine groups include compounds containing structural units of the following general formula (R 5 and R 6 having the meaning defined above) :
  • aldehydes and ketones used for this purpose include isobutyraldehyde, 2,2-dimethylpropanal, 2-ethylhexanal, hexahydrobenzaldehyde and especially those ketones which have a boiling point below 170°C and are readily volatile at room temperature, e.g. methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, diisobutyl ketone and methyl tert.-butyl ketone.
  • the polyamines used for the preparation of component B) containing ketimine or aldimine groups may in particular be organic compounds containing at least 2 aliphatically and/or cycloaliphatically bound primary amino groups. Although polyamines containing aromatically bound amino groups may also be used, they are less preferred.
  • the polyamines generally have a molecular weight of from 60 to 500, preferably from 88 to 400, although prepolymers with a relatively high molecular weight containing amino end groups may also be used as polyamine components for the preparation of component B).
  • Diprimary aliphatic and cycloaliphatic diamines are particularly preferred polyamines, e.g. tetramethylene diamine, hexamethylene diamine, isophorone diamine, bis(4-amino-cyclohexyl)-methane, bis-aminomethylhexahydro-4,7-methanoindane, 1,4-cyclohexanediamine, 1,3-cyclohexane diamine, 2-methylcyclohexane diamine, 4-methylcyclohexane diamine, 2,2,5-trimethylhexane diamine, 2,2,4-trimethylhexane diamine, 1,4-butane diol-bis(3-aminopropyl)-ether, 2,5-diamine-2,5-dimethylhexane, bis-aminomethylcyclohexane, bis(4-amino-3,5-dimethylcyclohexyl)-methane and mixtures thereof.
  • Tetramethylene diamine, hexamethylene diamine, isophorone diamine, bis-aminomethyl-cyclohexane, 1,4-cyclohexane diamine, bis-aminomethylhexahydro-4,7-methanoindane and bis(4-amino-cyclohexyl)-methane are particularly preferred.
  • the aldimines and ketimines may be prepared not only from these preferred diamines but also from prepolymers containing primary amino end groups, i.e. compounds in the molecular weight range of from 500 to 5,000, preferably from 500 to 2,000, containing at least two amino end groups.
  • These groups include, e.g. the amino polyethers known from polyurethane chemistry, such as these described, e.g. in EP-A-0-081701 or, e.g. compounds containing amide, urea, urethane or secondary amino groups obtained as reaction products of difunctional or higher functional carboxylic acids, isocyanates or epoxides with diamines of the type exemplified above, which reaction products still contain at least two primary amino groups. Mixtures of such relatively high molecular weight polyamines with the low molecular weight polyamines exemplified above may also be used.
  • aromatic polyamines which in principle may be used for the preparation of the aldimines or ketimines but are less preferred include, e.g. 2,4- and 2,6-diaminotoluene, 1,4-diaminobenzene and 4,4'-diaminodiphenylmethane.
  • the compound (B) containing bicyclic amide acetal groups can be obtained in a manner known per se by reaction of compounds containing epoxy or cyclic carbonate groups with cyclic amino esters such as, for example, oxazolines or oxazines.
  • cyclic amino esters such as, for example, oxazolines or oxazines.
  • the starting components in this reaction are used in such relative amounts that a total of 1.0 to 1.1 oxazoline or oxazine groups is present for every epoxy or cyclic carbonate group.
  • This type of reactions, which lead to compounds having bicyclic amide acetal groups are described in detail, e.g. in R.Feinauer, Liebigs Ann. Chem. 698 , 174 (1966).
  • the oxazolines or oxazines which are used for the preparation of the bicyclic amide acetals can be prepared by methods known from the literature, e.g. by reaction of carboxylic acids or anhydrides thereof with hydroxyamines with the elimination of water or by reaction of nitriles with hydroxyamines with the elimination of ammonia. This type of reactions is described, e.g. in J. Org. Chem. 26 , 3821 (1961), H.L. Wehrmeister, J. Org. Chem. 27 , 4418 (1962) and P. Allen, J. Org. Chem. 28 , 2759 (1963).
  • Oxazolines or oxazines which contain hydroxyl groups can also be converted into higher-functional oxazolines or oxazines, e.g. by reaction with organic polyisocyantes.
