[go: up one dir, main page]

WO2004111731A1 - Compositions sensibles aux rayonnements contenant un sensibilisateur a base de 1,4-dihydropyridine et elements imageables a base desdites compositions - Google Patents

Compositions sensibles aux rayonnements contenant un sensibilisateur a base de 1,4-dihydropyridine et elements imageables a base desdites compositions Download PDF

Info

Publication number
WO2004111731A1
WO2004111731A1 PCT/EP2004/006185 EP2004006185W WO2004111731A1 WO 2004111731 A1 WO2004111731 A1 WO 2004111731A1 EP 2004006185 W EP2004006185 W EP 2004006185W WO 2004111731 A1 WO2004111731 A1 WO 2004111731A1
Authority
WO
WIPO (PCT)
Prior art keywords
groups
group
optionally substituted
ring
radiation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2004/006185
Other languages
English (en)
Inventor
Hanz-Joachim Timpe
Harald Baumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Polychrome Graphics GmbH
Original Assignee
Kodak Polychrome Graphics GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Polychrome Graphics GmbH filed Critical Kodak Polychrome Graphics GmbH
Priority to US10/559,231 priority Critical patent/US20060154169A1/en
Publication of WO2004111731A1 publication Critical patent/WO2004111731A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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

  • compositions comprising a 1,4-dihydropyridine sensitizer and imageable elements based thereon
  • the present invention relates to radiation-sensitive compositions, in particular radiation-sensitive compositions comprising 1 ,4-dihydropyridine derivatives as sensitizers.
  • the invention furthermore relates to negative working imageable elements based thereon, a process for producing such elements, a process for imaging such elements, as well as to an imaged element such as e.g. a lithographic printing form.
  • 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.
  • 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. However, based on today's standards, these photopolymerizable compositions do not exhibit sufficient sensitivity.
  • US-A-4,181 ,531 and US-A-4,271 ,260 describe positive working systems containing 1 ,4-dihydropyridine derivatives and exhibiting sensitivity to UV light.
  • 1 ,4-dihydropyridines are used as solvent inhibitors for polymers in positive working IR-sensitive compositions.
  • negative working systems i.e. cross-linked plates
  • positive working systems negative working systems are preferred if a high degree of chemical resistance is desired.
  • Negative working systems containing 1 ,4-dihydropyridines are described in DD-A- 287 796.
  • the photopolymerizable compositions disclosed in this document comprise an onium compound as coinitiator. The sensitivity obtained with these systems cannot by far meet the requirements of today's printing plates.
  • This object is achieved by a radiation-sensitive composition comprising
  • sensitizer at least one sensitizer
  • coinitiator capable of forming free radicals together with the sensitizer (b) and selected from hexaarylbiimidazoles
  • the at least one sensitizer is a 1 ,4-dihydropyridine derivative of the formula (l)
  • R 1 is selected from a hydrogen atom, -C(0)OR 7 , an optionally substituted alkyl group, an optionally substituted aryl group and an optionally substituted aralkyl group,
  • R 2 and R 3 are independently selected from optionally substituted alkyl groups, optionally substituted aryl groups, CN and a hydrogen atom,
  • R 4 and R 5 are independently selected from -C(0)OR 7 , -C(0)R 7 , -C(0)NR 8 R 9 and
  • R 2 and R 4 together form an optionally substituted phenyl ring or a 5- to 7- membered carbocyclic or heterocyclic ring, wherein the unit
  • carbocyclic or heterocyclic ring is present in the carbocyclic or heterocyclic ring adjacent to position 5 of the 1 ,4- dihydropyridine ring and wherein the carbocyclic or heterocyclic ring optionally comprises additional substituents, or both R 2 and R 4 as well as R 3 and R 5 form either optionally substituted phenyl rings or 5- to 7-membered carbocyclic or heterocyclic rings, wherein the unit
  • carbocyclic or heterocyclic rings are present in the carbocyclic or heterocyclic rings adjacent to positions 3 and 5 of the dihydropyridine ring and wherein the carbocyclic or heterocyclic rings optionally comprise additional substituents, or one of the pairs R 2 /R 4 and R 3 /R 5 forms a 5- to 7-membered carbocyclic or heterocyclic ring, wherein the unit
