CA1337677C - Photopolymerizable recording material - Google Patents
Photopolymerizable recording materialInfo
- Publication number
- CA1337677C CA1337677C CA000606446A CA606446A CA1337677C CA 1337677 C CA1337677 C CA 1337677C CA 000606446 A CA000606446 A CA 000606446A CA 606446 A CA606446 A CA 606446A CA 1337677 C CA1337677 C CA 1337677C
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- Prior art keywords
- recording material
- polymer
- weight
- oxygen
- cover layer
- Prior art date
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Classifications
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
A photopolymerizable recording material is diclosed comprising a base material, a photopoly-merizable layer and a cover layer which comprises a water-soluble polymer which is substantially impermeable to atmospheric oxygen, and a polymer which binds atmospheric oxygen and is virtually completely soluble in water at 20°C. The material displays reduced sensitivity to atmospheric oxygen, even on prolonged storage and at elevated ambient temperatures and elevated atmospheric humidity.
Description
PHOTOPOLYMERIZABLE RECORDING MATERIAL
Background of the Invention The present invention relates to a photopolymerizable recording material comprising a base material, a photopolymerizable layer and a cover layer which is relatively impermeable to atmospheric oxygen. The material is suitable in particular for producing printing plates, in particular planographic printing plates.
Printing plates of the type mentioned are known for example from US-A-3,458,311. The cover layers described therein consist of water-soluble polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, gelatin or gum arabic. of these substances, polyvinyl alcohol is preferred, since its barrier effect in respect of oxygen is very high. However, it has been found that stored photopolymerizable printing plates having a cover layer made of polyvinyl alcohol lose some of their light sensitivity in the course of weeks and months.
It has also been observed that the protective effect 1`~37677 strongly decreases wlth lncreaslng temperature and increasing atmospheric humldlty. It has indeed been posslble to show that the oxygen permeabllity of polyvinyl alcohol strongly lncreases with temperature and atmospheric humldlty. This dlsadvantage ls partlcularly serlous in the case of highly light-sensitive photopolymerizable mlxtures containlng photooxldizable substances and speclal synergistlc lnltlator combinations. Such mlxtures are descrlbed in earller German Patent Appllcatlons DE-A 37 lO 279.6, DE-A 37 10 281.8, DE-A
37 10 282.6 and DE-A 37 43 454.3.
It ls also known to add to the photopolymerlzable layer ltself substances, for example tln salts or antloxldants, ln order to trap the oxygen dlffusing into the layer. Such additions are described, for example, in a paper by E.T. Denlsov et al. ln Chem. Rev. 1987, pp. 1313-1357.
Slnce such compounds usually have undeslrable slde effects and ln partlcular reduce the light sensltivity, they have not become established in practlce.
Summary of the Invention Accordingly, it is an ob~ect of the present invention to provide a photopolymerizable recording material having an oxygen-barrlng cover layer whose light sensitivity does not decrease at all or only X
to about the same extent as in existing materials of this type.
Another obiect of the present invention is to provide a photopolymerizable recording material whlch displays improved storage stability at elevated temperatures and atmospheric humidities.
According to one aspect of the present invention there is provided a photopolymerizable recording material which comprises a base material, a photopolymerizable layer comprising a polymerlc blnder, a free-radlcal polymerlzable compound havlng at least one photooxldizable group and at least one terminal ethylenically unsaturated group, and a polymerization initiator activatable by actinic radiation and a cover layer comprising (a) a water-soluble polymer which is substantially lmpermeable to oxygen and (b) a polymer which binds oxygen and is soluble in water at 20 C.
Other ob~ects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present inventlon, are glven by way of illustration and tB
1 ~3767~
not limitation. Many changes and modifications withln the scope of the present invention may be made without departing from the spirit thereof, and the invention includes all such modifications.
3a Detailed Description of Preferred Embodiments Suitable water-soluble polymers for binding atmospheric oxygen are in particular compounds having aliphatic amino groups which may be primary, secondary or tertiary. The polymers should preferably not contain any further functional groups in addition to the amino groups. Their molecular weights are in general within the range from about 300 to 1,000,000, preferably 1,000 to 200,000, in particular 10,000 to 200,000.
The amino-containing polymers used are preferably linear or branched polyalkyleneimines whose alkylene groups contain 2 to 8, in particular 2 to 4, carbon atoms. Of particular advantage are polyalkyleneimines, in particularpolyethyleneimines and polypropyleneimines, having molecular weights of about 18,000 to 80,000.
The polyalkyleneimines can be prepared by acid-catalyzed polymerization of alkyleneimines, for example ethyleneimine or propyleneimine, as described in US-A-2,223,930. Products having higher molecular weights can be obtained by reaction with bifunctional alkylating agents, for example 1,2-dichloroethane, and those having low molecular weights by addition of 1,2-ethylene~iamine, as described in US-A-3,519,687. Such polyalkyleneimines are commercial products. A preferred example contains about 30% of primary, 40% of secondary and 30% of tertiary amino groups.
- t 337677 -The polymer which is substantially impermeable to atmospheric oxygen can be one of the polymers indicated in US-A-3,458,311. Examples are in particular polyvinyl alcohol and partially hydrolyzed polyvinyl acetates, which may also contain vinyl ether and vinyl acetal units as long as the polymer remains water-soluble at 20C. It is also possible to use gelatin, gum arabic, copolymers of alkyl vinyl ethers and maleic anhydride, polyvinylpyrrolidones and water-soluble high molecular weight polymers of ethylene oxide (M =
100,000 to 3,000,000). Preference is given to those polymers whose oxygen permeability in a layer at 20C is less than 30, in particular less than 25, cm /m /d/bar.
The cover layer should transmit actinic light and in general has a thickness of about 0.5 to 10, preferably 1 to 4, ~m. The cover layer preferably has a basis weight of about 0.5 to 10 g/m2 It contains in general 3 to 60, preferably 5 to 40, %
by weight of oxygen-binding polymer, in particular polyalkyleneimine, based on the total solids content. The cover layer is applied on top of the photopolymerizable layer in a conventional manner from aqueous solution or from a mixture of water and organic solvent. The coating solution may contain, for better wetting properties, up to about 10% by weight, preferably up to 5% by weight, of a surface-active agent, based on its solids content. The usable surface-active substances include the anionic, cationic and nonionic surface-active agents, for example sodium alkyl sulfates and alkylsulfonates of 12 to 18 carbon atoms such as sodium dodecyl sulfate, N-cetylbetaines, C-cetylbetaines, alkylaminocarboxylates,alkylaminodicarboxylates and polyethylene glycols having an average molecular weight of up to 400.
The cover layers of the material according to the invention have a lower oxygen permeability than existing cover layers, which contain only an oxygen-barring polymer, for example polyvinyl alcohol, with or without a wetting agent. The protective effect is improved in particular at elevated temperatures and at elevated atmospheric humidity and lasts longer on prolonged storage than that of existing protective layers. Since the high specific protective effect permits the use of relatively thin cover layers (0.5 to 2.5 ~m), good optical resolution is obtained. This property is in need of improvement in particular in the case of offset printing plates based on photopolymerizable materials.
The photopolymerizable layers of the recording materials according to the invention comprise a polymeric binder, a free-radical-polymerizable compound having at least one, preferably at least two, terminal ethylenically unsaturated groups, and an actinically activable polymerization initiator or initiator combination.
~ ~37677 The photopolymerizable layer preferably has a basis weight of about 0.5 to 20 g/m2.
Polymerizable compounds suitable for the purposes of the invention are known and described for example in US-A-2,760,863 and -3,060,023.
Preferred examples are acrylic and methacrylic esters of dihydric or polyhydric alcohols, such as ethylene glycol diacrylate, polyethylene glycol dimethacrylate, acrylates and methacrylates of trimethylolethane, trimethylolpro-pane, pentaerythritol and dipentaerythritol and of polyhydric alicyclic alcohols or N-substituted acrylamides and methacrylamides. It is also advantageous to use reaction products of monoisocyanates or diisocyanates with partial esters of polyhydric alcohols. Such monomers are described in DE-A-2,064,079, -2,361,041 and -2,822,190.
Particular preference is given to polymeri-zable compounds which contain at least one photooxidizable group alone or together with one or more urethane groups in the molecule.
Suitable photooxidizable groups are in particular amino groups, urea groups, thio groups, which may also be the constituents of heterocyclic rings, and enol groups. Examples of such groups are triethanolamino, triphenylamino, thiourea, imidazole, oxazole, thiazole, acetylacetonyl, N-phenylglycine and ascorbic acid groups. Poly-merizable compounds having primary, secondary and in particular tertiary amino groups are preferred.
