WO2004074929A2 - Compositions radiosensibles comprenant des derives d'oxazole et elements pouvant former une image a base de telles compositions - Google Patents

Compositions radiosensibles comprenant des derives d'oxazole et elements pouvant former une image a base de telles compositions Download PDF

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Publication number
WO2004074929A2
WO2004074929A2 PCT/EP2004/001705 EP2004001705W WO2004074929A2 WO 2004074929 A2 WO2004074929 A2 WO 2004074929A2 EP 2004001705 W EP2004001705 W EP 2004001705W WO 2004074929 A2 WO2004074929 A2 WO 2004074929A2
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Prior art keywords
radiation
aryl
group
optionally
sensitive
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PCT/EP2004/001705
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English (en)
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WO2004074929A3 (fr
Inventor
Harald Baumann
Udo Dwars
Michael Flugel
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Kodak Polychrome Graphics Gmbh
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Publication of WO2004074929A2 publication Critical patent/WO2004074929A2/fr
Publication of WO2004074929A3 publication Critical patent/WO2004074929A3/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to radiation-sensitive compositions, in particular radiation-sensitive compositions comprising bisoxazole derivatives or analogues thereof as sensitizers.
  • the invention furthermore relates to imageable elements based thereon, a process for the production of such elements, a process for imaging such elements and an imaged element such as for example a lithographic printing plate.
  • the technical field of lithographic printing is based on the immiscibility of oil and water, wherein the oily material or the printing ink is preferably accepted by the image area, and the water or fountain solution is preferably accepted by the non-image area.
  • the background or non-image area accepts the water and repels the printing ink
  • the image area accepts the printing ink and repels the water.
  • the printing ink in the image area is then transferred to the surface of a material such as paper, fabric and the like, on which the image is to be formed.
  • the printing ink is first transferred to an intermediate material, referred to as blanket, which then in turn transfers the printing ink onto the surface of the material on which the image is to be formed; this technique is referred to as offset lithography.
  • a frequently used type of lithographic printing plate precursor comprises a photosensitive coating applied onto a substrate on aluminum basis.
  • the coating can react to radiation such that the exposed portion becomes so soluble that it is removed during the developing process.
  • Such a plate is referred to as positive working.
  • a plate is referred to as negative working if the exposed portion of the coating is hardened by the radiation.
  • the remaining image area accepts printing ink, i.e. is oleophilic
  • the non-image area (background) accepts water, i.e. is hydrophilic.
  • the differentiation between image and non- image areas takes place during exposure, for which a film is attached to the printing plate precursor under vacuum in order to guarantee good contact.
  • the plate is then exposed by means of a radiation source.
  • the plate can also be exposed digitally without a film, e.g. with a UV laser.
  • a positive plate the area on the film corresponding to the image on the plate is so opaque that the light does not reach the plate, while the area on the film corresponding to the non-image area is clear and allows light to permeate the coating, whose solubility increases.
  • a negative plate the opposite takes place: The area on the film corresponding to the image on the plate is clear, while the non-image area is opaque.
  • the coating beneath the clear film area is hardened due to the incident light, while the area not affected by the light is removed during developing.
  • the light-hardened surface of a negative working plate is therefore oleophilic and accepts printing ink, while the non-image area that used to be coated with the coating removed by the developer is desensitized and therefore hydrophilic.
  • Photosensitive mixtures have been used for years in photopolymerizable compositions for the production of photosensitive materials such as e.g. printing plate precursors.
  • an improved sensitivity in particular in the near UV and the visible spectral range is required for new and advanced applications (e.g. exposure by means of lasers) so that the exposure time can be shortened.
  • low-intensity radiation sources can be used, which are less expensive and more reliable than high-intensity radiation sources. Therefore, efforts have been made for some time to increase the sensitivity of photosensitive mixtures to be used in photopolymerizable compositions.
  • DE-A-3021599 discloses radiation-sensitive compositions comprising ethylenically unsaturated monomers as well as a 2-(halogenomethyl-phenyl)-4-halogen-oxazole derivative as photoinitiator.
  • the efficiency of the photoinitiator is insufficient.
  • UV-hardenable compositions for films and coatings which in addition to ethylenically unsaturated monomers comprise a photoinitiator selected from haloalkane benzoxazoles, benzimidazoles and benzothiazoles. In these compositions as well, the efficiency of the photoinitiator is insufficient.
  • EP-A-0741 333 describes photopolymerizable compositions which in addition to ethylenically unsaturated monomers and organic binders comprise a combination of an optical brightener and a photoinitiator selected from acyl and diacyl phosphine oxides.
  • optical brighteners those comprising a stilbene, triazine, thiazole, benzoxazole, coumarin, xanthene, triazole, oxazole, thiophene or pyrazoline unit are listed.
  • these photopolymerizable compositions do not exhibit sufficient sensitivity.