  • the carbocyclic or heterocyclic ring is present in the carbocyclic or heterocyclic ring adjacent to position 5 or 3 of the dihydropyridine ring and wherein the carbocyclic or heterocyclic ring optionally comprises additional substituents and the other pair forms an optionally substituted phenyl ring, or R 2 and R 1 or R 3 and R 1 form a 5- to 7-membered heterocyclic ring which can optionally comprise one or more substituents and which, in addition to the nitrogen atom it shares with the 1 ,4-dihydropyridine ring, optionally comprises additional nitrogen atoms, -NR 13 groups, -S- or -0-,
  • R 13 is selected from a hydrogen atom, an alkyl group, aryl group and aralkyl group
  • R 6 is selected from an alkyl group optionally substituted with a halogen atom or a -C(O) group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted heterocyclic group and the group
  • Y is an alkylene group or an arylene group
  • R 7 is a hydrogen atom, aryl group, aralkyl group or alkyl group, wherein the alkyl group and the alkyl unit of the aralkyl group optionally comprise one or more C-C double and/or C-C triple bonds, and R 8 and R 9 are independently selected from a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group and an optionally substituted aralkyl group, provided that the 1 ,4-dihydropyridine derivative of formula (I) does not contain any nitro groups bonded to an aromatic ring.
  • alkyl group refers to a straight-chain, branched or cyclic saturated hydrocarbon group which preferably comprises 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms and especially preferred 1 to 6 carbon atoms.
  • the alkyl group can optionally comprise one or more substituents (preferably 0 or 1 substituent) selected for example from halogen atoms (fluorine, chlorine, bromine, iodine), CN, NR 13 2 , C(0)OR 13 and OR 13 (R 13 independently represents a hydrogen atom, an alkyl group, aryl group or aralkyl group).
  • substituents preferably 0 or 1 substituent
  • R 13 independently represents a hydrogen atom, an alkyl group, aryl group or aralkyl group.
  • aryl group refers to an aromatic carbocyclic group with one or more fused rings, which preferably comprises 6 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, NR 13 2 , S0 3 H, COOR 13 and OR 13 (wherein each R 13 is independently selected from hydrogen, alkyl, aryl and aralkyl).
  • substituents preferably 0 to 3
  • substituents preferably 0 to 3
  • substituents preferably 0 to 3
  • each R 13 is independently selected from hydrogen, alkyl, aryl and aralkyl.
  • Preferred examples are a phenyl group and a naphthyl group, which can optionally be substituted.
  • a fused ring or ring system indicates a ring that shares two atoms with the ring to which it is fused.
  • heterocyclic group refers to a 5- to 7-membered (preferably 5- or 6-membered) saturated, unsaturated (non-aromatic) or aromatic ring, wherein one or more ring carbon atoms are replaced with heteroatoms selected from N, NR 13 , S and O (preferably N or NR 13 ).
  • the heterocyclic ring can optionally comprise one or more substituents, selected for example from alkyl groups, aryl groups, aralkyl groups, halogen atoms, -OR 13 , -NR 3 2) -C(0)OR 13 , C(0)NR 13 2 and CN (wherein each R 13 is independently selected from hydrogen, alkyl, aryl and aralkyl). It goes without saying that due to the given basic structures (I) and (la) to (Ig), not every heterocyclic ring can be saturated or unsaturated or aromatic.
  • a carbocyclic ring is a 5- to 7-membered (preferably 5- or 6-membered) saturated or unsaturated ring.
  • the carbocyclic ring can optionally comprise one or more substituents, selected for example from alkyl groups, aryl groups, aralkyl groups, halogen atoms, CN, -NR 13 2 , -C(0)OR 13 , -C(0)NR 13 2 and -OR 13 (wherein R 13 is as defined above). It goes without saying that due to the given basic structures (I) and (la) to (Ig), not every carbocyclic ring can be unsaturated or saturated.