Examples of compounds having photooxidizable groups are acrylic and alkacrylic esters of the formula I
R( )Q[t-CH2-CO) -CONH(X1-NHCOO)b-X2(-OOC-C=CH2)c]n (I) where /D \
Q is -N-, -N-E-N-, -N~ / N- or -S-R is an alkyl, hydroxyalkyl or aryl group, R1 and R2 are each a hydrogen atom, an alkyl group or an alkoxyalkyl group, R3 is a hydrogen atom or a methyl or ethyl group, X1 is a saturated hydrocarbon group of 2 to 12 carbon atoms, X2 is a (c+l)-valent saturated hydrocarbon group in which up to 5 methylene groups may have been replaced by oxygen atoms, D1 and D2 are each a saturated hydrocarbon group of 1 to 5 carbon atoms, E is a saturated hydrocarbon group of 2 to 12 carbon atoms, a cycloaliphatic group of 5 to 7 ring members which may contain up to two N, O or S atoms as ring members, an arylene group of 6 to 12 -carbon atoms or a heterocycllc aromatlc group of 5 or 6 rlng members, a ls 0 or an lnteger from 1 to 4, b ls 0 or 1, c ls an lnteger from 1 to 3, m ls 2, 3 or 4, dependlng on the valence of Q, and n ls an lnteger from 1 to m, wlth all the symbols of ldentlcal deflnltlon belng ldentlcal to or dlfferent from one another.
The compounds of thls formula, and the preparatlon and use thereof are descrlbed ln detall ln earller German Patent Appllcatlon DE-A 37 10 279.6.
If ln the compound of the general formula I more than one radlcal R or more than one radlcal of the type lndlcated ln square brackets ls bonded to the central group Q, these radlcals can be dlfferent from one another.
Compounds ln whlch all the substltuents of Q are polymerlzable radlcals, l.e. where m ls n, are ln general preferred.
In general, not more than one radlcal a ls 0;
preferably a ls 1.
An alkyl or hydroxyalkyl group R generally has 2 to 8, preferably 2 to 4, carbon atoms. An aryl radlcal R can ln general be monocycllc or blcycllc, preferably monocycllc, and may be substltuted by X, - ~ 337677 alkyl or alkoxy groups of up to 5 carbon atoms or halogen atoms.
Alkyl and alkoxyalkyl groups Rl and R2 can contain 1 to 5 carbon atoms.
R3 is preferably a hydrogen atom or a methyl group, in particular a methyl group.
Xl is preferably a straight-chain or branched aliphatic or cycloaliphatic radical of preferably 4 to 10 carbon atoms.
X2 preferably has 2 to 15 carbon atoms, of which up to 5 may have been replaced by oxygen atoms. In the case of pure carbon chains, generally those having 2 to 12, preferably 2 to 6, carbon atoms are used. x2 can also be a cycloaliphatic group of 5 to 10 carbon atoms, in particular a cyclohexylene group.
D1 and D2 can be identical or different, and together with the two nitrogen atoms form a saturated heterocyclic ring of 5 to 10, preferably 6, ring members.
An alkylene group E preferably has 2 to 6 carbon atoms, and an arylene group E is preferably a phenylene group. Preferred cycloaliphatic groups are cyclohexylene groups and preferred aromatic heterocycles are those having N or S as heteroatoms and 5 or 6 ring members.
The value of c is preferably 1.
The polymerizable compounds of the formula I
which contain two urethane groups in every radical t337677 (b = l) are prepared by reacting acrylic or alkylacrylic esters which contain free hydroxyl groups in a conventional manner with the same molar amount of diisocyanates and reacting the excess isocyanate group with hydroxyalkylamines, N,N-bishydroxyalkylpiperazines or N,N,N',N'-tetrahydroxyalkylalkylenediamines, in each of which individual hydroxyalkyl groups may have been replaced by alkyl or aryl groups R. If a is 0, the result is a urea grouping.
Examples of the hydroxyalkylamine starting materials are triethanolamine, N-alkyl-N,N-di(hydroxyalkyl)amines, diethanolamine, tris(2-hydroxypropyl)amine and tris(2-hydroxybutyl)amine.
Examples of diisocyanate starting materials are hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate and 1,1,3-trimethyl-3-isocyanatomethyl-5-isocyanatocyclohexane.
The hydroxyl-containing esters used are in particular hydroxyethyl methacrylate and hydroxypropyl methacrylate (n or iso) and the corresponding acrylates.
The polymerizable compounds of the formula I
where b is 0 are prepared by reacting the above-described hydroxyalkylamino compounds with isocyanato-containing acrylic or alkylacrylic esters. An isocyanato-containing ester used in particular is isocyanatoethyl (meth)acrylate.
-Further sultable compounds havlng photooxldlzable groups are compounds of the formula ~(~CH2lc)a(-cH2 ~ CH - O) -H]
R CH2 (II) OOC-C=CH2 where Q, R, Rl, R2, R3, a, m and n are each as deflned above and Q can addltlonally be a group -N-E'-N-where E' ls a group of the formula III
-CH2-CHOH-CH2- [ - ~ -C- ~ -o-cH2-cHoH-cH2 ] c The compounds of the formula II are prepared slmllar-ly to those of the formula I, except that the hydroxyalkyl (alk)acrylates are replaced by the correspondlng glycldyl (alk)acrylates.
The compounds of thls formula and the preparatlon and use thereof are descrlbed ln detall ln earller Patent Appllca-tlon DE-A 37 38 864.9.
Further sultable compounds havlng photooxldlzable groups are acryllc and alkacryllc esters of the formula IV
Q~[(-xl -CH2O)a-CONH(-Xl-NHCOO)b-X2-OOC-C=CH21n, `X
~ 337677 -where Dl Q' is Q' -N-, -N N- or ~N-, X1 is ClH2, or ClH2,lO-CONH(-X1 -NHCOO)b-X2 -ooC-C=CH2, D3 is a saturated hydrocarbon group of 4 to 8 carbon atoms which together with the nitrogen atom forms a 5- or 6-membered ring, Z is a hydrogen atom or a radical of the formula R3 CkH2k-0-COl~H ( -Xl -NHCOO) b-X2 -OOC-CH2, i and k are integers from 1 to 12, n' is 1, 2 or 3 depending on the valence of Q' and R3, X1, X2, D1, D2' a and b are each as defined at the formula I, with all the symbols of identical definition being identical or different from one another and in at least one substituent on the group Q a being 0.
Of the compounds of the formula IV, those which contain at least one urethane group as well as a urea group are preferred. Urea groups are for the purposes of the present invention groups of the formula r ~N - CO - N
where the valences on the nltrogen are saturated by substltuted or unsubstltuted hydrocarbon radlcals. However, lt ls also posslble for one valence on one nltrogen atom to be bonded to a further carbonylamlde group (CONH), produclng a bluret structure.
The symbol a ln the formula IV ls preferably 0 or 1;
1 ls preferably a number from 2 to 10.
The polymerlzable compounds of the formula IV are prepared ln the same way as compounds of the formula I.
The compounds of the formula IV and the preparatlon thereof are descrlbed ln detall ln Canadlan Patent Appllcation no. 606,332.
The proportlon of photopolymerlzable compound ln the photopolymerlzable layer ls ln general about 10 to 80, prefer-ably 20 to 60, % by welght, based on the nonvolatlle constltu-ents.
Examples of usable blnders are chlorlnated polyethylene, chlorlnated polypropylene, poly[alkyl tmeth)-acrylates] where the alkyl group ls for example methyl, ethyl, n-butyl, l-butyl, n-hexyl or 2-ethylhexyl, copolymers of sald alkyl(meth)acrylates wlth at least one monomer, such as acrylonltrlle, vlnyl chlorlde, vlnylldene chlorlde, styrene or butadlene, polyvlnyl chlorlde, vlnyl chlorlde/acrylonltrlle copolymers, polyvlnylldene chlorlde, vlnylldene chlor-lde/acrylonltrlle copolymers, polyvlnyl acetate, polyvlnyl alcohol, polyacrylonltrlle, acrylonltrlle/styrene copolymers, 1~' acrylonitrile/butadiene/styrene/copolymers, polystyrene, polymethylstyrene, polyamides (for example nylon-6), polyurethanes, methylcellulose, ethylcellulose, acetylcellulose, polyvinyl/formal and polyvinyl butyral.
Of particular suitability are binders which are insoluble in water, soluble in organic solvents and soluble or at least swellable in aqueous alkaline solutions.
A special mention should be made of carboxyl-containing binders, for example copolymers of (meth)acrylic acid and/or unsaturated homologs thereof, such as crotonic acid, copolymers of maleic anhydride or monoesters thereof, reaction products of hydroxyl-containing polymers with dicarboxylic anhydrides, and mixtures thereof.
It is also possible to use reaction products of polymers which carry acidic H groups which have been wholly or partly reacted with activated isocyanates, for example reaction products of hydroxyl-containing polymers with aliphatic or aromatic sulfonyl isocyanates or phosphinoyl isocyanates.
Also suitable are: hydroxyl-containing polymers, for example copolymers of hydroxyalkyl (meth)acrylates, copolymers of allyl alcohol, copolymers of vinyl alcohol, polyurethanes or polyesters, and also epoxy resins, provided they carry a sufficient number of free OH groups, or have been modified in such a way that they are soluble in aqueous alkaline solutions, or those polymers which carry aromatically bonded hydroxyl groups, for example condensation products of condensable carbonyl compounds, in particular formaldehyde, acetaldehyde or acetone, with phenols or copolymers of hydroxystyrenes. Finally, it is also possible to use copolymers of (meth)acrylamide with alkyl (meth)acrylates.
The above-described polymers are suitable in particular when they have a molecular weight between about 500 and 200,000 or higher, preferably 1,000 to 100,000, and either acid numbers between 10 and 250, preferably 20 to 200 or hydroxyl numbers between 50 and 750, preferably 100 to 500.