  • Bicyclic amide aminals which are suitable according to the invention as component B) can be obtained, e.g. by reaction of tetrahydropyrimidines or dihydroimidazoles with organic epoxides or cyclic carbonates.
  • monofunctional tetrahydropyrimidines or dihydroimidazoles can be reacted with monofunctional epoxides or carbonates, polyfunctional tetrahydropyrimidines or dihydroimidazoles with monofunctional epoxides or carbonates, monofunctional tetrahydropyrimidines or dihydroimidazoles with polyfunctional epoxides or carbonates.
  • the tetrahydropyrimidines or dihydroimidazoles used for the preparation of the bicyclic amide aminals can be prepared by methods known from the literature, e.g. by reaction of carboxylic acids with diamines with the elimination of water, or by reaction of nitriles with diamines with the elimination of ammonia. This type of reaction is described, e.g. in DE-OS (German Offenlegungsschrift) 3 640 239.
  • Compounds containing oxazolane groups of the general formula (VI) are especially preferred as component B). They are preferably compounds in which R 5 and R 6 , which may be identical or different, denote hydrogen, aliphatic hydrocarbon groups containing from 1 to 18 carbon atoms, cycloaliphatic hydrocarbon groups containing from 5 to 10 carbon atoms, araliphatic hydrocarbon groups containing from 7 to 18 carbon atoms or phenyl groups, or the two groups R 5 and R 6 together with the adjacent carbon atom may form a five- six-membered cycloaliphatic ring, and R 7 denotes a divalent aliphatic hydrocarbon group containing 2 to 6 carbon atoms, with the proviso that there are 2 or 3 carbon atoms between both nitrogen atoms.
  • R 5 and R 6 which may be identical or different, denote hydrogen, aliphatic hydrocarbon groups containing from 1 to 18 carbon atoms, cycloaliphatic hydrocarbon groups containing from 5 to 10 carbon atoms,
  • Components B) containing oxazolane groups may be prepared in known manner by reaction of the corresponding aldehydes or ketones corresponding to the following general formula (R 5 and R 6 having the meaning defined above) : with suitable hydroxylamines of the type described hereinafter.
  • aldehydes or ketones used may be selected from those already mentioned above as examples.
  • Preferred aldehydes and ketones include isobutyraldehyde, 2-ethylhexanal, hexahydrobenzaldehyde, cyclopentanone, cyclohexanone, methylcyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • the hydroxylamines may be in particular organic compounds containing at least 1 aliphatic amino group and at least 1 aliphatically bound hydroxyl group. Although hydroxylamines containing aromatically or cycloaliphatically bound amino or hydroxyl groups may be used, they are less preferred.
  • the hydroxylamines generally have a molecular weight of from 61 to 500, preferably from 61 to 300.
  • hydroxylamines bis(2-hydroxyethyl)-amine, bis(2-hydroxypropyl)-amine, bis(2-hydroxybutyl)-amine, bis(3-hydroxypropyl)-amine, bis(3-hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(2-hydroxyethyl)-amine, 2-(methylamino)-ethanol, 2-(ethylamino)-ethanol, 2-(propylamino)-ethanol, 2-(butylamino)-ethanol, 2-(hexylamino)-ethanol, 2-(cyclohexylamino)-ethanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, 2-amino-2-propyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-3-methyl-3-hydroxybutane, propanolamine and ethanolamine.
  • bis(2-hydroxy-ethyl)-amine bis(2-hydroxypropyl)-amine, bis(2-hydroxy-butyl)-amine, bis(3-hydroxyhexyl)-amine, 2-(methylamino)-ethanol, 2-(ethylamino)-ethanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, propanolamine and ethanolamine.
  • component (B) contains oxazolane groups it can be prepared by allowing to react the above-defined reactants in such quantitative ratios that based on the carbonyl groups of the aldehydes or ketones, the hydroxyamines are present in 1 to 1.5 times the equivalent quantity in the oxazolane formation.
  • Catalytic quantities of acidic substances e.g. p-toluene sulphonic acid, hydrogen chloride, sulphuric acid or aluminium chloride, may be used to accelerate the reaction.
  • a suitable reaction temperature is in the range of 60 to 180 °C, the water formed in the reaction being removed by distillation using an entraining agent as described in US-P 4,975,493.