  • 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, di(trimethylol propane) tetraacrylate and -methacrylate, diethylene glycol diacrylate and -methacrylate, triethylene glycol diacrylate and -methacrylate or tetraethylene glycol 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 isocyanato(meth)acrylates unsaturated polyesters; (meth)acrylate-terminated polystyrenes, poly(meth)acrylic acid ester, poly(meth)acrylic acids, po!y(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.
  • a sensitizer as referred to in the present invention is a compound which can absorb radiation when it is exposed 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.
  • R 1 is selected from a hydrogen atom, -C(0)OR 7 , an optionally substituted alkyl group, an optionally substituted aryl group and an optionally substituted aralkyl group,
  • R 2 and R 3 are independently selected from optionally substituted alkyl groups, optionally substituted aryl groups, CN and a hydrogen atom
  • R 4 and R 5 are independently selected from -C(0)OR 7 , -C(0)R 7 , -C(0)NR 8 R 9 and
  • R 2 and R 4 together form an optionally substituted phenyl ring or a 5- to 7- membered carbocyclic or heterocyclic ring, wherein the unit
  • carbocyclic or heterocyclic ring is present in the carbocyclic or heterocyclic ring adjacent to position 5 of the dihydropyridine ring and wherein the carbocyclic or heterocyclic ring optionally comprises additional substituents, or both R 2 and R 4 as well as R 3 and R 5 form either optionally substituted phenyl rings or 5- to 7-membered carbocyclic or heterocyclic rings, wherein the unit
  • carbocyclic or heterocyclic rings are present in the carbocyclic or heterocyclic rings adjacent to positions 3 and 5 of the dihydropyridine ring and wherein the carbocyclic or heterocyclic rings optionally comprise additional substituents, or one of the pairs R 2 /R 4 and R 3 /R 5 forms a 5- to 7-membered carbocyclic or heterocyclic ring, wherein the unit
  • the carbocyclic or heterocyclic ring optionally comprises additional substituents and the other pair forms an optionally substituted phenyl ring, or R 2 and R 1 or R 3 and R 1 form a 5- to 7-membered heterocyclic ring which can optionally comprise one or more substituents and which, in addition to the nitrogen atom it shares with the 1 ,4-dihydropyridine ring, optionally comprises additional nitrogen atoms, -NR 13 groups, -S- or -0-, R 13 is selected from a hydrogen atom, an alkyl group, aryl group and aralkyl group, R 6 is selected from an alkyl group optionally substituted with a halogen atom or a -C(O) group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted heterocyclic group and the group
  • Y is an alkylene group or an arylene group
  • R 7 is a hydrogen atom, aryl group, aralkyl group or alkyl group, wherein the alkyl group and the alkyl unit of the aralkyl group optionally comprise one or more C-C double and/or C-C triple bonds, and R 8 and R 9 are independently selected from a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group and an optionally substituted aralkyl group, provided that the 1 ,4-dihydropyridine derivative of formula (I) does not contain any nitro groups bonded to an aromatic ring.
  • R 1 is a hydrogen atom.
  • R 2 and R 3 do not form rings with adjacent substituents, they are preferably independently selected from C C 5 alkyl groups or aryl groups.
  • R 4 and R 5 do not form rings with adjacent substituents, they are preferably independently selected from -C(0)OR 7 .
  • R 6 is preferably selected from CrC 5 alkyl groups or aryl groups.
  • R 7 is preferably selected from C 1 -C5 alkyl groups and it is especially preferred that it represents a methyl group.
  • R 2 and R 3 are independently selected from optionally substituted alkyl groups, optionally substituted aryl groups, CN and a hydrogen atom
  • R 4 and R 5 are independently selected from -C(0)OR 7 , -C(0)R 7 , -C(0)NR 8 R 9 and CN.
  • sensitizers are 1 ,4-dihydropyridine derivatives of formula (la)
  • R 1 and R 6 are as defined above, the groups R 8a to R 8d and R 9a to R 9d are independently selected from a hydrogen atom, alkyl groups and aryl groups, wherein two groups R 9 and/or two groups R 8 of adjacent ring carbon atoms can also form a saturated or unsaturated carbocyclic or heterocyclic ring or fused aromatic ring together, each Z is independently selected from CR 13 2 , O, S and NR 13 and each R 13 independently represents a hydrogen atom, alkyl, aralkyl or aryl group, of formula (lb)
  • R 1 and R 6 are as defined above, and