  • US-A-3,647,467 describes "photo-activable" compositions comprising a hexaarylbiimidazole and a heterocyclic compound A ⁇ -G-Ar 2 (wherein Ar 1 is an aryl group with 6 to 12 ring carbon atoms, Ar 2 is either Ar 1 or a group arylene-G-Ar 1 and G is a divalent furan, oxazole or oxadiazole ring).
  • Ar 1 is an aryl group with 6 to 12 ring carbon atoms
  • Ar 2 is either Ar 1 or a group arylene-G-Ar 1 and G is a divalent furan, oxazole or oxadiazole ring.
  • the radiation sensitivity of these compositions does not meet present-day requirements.
  • oxazole derivatives are used as photoconductive substances in electrophotographic elements.
  • the at least one sensitizer is a compound of the formula (I)
  • X is a spacer group comprising at least one C-C double bond conjugated to the heterocycles
  • Y and Z independently represent an optionally substituted fused aromatic ring
  • V and W are independently selected from O, S and NR, wherein R is selected from an alkyl, aryl and aralkyl group which can optionally be mono- or polysubstituted.
  • alkyl group refers to a straight-chain, branched or cyclic saturated hydrocarbon group preferably comprising 1 to 18 carbon atoms, especially preferred 1 to 10 carbon atoms and most preferred 1 to 6 carbon atoms.
  • the alkyl group can optionally comprise one or more substituents (preferably 0 of 1 substituent) selected for example from halogen atoms (fluorine, chlorine, bromine, iodine), CN, N0 , NR' 2 , COOR' and OR' (R' independently represents a hydrogen atom or an alkyl group).
  • substituents preferably 0 of 1 substituent
  • aryl group refers to an aromatic carbocyclic group with one or more fused rings, which preferably comprises 5 to 14 carbon atoms.
  • the aryl group can optionally comprise one or more substituents (preferably 0 to 3) selected for example from halogen atoms, alkyl groups, alkoxy groups, CN, N0 2 , NR'2, COOR' and OR' (wherein each R' is independently selected from hydrogen and alkyl).
  • substituents preferably 0 to 3
  • substituents preferably 0 to 3
  • substituents preferably 0 to 3
  • alkyl groups alkoxy groups
  • CN N0 2 , NR'2, COOR' and OR'
  • R' is independently selected from hydrogen and alkyl.
  • Preferred examples include a phenyl group and a naphthyl group which can optionally be substituted.
  • a fused ring or ring system as referred to in the present invention is a ring that shares two carbon atoms with the ring to which it is fused.
  • All monomers, oligomers and polymers which are free-radical polymerizable and comprise at least one C-C double bond can be used as ethylenically unsaturated monomers, oligomers and polymers.
  • Monomers, oligomers and polymers with C-C triple bonds can also be used, but they are not preferred.
  • Suitable compounds are well known to the person skilled in the art and can be used in the present invention without any particular limitations.
  • Esters of acrylic and methacrylic acids, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and fumaric acid with one or more unsaturated groups in the form of monomers, oligomers or prepolymers are preferred.
  • Compounds suitable as monomers include for instance trimethylol propane triacrylate and methacrylate, pentaerythritol triacrylate and methacrylate, dipentaerythritol- monohydroxy pentaacrylate and methacrylate, dipentaerythritol hexaacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, ditrimethylol propane tetraacrylate and methacrylate, diethyleneglycol diacrylate and methacrylate, triethyleneglycol diacrylate and methacrylate or tetraethyleneglycol diacrylate and methacrylate.
  • Suitable oligomers and/or prepolymers are for example urethane acrylates and methacrylates, epoxide acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates or unsaturated polyester resins.
  • polymers comprising free- radical polymerizable C-C double bonds in the main or side chains.
  • examples thereof include reaction products of maleic acid anhydride olefin copolymers and hydroxyalkyl(meth)acrylates (cf. e.g. DE-A-4311738); (meth)acrylic acid polymers, partially or fully esterified with allyl alcohol (cf. e.g.
  • reaction products of polymeric polyalcohols and iso- cyanato(meth)acrylates unsaturated polyesters; (meth)acrylate-terminated polystyrenes, poly(meth)acrylic acid ester, poly(meth)acrylic acids, poly(meth)acrylamides; (meth)acrylic acid polymers, partially or fully esterified with epoxides comprising free-radical polymerizable groups; and polyethers.
  • the prefix "(meth)" indicates that both derivatives of acrylic acid and of methacrylic acid can be used. Additional suitable C-C-unsaturated free-radical polymerizable compounds are described e.g. in EP-A-1 176 007.
  • the free-radical polymerizable monomers/oligomers/polymers are preferably present in an amount of 5 to 95 wt.-%; if monomers/oligomers are used, especially preferred 20 to 85 wt.-%, based on the dry layer weight of a radiation-sensitive coating prepared from the radiation-sensitive composition of the present invention.