  • mono-oxazolanes according to the above mentioned general formula (V) are allowed to react through hydrogen on their nitrogen atom with a polyfunctional reactant, e.g. polyisocyanate, polyepoxide, polycarboxylic acid, partially esterified polycarboxylic acid or polyacid anhydride.
  • a polyfunctional reactant e.g. polyisocyanate, polyepoxide, polycarboxylic acid, partially esterified polycarboxylic acid or polyacid anhydride.
  • the reaction with organic polyisocyanates is preferred and may be carried out as described in DE-OS 2 446 438.
  • polyisocyanates which are suitable for this modifying reaction are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates, such as those described, e.g. by W. Siefken in Justus Liebigs Annalen de Chemie, 562 , p. 75 to 136, e.g.
  • German Patent Specification 1 092 007 polyisocyanates having allophanate groups (as described e.g. in GB-P 994,890), polyisocyanates having isocyanurate groups (as described e.g.in in German Patent Specifications 1 022 789 and 1 222 067) polyisocyanates having urethane groups (as described e.g. in US-P 3,394,164) or polyisocyanates prepared by reaction of at least one difunctional hydroxyl compound with excess of at least one difunctional isocyanate, polyisocyanates having biuret groups (as described e.g. in German Patent Specification 1 101 394) and prepolymer or polymer substances having at least two isocyanate groups.
  • Suitable polyisocyanate compounds are further given in the book High Polymers, Volume XVI dealing with “Polyurethanes, Chemistry and Technology” Interscience Publishers, New York, London, and further also in Volume I, 1962, p. 32-42 and 45-54 and Volume II, 1964, p. 5-6 and 198-199, and also in Kunststoffhandbuch (Handbook of Plastics), Volume VI, Vieweg-Höchtlen, Carl-Hanser Verlag, Kunststoff, 1966, p. 45-71.
  • Particularly preferred polyisocyanates for preparing polyfunctional oxazolanes are low molecular weight (cyclo)aliphatic diisocyanates, e.g. : hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane or relatively high molecular weight isocyanate prepolymers based on such diisocyanates.
  • said preferred polyisocyanates are allowed to react with monooxazolanes according to the above-mentioned general formula (VI) wherein nitrogen is linked to a HO-CH 2 -CH 2 - group to form an urethane linkage, R 5 represents hydrogen, R 6 an ethyl-1-pentyl group, and R 7 is an ethylene group.
  • Polyepoxides suitable for use in the preparation of polyfunctional oxazolanes are organic compounds containing at least two epoxide groups.
  • Preferred polyepoxides for such use are aliphatic bisepoxides having epoxide equivalent weights of 43 to 300, e.g. 1,3-butadiene bisepoxide, 1,5-hexadiene bisepoxide, ethylene glycol diglycidyl ether, glycerol-1,3-diglycidyl ether, 3,4-epoxycyclohexyl, methyl-3',4'-epoxycyclohexane carboxylate, and adipic acid-(3,4-epoxycyclohexyl)-bisester.
  • 1,3-butadiene bisepoxide 1,5-hexadiene bisepoxide
  • ethylene glycol diglycidyl ether glycerol-1,3-diglycidyl ether
  • 3,4-epoxycyclohexyl methyl-3',4'-epoxycyclohexane carboxylate
  • the molecular weight and functionality of the oxazolanes of relatively high functionality may be adjusted readily through the choice of the reactants.
  • di- and/or trifunctional oxazolanes are applied preferably in conjunction with a copolymer of maleic anhydride and other monomers, e.g. styrene, methyl methacrylate and butyl acrylate, containing at least 10 % by weight of polymerised maleic anhydride units.
  • Part I is introduced initially into a reaction vessel equipped with a stirring, cooling and heating system, heated to the reaction temperature.
  • Part II is added over a period of 3 hours and part III over a period of 3,5 hours, followed by stirring for 2 hours.
  • reaction temperatures and the composition of parts I - III are shown in the following Table 1 together with the solids content and viscosity of the maleic anhydride (MA) copolymer solutions obtained.
  • the hydroxyamines, the carbonyl compounds and, optionally, the entraining agent are mixed and 0.01 to 0.1 % of an acidic catalyst is added optionally to the resulting mixture.
  • the reaction mixture is then heated under reflux in an inert gas atmosphere (e.g. N 2 , Ar) on a water separator until the theoretical quantity of water has separated off or until no more water separates off.