  • R ⁇ o a t0 R ⁇ o d and R n a tQ R n d ar ⁇ j ⁇ rjependently selected from a hydrogen atom, alkyl groups, aryl groups, aralkyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), CN, NR 13 2 , C(0)OR 13 and OR 13 (each R 13 independently represents a hydrogen atom, an alkyl group, aryl group or aralkyl group), wherein two groups R 11 and/or two groups R 10 of adjacent ring carbon atoms can also form an unsaturated carbocyclic or heterocyclic ring or fused aromatic ring together, of formula (lc)
  • R 1 , R 3 , R 5 and R 6 are as defined above and the groups R 9a to R 9f are independently selected from a hydrogen atom, alkyl groups, aryl groups, aralkyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), CN, NR 13 2l C(0)OR 13 and OR 13 (R 13 independently represents a hydrogen atom, an alkyl group, aryl group or aralkyl group), wherein two groups R 9 of adjacent ring carbon atoms can also form a saturated or unsaturated carbocyclic or heterocyclic ring or fused aromatic ring together, of formula (Id)
  • R 1 , R 2 , R 3 , R 4 and R 5 independently is as defined above and Y is selected from alkylene and arylene, of formula (Ie)
  • R , R 4 , R° and R are as defined above and groups R 9 a a a * to ⁇ D R9 a f r are defined as are groups R 9a to R 9d of formula (la) above, of formula (If)
  • R , R 4 , R° and R are as defined above and the groups R 1 1 1 1a to R j11d are independently selected from a hydrogen atom, alkyl groups, aryl groups, aralkyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), CN, NR 13 2 , C(0)OR 13 and OR 13 (R 13 independently represents a hydrogen atom, an alkyl group, aryl group or aralkyl group), wherein two adjacent groups R 11 of adjacent ring carbon atoms can also form an unsaturated carbocyclic or heterocyclic ring or fused aromatic ring together.
  • R 8 or R 9 in formulas (la), (lc), (Ie) and (If) is reduced if two groups R 8 or R 9 of adjacent ring carbon atoms together form a fused aromatic ring.
  • R 1 is preferably a hydrogen atom
  • R 6 is a methyl or phenyl group and Z is preferably O or CH 2
  • the substituents R 8 a tQ R s d and R 9 a t0 R 9d ar ⁇ indepen entl preferably selected from hydrogen atoms and methyl groups.
  • those with symmetrical substitution at the dihydropyridine ring are especially preferred.
  • R 1 is preferably a hydrogen atom and R 6 is preferably a methyl or phenyl group.
  • the substituents R 10a to R 10d and R 11a to R 11d are independently preferably selected from C C 5 alkyl groups, OR 13 and halogen atoms; a symmetrical substitution of the two aromatic rings is especially preferred.
  • R 1 is preferably a hydrogen atom
  • R 6 is preferably a methyl or phenyl group
  • R 3 is preferably a methyl group
  • R 5 is preferably C(0)OR 7 (wherein R 7 is as defined above).
  • the substituents R 9a to R 9 are independently preferably selected from C1-C 5 alkyl groups. A methyl group is especially preferred.
  • Y is preferably a 1 ,4-phenylene or 1 ,2-ethylene group.
  • both groups R 1 be the same, both groups R 2 be the same, both groups R 3 be the same, both groups R 4 be the same and both groups R 5 be the same; the preferred definitions given with respect to formula (I) apply to all groups R 1 to R 5 .
  • R 2 is preferably C1-C 5 alkyl
  • R 4 is preferably -C(0)OR 7
  • R 5 is preferably C(0)OR 7
  • R 6 is preferably C C 5 alkyl or phenyl groups (R 7 is as defined above).
  • the substituents R 9a to R 9f are preferably independently selected from C r C 5 alkyl groups.
  • R 2 is preferably C ⁇ -C 5 alkyl
  • R 4 is preferably C(0)OR 7
  • R 5 is preferably C(0)OR 7
  • R 6 is preferably a C 1 -C 5 alkyl or a phenyl group (wherein R 7 is as defined above).
  • the substituents R 9a to R 9h are preferably independently selected from C 1 -C 5 alkyl groups.
  • R 2 is preferably C 1 -C 5 alkyl
  • R 4 is preferably C(0)OR 7
  • R 5 is preferably C(0)OR 7
  • R 6 is preferably a C 1 -C 5 alkyl or a phenyl group.
  • the substituents R 11 are preferably independently selected from C 1 -C 5 alkyl groups.
  • the 1 ,4-dihydropyridine derivatives used in the present invention can be prepared according to processes well known to the person skilled in the art, such as the Hantzsch synthesis.
  • processes well known to the person skilled in the art such as the Hantzsch synthesis.