  • dry layer weight of the radiation-sensitive coating is therefore synonymous with the term "solids of the radiation-sensitive composition".
  • a sensitizer as referred to in the present invention is a compound which can absorb radiation when it is exposed to radiation but which cannot by itself, i.e. without the addition of coinitiators, form free radicals.
  • one sensitizer or a mixture of two or more can be used.
  • a compound of the formula (I) is used as a sensitizer
  • X is a spacer group comprising at least one C-C double bond conjugated to the heterocycles
  • Y and Z independently represent an optionally substituted fused aromatic ring
  • V and W are independently selected from O, S and NR, wherein R is selected from an alkyl, aryl and aralkyl group which can optionally be mono- or polysubstituted.
  • V W and represents O or NR.
  • R is preferably C ⁇ -C 12 alkyl.
  • the spacer group X can be a chain-like or cyclic unit or a combination thereof. It is preferably selected from:
  • Phenylene optionally comprising one or more benzofused aromatic rings (e.g. naphthylene), wherein the binding sites to the two heterocycles can be located at the same ring or at different rings,
  • the binding sites be in the Imposition, in the five-membered rings, the 2,5-position is preferred.
  • the five- and six-membered rings shown above can optionally comprise one or more substituents such as e.g. Ci-Cio alkyl and halogen atoms, even if they are not shown in the above formulas.
  • Preferred sensitizers are represented by formulas (II), (Hi) and (IV):
  • n are independently 0 or an integer from 1 to 4 (preferably 0 or 1), each group
  • R and R is independently selected from a halogen atom, an alkyl, aryl, aralkyl, alkoxy, aryloxy, aralkyloxy group, a saturated or non-aromatic unsaturated carbocyclic ring, a fused aryl group, -S0 3 H, -NR 3 2 , -COOR 4 and -COR 4 , each group R 3 is independently a hydrogen atom or an alkyl group and each group R 4 is independently selected from a hydrogen atom, and alkyl and an aryl group, and
  • X and R are as defined above.
  • R and R are preferably independently selected from -NR 2 , an alkoxy group and an alkyl group.
  • R 3 is preferably - o alkyl.
  • R 4 is preferably C1-C10 alkyl.
  • Y and Z preferably represent fused aromatic rings which can optionally be substituted.
  • the sensitizers used in the present invention can be prepared according to processes well known to the person skilled in the art. In this connection, reference is made to A. Dorlars et al., Angew. Chemie [Applied Chemistry], Vol. 87 (1975), 693-707; the processes described therein can also be used for the synthesis of compounds not explicitly disclosed therein by varying the starting compounds accordingly.
  • the sensitizers are used in combination with one or more coinitiators.
  • the amount of sehsitizer(s) is not particularly restricted; however, it is preferably in the range of 0.2 to 25 wt.-%, based on the solids content or the dry layer weight of a coating produced from the composition, especially preferred 0.5 to 15 wt.- .
  • a coinitiator as referred to in the present invention is a compound that is essentially unable to absorb when exposed to radiation but forms free radicals together with the radiation-absorbing sensitizers used according to the present invention.
  • the coinitiators are selected from amines, such as alkanols amines; onium salts, such as e.g. ammonium salts, diaryliodonium salts, triarylsulfonium salts, aryldiazoniumsalts and N- alkoxypyridinium salts; N,N-dialkylaminobenzoic acid esters; N-arylglycines and derivatives thereof (e.g.
  • N-phenylglycine aromatic sulfonylhalides; trihalogenomethylsulfones; imides such as N-benzoyloxyphthalimide; diazosulfonates; 9,10-dihydroanthracene derivatives; N-aryl, S-aryl or O-aryl polycarboxylic acids with at least 2 carboxyl groups of which at least one is bonded to the nitrogen, oxygen or sulfur atom of the aryl unit (e.g. aniline diacetic acid and derivatives thereof and other coinitiators described in US-A-5,629,354); a hexaarylbiimidazole such as e.g.
  • thiol compounds e.g. mercaptobenzthiazole, mercaptobenzimidazole and mercaptotriazole
  • 1,3,5-triazine derivatives with 1 to 3 CX 3 groups wherein every X is independently selected from a chlorine or bromine atom, and is preferably a chlorine atom
  • every X is independently selected from a chlorine or bromine atom, and is preferably a chlorine atom
  • Acylphosphine oxides and diacylphosphine oxides have been found to be unsuitable coinitiators for the sensitizers of formula (I) used in the present invention.
  • Metallocenes have been found to deteriorate the composition's stability to yellow light conditions so that it is not desired to use metallocenes.
  • one of the above coinitiators or a mixture thereof can be used.
  • the amount of coinitiator(s) is not particularly restricted; however, it is preferably 0.2 to 25 wt.-%, based on the dry layer weight, especially preferred 0.5 to 15 wt.-%.
  • the photosensitive composition of the present invention can also comprise a binder or a mixture of binders.