Preferred alkali-soluble binders are:
copolymers of (meth)acrylic acid with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of crotonic acid with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of vinylacetic acid with alkyl (meth)acrylates, copolymers of maleic anhydride with substituted or unsubstituted styrenes, unsaturated hydrocarbons, unsaturated ethers or esters, esterification products of copolymers of maleic anhydride, esterification products of hydroxyl-containing polymers with anhydrides of di- or polycarboxylic acids, copolymers of hydroxyalkyl (meth)acrylates with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of allyl alcohol with substituted or unsubstituted styrenes, copolymers of vlnyl alcohol with alkyl (meth)acrylates or other polymerlzable unsaturated compounds, polyurethanes, provlded they have a sufficlent number of free OH groups, epoxy reslns, polyesters, partlally hydrolyzed vlnyl acetate copolymers, polyvlnyl acetals havlng free OH groups, copolymers of hydroxystyrenes wlth alkyl (meth)-acrylates or the llke, phenol-formaldehyde reslns, for example novolaks.
The amount of blnder ln the llght-sensltlve layer ls ln general about 20 to 90, preferably 40 to 80, % by welght.
The photolnltlators used can be a large number of substances. Examples are those whlch are derlved from the baslc skeleton of benzophenones, acetophenones, benzolns, benzlls, benzll monoketals, fluorenone, thloxanthone, polycycllc qulnones, acrldlnes and qulnazollnes, and also trlchloromethyl-s-trlazlnes, 2-halomethyl-5-vlnyl-1,3,4-oxadlazole derlvatlves, trlchloromethyl-substltuted halooxazoles or trlhalomethyl-contalnlng carbonylmethylene heterocycles as descrlbed ln DE-A-3,333,450.
Preferred photolnltlators are photoreduclble dyes, ln partlcular lf comblned with radlatlon-cleavable trlhalomethyl compounds and perhaps wlth acrldlne, phenazlne or qulnoxallne photolnltlator compounds as descrlbed ln earller German Patent Appllcatlons DE-A 37 10 281.8, and DE-A 37 10 282.6.
Sultable photoreduclble dyes are ln partlcular xanthene, benzoxanthene, benzothloxanthene, thlazlne, pyronlne, porphyrlne and acrldlne dyes. The amount of dye ls ln general between about 0.01 and 10, preferably between 0.05 and 4, % by welght, based on the nonvolltlle constltuents of 1~
1~37677 the layer.
To lncrease the light sensltlvlty, layers may have added to them compounds havlng photolytlcally cleavable trlhalomethyl groups whlch are known per se for use as free radlcal-formlng photlnltlators for photopolymerlzable mlx-tures. Proven colnltlators of thls type are ln partlcular compounds contalnlng chlorlne and bromlne, ln partlcular chlorlne, as halogens. The trlhalomethyl groups can be bonded dlrectly or vla a fully con~ugated chaln to an aromatlc carbocycllc or heterocycllc rlng. Preference ls glven to compounds havlng a trlazlne rlng ln the baslc skeleton whlch preferably carrles 2 trlhalomethyl groups, in partlcular to those descrlbed ln EP-A-137,452, DE-A-2,718,259 and DE-A-2,243,621. These compounds are strongly absorblng ln the near UV, for example around 350-400 nm. It ls also posslble to use colnltlators whlch themselves show llttle lf any absorptlon ln the spectral reglon of the copylng llght, such as trlhalomethyltrlazlnes whlch contaln substltuents havlng comparatlvely short mesomerlzatlon-capable 1 ~37677 electron systems or aliphatic substituents. It is also possible to use compounds having a different basic structure which absorb in the shorter-wave UV
region, for example phenyl trihalomethyl sulfones or phenyl trihalomethyl ketones, for example phenyl tribromomethyl sulfone.
These components are in general only used in an amount of 0.01 to 10, preferably 0.05 to 6, % by weight, based on the nonvolatile constituents of the layer.
The materials according to the invention preferably contain as a further initiator constituent an acridine, phenazine or quinoxaline compound. These compounds are known for use as photoinitiators and are described in DE-C-2,027,467 and -2,039,861. These compounds increase the sensitivity of the mixture in particular in the near ultraviolet region. The amount of this component is likewise within the range from about 0.01 to 10% by weight, preferably between 0.05 and 5% by weight.
If a further increase in the sensitivity in the visible region of the spectrum is desired, it can be brought about by adding a compound of the dibenzalacetone or coumarin type. This addition gives a more highly resolved copy and complete sensitization of the mixture to the visible region of the spectrum up to wavelengths of about 600 nm.
The amount of this compound is likewise within the range from about 0.01 to 10, preferably from 0.05 to 4, % by weight.
The total amount of polymerization initiator is in general about 0.05 to 20, preferably 0.1 to 10, % by weight.
The photopolymerizable layers may contain various substances as additives depending on the intended use and the desired properties. Examples are: inhibitors for preventing thermal polymerization of the monomers, hydrogen donors, dyes, colored and uncolored pigments, dye-forming components, indicators, plasticizers and chain transfer agents. These constituents are usefully selected in such a way that they absorb as little as possible of the actinic radiation important for the process of initiation.
For the purposes of the present invention, actinic radiation is any radiation whose energy is at least equal to that of visible light. It is possible to use in particular visible light and long-wave W radiation, but also short-wave UV
radiation, laser light, electron beams and X-rays.
The light sensitivity ranges from about 200 nm to 800 nm and hence covers a very wide range.
Suitable applications for the material according to the invention are: recording layers for the photomechanical production of printing plates for letterpress printing, planographic printing, intaglio printing and screen printing, relief copies, for example production of texts in braille, individual copies, tanned images, pigment images, etc. The mixtures can also be used for the photomechanical production of discharge resists, for example for fabricating name tags, copied circuits and chemical milling. The mixtures according to the invention are particularly important as recording layers for the production of planographic printing plates and for photoresist technology.
Suitable base materials for the recording material according to the invention are for example aluminum, steel, zinc and copper foils, plastics films, for example polyethylene terephthalate or cellulose acetate films, and screen printing materials, such as Perlon gauze. It is in many cases advantageous to subject the surface of the base material to a pretreatment (chemical or mechanical) with the aim of correctly adjusting the adhesion of the layer, improving the lithographic properties of the surface of the base material, or reducing the reflectivity of the base material in the actinic region of the copying layer (antihalation protection).
The light-sensitive materials are fabricated in a conventional manner. For instance, it is possible to take up the layer constituents in a solvent, to apply the solution or dispersion to the intended base material by casting, spraying, dipping, roller coating and the like, and then to dry.
Owing to the broad spectral sensitivity of the recording material according to the invention, it is possible to use any light source familiar to * tra~
those skilled in the art, for example fluorescent tubes, pulsed xenon lamps, metal-halide-doped high-pressure mercury vapor lamps and carbon arc lamps.
In addition, it is possible to irradiate the light-sensitive mixtures acccording to the invention inconventional protection and magnification equipment with the light from metal filament lamps and by contact exposure with customary incandescent lamps.
Irradiation can also be effected with the coherent light of a laser. Suitable for the purposes of the present invention are lasers of the right power, for example argon ion, krypton ion, dye, helium-cadmium and helium-neon lasers, which emit in particular in the range from 250 to 650 nm. The laser beam can be controlled by means of a preprogrammed line and/or scanning movement.
The materials are further processed in a conventional manner. To effect better crosslinking in the layer, it is possible to heat after exposure.
To develop them, they are treated with a suitable developer solution, for example with organic solvents, but preferably with a weakly alkaline aqueous solution, which serves to remove the unexposed areas of the layer, leaving behind the exposed areas of the copying layer on the base material. The developer solutions may contain a small amount, preferably less than 5% by weight, of water-miscible organic solvents. They may further contain wetting agents, dyes, salts and other additions. In the course of development, the entire cover layer is removed together with the unexposed areas of the photopolymerizable layer.
In what follows, the invention is described with reference to illustrative embodiments. Parts by weight bear the same relation to parts by volume as the g to the ccm. Percentages and mixing ratios are by weight, unless otherwise stated.
Example 1 (comparative example) The base material used for printing plates was electrochemically roughened and anodized aluminum which had an oxide layer of 3 g/m2 and had been pretreated with an aqueous solution of polyvinylphosphonic acid. The base material was coated with a solution of the following composition:
2.84 parts by weight of a 22.3% strength solution of a terpolymerof styrene, n-hexyl methacrylate and methacrylic acid (10:60:30) of acid number l90 in methyl ethyl ketone, 1.49 parts by weight of the reaction product of triethanolamine with 3 moles o f iso cy a na to eth y l methacrylate, 0.04 part by weight of eosin alcohol-soluble (C.I.
45 386), 0.03 part by weight of 2,4- bistrichloromethyl-6-(4-styrylphenyl)-s-triazine and 0.049 part by weight of 9-phenylacridine in 22 parts by weight of propylene glycol monoethyl ether.
Application was by spincoating in such a way that a dry weight of 2.8 to 3 g/m2 was obtained. The plate was then dried at 100C in a through-circulation cabinet for two minutes. The plate wasthen coated with a 15% strength aqueous solution of polyvinyl alcohol (12% of residual acetyl groups, K
value 4). Drying left a cover layer having a weight of 4 to 5 g/m2. The printing plate obtained was irradiated with a 5 kW metal halide lamp at a distance of 110 cm under a 13-step irradiation wedge with density increments of 0.15 onto which, as far as indicated, in addition a silver film of uniform blacking (density 1.57) and uniform absorption across the entire spectrum was mounted as a gray filter. To test the sensitivity of the printing plate in visible light, 3 mm thick edge filters from Schott having the edge transmissibilities indicated in the table were mounted on the irradiation wedge.