  • the amount of sensitizer(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, preferably 0.5 to 15 wt.-%.
  • a coinitiator as referred to in the present invention is a compound that forms free radicals together with the sensitizers used according to the present invention.
  • the coinitiators are selected from 2,2' 1 4,4',5,5 I - hexaarylbiimidazoles (in the following simply referred to as hexaarylbiimidazoles).
  • Suitable hexaarylbiimidazoles are for example represented by the formula (II) below:
  • a 1 -A 6 are substituted or unsubstituted C5-C20 aryl groups which are identical or different from each other and in whose rings one or more carbon atoms can optionally be substituted by heteroatoms selected from O, N and S.
  • Suitable substituents for the aryl groups are those that do not inhibit the light-induced dissociation to triarylimidazolyl radicals, e.g.
  • halogen atoms fluorine, chlorine, bromine, iodine
  • -CN halogen atoms
  • CrC 6 alkyl optionally with one or more substituents selected from halogen atoms, -CN and -OH
  • CrC 6 alkoxy CrC 6 alkylthio
  • C ⁇ -C 6 alkyl sulfonyl
  • Preferred aryl groups are substituted and unsubstituted phenyl, biphenyl, naphthyl, pyridyl, furyl and thienyl groups. Especially preferred are substituted and unsubstituted phenyl groups, and particularly preferred are halogen-substituted phenyl groups.
  • Examples include:
  • Suitable hexaarylbiimidazoles are for example described in US-A-4,565,769 and US-A-3,445,232 and can be prepared according to known processes, such as e.g. the oxidative dimerization of triarylimidazoles.
  • one hexaarylbiimidazole or a mixture of several can be used as coinitiator.
  • the amount of coinitiator(s) is not particularly restricted; however, it is preferably in the range of 0.2 to 25 wt.-%, based on the dry layer weight, especially preferred 0.5 to 15 wt.-%.
  • the radiation-sensitive coating of the present invention can also comprise an alkali-soluble binder or a mixture of such 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 that are capable of undergoing a cycloaddition (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 an 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 non-absorbable thermopolymerization 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.
  • the colorant has to be selected such that the hexaarylbiimidazole is not sensitized and broken down; the person skilled in the art can determine suitable colorants by means of simple experiments or calculations on the basis of redox data.
  • colorants include e.g. phthalocyanine pigments, azo pigments, carbon black, titanium dioxide, azo dyes, triarylmethane dyes, anthraquinone dyes and cyanine dyes.
  • the use of pigments is preferred since the phase separation suppresses the sensitization of the hexaarylbiimidazole.
  • 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.
  • plasticizers include e.g. dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin und tricresyl phosphate.
  • 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 such as e.g. mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 3-mercaptotriazole. 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.-%.
  • 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. AI2O3 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. AI2O3 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 several organic solvents.
  • Suitable solvents include low alcohols (e.g. methanol, ethanol, propanol and butanol), glycolether derivatives (e.g. ethylene glycol monomethylether, ethylene glycol dimethylether, propylene glycol monomethylether, ethylene glycol monomethylether acetate, ethylene glycol monoethylether acetate, propylene glycol monomethylether acetate, propylene glycol monoethylether acetate, ethylene glycol monoisopropylether acetate, ethylene glycol monobutylether acetate, diethylene glycol monomethylether, diethylene glycol monoethylether), ketones (e.g.
  • esters e.g. methyl lactate, ethyl lactate, acetic acid ethyl ester, 3- methoxypropyl acetate and butyl acetate
  • aromatics e.g. toluene and xylene
  • cyclohexane methoxymethoxyethanol
  • y-butyrolactone dipolar aprotic solvents (e.g. THF, dimethylsulfoxide, dimethylformamide and N-methylpropyrrolidone).
  • 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 pyrrolidone/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 poly(vinyl- imidazole).