  • the binder is preferably selected from polyvinyl acetals, acrylic polymers, polyurethanes and copolymers thereof. It is preferred that the binder contain acid groups, especially preferred carboxyl groups. Most preferred are acrylic polymers. Binders with acid groups preferably have acid numbers in the range of 20 to 180 mg KOH/g polymer.
  • the binder can comprise groups capable of undergoing a cycloaddition reaction (e.g. photocycloaddition).
  • the amount of binder is not particularly restricted and is preferably in the range of 0 to 90 wt.-%, especially preferred 5 to 60 wt.-%.
  • the radiation-sensitive coating can optionally also comprise small amounts of a thermopolymerization inhibitor.
  • Suitable examples of inhibitors of undesired thermopolymerization include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrrogallol, t-butylcatechol, benzoquinone, 4,4' -thio-bis-(3-methyl-6-t-butylphenol), 2,2' -methylene-bis-(4-methyl-6-t- butylphenol) and N-nitrosophenylhydroxylamine salts.
  • the amount of the non-absorbable polymerization inhibitor in the radiation-sensitive coating is preferably 0 to 5 wt.-%, based on the dry layer weight, especially preferred 0.01 to 2 wt.-%.
  • Such inhibitors are often introduced into the radiation-sensitive coating via commercial monomers or oligomers and are therefore not expressly mentioned.
  • the radiation-sensitive coating of the present invention can comprise dyes or pigments for coloring the layer.
  • colorants include e.g. phthalocyanine pigments, azo pigments, carbon black and titanium dioxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes and cyanine dyes.
  • the amount of colorant is preferably 0 to 20 wt.-%, based on the dry layer weight, especially preferred 0.5 to 10 wt.-%.
  • the radiation-sensitive coating can additionally comprise further additives such as plasticizers or inorganic fillers. Suitable plasticizers include e.g.
  • the amount of plasticizer is not particularly restricted, however, it is preferably 0 to 10 wt.-%, based on the dry layer weight, especially preferred 0.25 to 5 wt.-%.
  • the radiation-sensitive coating can also comprise known chain transfer agents. They are preferably used in an amount of 0 to 15 wt.-%, based on the dry layer weight, especially preferred 0.5 to 5 wt.- .
  • the radiation-sensitive coating can comprise leuco dyes such as e.g. leuco crystal violet and leucomalachite green. They are preferably present in an amount of 0 to 10 wt.-%, based on the dry layer weight, especially preferred 0.5 to 5 wt.-%.
  • leuco dyes such as e.g. leuco crystal violet and leucomalachite green. They are preferably present in an amount of 0 to 10 wt.-%, based on the dry layer weight, especially preferred 0.5 to 5 wt.-%.
  • the radiation-sensitive coating can comprise surfactants.
  • Suitable surfactants include siloxane-containing polymers, fluorine-containing polymers and polymers with ethylene oxide and/or propylene oxide groups. They are preferably present in an amount of 0 to 10 wt.-%, based on the dry layer weight, especially preferred 0.2 to 5 wt.-%.
  • the radiation-sensitive coating include inorganic fillers such as e.g. A1 2 0 3 and Si0 2 (they are preferably present in an amount of 0 to 20 wt.-%, based on the dry layer weight, especially preferred 0.1 to 5 wt.-%).
  • inorganic fillers such as e.g. A1 2 0 3 and Si0 2 (they are preferably present in an amount of 0 to 20 wt.-%, based on the dry layer weight, especially preferred 0.1 to 5 wt.-%).
  • Exposure indicators such as e.g. 4-phenylazodiphenylamine, can also be present as optional components of the radiation-sensitive coating; they are preferably present in an amount of 0 to 5 wt.-%, especially preferred 0 to 2 wt.-%, based on the dry layer weight.
  • the radiation-sensitive elements of the present invention can for example be printing plate precursors (in particular precursors of lithographic printing plates), printed circuit boards for integrated circuits or photomasks.
  • a dimensionally stable plate or foil-shaped material is preferably used as a substrate in particular in the production of printing plate precursors.
  • a material is used as dimensionally stable plate or foil-shaped material that has already been used as a substrate for printing matters.
  • substrates include paper, paper coated with plastic materials (such as polyethylene, polypropylene, polystyrene), a metal plate or foil, such as e.g. aluminum (including aluminum alloys), zinc and copper plates, plastic films made e.g.
  • an aluminum plate or foil is especially preferred since it shows a remarkable degree of dimensional stability, is inexpensive and furthermore exhibits excellent adhesion to the coating.
  • a composite film can be used wherein an aluminum foil has been laminated onto a polyethylene terephthalate film.
  • a metal substrate in particular an aluminum substrate, is preferably subjected to at least one treatment selected from graining (e.g. by brushing in a dry state or brushing with abrasive suspensions, or electrochemical graining, e.g. by means of a hydrochloric acid electrolyte), anodizing (e.g. in sulfuric acid or phosphoric acid) and hydrophilizing.