  • an inert gas atmosphere e.g. N 2 , Ar
  • the products may be used for the combinations according to the invention without any further purification or separation step.
  • the products may be purified, e.g. by vacuum distillation.
  • a mixture of components (A) and (B) is made in a water-free organic solvent or solvent mixture and the charge generating material particles are dispersed therein to form a charge generating layer composition ready for coating.
  • the solvent(s) are used in a quantity necessary to obtain the required coating composition viscosity adapted to the applied coating system.
  • the quantity of solvent may be kept fairly small by applying low molecular weight maleic anhydride copolymers.
  • a liquid monomer or mixture of monomers that acts as solvent for the applied components (A) and (B).
  • Said monomer or mixture of monomers, which has not to be removed by evaporation, can be polymerised at elevated temperature in the presence of a thermally activatable radical former for addition polymerisation.
  • the hardening of the binder obtained by reaction of components (A) and (B) proceeds quickly in the presence of atmospheric moisture entering the coating after its application.
  • the hardening may be accelerated by heat e.g. in the temperature range of 40 to 130 °C, temperature at which applied solvents are removed by evaporation.
  • the resins obtained by reaction of said components (A) and (B) with moisture may be used in combination with at least one other polymer serving as binding agent, e.g. in combination with acrylate and methacrylate resins, copolyesters of a diol, e.g. glycol, with isophthalic and/or terephthalic acid, polyacetals, polyurethanes, polyester-urethanes, aromatic polycarbonates.
  • Useful resin combinations contain at least 50 % by weight of said resins obtained by moisture-hardening of a mixture of components (A) and (B) in the total binder content.
  • a polyester resin particularly suited for use in combination with said hardened resins is a polyester sold under the tradename DYNAPOL L 206 (DYNAPOL is a registered trade mark of Dynamit Nobel for a copolyester of terephthalic acid and isophthalic acid with ethylene glycol and neopentyl glycol, the molar ratio of tere- to isophthalic acid being 3/2).
  • Said polyester resin improves the adherence of the charge generating layer to aluminium that may form a conductive coating on the support of the recording material.
  • Aromatic polycarbonates that are suitable for use in admixture with said resins (1) and/or (2) hardened with polyisocyanates are aromatic polycarbonates that can be prepared by methods such as those described by D.Freitag, U.Grigo, P.R.Müller and W.Nouvertné in the Encyclopedia of Polymer Science and Engineering, 2nd ed., Vol.
  • X represents S, SO 2
  • each of R 11 , R 12 , R 13 , R 14 , R 17 and R 18 represents hydrogen, an alkyl group or an aryl group
  • each of R 15 and R 16 represents hydrogen, an alkyl group, an aryl group or together represent the necessary atoms to close a cycloaliphatic ring, e.g. a cyclohexane ring.
  • Aromatic polycarbonates having a molecular weight in the range of 10,000 to 200,000 are preferred. Suitable polycarbonates having such a high molecular weight are sold under the registered trade mark MAKROLON of Bayer AG, W-Germany.
  • Suitable electronically inactive binder resins for use in unhardened active layers of the present photoconductive recording material are cellulose esters, acrylate and methacrylate resins, e.g. cyanoacrylate resins, polyvinyl chloride, and copolymers of vinyl chloride, e.g. copolyvinyl chloride/acetate and copolyvinyl chloride/maleic anhydride, polyester resins e.g. copolyesters of isophthalic acid and terephthalic acid with glycol and aromatic polycarbonate resins.
  • unhardened binder resins for an active layer are silicone resins, polystyrene and copolymers of styrene and maleic anhydride and copolymers of butadiene and styrene.
  • a charge transport layer in the photoconductive recording materials of the present invention preferably has a thickness in the range of 5 to 50 ⁇ m, more preferably in range of 5 to 30 ⁇ m. If such a layer contains low molecular weight charge transport molecules, such compounds will preferably be present in concentrations of 30 to 70 % by weight.
  • Preferred binders for a negative charge transporting (CTL) layer in the recording material of the present invention are homo- or co-polycarbonates within the scope of the general formula (Z) above, more particularly specific polycarbonates and copoly-carbonates with recurring units B1 to B7.
  • spectral sensitizing agents can have an advantageous effect on the charge transport.