Following irradiation, the plate was heated at 100C
for one minute. It was then developed in a developer of the following composition:
120 parts by weight of sodium metasilicate .
9 H20, 2.13 parts by weight of strontium chloride, 1.2 parts by weight of non-ionic wetting agent (cocoa fatty alcohol polyoxyethylene ether containing about 8 ethyleneoxy units) and 0.12 part by weight of antifoam agent in 4,000 parts by weight of fully demineralized water.
The plate was inked with a greasy printing ink. The fully crosslinked wedge steps indicated below were obtained. The resolving power of the printing plate was determined with a test original, the PMS wedge (FOGRA), and read off on the copy.
Irradiation Gray Edge Wedge Resolution (seconds) filter filter steps (~m) 0 yes - ll 25 no 455 9 25 The printed plate was tested in respect of its shelflife. To this end, samples thereof were stored at 80C in a through-circulation cabinet for several hours. Following the times indicated in Table I they were irradiated and developed as described above. The following numbers of fully crosslinked wedge steps were obtained under the edge filter 455 nm:
Table I
Storage tes at 80C
HoursIrradiationFully crosslinked (seconds) wedge steps 0.5 10 8 3 10 2*
Background of the Invention The present invention relates to a photopolymerizable recording material comprising a base material, a photopolymerizable layer and a cover layer which is relatively impermeable to atmospheric oxygen. The material is suitable in particular for producing printing plates, in particular planographic printing plates.
Printing plates of the type mentioned are known for example from US-A-3,458,311. The cover layers described therein consist of water-soluble polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, gelatin or gum arabic. of these substances, polyvinyl alcohol is preferred, since its barrier effect in respect of oxygen is very high. However, it has been found that stored photopolymerizable printing plates having a cover layer made of polyvinyl alcohol lose some of their light sensitivity in the course of weeks and months.
It has also been observed that the protective effect 1`~37677 strongly decreases wlth lncreaslng temperature and increasing atmospheric humldlty. It has indeed been posslble to show that the oxygen permeabllity of polyvinyl alcohol strongly lncreases with temperature and atmospheric humldlty. This dlsadvantage ls partlcularly serlous in the case of highly light-sensitive photopolymerizable mlxtures containlng photooxldizable substances and speclal synergistlc lnltlator combinations. Such mlxtures are descrlbed in earller German Patent Appllcatlons DE-A 37 lO 279.6, DE-A 37 10 281.8, DE-A
37 10 282.6 and DE-A 37 43 454.3.
It ls also known to add to the photopolymerlzable layer ltself substances, for example tln salts or antloxldants, ln order to trap the oxygen dlffusing into the layer. Such additions are described, for example, in a paper by E.T. Denlsov et al. ln Chem. Rev. 1987, pp. 1313-1357.
Slnce such compounds usually have undeslrable slde effects and ln partlcular reduce the light sensltivity, they have not become established in practlce.
Summary of the Invention Accordingly, it is an ob~ect of the present invention to provide a photopolymerizable recording material having an oxygen-barrlng cover layer whose light sensitivity does not decrease at all or only X
to about the same extent as in existing materials of this type.
Another obiect of the present invention is to provide a photopolymerizable recording material whlch displays improved storage stability at elevated temperatures and atmospheric humidities.
According to one aspect of the present invention there is provided a photopolymerizable recording material which comprises a base material, a photopolymerizable layer comprising a polymerlc blnder, a free-radlcal polymerlzable compound havlng at least one photooxldizable group and at least one terminal ethylenically unsaturated group, and a polymerization initiator activatable by actinic radiation and a cover layer comprising (a) a water-soluble polymer which is substantially lmpermeable to oxygen and (b) a polymer which binds oxygen and is soluble in water at 20 C.
Other ob~ects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present inventlon, are glven by way of illustration and tB
1 ~3767~
not limitation. Many changes and modifications withln the scope of the present invention may be made without departing from the spirit thereof, and the invention includes all such modifications.
3a Detailed Description of Preferred Embodiments Suitable water-soluble polymers for binding atmospheric oxygen are in particular compounds having aliphatic amino groups which may be primary, secondary or tertiary. The polymers should preferably not contain any further functional groups in addition to the amino groups. Their molecular weights are in general within the range from about 300 to 1,000,000, preferably 1,000 to 200,000, in particular 10,000 to 200,000.
The amino-containing polymers used are preferably linear or branched polyalkyleneimines whose alkylene groups contain 2 to 8, in particular 2 to 4, carbon atoms. Of particular advantage are polyalkyleneimines, in particularpolyethyleneimines and polypropyleneimines, having molecular weights of about 18,000 to 80,000.
The polyalkyleneimines can be prepared by acid-catalyzed polymerization of alkyleneimines, for example ethyleneimine or propyleneimine, as described in US-A-2,223,930. Products having higher molecular weights can be obtained by reaction with bifunctional alkylating agents, for example 1,2-dichloroethane, and those having low molecular weights by addition of 1,2-ethylene~iamine, as described in US-A-3,519,687. Such polyalkyleneimines are commercial products. A preferred example contains about 30% of primary, 40% of secondary and 30% of tertiary amino groups.
- t 337677 -The polymer which is substantially impermeable to atmospheric oxygen can be one of the polymers indicated in US-A-3,458,311. Examples are in particular polyvinyl alcohol and partially hydrolyzed polyvinyl acetates, which may also contain vinyl ether and vinyl acetal units as long as the polymer remains water-soluble at 20C. It is also possible to use gelatin, gum arabic, copolymers of alkyl vinyl ethers and maleic anhydride, polyvinylpyrrolidones and water-soluble high molecular weight polymers of ethylene oxide (M =
100,000 to 3,000,000). Preference is given to those polymers whose oxygen permeability in a layer at 20C is less than 30, in particular less than 25, cm /m /d/bar.
The cover layer should transmit actinic light and in general has a thickness of about 0.5 to 10, preferably 1 to 4, ~m. The cover layer preferably has a basis weight of about 0.5 to 10 g/m2 It contains in general 3 to 60, preferably 5 to 40, %
by weight of oxygen-binding polymer, in particular polyalkyleneimine, based on the total solids content. The cover layer is applied on top of the photopolymerizable layer in a conventional manner from aqueous solution or from a mixture of water and organic solvent. The coating solution may contain, for better wetting properties, up to about 10% by weight, preferably up to 5% by weight, of a surface-active agent, based on its solids content. The usable surface-active substances include the anionic, cationic and nonionic surface-active agents, for example sodium alkyl sulfates and alkylsulfonates of 12 to 18 carbon atoms such as sodium dodecyl sulfate, N-cetylbetaines, C-cetylbetaines, alkylaminocarboxylates,alkylaminodicarboxylates and polyethylene glycols having an average molecular weight of up to 400.
The cover layers of the material according to the invention have a lower oxygen permeability than existing cover layers, which contain only an oxygen-barring polymer, for example polyvinyl alcohol, with or without a wetting agent. The protective effect is improved in particular at elevated temperatures and at elevated atmospheric humidity and lasts longer on prolonged storage than that of existing protective layers. Since the high specific protective effect permits the use of relatively thin cover layers (0.5 to 2.5 ~m), good optical resolution is obtained. This property is in need of improvement in particular in the case of offset printing plates based on photopolymerizable materials.
The photopolymerizable layers of the recording materials according to the invention comprise a polymeric binder, a free-radical-polymerizable compound having at least one, preferably at least two, terminal ethylenically unsaturated groups, and an actinically activable polymerization initiator or initiator combination.
~ ~37677 The photopolymerizable layer preferably has a basis weight of about 0.5 to 20 g/m2.
Polymerizable compounds suitable for the purposes of the invention are known and described for example in US-A-2,760,863 and -3,060,023.
Preferred examples are acrylic and methacrylic esters of dihydric or polyhydric alcohols, such as ethylene glycol diacrylate, polyethylene glycol dimethacrylate, acrylates and methacrylates of trimethylolethane, trimethylolpro-pane, pentaerythritol and dipentaerythritol and of polyhydric alicyclic alcohols or N-substituted acrylamides and methacrylamides. It is also advantageous to use reaction products of monoisocyanates or diisocyanates with partial esters of polyhydric alcohols. Such monomers are described in DE-A-2,064,079, -2,361,041 and -2,822,190.
Particular preference is given to polymeri-zable compounds which contain at least one photooxidizable group alone or together with one or more urethane groups in the molecule.
Suitable photooxidizable groups are in particular amino groups, urea groups, thio groups, which may also be the constituents of heterocyclic rings, and enol groups. Examples of such groups are triethanolamino, triphenylamino, thiourea, imidazole, oxazole, thiazole, acetylacetonyl, N-phenylglycine and ascorbic acid groups. Poly-merizable compounds having primary, secondary and in particular tertiary amino groups are preferred.