  • graining e.g. by brushing in a dry state or brushing with abrasive suspensions, or electrochemical graining, e.g. by means of a hydrochloric acid electrolyte
  • anodizing e.g. in sulfuric acid or phosphoric acid
  • hydrophilizing e.g. in sulfuric acid or phosphoric acid
  • the metal substrate can be subjected to an aftertreatment with an aqueous solution of sodium silicate, calcium zirconium fluoride, polyvinylphosphonic acid or phosphoric acid.
  • an aqueous solution of sodium silicate, calcium zirconium fluoride, polyvinylphosphonic acid or phosphoric acid within the framework of the present invention, the term "substrate” also encompasses an optionally pre-treated substrate exhibiting, for example, a hydrophilizing layer on its surface.
  • the radiation-sensitive composition of the present invention is applied to the surface of the substrate by means of common coating processes (e.g. spin coating, dip coating, coating by means of doctor blades). It is also possible to apply the radiation-sensitive composition on both sides of the substrate; however, for the elements of the present invention, it is preferred that the radiation-sensitive coating be only applied to one side of the substrate.
  • the radiation-sensitive composition comprises one or more organic solvents.
  • Suitable solvents include low alcohols (e.g. methanol, ethanol, propanol and butanol), glycolether derivatives (e.g. ethyleneglycol monomethylether, ethyleneglycol dimethylether, propyleneglycol monomethylether, ethyleneglycol monomethylether acetate, ethyleneglycol monoethylether acetate, propyleneglycol monomethylether acetate, propyleneglycol monoethylether acetate, ethyleneglycol monoisopropylether acetate, ethyleneglycol monobutylether acetate, diethyleneglycol monomethylether, diethyleneglycol monoethylether), ketones (e.g.
  • diacetone alcohol acetyl acetone, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone
  • esters e.g. z.B. methyl lactate, ethyl lactate, ethyl acetate, 3-methoxypropyl acetate and butyl acetate
  • aromatics e.g. toluene and xylene
  • cyclohexane 3-methoxy-2- propanol, l-methoxy-2-propanol, methoxymethoxyethanol, ⁇ -butyrolactone and dipolar apfotic solvents (e.g.
  • the solids content of the radiation-sensitive mixture to be applied depends on the coating method that is used and is preferably 1 to 50 wt.-%.
  • the additional application of a water-soluble oxygen-impermeable overcoat onto the radiation- sensitive layer can be advantageous.
  • the polymers suitable for such an overcoat include, inter alia, polyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl pyrrohdone/polyvinyl acetate copolymers, polyvinyl methylethers, ring-opened copolymers of maleic acid anhydride and a comonomer such as methylvinylether, polyacrylic acid, cellulose ether, gelatin, etc.; polyvinyl alcohol is preferred.
  • the composition for the oxygen-impermeable overcoat is applied in the form of a solution in water or in a solvent miscible with water; in any case, the solvent is selected such that the radiation-sensitive coating already present on the substrate does not dissolve.
  • the layer weight of the overcoat can e.g. be 0.1 to 6 g/m 2 , preferably 0.5 to 6 g/m 2 .
  • the printing plate precursors according to the present invention show excellent properties even without an overcoat.
  • the overcoat can also comprise matting agents (i.e. organic or inorganic particles with a particle size of 2 to 20 ⁇ m) which facilitate the planar positioning of the film during contact exposure.
  • the overcoat can comprise adhesion promoters such as e.g. poly(vinylpyrrolidone), poly(ethyleneimine) and po ⁇ y(vinyUmidazole).
  • adhesion promoters such as e.g. poly(vinylpyrrolidone), poly(ethyleneimine) and po ⁇ y(vinyUmidazole).
  • Suitable overcoats are described for example in WO 99/06890.
  • the thus produced radiation-sensitive elements are image- wise exposed in a manner known, to the person skilled in the art with UV radiation of a wavelength of >300 nm (preferably 350 to 450 nm) and subsequently developed with a commercially available aqueous alkaline developer.
  • UV laser diodes emitting UV radiation in the range of about 405 nm (e.g. 405 ⁇ 10 nm) are of particular interest as a radiation source.
  • a heat treatment can be carried out at 50 to 180°C, preferably 90 to 150°C.
  • the developed elements can be treated with a preservative ("gumming") using a common method.
  • the preservatives are aqueous solutions of hydrophilic polymers, wetting agents and other additives.
  • baking For certain applications (e.g. in the case of printing plates), it is furthermore advantageous to increase the mechanical strength of the portions of the coating remaining after developing by subjecting them to a heat treatment (what is referred as "baking") and/or overall exposure (e.g. to UV light).
  • a heat treatment what is referred as "baking"
  • overall exposure e.g. to UV light
  • the developed element prior to the treatment, the developed element is treated with a solution that protects the non-image areas such that the heat treatment does not cause these areas to accept ink.