  • these dyes are used in an amount not substantially reducing the transparency in the visible light region (420 - 750 nm) of the charge transporting layer so that the underlying charge generating layer still can receive a substantial amount of the exposure light when exposed through the charge transporting layer.
  • the charge transporting layer may contain compounds substituted with electron-donor groups forming an intermolecular charge transfer complex, i.e. donor-acceptor complex wherein the hydrazone compound represents an electron donating compound.
  • useful compounds having electron-donating groups are hydrazones such as 4-N,N-diethylamino-benzaldehyde-1,1-diphenylhydrazone (DEH), amines such as tris(p-tolylamine) (TTA) and N,N'-diphenyl-N,N'-bis(3-methyl-phenyl)-[1,1-biphenyl]-4,4'-diamine (TPD) etc.
  • the optimum concentration range of said derivatives is such that the acceptor/donor weight ratio range is from 2.5:1 to 1,000:1.
  • UV-stabilizers Compounds acting as stabilising agents against deterioration by ultra-violet radiation, so-called UV-stabilizers, may also be incorporated in said charge transport layer.
  • UV-stabilizers are benztriazoles.
  • silicone oils For controlling the viscosity of the coating compositions and controlling their optical clarity silicone oils may be added to the charge transport layer.
  • any of the organic pigment dyes belonging to one of the following classes and able to transfer electrons to electron transporting materials may be used :
  • Inorganic substances suited for photogenerating negative charges in a recording material according to the present invention are e.g. amorphous selenium and selenium alloys e.g. selenium-tellurium, selenium-tellurium-arsenic and selenium-arsenic and inorganic photoconductive crystalline compounds such as cadmium sulphoselenide, cadmiumselenide, cadmium sulphide and mixtures thereof as disclosed in US-P 4,140,529.
  • the thickness of the charge generating layer is preferably not more than 10 ⁇ m, more preferably not more than 5 ⁇ m.
  • an adhesive layer or barrier layer may be present between the charge generating layer and the support or the charge transport layer and the support.
  • Useful for that purpose are e.g. a polyamide layer, nitrocellulose layer, hydrolysed silane layer, or aluminium oxide layer acting as blocking layer preventing positive or negative charge injection from the support side.
  • the thickness of said barrier layer is preferably not more than 1 micron.
  • the conductive support may be made of any suitable conductive material.
  • Typical conductors include aluminium, steel, brass and paper and resin materials incorporating or coated with conductivity enhancing substances.
  • An insulating support such as a resin support is e.g. provided with a conductive coating, e.g. vacuum-deposited metal such as aluminium, dispersed carbon black, graphite and conductive monomeric salts or a conductive polymer, e.g. a polymer containing quaternized nitrogen atoms as in Calgon Conductive polymer 261 (trade mark of Calgon Corporation, Inc., Pittsburgh, Pa., U.S.A.) described in US-P 3,832,171.
  • a conductive coating e.g. vacuum-deposited metal such as aluminium, dispersed carbon black, graphite and conductive monomeric salts
  • a conductive polymer e.g. a polymer containing quaternized nitrogen atoms as in Calgon Conductive polymer 261 (trade mark of Calgon Corporation, Inc., Pittsburgh, Pa., U.S.A.) described in US-P 3,832,171.
  • the support may be in the form of a foil, web or be part of a drum.
  • An electrophotographic recording process comprises the steps of :
  • a photosensitive charge generating layer that contains as binder essentially at least one resin obtained by the reaction in the presence of moisture of said components (A) and (B), in contiguous relationship with a charge transporting layer, the photo-exposure of the charge generating layer proceeds preferably through the charge transporting layer but may be direct if the charge generating layer is uppermost or may proceed likewise through the conductive support if the latter is transparent enough to the exposure light.
  • the development of the latent electrostatic image commonly occurs preferably with finely divided electrostatically attractable material, called toner particles that are attracted by coulomb force to the electrostatic charge pattern.
  • the toner development is a dry or liquid toner development known to those skilled in the art.
  • toner particles deposit on those areas of the charge carrying surface which are in positive-positive relation to the original image.
  • toner particles migrate and deposit on the recording surface areas which are in negative-positive image value relation to the original.