  • adhesion promoters such as e.g. poly(vinylpyrrolidone), poly(ethyleneimine) and poly(vinyl- imidazole).
  • 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 (preferably 250 to 450 nm) and subsequently developed with a commercially available aqueous alkaline developer.
  • Mercury lamps doped with a metal halide and diodes emitting UV light (UV-LED) can for example be used as a radiation source.
  • 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 a heat treatment
  • overall exposure e.g. to UV light
  • 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 as well as printing plates prepared from radiation-sensitive elements according to the present invention show excellent properties even without having been subjected to a heat treatment.
  • 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 HCl) grained and anodized aluminum foil was subjected to a treatment with an aqueous solution of polyvinylphosphonic acid (PVPA) and after drying was coated with a solution as described in Table 2 and dried.
  • PVPA polyvinylphosphonic acid
  • the solution was filtered, applied to the lithographic substrate and the coating was dried for 4 minutes at 90°C.
  • the dry layer weight of the photopolymer layer was about 1.6 g/m 2 .
  • An overcoat was applied to the resulting samples by coating them with an aqueous solution of poly(vinylalcohol) (Airvol 203 from Airproducts, degree of hydrolysis: 88%); after drying for 4 minutes at 90°C, the overcoat had a dry layer weight of about 2 g/m 2 .
  • poly(vinylalcohol) Airvol 203 from Airproducts, degree of hydrolysis: 88%
  • the printing plate precursor was exposed to the light of a Ga-doped MH lamp with an energy of 1.7 mJ/cm 2 in a vacuum frame using a gray scale having a tonal range of 0.15 to 1.95, wherein the density increments amounted to 0.15 (UGRA gray scale). 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
  • 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 and gummed 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.
  • Example 4 The same coating composition as used in Example 4 was used in Example 5.
  • Comparative Example 1 The same coating composition as used in Comparative Example 1 was used in Comparative Example 7. Both plates were exposed with an energy of 300 ⁇ J/cm 2 by means of a laser diode emitting at 405 nm using the UGRA gray scale. The plates were then developed as described in Examples 1 to 4 and Comparative Examples 1 to 6.
  • Example 5 gray scale 3/7; gray scale 3/7 for the plate after storage for 60 minutes at 90°C Comparative Example 7: no image was obtained
  • the examples according to the present invention confirm the synergistic effect of the combination of 1 ,4-dihydropyridines and hexaarylbiimidazoles during the initiation of free-radical polymerization; the compositions of the present invention are characterized by a very high photospeed.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition sensible aux rayonnements. Cette composition contient : a) au moins un type de monomères et/ou d'oligomères et/ou de polymères, chacun contenant au moins un groupe éthylèniquement insaturé, accessible à une polymérisation à radicaux libres ; b) au moins un sensibilisateur ; c) au moins un co-initiateur pouvant former des radicaux libres avec le sensibilisateur b), ledit co-initiateur étant choisi parmi des hexaarylbiimidazoles ; et d) facultativement au moins un composant choisi parmi des liants solubles dans l'alcali, des colorants, des indicateurs d'exposition, des plastifiants, des agents de transfert de chaînes, des colorants leuco, des tensioactifs, des charges inorganiques et des inhibiteurs de thermopolymérisation. La composition selon l'invention se caractérise en ce que le sensibilisateur au moins représente un dérivé 1,4-dihydropyridine de formule (I) ne contenant pas de groupe nitro lié à un cycle aromatique.
PCT/EP2004/006185 2003-06-11 2004-06-08 Compositions sensibles aux rayonnements contenant un sensibilisateur a base de 1,4-dihydropyridine et elements imageables a base desdites compositions Ceased WO2004111731A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/559,231 US20060154169A1 (en) 2003-06-11 2004-06-08 Radiation-sensitive compositions comprising a 1,4-dihydropyridine sensitizer and imageable elements based thereon