  • a solution suitable for this purpose is e.g. described in US-A-4,355,096. Baking takes place at a temperature in the range of 150 to 250°C.
  • elements like printing plates prepared from radiation-sensitive elements according to the present invention show excellent properties even without having been subjected to a heat treatment. When both baking and overall exposure are carried out, the two treatment steps can be performed simultaneously or one after the other.
  • the radiation-sensitive elements according to the present invention are characterized by excellent stability under yellow light conditions, a high degree of photosensitivity and excellent resolution in combination with good storage stability.
  • the developed printing plates exhibit excellent abrasion resistance which allows a large number of copies.
  • An electrochemically (in HC1) grained and anodized aluminum foil was subjected to a treatment with an aqueous solution of polyvinyl phosphoric acid (PVPA) and after drying was coated with a solution as described in Table 1 and dried.
  • PVPA polyvinyl phosphoric acid
  • the solution was filtered, applied to the hthographic substrate and the coating was dried for 4 minutes at 90°C.
  • the dry layer weight of the photopolymer layer was about 1.5 g/m .
  • the obtained samples were coated with an overcoat by applying an aqueous solution of poly(vinylalcohol) (Airvol 203 available from Airproducts; degree of hydrolysis: 88%); after drying for 4 minutes at 90°C, the overcoat had a dry layer weight of about 3 g/m 2 .
  • the printing plate precursor was exposed with a tungsten lamp having a metal interference filter for 405 nm through a gray scale having a tonal range of 0.15 to 1.95, wherein the density increments amount to 0.15 (UGRA gray scale) with 1 ⁇ W/cm 2 . Immediately after exposure, the plate was heated in an oven for 2 minutes at 90°C.
  • Rewopol NLS 28 ® available from REWO
  • Nekal BX Paste available from BASF
  • 4-toluene sulfonic acid 93.7 parts by weight water
  • the developer solution was again rubbed over the surface for another 30 seconds using a tampon and then the entire plate was rinsed with water. After this treatment, the exposed portions remained on the plate.
  • the plate was blackened in a wet state with printing ink.
  • the unexposed printing plate precursors were stored for 60 minutes in a 90°C oven, then exposed and developed as described above (storage stability test).
  • a printing layer was applied to the aluminum foil, as explained above, exposed, heated, developed, and after rinsing with water, the developed plate was rubbed with an aqueous solution of 0.5% phosphoric acid and 6% gum arabic.
  • the thus prepared plate was loaded in a sheet-fed offset printing machine and used for printing with an abrasive printing ink (Offset S 7184 available from Sun Chemical, containing 10% potassium carbonate).
  • the first value indicates the solid steps of the blackened gray scale and the second value indicates the first step that did not accept printing ink.
  • bisoxazole 4 has the following structure:

Abstract

L'invention concerne un élément radiosensible comprenant : (a) au moins un type de monomère comprenant au moins un groupe éthyléniquement insaturé susceptible d'une polymérisation radicalaire ; (b) au moins un sensibilisateur ; (c) au moins un coinitiateur pouvant former des radicaux libres avec le sensibilisateur (b) et sélectionné dans les classes de composés suivantes : métallocènes, dérivés de 1,3,5-triazine comportant un à trois groupes CX3, où X représente chlore ou brome, peroxydes, hexaarylbiimidazoles, éthers d'oxyde, esters d'oxyme, N-arylglycines et dérivés de celles-ci, composés thiol, acides N-arylpolycarboxylique, S-arylpolycarboxylique et O-arylpolycarboxylique comportant au moins deux groupes carboxyle dont au moins un est lié à l'atome N, S ou O de l'unité aryle, alkyltriarylborates, éthers de benzoïne, esters de benzoïne, trihalogénométhylarylsulfones, amines, esters d'acide N,N-dialkylaminobenzoïque, halogénures de sulfonyle aromatiques; trihalogénométhylsulfones, imides, diazosulfonates, dérivés de 9,10-dihydroanthracène, acétophénones α-hydroxy et α-amino ; et (d) éventuellement au moins un composant sélectionné parmi les liants solubles dans l'alcali, les colorants, les indicateurs d'exposition, les plastifiants, les agents de migration de chaîne, les leuco-colorants, les tensioactifs, les charges inorganiques et les inhibiteurs de thermopolymérisation. Cet élément radiosensible se caractérise en ce que le ou les sensibilisateur(s) sont un dérivé d'oxyzole correspondant à la formule (I), dans laquelle chaque substituant R1, R2, (R3) est sélectionné, indépendamment l'un de l'autre, parmi un atome d'halogène, un groupe alkyle éventuellement substitué, un groupe aryle éventuellement substitué, qui peut aussi être fusionné, un groupe aralkyle éventuellement substitué, un groupe -NR4R5, et un groupe -OR6, où R4 et R5 sont sélectionnés indépendamment l'un de l'autre parmi un atome d'hydrogène, un groupe alkyle, aryle ou aralkyle, et R6 est un groupe alkyle, aryle ou aralkyle ou un atome d'hydrogène, k, m et n représentant indépendamment 0 ou un nombre entier de 1 à 5.