  • the areas discharged by photo-exposure obtain by induction through a properly biased developing electrode a charge of opposite charge sign with respect to the charge sign of the toner particles so that the toner becomes deposited in the photo-exposed areas that were discharged in the imagewise exposure (ref. : R.M. Schaffert "Electrophotography” - The Focal Press - London, New York, enlarged and revised edition 1975, p. 50-51 and T.P. Maclean "Electronic Imaging” Academic Press London, 1979, p. 231).
  • electrostatic charging e.g. by corona
  • the imagewise photo-exposure proceed simultaneously.
  • Residual charge after toner development may be dissipated before starting a next copying cycle by overall exposure and/or alternating current corona treatment.
  • Recording materials according to the present invention depending on the spectral sensitivity of the charge generating layer may be used in combination with all kinds of photon-radiation, e.g. light of the visible spectrum, infra-red light, near ultra-violet light and likewise X-rays when electron-positive hole pairs can be formed by said radiation in the charge generating layer.
  • photon-radiation e.g. light of the visible spectrum, infra-red light, near ultra-violet light and likewise X-rays when electron-positive hole pairs can be formed by said radiation in the charge generating layer.
  • they can be used in combination with incandescent lamps, fluorescent lamps, laser light sources or light emitting diodes by proper choice of the spectral sensitivity of the charge generating substance or mixtures thereof.
  • the toner image obtained may be fixed onto the recording material or may be transferred to a receptor material to form thereon after fixing the final visible image.
  • a recording material according to the present invention showing a particularly low fatigue effect can be used in recording apparatus operating with rapidly following copying cycles including the sequential steps of overall charging, imagewise exposing, toner development and toner transfer to a receptor element.
  • the evaluations of electrophotographic properties determined on the recording materials of the following examples relate to the performance of the recording materials in an electrophotographic process with a reusable photoreceptor.
  • the measurements of the performance characteristics were carried out by using a sensitometric measurement in which the discharge was obtained for 16 different exposures in addition to zero exposure.
  • the photoconductive recording sheet material was mounted with its conductive backing on an aluminium drum which was earthed and rotated at a circumferential speed of 10 cm/s.
  • the recording material was sequentially charged with a positive corona at a voltage of + 5.7 kV operating with a grid voltage of + 600 V.
  • the recording material was exposed (simulating image-wise exposure) with a light dose of monochromatic light obtained from a monochromator positioned at the circumference of the drum at an angle of 45° with respect to the corona source.
  • the photo-exposure lasted 200 ms.
  • the exposed recording material passed an electrometer probe positioned at an angle of 180° with respect to the corona source.
  • a halogen lamp producing 355 mJ/m2 positioned at an angle of 270° with respect to the corona source a new copying cycle started.
  • Each measurement relates to 80 copying cycles in which the photoconductor is exposed to the full light source intensity for the first 5 cycles, then sequentially to the light source the light output of which is moderated by grey filters of optical densities 0.2, 0.38, 0.55, 0.73, 0.92, 1.02, 1.20, 1.45, 1.56, 1.70, 1.95, 2.16, 2.25, 2.51 and 3.21 each for 5 cycles and finally to zero light intensity for the last 5 cycles.
  • the electro-optical results quoted in the EXAMPLES 1 to .. hereinafter refer to charging level at zero light intensity (CL) and to discharge at a light intensity corresponding to the light source intensity moderated by a grey filter to the exposure indicated to a residual potential RP.
  • the % discharge is : (CL-RP) CL x 100
  • the charging level CL is only dependent upon the thickness of the charge transport layer and its specific resistivity.
  • CL expressed in volts should be preferably ⁇ 30 d, where d is the thickness in ⁇ m of the charge transport layer.
  • Charge generating materials (CGM's) used in the following examples have the following formulae : X-H 2 Pc(CN) 0.36 : mixed crystalline pigment consisting of 1.75:1 molar ratio of H 2 Pc and
  • Negative charge transporting compounds i.e. electron-transporting compounds, (N1 to N8) used in the following Examples are given hereinafter : All parts, ratios and percentages are by weight unless otherwise stated.
  • Said dispersion was prepared by mixing 2 g of metal-free X-phthalocyanine (FASTOGEN Blue 8120B from Dainippon Ink and Chemical Inc.); 0.5 g of MA-copolymer A 7 (see Table 1); 9.71 g of butan-2-one and 16.54 g of methylene chloride for 40 hours in a ball mill. 0.7 g of said MA-copolymer A 7 , 1 g of poly-oxazolane B 8 [70 % solution in butyl acetate], 8.25 g of methylene chloride and 4.85 g of butan-2-one were then added to the dispersion and mixing continued for a further 15 minutes.