Examples of compounds having photooxidizable groups are acrylic and alkacrylic esters of the formula I
R( )Q[t-CH2-CO) -CONH(X1-NHCOO)b-X2(-OOC-C=CH2)c]n (I) where /D \
Q is -N-, -N-E-N-, -N~ / N- or -S-R is an alkyl, hydroxyalkyl or aryl group, R1 and R2 are each a hydrogen atom, an alkyl group or an alkoxyalkyl group, R3 is a hydrogen atom or a methyl or ethyl group, X1 is a saturated hydrocarbon group of 2 to 12 carbon atoms, X2 is a (c+l)-valent saturated hydrocarbon group in which up to 5 methylene groups may have been replaced by oxygen atoms, D1 and D2 are each a saturated hydrocarbon group of 1 to 5 carbon atoms, E is a saturated hydrocarbon group of 2 to 12 carbon atoms, a cycloaliphatic group of 5 to 7 ring members which may contain up to two N, O or S atoms as ring members, an arylene group of 6 to 12 -carbon atoms or a heterocycllc aromatlc group of 5 or 6 rlng members, a ls 0 or an lnteger from 1 to 4, b ls 0 or 1, c ls an lnteger from 1 to 3, m ls 2, 3 or 4, dependlng on the valence of Q, and n ls an lnteger from 1 to m, wlth all the symbols of ldentlcal deflnltlon belng ldentlcal to or dlfferent from one another.
The compounds of thls formula, and the preparatlon and use thereof are descrlbed ln detall ln earller German Patent Appllcatlon DE-A 37 10 279.6.
If ln the compound of the general formula I more than one radlcal R or more than one radlcal of the type lndlcated ln square brackets ls bonded to the central group Q, these radlcals can be dlfferent from one another.
Compounds ln whlch all the substltuents of Q are polymerlzable radlcals, l.e. where m ls n, are ln general preferred.
In general, not more than one radlcal a ls 0;
preferably a ls 1.
An alkyl or hydroxyalkyl group R generally has 2 to 8, preferably 2 to 4, carbon atoms. An aryl radlcal R can ln general be monocycllc or blcycllc, preferably monocycllc, and may be substltuted by X, - ~ 337677 alkyl or alkoxy groups of up to 5 carbon atoms or halogen atoms.
Alkyl and alkoxyalkyl groups Rl and R2 can contain 1 to 5 carbon atoms.
R3 is preferably a hydrogen atom or a methyl group, in particular a methyl group.
Xl is preferably a straight-chain or branched aliphatic or cycloaliphatic radical of preferably 4 to 10 carbon atoms.
X2 preferably has 2 to 15 carbon atoms, of which up to 5 may have been replaced by oxygen atoms. In the case of pure carbon chains, generally those having 2 to 12, preferably 2 to 6, carbon atoms are used. x2 can also be a cycloaliphatic group of 5 to 10 carbon atoms, in particular a cyclohexylene group.
D1 and D2 can be identical or different, and together with the two nitrogen atoms form a saturated heterocyclic ring of 5 to 10, preferably 6, ring members.
An alkylene group E preferably has 2 to 6 carbon atoms, and an arylene group E is preferably a phenylene group. Preferred cycloaliphatic groups are cyclohexylene groups and preferred aromatic heterocycles are those having N or S as heteroatoms and 5 or 6 ring members.
The value of c is preferably 1.
The polymerizable compounds of the formula I
which contain two urethane groups in every radical t337677 (b = l) are prepared by reacting acrylic or alkylacrylic esters which contain free hydroxyl groups in a conventional manner with the same molar amount of diisocyanates and reacting the excess isocyanate group with hydroxyalkylamines, N,N-bishydroxyalkylpiperazines or N,N,N',N'-tetrahydroxyalkylalkylenediamines, in each of which individual hydroxyalkyl groups may have been replaced by alkyl or aryl groups R. If a is 0, the result is a urea grouping.
Examples of the hydroxyalkylamine starting materials are triethanolamine, N-alkyl-N,N-di(hydroxyalkyl)amines, diethanolamine, tris(2-hydroxypropyl)amine and tris(2-hydroxybutyl)amine.
Examples of diisocyanate starting materials are hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate and 1,1,3-trimethyl-3-isocyanatomethyl-5-isocyanatocyclohexane.
The hydroxyl-containing esters used are in particular hydroxyethyl methacrylate and hydroxypropyl methacrylate (n or iso) and the corresponding acrylates.
The polymerizable compounds of the formula I
where b is 0 are prepared by reacting the above-described hydroxyalkylamino compounds with isocyanato-containing acrylic or alkylacrylic esters. An isocyanato-containing ester used in particular is isocyanatoethyl (meth)acrylate.
-Further sultable compounds havlng photooxldlzable groups are compounds of the formula ~(~CH2lc)a(-cH2 ~ CH - O) -H]
R CH2 (II) OOC-C=CH2 where Q, R, Rl, R2, R3, a, m and n are each as deflned above and Q can addltlonally be a group -N-E'-N-where E' ls a group of the formula III
-CH2-CHOH-CH2- [ - ~ -C- ~ -o-cH2-cHoH-cH2 ] c The compounds of the formula II are prepared slmllar-ly to those of the formula I, except that the hydroxyalkyl (alk)acrylates are replaced by the correspondlng glycldyl (alk)acrylates.
The compounds of thls formula and the preparatlon and use thereof are descrlbed ln detall ln earller Patent Appllca-tlon DE-A 37 38 864.9.
Further sultable compounds havlng photooxldlzable groups are acryllc and alkacryllc esters of the formula IV
Q~[(-xl -CH2O)a-CONH(-Xl-NHCOO)b-X2-OOC-C=CH21n, `X
~ 337677 -where Dl Q' is Q' -N-, -N N- or ~N-, X1 is ClH2, or ClH2,lO-CONH(-X1 -NHCOO)b-X2 -ooC-C=CH2, D3 is a saturated hydrocarbon group of 4 to 8 carbon atoms which together with the nitrogen atom forms a 5- or 6-membered ring, Z is a hydrogen atom or a radical of the formula R3 CkH2k-0-COl~H ( -Xl -NHCOO) b-X2 -OOC-CH2, i and k are integers from 1 to 12, n' is 1, 2 or 3 depending on the valence of Q' and R3, X1, X2, D1, D2' a and b are each as defined at the formula I, with all the symbols of identical definition being identical or different from one another and in at least one substituent on the group Q a being 0.
Of the compounds of the formula IV, those which contain at least one urethane group as well as a urea group are preferred. Urea groups are for the purposes of the present invention groups of the formula r ~N - CO - N
where the valences on the nltrogen are saturated by substltuted or unsubstltuted hydrocarbon radlcals. However, lt ls also posslble for one valence on one nltrogen atom to be bonded to a further carbonylamlde group (CONH), produclng a bluret structure.
The symbol a ln the formula IV ls preferably 0 or 1;
1 ls preferably a number from 2 to 10.
The polymerlzable compounds of the formula IV are prepared ln the same way as compounds of the formula I.
The compounds of the formula IV and the preparatlon thereof are descrlbed ln detall ln Canadlan Patent Appllcation no. 606,332.
The proportlon of photopolymerlzable compound ln the photopolymerlzable layer ls ln general about 10 to 80, prefer-ably 20 to 60, % by welght, based on the nonvolatlle constltu-ents.
Examples of usable blnders are chlorlnated polyethylene, chlorlnated polypropylene, poly[alkyl tmeth)-acrylates] where the alkyl group ls for example methyl, ethyl, n-butyl, l-butyl, n-hexyl or 2-ethylhexyl, copolymers of sald alkyl(meth)acrylates wlth at least one monomer, such as acrylonltrlle, vlnyl chlorlde, vlnylldene chlorlde, styrene or butadlene, polyvlnyl chlorlde, vlnyl chlorlde/acrylonltrlle copolymers, polyvlnylldene chlorlde, vlnylldene chlor-lde/acrylonltrlle copolymers, polyvlnyl acetate, polyvlnyl alcohol, polyacrylonltrlle, acrylonltrlle/styrene copolymers, 1~' acrylonitrile/butadiene/styrene/copolymers, polystyrene, polymethylstyrene, polyamides (for example nylon-6), polyurethanes, methylcellulose, ethylcellulose, acetylcellulose, polyvinyl/formal and polyvinyl butyral.
Of particular suitability are binders which are insoluble in water, soluble in organic solvents and soluble or at least swellable in aqueous alkaline solutions.
A special mention should be made of carboxyl-containing binders, for example copolymers of (meth)acrylic acid and/or unsaturated homologs thereof, such as crotonic acid, copolymers of maleic anhydride or monoesters thereof, reaction products of hydroxyl-containing polymers with dicarboxylic anhydrides, and mixtures thereof.
It is also possible to use reaction products of polymers which carry acidic H groups which have been wholly or partly reacted with activated isocyanates, for example reaction products of hydroxyl-containing polymers with aliphatic or aromatic sulfonyl isocyanates or phosphinoyl isocyanates.
Also suitable are: hydroxyl-containing polymers, for example copolymers of hydroxyalkyl (meth)acrylates, copolymers of allyl alcohol, copolymers of vinyl alcohol, polyurethanes or polyesters, and also epoxy resins, provided they carry a sufficient number of free OH groups, or have been modified in such a way that they are soluble in aqueous alkaline solutions, or those polymers which carry aromatically bonded hydroxyl groups, for example condensation products of condensable carbonyl compounds, in particular formaldehyde, acetaldehyde or acetone, with phenols or copolymers of hydroxystyrenes. Finally, it is also possible to use copolymers of (meth)acrylamide with alkyl (meth)acrylates.