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10326324.1 2003-06-11
DE2003126324 DE10326324B4 (de) 2003-06-11 2003-06-11 Lithographiedruckplatten-Vorläufer mit 1,4-Dihydropyridin-Sensibilisator enthaltender Beschichtung, Verfahren zum Bebildern und Bebilderte Lithographiedruckplatte

Publications (1)

Publication Number Publication Date
WO2004111731A1 true WO2004111731A1 (fr) 2004-12-23

Family

ID=33494960

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/006185 Ceased WO2004111731A1 (fr) 2003-06-11 2004-06-08 Compositions sensibles aux rayonnements contenant un sensibilisateur a base de 1,4-dihydropyridine et elements imageables a base desdites compositions

Country Status (2)

Country Link
DE (1) DE10326324B4 (fr)
WO (1) WO2004111731A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7574959B2 (en) * 2003-12-05 2009-08-18 Kodak Graphic Communications, Gmbh Radiation-sensitive compositions and imageable elements based thereon
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
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
US9315009B2 (en) 2007-05-08 2016-04-19 Esko-Graphics Imaging Gmbh Exposing printing plates using light emitting diodes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595651A (en) * 1983-09-29 1986-06-17 E. I. Du Pont De Nemours And Company Process for producing equidensity images using photohardenable materials
DD287796A5 (de) * 1989-09-14 1991-03-07 Tech Hochschule C Schorlemmer Spektral sensibilisiertes photopolymerisierbares material

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2710417C3 (de) * 1976-03-17 1980-08-14 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Photopolymerisierbares Gemisch und Verfahren zur Erzeugung von positiven oder negativen Bildern
DE2758209C3 (de) * 1977-12-27 1980-07-10 Du Pont De Nemours (Deutschland) Gmbh, 4000 Duesseldorf Lichtempfindliches Aufzeichnungsmaterial
DE2758210A1 (de) * 1977-12-27 1979-06-28 Du Pont Deutschland Lichtempfindliches aufzeichnungsmaterial
DE2945564A1 (de) * 1978-11-13 1980-05-22 Du Pont Verfahren zur herstellung von mehrfarbenbildern
US4292394A (en) * 1978-11-13 1981-09-29 E. I. Du Pont De Nemours And Company Process for preparing multicolor toned images on a single photosensitive layer
DE3048490C2 (de) * 1980-12-22 1982-09-02 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Lichtempfindliches Aufzeichnungsmaterial
DE3540796C1 (de) * 1985-11-16 1987-04-16 Du Pont Deutschland Verfahren zur Herstellung von zur Vorlage positiven aus Pulvern bestehenden Mustern
DE3540804C1 (de) * 1985-11-16 1987-04-16 Du Pont Deutschland Verfahren zur Herstellung von zur Vorlage negativen,aus mehreren verschiedenen Pulvern bestehenden Mustern
DE4228141C1 (de) * 1992-08-25 1993-09-30 Du Pont Deutschland Verfahren zur Herstellung von Bildern
DE4228790C1 (de) * 1992-08-29 1993-11-25 Du Pont Deutschland Tonbares strahlungsempfindliches Gemisch und Verfahren zur Herstellung von Mehrfarbenbildern mittels solch eines Gemischs