  • metal-free X-phthalocyanine FASTOGEN Blue 8120B from Dainippon Ink and Chemical Inc.
  • the applied layer was dried and thermally moisture-hardened for 2 hours at 50 °C and the overcoated using a doctor-blade coater with a filtered solution of 2.5 g of the CTM N2; 3.05 g of MAKROLON 5700 (tradename for a bisphenol A-polycarbonate from Bayer AG); and 40.7 g of methylene chloride to a thickness of 11.1 ⁇ m after drying at 50 °C for 16 hours.
  • the photoconductive recording materials of examples 2 and 3 were produced as described for example 1 except that the amounts of MA-copolymer A 7 and polyoxazolane B 8 and were varied as given in Table 1 together with the CTL layer thicknesses (d CTL ).
  • the photoconductive recording materials of examples 4 to 8 were produced as described for example 1 except that alternative CTM's were used instead of N2.
  • the CTL layer thicknesses are given in Table 2 together with the CTM concentrations used.
  • the photoconductive recording materials of examples 9 to 10 were produced as described for example 1 except that different CGM's were used.
  • the CTL layer thicknesses are given in Table 4.

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Claims (10)

  1. Un matériau d'enregistrement photoconducteur contenant un support et une couche générant des charges (CGC) en relation contigüe avec une couche transportant des charges (CTC) contenant un matériau transportant n-charges (n-MTC), caractérisé en ce que le liant de ladite couche générant des charges (CGC) est faite insoluble dans du chlorure de méthylène par réticulation, et est composé essentiellement d'une composition de liant durcie sous l'influence de l'humidité et préparée en mélangeant les composantes suivantes (A) et (B):
    (A) 30 à 99 parties en poids d'au moins un copolymère de composés oléfiniquement insaturés ayant un poids moléculaire moyen en poids [ M ¯
    Figure imgb0047
    w] d'au moins 1500 et contenant des fractions chimiquement incorporées capables de subir une réaction d'addition avec des groupes amino, et
    (B) 1 à 70 parties en poids de substances organiques contenant des groupes amino neutralisés à partir desquelles substances sont formés - sous l'influence de l'humidité - des composés possédant des groupes amino libres primaires et/ou secondaires, et
    dans laquelle i) les copolymères de la composante (A) contiennent des fractions d'anhydride carboxylique liées intramoléculairement, le poids équivalent d'anhydride des copolymères étant de 393 à 9800 et ii) la composition du liant contient de 0,25 à 10 fractions d'anhydride pour chaque groupe amino neutralisé.
  2. Matériau d'enregistrement photoconducteur selon la revendication 1, caractérisé en ce que ladite composante (A) se compose essentiellement d'un copolymère de:
    a) 3 à 25 parties en poids d'anhydride maléique, et
    b) 75 à 97 parties en poids d'au moins un monomère copolymérisable qui correspond à une des formules générales suivantes (I), (II) et (III):
    Figure imgb0048
    dans lesquelles:
    R1 et R4, l'un indépendamment de l'autre, représentent chacun un groupe hydrocarbure aliphatique ou cycloaliphatique en C1-C18, dans lequel un ou plusieurs atomes de carbone peuvent être remplacés par des hétéroatomes choisi du groupe composé d'oxygène, de soufre et d'azote,
    R2 représente un atome d'hydrogène, un groupe méthyle, un groupe éthyle, un atome de fluor ou un atome de chlore, et R3 est un groupe hydrocarbure aliphatique en C2-C15, un groupe hydrocarbure cycloaliphatique en C5-C10, un groupe hydrocarbure araliphatique en C7-C18, un groupe hydrocarbure aromatique en C6-C12 contenant un ou plusieurs hétéroatomes choisi du groupe composé d'oxygène, de soufre et d'azote sous la forme d'un groupe éther, ester, amide, uréthane, urée, thioester, oxirane, cétone, lactame ou lactone; et caractérisé en ce que la composante (B) est un composé choisi du groupe composé d'une aldimine, une cétimine, un oxazolane, une hexahydropyrimidine, un tétrahydroïmidazole, un dihydroïmidazole, une tétrahydropyrimidine, un amidacétal et un amidaminal.