The above-described polymers are suitable in particular when they have a molecular weight between about 500 and 200,000 or higher, preferably 1,000 to 100,000, and either acid numbers between 10 and 250, preferably 20 to 200 or hydroxyl numbers between 50 and 750, preferably 100 to 500.
Preferred alkali-soluble binders are:
copolymers of (meth)acrylic acid with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of crotonic acid with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of vinylacetic acid with alkyl (meth)acrylates, copolymers of maleic anhydride with substituted or unsubstituted styrenes, unsaturated hydrocarbons, unsaturated ethers or esters, esterification products of copolymers of maleic anhydride, esterification products of hydroxyl-containing polymers with anhydrides of di- or polycarboxylic acids, copolymers of hydroxyalkyl (meth)acrylates with alkyl (meth)acrylates, (meth)acrylonitrile or the like, copolymers of allyl alcohol with substituted or unsubstituted styrenes, copolymers of vlnyl alcohol with alkyl (meth)acrylates or other polymerlzable unsaturated compounds, polyurethanes, provlded they have a sufficlent number of free OH groups, epoxy reslns, polyesters, partlally hydrolyzed vlnyl acetate copolymers, polyvlnyl acetals havlng free OH groups, copolymers of hydroxystyrenes wlth alkyl (meth)-acrylates or the llke, phenol-formaldehyde reslns, for example novolaks.
The amount of blnder ln the llght-sensltlve layer ls ln general about 20 to 90, preferably 40 to 80, % by welght.
The photolnltlators used can be a large number of substances. Examples are those whlch are derlved from the baslc skeleton of benzophenones, acetophenones, benzolns, benzlls, benzll monoketals, fluorenone, thloxanthone, polycycllc qulnones, acrldlnes and qulnazollnes, and also trlchloromethyl-s-trlazlnes, 2-halomethyl-5-vlnyl-1,3,4-oxadlazole derlvatlves, trlchloromethyl-substltuted halooxazoles or trlhalomethyl-contalnlng carbonylmethylene heterocycles as descrlbed ln DE-A-3,333,450.
Preferred photolnltlators are photoreduclble dyes, ln partlcular lf comblned with radlatlon-cleavable trlhalomethyl compounds and perhaps wlth acrldlne, phenazlne or qulnoxallne photolnltlator compounds as descrlbed ln earller German Patent Appllcatlons DE-A 37 10 281.8, and DE-A 37 10 282.6.
Sultable photoreduclble dyes are ln partlcular xanthene, benzoxanthene, benzothloxanthene, thlazlne, pyronlne, porphyrlne and acrldlne dyes. The amount of dye ls ln general between about 0.01 and 10, preferably between 0.05 and 4, % by welght, based on the nonvolltlle constltuents of 1~
1~37677 the layer.
To lncrease the light sensltlvlty, layers may have added to them compounds havlng photolytlcally cleavable trlhalomethyl groups whlch are known per se for use as free radlcal-formlng photlnltlators for photopolymerlzable mlx-tures. Proven colnltlators of thls type are ln partlcular compounds contalnlng chlorlne and bromlne, ln partlcular chlorlne, as halogens. The trlhalomethyl groups can be bonded dlrectly or vla a fully con~ugated chaln to an aromatlc carbocycllc or heterocycllc rlng. Preference ls glven to compounds havlng a trlazlne rlng ln the baslc skeleton whlch preferably carrles 2 trlhalomethyl groups, in partlcular to those descrlbed ln EP-A-137,452, DE-A-2,718,259 and DE-A-2,243,621. These compounds are strongly absorblng ln the near UV, for example around 350-400 nm. It ls also posslble to use colnltlators whlch themselves show llttle lf any absorptlon ln the spectral reglon of the copylng llght, such as trlhalomethyltrlazlnes whlch contaln substltuents havlng comparatlvely short mesomerlzatlon-capable 1 ~37677 electron systems or aliphatic substituents. It is also possible to use compounds having a different basic structure which absorb in the shorter-wave UV
region, for example phenyl trihalomethyl sulfones or phenyl trihalomethyl ketones, for example phenyl tribromomethyl sulfone.
These components are in general only used in an amount of 0.01 to 10, preferably 0.05 to 6, % by weight, based on the nonvolatile constituents of the layer.
The materials according to the invention preferably contain as a further initiator constituent an acridine, phenazine or quinoxaline compound. These compounds are known for use as photoinitiators and are described in DE-C-2,027,467 and -2,039,861. These compounds increase the sensitivity of the mixture in particular in the near ultraviolet region. The amount of this component is likewise within the range from about 0.01 to 10% by weight, preferably between 0.05 and 5% by weight.
If a further increase in the sensitivity in the visible region of the spectrum is desired, it can be brought about by adding a compound of the dibenzalacetone or coumarin type. This addition gives a more highly resolved copy and complete sensitization of the mixture to the visible region of the spectrum up to wavelengths of about 600 nm.
The amount of this compound is likewise within the range from about 0.01 to 10, preferably from 0.05 to 4, % by weight.
The total amount of polymerization initiator is in general about 0.05 to 20, preferably 0.1 to 10, % by weight.
The photopolymerizable layers may contain various substances as additives depending on the intended use and the desired properties. Examples are: inhibitors for preventing thermal polymerization of the monomers, hydrogen donors, dyes, colored and uncolored pigments, dye-forming components, indicators, plasticizers and chain transfer agents. These constituents are usefully selected in such a way that they absorb as little as possible of the actinic radiation important for the process of initiation.
For the purposes of the present invention, actinic radiation is any radiation whose energy is at least equal to that of visible light. It is possible to use in particular visible light and long-wave W radiation, but also short-wave UV
radiation, laser light, electron beams and X-rays.
The light sensitivity ranges from about 200 nm to 800 nm and hence covers a very wide range.
Suitable applications for the material according to the invention are: recording layers for the photomechanical production of printing plates for letterpress printing, planographic printing, intaglio printing and screen printing, relief copies, for example production of texts in braille, individual copies, tanned images, pigment images, etc. The mixtures can also be used for the photomechanical production of discharge resists, for example for fabricating name tags, copied circuits and chemical milling. The mixtures according to the invention are particularly important as recording layers for the production of planographic printing plates and for photoresist technology.
Suitable base materials for the recording material according to the invention are for example aluminum, steel, zinc and copper foils, plastics films, for example polyethylene terephthalate or cellulose acetate films, and screen printing materials, such as Perlon gauze. It is in many cases advantageous to subject the surface of the base material to a pretreatment (chemical or mechanical) with the aim of correctly adjusting the adhesion of the layer, improving the lithographic properties of the surface of the base material, or reducing the reflectivity of the base material in the actinic region of the copying layer (antihalation protection).
The light-sensitive materials are fabricated in a conventional manner. For instance, it is possible to take up the layer constituents in a solvent, to apply the solution or dispersion to the intended base material by casting, spraying, dipping, roller coating and the like, and then to dry.
Owing to the broad spectral sensitivity of the recording material according to the invention, it is possible to use any light source familiar to * tra~
those skilled in the art, for example fluorescent tubes, pulsed xenon lamps, metal-halide-doped high-pressure mercury vapor lamps and carbon arc lamps.
In addition, it is possible to irradiate the light-sensitive mixtures acccording to the invention inconventional protection and magnification equipment with the light from metal filament lamps and by contact exposure with customary incandescent lamps.
Irradiation can also be effected with the coherent light of a laser. Suitable for the purposes of the present invention are lasers of the right power, for example argon ion, krypton ion, dye, helium-cadmium and helium-neon lasers, which emit in particular in the range from 250 to 650 nm. The laser beam can be controlled by means of a preprogrammed line and/or scanning movement.
The materials are further processed in a conventional manner. To effect better crosslinking in the layer, it is possible to heat after exposure.
To develop them, they are treated with a suitable developer solution, for example with organic solvents, but preferably with a weakly alkaline aqueous solution, which serves to remove the unexposed areas of the layer, leaving behind the exposed areas of the copying layer on the base material. The developer solutions may contain a small amount, preferably less than 5% by weight, of water-miscible organic solvents. They may further contain wetting agents, dyes, salts and other additions. In the course of development, the entire cover layer is removed together with the unexposed areas of the photopolymerizable layer.
In what follows, the invention is described with reference to illustrative embodiments. Parts by weight bear the same relation to parts by volume as the g to the ccm. Percentages and mixing ratios are by weight, unless otherwise stated.
Example 1 (comparative example) The base material used for printing plates was electrochemically roughened and anodized aluminum which had an oxide layer of 3 g/m2 and had been pretreated with an aqueous solution of polyvinylphosphonic acid. The base material was coated with a solution of the following composition:
2.84 parts by weight of a 22.3% strength solution of a terpolymerof styrene, n-hexyl methacrylate and methacrylic acid (10:60:30) of acid number l90 in methyl ethyl ketone, 1.49 parts by weight of the reaction product of triethanolamine with 3 moles o f iso cy a na to eth y l methacrylate, 0.04 part by weight of eosin alcohol-soluble (C.I.