PCT/EP2004/001705 2003-02-21 2004-02-20 Compositions radiosensibles comprenant des derives d'oxazole et elements pouvant former une image a base de telles compositions WO2004074929A2 (fr)

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DE10307451.1 2003-02-21

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EP2098367A1 (fr) 2008-03-05 2009-09-09 Eastman Kodak Company Combinaison de sensibilisateur/initiateur pour compositions thermosensibles à action négative utilisables pour des plaques lithographiques
EP2194429A1 (fr) 2008-12-02 2010-06-09 Eastman Kodak Company Compositions de gommage avec nanoparticules pour l'amélioration de la sensibilité aux éraflures et des zones sans images des plaques d'impression lithographiques
EP2196851A1 (fr) 2008-12-12 2010-06-16 Eastman Kodak Company Précurseurs de plaque d'impression lithographique à action négative comportant une liaison réactive contenant des caractéristiques aliphatiques bi ou polycycliques
WO2010077273A1 (fr) 2008-12-17 2010-07-08 Eastman Kodak Company Empilement d'éléments imageables fonctionnant en négatif
WO2010093413A1 (fr) 2009-02-13 2010-08-19 Eastman Kodak Company Eléments négatifs pouvant être imagés
WO2010101632A1 (fr) 2009-03-04 2010-09-10 Eastman Kodak Company Eléments imageables avec colorants
WO2010104560A1 (fr) 2009-03-13 2010-09-16 Eastman Kodak Company Eléments négatifs pouvant être imagés dotés d'un revêtement
WO2010144117A1 (fr) 2009-06-12 2010-12-16 Eastman Kodak Company Préparation de plaques lithographiques présentant un contraste renforcé
WO2010144119A1 (fr) 2009-06-12 2010-12-16 Eastman Kodak Company Eléments imageables en négatif
EP2284005A1 (fr) 2009-08-10 2011-02-16 Eastman Kodak Company Précurseurs de plaque d'impression lithographique dotés d'agents de réticulation à base de bêta-hydroxyalkylamide
EP2293144A1 (fr) 2009-09-04 2011-03-09 Eastman Kodak Company Procédé et appareil pour le séchage consécutif à un processus à étape unique de plaques d'impression lithographique
WO2011028393A1 (fr) 2009-08-25 2011-03-10 Eastman Kodak Company Précurseurs et empilements de plaques d'impression lithographiques
WO2011056905A2 (fr) 2009-11-05 2011-05-12 Eastman Kodak Company Précurseurs de plaques d'impression lithographiques négatives
WO2012074903A1 (fr) 2010-12-03 2012-06-07 Eastman Kodak Company Développement simple de précurseurs de plaques d'impression lithographiques
WO2012075062A1 (fr) 2010-12-03 2012-06-07 Eastman Kodak Company Développateur et son utilisation pour préparer des plaques d'impression lithographique
WO2012109077A1 (fr) 2011-02-08 2012-08-16 Eastman Kodak Company Préparation de plaques d'impression lithographique
WO2013032780A1 (fr) 2011-08-31 2013-03-07 Eastman Kodak Company Précurseurs de plaque d'impression lithographique pour un développement sur presse
WO2013032776A1 (fr) 2011-08-31 2013-03-07 Eastman Kodak Company Substrats en aluminium et précurseurs de plaque d'impression lithographique
JP2013246387A (ja) * 2012-05-29 2013-12-09 Asahi Kasei E-Materials Corp 感光性樹脂組成物
WO2014031582A1 (fr) 2012-08-22 2014-02-27 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative et utilisation
WO2014062244A1 (fr) 2012-05-29 2014-04-24 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative
EP2735903A1 (fr) 2012-11-22 2014-05-28 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative comprenant un matériau liant hyper-ramifié
WO2014133807A1 (fr) 2013-02-28 2014-09-04 Eastman Kodak Company Précurseurs de plaque d'impression lithographique et leur utilisation
EP2778782A1 (fr) 2013-03-13 2014-09-17 Kodak Graphic Communications GmbH Éléments sensibles au rayonnement de travail négatif
WO2015050713A1 (fr) 2013-10-03 2015-04-09 Eastman Kodak Company Précurseur de plaque d'impression lithographique négative
JP2016139154A (ja) * 2016-04-07 2016-08-04 旭化成株式会社 感光性樹脂組成物
EP3132932A2 (fr) 2015-07-24 2017-02-22 Presstek, LLC. Imagerie et impression lithographiques avec éléments d'impression photosensibles négatifs
WO2021150430A1 (fr) 2020-01-22 2021-07-29 Eastman Kodak Company Procédé de réalisation de plaques d'impression lithographique