  3. Un matériau d'enregistrement photoconducteur selon la revendication 2, caractérisé en ce que lesdits copolymères d'anhydride maléique (A) ont un poids moléculaire moyen en poids [ M ¯
    Figure imgb0049
    w] déterminé par la chromatographie sur gel de 3000 à 50.000, et que leur poids équivalent d'anhydride (= la quantité en g contenant 1 mol de groupes anhydride) est de 3800 à 393.
  4. Matériau d'enregistrement photoconducteur selon la revendication 2, caractérisé en ce que lesdits copolymères d'anhydride maléique (A) contiennent des unités de styrène, de méthacrylate et/ou d'acrylate.
  5. Matériau d'enregistrement photoconducteur selon la revendication 1, caractérisé en ce que la composante (B) contient une moyenne statistique de 1 à 50 unités structurales correspondant à au moins une des formules générales suivantes (IV), (V), (VI), (VII), (VIII) et (IX):
    Figure imgb0050
    Figure imgb0051
     dans lesquelles:
    R5 et R6, l'un indépendamment de l'autre, représentent chacun un atome d'hydrogène, un groupe hydrocarbure aliphatique contenant 1 à 18 atomes de carbone, un groupe hydrocarbure cycloaliphatique contenant 5 à 10 atomes de carbone, un groupe hydrocarbure araliphatique contenant 7 à 18 atomes de carbone ou un groupe phényle, ou
    R5 et R6 représentent ensemble les atomes nécessaires pour former un noyau cycloaliphatique pentagonal ou hexagonal avec l'atome de carbone auquel ils sont normalement liés, R7 représente un groupe hydrocarbure aliphatique bivalent contenant 2 à 6 atomes de carbone, mais possédant seulement une chaîne de 2 à 3 atomes de carbone entre les hétéroatomes définis du noyau,
    R8 représente un groupe hydrocarbure aliphatique bivalent ayant 2 à 10 atomes de carbone, mais possédant seulement 2 ou 3 atomes de carbone entre les hétéroatomes auxquels ce groupe est lié.
  6. Matériau d'enregistrement photoconducteur selon la revendication 5, caractérisé en ce que la composante (B) est un polyoxazolane que l'on obtient en laissant réagir un mono-oxazolane selon la formule générale (V) par l'hydrogène sur son atome d'azote avec un réactif polyfonctionnel choisi parmi un polyisocyanate, un polyépoxyde, un acide polycarboxylique, un acide polycarboxilique partiellement estérifié ou un anhydride de polyacide.
  7. Matériau d'enregistrement photoconducteur selon la revendication 1, caractérisé en ce que ladite couche générant des charges contient comme seul liant une ou plusieurs résines obtenues par une réaction de durcissement par l'humidité des composantes mélangées (A) et (B).
  8. Matériau d'enregistrement photoconducteur selon la revendication 1, caractérisé en ce que lesdites résines obtenues par une réaction de durcissement par l'humidité des composantes mélangées (A) et (B) sont présentes en combinaison avec au moins un autre polymère faisant fonction de liant.
  9. Matériau d'enregistrement photoconducteur selon la revendication 8, caractérisé en ce que ledit autre polymère est choisi du groupe composé d'une résine d'acrylate, d'une résine de méthacrylate, d'un copolyester d'un diol avec de l'acide isophtalique et/ou téréphtalique, d'un polyacétal, d'un polyuréthane, d'un polyester-uréthane et d'un polycarbonate aromatique.
  10. Matériau d'enregistrement photoconducteur selon la revendication 1, caractérisé en ce que ledit support est composé d'aluminium ou est un support muni d'une couche d'aluminium formant un revêtement conducteur.
EP93201267A 1992-06-04 1993-05-04 Matériau d'enregistrement photoconducteur ayant un système de liant durcissable sous l'influence de l'humidité Expired - Lifetime EP0573085B1 (fr)

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US4562132A (en) * 1984-11-19 1985-12-31 Xerox Corporation Photoresponsive imaging members containing electron transport overcoatings
DE3710963A1 (de) * 1987-04-01 1988-10-20 Bayer Ag Unter dem einfluss von feuchtigkeit haertbare bindemittelkombinationen, ein verfahren zu ihrer herstellung und ihre verwendung
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