45 386), 0.03 part by weight of 2,4- bistrichloromethyl-6-(4-styrylphenyl)-s-triazine and 0.049 part by weight of 9-phenylacridine in 22 parts by weight of propylene glycol monoethyl ether.
Application was by spincoating in such a way that a dry weight of 2.8 to 3 g/m2 was obtained. The plate was then dried at 100C in a through-circulation cabinet for two minutes. The plate wasthen coated with a 15% strength aqueous solution of polyvinyl alcohol (12% of residual acetyl groups, K
value 4). Drying left a cover layer having a weight of 4 to 5 g/m2. The printing plate obtained was irradiated with a 5 kW metal halide lamp at a distance of 110 cm under a 13-step irradiation wedge with density increments of 0.15 onto which, as far as indicated, in addition a silver film of uniform blacking (density 1.57) and uniform absorption across the entire spectrum was mounted as a gray filter. To test the sensitivity of the printing plate in visible light, 3 mm thick edge filters from Schott having the edge transmissibilities indicated in the table were mounted on the irradiation wedge.
Following irradiation, the plate was heated at 100C
for one minute. It was then developed in a developer of the following composition:
120 parts by weight of sodium metasilicate .
9 H20, 2.13 parts by weight of strontium chloride, 1.2 parts by weight of non-ionic wetting agent (cocoa fatty alcohol polyoxyethylene ether containing about 8 ethyleneoxy units) and 0.12 part by weight of antifoam agent in 4,000 parts by weight of fully demineralized water.
The plate was inked with a greasy printing ink. The fully crosslinked wedge steps indicated below were obtained. The resolving power of the printing plate was determined with a test original, the PMS wedge (FOGRA), and read off on the copy.
Irradiation Gray Edge Wedge Resolution (seconds) filter filter steps (~m) 0 yes - ll 25 no 455 9 25 The printed plate was tested in respect of its shelflife. To this end, samples thereof were stored at 80C in a through-circulation cabinet for several hours. Following the times indicated in Table I they were irradiated and developed as described above. The following numbers of fully crosslinked wedge steps were obtained under the edge filter 455 nm:
Table I
Storage tes at 80C
HoursIrradiationFully crosslinked (seconds) wedge steps 0.5 10 8 3 10 2*
- no crosslinking/ *plate not tone-free Examples 2 to 8 The base material and the photopolymer layer of Example 1 were covered with-oxygen-inhibiting layers in a dry layer weight of about 2 g/m2 from the following solutions:
100 parts by weight of a 7% strength aqueous solu-tion of polyvinyl alcohol (12%
of residual acetyl groups, K
value 4, i.e. viscosity of a 4% strength aqueous solution at 20C: 4.0 mPa.s) 0.4 part by weight of polymer as per Table II
Table II
Example Polymer Viscosity by Molecular Tradename/
No. Brookfield weight manufacturer (mPa.s) 2 PEI17,000-28,000 Polymin P (BASF) 3 "500- 1,000 Polymin SK "
4 "450- 1,500 Polymin SR "
" 400- 900 Polymin RN "
6 " 60,000Corcat P600 (Virginia Chemicals) 7 " 1,800Corcat P18* "
8 " 1,200Corcat P12* "
PEI = polyethyleneimine * = Chemical Abstracts registry number CAS 9002-98-6 The printing plates were processed as described in Example 1. The fully crosslinked wedge steps indicated in the table below were obtained under the edge filter 455 nm in the course of an irradiation time of 10 seconds and following storage in a through-circulation cabinet at 80C.
Table III
Storage test at 80C
Example No. Storage time (hours) 0 0.5 1 2 3 4 Example 9 The base material and the photopolymer layer of Example 1 were covered with an oxygen-inhibiting layer in a dry weight of about 2 g/m2 from the following solution:
100 parts by weight of a 7% strength aqueous solu-tion of polyvinyl alcohol (12%
of residual acetyl groups, K
value 8) 0.4 part by weight of polyethyleneimine (Polymin P) This printing plate was subjected to a storage test at 100C. Following 10 seconds' irradiation under the edge filter 455 nm and development as described in Example 1, the fully crosslinked wedge steps indicated in the following table were obtained:
Table IV
Storage test at 100C
10 Hours Wedge steps Examples 10 and 11 The base material indicated in Example 1 was spincoated under the same conditions as indicated there with a solution of the following composition in such a way as to produce a layer weight of 2 g/m2:
4.0 parts by weight of a 34.8% strength solution of a copolymer of methyl methacrylate and methacrylic acid having an acid number of 110 and an average molecular weight of 35,000 in 2-butanone, 2.8 parts by weight of the reaction product of triethanolamine with 3 moles of glycidyl methacrylate, 0.04 part by weight of eosin (alcohol-soluble) C.I. 45386, 0.03 part by weight of 2, 4-bistrichloromethyl-6-(4-styrlphenyl)-s-triazine and 0.049 part by weight of 9-phenylacridine in 22.0 parts by weight ofpropylene glycol monomethyl ether.
This plate was covered on the one hand with the cover layer of Example 9 in a layer weight of 2 g/m2 (Example 10) and for comparison with the cover layer of Example 1 in the same thickness (Example 11). The two plates were subjected to a long-term storage test at 53~C. The results given in Table V
were obtained. The printing plates were irradiated for 10 seconds under the edge filter 455 nm and developed as described in Example 1.
~ 337677 Table V
Storage test at 5 3 C
Storage time Fully crosslinked wedge steps 5 days Example 10 Example 11 (V) 3 6 2*
15 - no crosslinking/ *plate not tone-free It is evident that the printing plate having polyethyleneimine in the cover layer has a significantly longer shelf life. The inhibiting ef fect of the cover layer on oxygen is much improved 20 even over prolonged periods.
Examples 12 to 14 The base material and the photopolymer layer of Example 1 were covered with the oxygen-inhibiting cover layers listed in Table VI in a dry layer 25 weight of about 2 g/m2 from the following solution:
100 parts by weight of polyvinyl alcohol solutions as in Example 2, x parts by weight of p o 1 y e t h y 1 e n e i m i n e 3 ( Polymin P) as in Table VI.
Table VI
Example No. Parts by weight of Polymin P
1~ 0.8 13 1.2 14 1.6 These printing plates were subjected to a storage test at 80C. Following 10 seconds' irradiation under the edge filter 455 nm and development as indicated in Example 1, the fully crosslinked wedge steps indicated in Table VII were obtained.
Table VII
Storage test at 80C
Example No. Storage time (hours) 0 0.5 1 2 3 4
100 parts by weight of a 7% strength aqueous solu-tion of polyvinyl alcohol (12%
of residual acetyl groups, K
value 4, i.e. viscosity of a 4% strength aqueous solution at 20C: 4.0 mPa.s) 0.4 part by weight of polymer as per Table II
Table II
Example Polymer Viscosity by Molecular Tradename/
No. Brookfield weight manufacturer (mPa.s) 2 PEI17,000-28,000 Polymin P (BASF) 3 "500- 1,000 Polymin SK "
4 "450- 1,500 Polymin SR "
" 400- 900 Polymin RN "
6 " 60,000Corcat P600 (Virginia Chemicals) 7 " 1,800Corcat P18* "
8 " 1,200Corcat P12* "
PEI = polyethyleneimine * = Chemical Abstracts registry number CAS 9002-98-6 The printing plates were processed as described in Example 1. The fully crosslinked wedge steps indicated in the table below were obtained under the edge filter 455 nm in the course of an irradiation time of 10 seconds and following storage in a through-circulation cabinet at 80C.
Table III
Storage test at 80C
Example No. Storage time (hours) 0 0.5 1 2 3 4 Example 9 The base material and the photopolymer layer of Example 1 were covered with an oxygen-inhibiting layer in a dry weight of about 2 g/m2 from the following solution:
100 parts by weight of a 7% strength aqueous solu-tion of polyvinyl alcohol (12%
of residual acetyl groups, K
value 8) 0.4 part by weight of polyethyleneimine (Polymin P) This printing plate was subjected to a storage test at 100C. Following 10 seconds' irradiation under the edge filter 455 nm and development as described in Example 1, the fully crosslinked wedge steps indicated in the following table were obtained:
Table IV
Storage test at 100C
10 Hours Wedge steps Examples 10 and 11 The base material indicated in Example 1 was spincoated under the same conditions as indicated there with a solution of the following composition in such a way as to produce a layer weight of 2 g/m2:
4.0 parts by weight of a 34.8% strength solution of a copolymer of methyl methacrylate and methacrylic acid having an acid number of 110 and an average molecular weight of 35,000 in 2-butanone, 2.8 parts by weight of the reaction product of triethanolamine with 3 moles of glycidyl methacrylate, 0.04 part by weight of eosin (alcohol-soluble) C.I. 45386, 0.03 part by weight of 2, 4-bistrichloromethyl-6-(4-styrlphenyl)-s-triazine and 0.049 part by weight of 9-phenylacridine in 22.0 parts by weight ofpropylene glycol monomethyl ether.
This plate was covered on the one hand with the cover layer of Example 9 in a layer weight of 2 g/m2 (Example 10) and for comparison with the cover layer of Example 1 in the same thickness (Example 11). The two plates were subjected to a long-term storage test at 53~C. The results given in Table V
were obtained. The printing plates were irradiated for 10 seconds under the edge filter 455 nm and developed as described in Example 1.