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WO1997035232A1 (fr) * 1996-03-19 1997-09-25 Minnesota Mining And Manufacturing Company Compositions durcissables aux ultraviolets comprenant un oxyde d'acylphosphine et un azurant optique
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2098367A1 (fr) 2008-03-05 2009-09-09 Eastman Kodak Company Combinaison de sensibilisateur/initiateur pour compositions thermosensibles à action négative utilisables pour des plaques lithographiques
EP2194429A1 (fr) 2008-12-02 2010-06-09 Eastman Kodak Company Compositions de gommage avec nanoparticules pour l'amélioration de la sensibilité aux éraflures et des zones sans images des plaques d'impression lithographiques
EP2196851A1 (fr) 2008-12-12 2010-06-16 Eastman Kodak Company Précurseurs de plaque d'impression lithographique à action négative comportant une liaison réactive contenant des caractéristiques aliphatiques bi ou polycycliques
WO2010077273A1 (fr) 2008-12-17 2010-07-08 Eastman Kodak Company Empilement d'éléments imageables fonctionnant en négatif
WO2010093413A1 (fr) 2009-02-13 2010-08-19 Eastman Kodak Company Eléments négatifs pouvant être imagés
WO2010101632A1 (fr) 2009-03-04 2010-09-10 Eastman Kodak Company Eléments imageables avec colorants
WO2010104560A1 (fr) 2009-03-13 2010-09-16 Eastman Kodak Company Eléments négatifs pouvant être imagés dotés d'un revêtement
WO2010144117A1 (fr) 2009-06-12 2010-12-16 Eastman Kodak Company Préparation de plaques lithographiques présentant un contraste renforcé
WO2010144119A1 (fr) 2009-06-12 2010-12-16 Eastman Kodak Company Eléments imageables en négatif
EP2284005A1 (fr) 2009-08-10 2011-02-16 Eastman Kodak Company Précurseurs de plaque d'impression lithographique dotés d'agents de réticulation à base de bêta-hydroxyalkylamide
WO2011028393A1 (fr) 2009-08-25 2011-03-10 Eastman Kodak Company Précurseurs et empilements de plaques d'impression lithographiques
EP2293144A1 (fr) 2009-09-04 2011-03-09 Eastman Kodak Company Procédé et appareil pour le séchage consécutif à un processus à étape unique de plaques d'impression lithographique
WO2011026907A1 (fr) 2009-09-04 2011-03-10 Eastman Kodak Company Procédé et appareil de séchage après un traitement en continu de plaques d'impression lithographiques
WO2011056905A2 (fr) 2009-11-05 2011-05-12 Eastman Kodak Company Précurseurs de plaques d'impression lithographiques négatives
WO2012074903A1 (fr) 2010-12-03 2012-06-07 Eastman Kodak Company Développement simple de précurseurs de plaques d'impression lithographiques
WO2012075062A1 (fr) 2010-12-03 2012-06-07 Eastman Kodak Company Développateur et son utilisation pour préparer des plaques d'impression lithographique
WO2012109077A1 (fr) 2011-02-08 2012-08-16 Eastman Kodak Company Préparation de plaques d'impression lithographique
WO2013032780A1 (fr) 2011-08-31 2013-03-07 Eastman Kodak Company Précurseurs de plaque d'impression lithographique pour un développement sur presse
WO2013032776A1 (fr) 2011-08-31 2013-03-07 Eastman Kodak Company Substrats en aluminium et précurseurs de plaque d'impression lithographique
WO2014062244A1 (fr) 2012-05-29 2014-04-24 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative
JP2013246387A (ja) * 2012-05-29 2013-12-09 Asahi Kasei E-Materials Corp 感光性樹脂組成物
WO2014031582A1 (fr) 2012-08-22 2014-02-27 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative et utilisation
EP2735903A1 (fr) 2012-11-22 2014-05-28 Eastman Kodak Company Précurseurs de plaque d'impression lithographique négative comprenant un matériau liant hyper-ramifié
WO2014133807A1 (fr) 2013-02-28 2014-09-04 Eastman Kodak Company Précurseurs de plaque d'impression lithographique et leur utilisation
EP2778782A1 (fr) 2013-03-13 2014-09-17 Kodak Graphic Communications GmbH Éléments sensibles au rayonnement de travail négatif
WO2015050713A1 (fr) 2013-10-03 2015-04-09 Eastman Kodak Company Précurseur de plaque d'impression lithographique négative
EP3132932A2 (fr) 2015-07-24 2017-02-22 Presstek, LLC. Imagerie et impression lithographiques avec éléments d'impression photosensibles négatifs
JP2016139154A (ja) * 2016-04-07 2016-08-04 旭化成株式会社 感光性樹脂組成物
WO2021150430A1 (fr) 2020-01-22 2021-07-29 Eastman Kodak Company Procédé de réalisation de plaques d'impression lithographique

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