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595651A (en) * 1983-09-29 1986-06-17 E. I. Du Pont De Nemours And Company Process for producing equidensity images using photohardenable materials
DD287796A5 (de) * 1989-09-14 1991-03-07 Tech Hochschule C Schorlemmer Spektral sensibilisiertes photopolymerisierbares material

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7574959B2 (en) * 2003-12-05 2009-08-18 Kodak Graphic Communications, Gmbh Radiation-sensitive compositions and imageable elements based thereon
US10766247B2 (en) 2007-05-08 2020-09-08 Esko-Graphics Imaging Gmbh Exposing printing plates using light emitting diodes
US9315009B2 (en) 2007-05-08 2016-04-19 Esko-Graphics Imaging Gmbh Exposing printing plates using light emitting diodes
US9849663B2 (en) 2007-05-08 2017-12-26 Esko-Graphics Imaging Gmbh Exposing printing plates using light emitting diodes
US20180072041A1 (en) * 2007-05-08 2018-03-15 Esko-Graphics Imaging Gmbh Exposing printing plates using light emitting diodes
US10766248B2 (en) 2007-05-08 2020-09-08 Esko-Graphics Imaging Gmbh Method and apparatus for exposing printing plates using light emitting diodes
US11318730B2 (en) 2007-05-08 2022-05-03 Esko-Graphics Imaging Gmbh Printing plate imaging and exposure apparatus and method
US12202246B2 (en) 2007-05-08 2025-01-21 Esko-Graphics Imaging Gmbh Printing plate imaging and exposure apparatus and method
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
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
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

Also Published As

Publication number Publication date
DE10326324B4 (de) 2007-02-08
DE10326324A1 (de) 2005-01-05

Similar Documents

Publication Publication Date Title
EP1595183B1 (fr) Compositions photosensibles contenant des derives oxazoles et elements pouvant former une image a base de telles compositions
EP1690138B1 (fr) Compositions sensibles aux rayonnements et elements imageables a base de celles-ci
US7615323B2 (en) Lithographic printing plate precursors with oligomeric or polymeric sensitizers
EP1565790B1 (fr) Elements sensibles au rayonnement et leur stabilite au stockage
US8632937B2 (en) UV-sensitive lithographic printing plate precursor with benzoxazole derivative and analogues thereof as sensitizer
US20060063101A1 (en) Radiation-sensitive elements
WO2004074929A2 (fr) Compositions radiosensibles comprenant des derives d'oxazole et elements pouvant former une image a base de telles compositions
EP1969426B1 (fr) Composition de photopolymere pour plaques d impression lithographique
US7169534B2 (en) Photopolymer composition suitable for lithographic printing plates
WO2004111731A1 (fr) Compositions sensibles aux rayonnements contenant un sensibilisateur a base de 1,4-dihydropyridine et elements imageables a base desdites compositions
US20060154169A1 (en) Radiation-sensitive compositions comprising a 1,4-dihydropyridine sensitizer and imageable elements based thereon
JP3825186B2 (ja) 光重合性組成物及び光重合性平版印刷版
EP1910896A2 (fr) Composition photopolymere appropriee pour plaques d'impression lithographique
WO2008058939A2 (fr) Éléments sensibles aux uv contenant des dérivés de triarylamine comme sensibilisateurs pour l'exposition ctp

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2006154169

Country of ref document: US

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 10559231

Country of ref document: US

122 Ep: pct application non-entry in european phase
WWP Wipo information: published in national office

Ref document number: 10559231

Country of ref document: US