~ 337677 Table V
Storage test at 5 3 C
Storage time Fully crosslinked wedge steps 5 days Example 10 Example 11 (V) 3 6 2*
15 - no crosslinking/ *plate not tone-free It is evident that the printing plate having polyethyleneimine in the cover layer has a significantly longer shelf life. The inhibiting ef fect of the cover layer on oxygen is much improved 20 even over prolonged periods.
Examples 12 to 14 The base material and the photopolymer layer of Example 1 were covered with the oxygen-inhibiting cover layers listed in Table VI in a dry layer 25 weight of about 2 g/m2 from the following solution:
100 parts by weight of polyvinyl alcohol solutions as in Example 2, x parts by weight of p o 1 y e t h y 1 e n e i m i n e 3 ( Polymin P) as in Table VI.
Table VI
Example No. Parts by weight of Polymin P
1~ 0.8 13 1.2 14 1.6 These printing plates were subjected to a storage test at 80C. Following 10 seconds' irradiation under the edge filter 455 nm and development as indicated in Example 1, the fully crosslinked wedge steps indicated in Table VII were obtained.
Table VII
Storage test at 80C
Example No. Storage time (hours) 0 0.5 1 2 3 4
Claims (15)
1. A photopolymerizable recording material which comprises a base material, a photopolymerizable layer comprising a polymeric binder, a free-radical polymerizable compound having at least one photooxidizable group and at least one terminal ethylenically unsaturated group, and a polymerization initiator activatable by actinic radiation and a cover layer comprising (a) a water-soluble polymer which is substantially impermeable to oxygen and (b) a polymer which binds oxygen and is soluble in water at 20°C.
2. The recording material as claimed in claim 1, wherein the cover layer has an oxygen permeability of less than 30 cm3/M2/d/bar at 20°C.
3. The recording material as claimed in claim 1, wherein the polymer which binds oxygen comprises a plurality of aliphatic amino groups.
4. The recording material as claimed in claim 3, wherein the polymer comprising aliphatic amino groups is a polyalkyleneimine.
5. The recording material as claimed in claim 4, wherein the polyalkyleneimine is a polyethylene or a polypropyleneimine.
6. The recording material as claimed in claim 1, wherein the cover layer has a basis weight of about 0.5 to 10 g/m2.
7. The recording material as claimed in claim 1, wherein the polymer which binds oxygen has a molecular weight of about 300 to 1,000,000.
8. The recording material as claimed in claim 1, wherein the polymer which is substantially impermeable to oxygen is a polyvinyl alcohol or a partially hydrolyzed polyvinyl acetate.
9. The recording material as claimed in claim 1, wherein the cover layer comprises about 40 to 97% by weight of polymer (a) and about 3 to 60% by weight of polymer (b).
10. The recording material as claimed in claim 1, wherein the cover layer further comprises a surface-active agent.
11. The recording material claimed as in claim 1, wherein the polymerizable compound further comprises at least one urethane group.
12. The recording material as claimed in claim 1, wherein the polymerization initiator comprises a photoreducible dye.
13. The recording material as claimed in claim 1, wherein the binder is water-insoluble and soluble in aqueous alkaline solutions.
14. The recording material as claimed in claim 1, wherein the photopolymerizable layer has a weight of about 0.5 to 20 g/m2.
15. The recording material as claimed in claim 1, wherein the base material has a hydrophilic surface suitable for planographic printing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3825836A DE3825836A1 (en) | 1988-07-29 | 1988-07-29 | PHOTOPOLYMERIZABLE RECORDING MATERIAL |
| DEP3825836.6 | 1988-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337677C true CA1337677C (en) | 1995-12-05 |
Family
ID=6359860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000606446A Expired - Fee Related CA1337677C (en) | 1988-07-29 | 1989-07-24 | Photopolymerizable recording material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0352630B1 (en) |
| JP (1) | JP2736124B2 (en) |
| KR (1) | KR0135076B1 (en) |
| CA (1) | CA1337677C (en) |
| DE (2) | DE3825836A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0971765A (en) * | 1995-06-29 | 1997-03-18 | Nippon Zeon Co Ltd | Antitack composition |
| DE10022786B4 (en) | 1999-05-12 | 2008-04-10 | Kodak Graphic Communications Gmbh | On the printing machine developable printing plate |
| US7439537B2 (en) | 2004-07-30 | 2008-10-21 | Agfa Graphics, N.V. | Divinylfluorenes |
| JP4151673B2 (en) | 2005-05-31 | 2008-09-17 | ブラザー工業株式会社 | Sheet discharging apparatus and image forming apparatus. |
| ATE445861T1 (en) | 2005-08-26 | 2009-10-15 | Agfa Graphics Nv | PHOTOPOLYMER PRINTING PLATE PRECURSOR |
| US20070117040A1 (en) * | 2005-11-21 | 2007-05-24 | International Business Machines Corporation | Water castable-water strippable top coats for 193 nm immersion lithography |
| JP4945432B2 (en) | 2006-12-28 | 2012-06-06 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP2009080445A (en) | 2007-01-17 | 2009-04-16 | Fujifilm Corp | Method for preparing lithographic printing plate |
| JP4914864B2 (en) | 2008-03-31 | 2012-04-11 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| BRPI0918828A2 (en) | 2008-09-24 | 2018-04-24 | Fujifilm Corporation | A manufacturing method of a lithographic printing plate |
| EP2194429A1 (en) | 2008-12-02 | 2010-06-09 | Eastman Kodak Company | Gumming compositions with nano-particles for improving scratch sensitivity in image and non-image areas of lithographic printing plates |
| EP2196851A1 (en) | 2008-12-12 | 2010-06-16 | Eastman Kodak Company | Negative working lithographic printing plate precursors comprising a reactive binder containing aliphatic bi- or polycyclic moieties |
| US8034538B2 (en) | 2009-02-13 | 2011-10-11 | Eastman Kodak Company | Negative-working imageable elements |
| US20100215919A1 (en) | 2009-02-20 | 2010-08-26 | Ting Tao | On-press developable imageable elements |
| US8247163B2 (en) | 2009-06-12 | 2012-08-21 | Eastman Kodak Company | Preparing lithographic printing plates with enhanced contrast |
| US8257907B2 (en) | 2009-06-12 | 2012-09-04 | Eastman Kodak Company | Negative-working imageable elements |
| EP2284005B1 (en) | 2009-08-10 | 2012-05-02 | Eastman Kodak Company | Lithographic printing plate precursors with beta-hydroxy alkylamide crosslinkers |
| EP2293144B1 (en) | 2009-09-04 | 2012-11-07 | Eastman Kodak Company | Method of drying lithographic printing plates after single-step-processing |
| BR112012024532A2 (en) * | 2010-03-26 | 2016-09-06 | Fujifilm Corp | lithographic printing plate precursor and method of production |
| US20130137040A1 (en) * | 2010-03-26 | 2013-05-30 | Fujifilm Corporation | Lithographic printing plate precursor and method of producing thereof |
| EP2735903B1 (en) | 2012-11-22 | 2019-02-27 | Eastman Kodak Company | Negative working lithographic printing plate precursors comprising a hyperbranched binder material |
| EP2778782B1 (en) | 2013-03-13 | 2015-12-30 | Kodak Graphic Communications GmbH | Negative working radiation-sensitive elements |
| JP6074599B2 (en) * | 2013-10-09 | 2017-02-08 | パナソニックＩｐマネジメント株式会社 | greenhouse |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3458311A (en) * | 1966-06-27 | 1969-07-29 | Du Pont | Photopolymerizable elements with solvent removable protective layers |
| DE2036585A1 (en) * | 1970-07-23 | 1972-02-03 | Kalle AG, 6202 Wiesbaden Biebnch | Photopolymerizable copying material |
| JPS6055335A (en) * | 1983-09-07 | 1985-03-30 | Toyobo Co Ltd | Manufacture of photosensitive resin laminate |
| JPS60186835A (en) * | 1984-03-06 | 1985-09-24 | Toyobo Co Ltd | Photosensitive laminate |
| DE3736980A1 (en) * | 1987-10-31 | 1989-05-18 | Basf Ag | MULTILAYER, SURFACE-SHAPED, LIGHT-SENSITIVE RECORDING MATERIAL |
-
1988
- 1988-07-29 DE DE3825836A patent/DE3825836A1/en not_active Withdrawn
-
1989
- 1989-07-20 DE DE58908207T patent/DE58908207D1/en not_active Expired - Lifetime
- 1989-07-20 EP EP89113306A patent/EP0352630B1/en not_active Expired - Lifetime
- 1989-07-24 CA CA000606446A patent/CA1337677C/en not_active Expired - Fee Related
- 1989-07-28 JP JP1194419A patent/JP2736124B2/en not_active Expired - Lifetime
- 1989-07-29 KR KR1019890010797A patent/KR0135076B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02103051A (en) | 1990-04-16 |
| DE58908207D1 (en) | 1994-09-22 |
| EP0352630B1 (en) | 1994-08-17 |
| JP2736124B2 (en) | 1998-04-02 |
| KR0135076B1 (en) | 1998-04-18 |
| EP0352630A3 (en) | 1990-08-01 |
| EP0352630A2 (en) | 1990-01-31 |
| DE3825836A1 (en) | 1990-02-08 |
| KR910003606A (en) | 1991-02-27 |
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