CA2097038A1 - Photopolymerizable mixture and recording material prepared therefrom - Google Patents
Photopolymerizable mixture and recording material prepared therefromInfo
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- CA2097038A1 CA2097038A1 CA 2097038 CA2097038A CA2097038A1 CA 2097038 A1 CA2097038 A1 CA 2097038A1 CA 2097038 CA2097038 CA 2097038 CA 2097038 A CA2097038 A CA 2097038A CA 2097038 A1 CA2097038 A1 CA 2097038A1
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- Prior art keywords
- mixture
- compound
- photopolymerizable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Abstract of the Disclosure Photopolymerizable Mixture and Recording Material Prepared Therefrom A photopolymerizable mixture is described which comprises from about 5 to about 25% of a polymeric binder, from about 60 to about 90% of a free-radically polymerizable compound, and as photoinitiators in total from about 3 to about 20% of a photoreducible dye, a radiolyzable trihalomethyl compound and a metallocene compound. The mixture can be used to produce photoresists or printing plates and has a particularly high light sensitivity.
Description
2'097~38 PhotopolYmerizable Mixture and Recordinq Material Pre~ared Therefrom The invention relates to a photopolymerizable mixture that comprises a polymeric binder, a polymerizable compound, preferably an acrylic or alkylacrylic acid ester, and also a photoinitiator combination.
Photopolymerizable mixtures of the aforementioned general type are known.
Examples of such photopolymerizable mixtures are described in EP-A 287 817, which comprise (meth)acrylic acid esters having urethane groups, tertiary amino i groups and, if desired, urea groups in the molecule, polymeric binders and, as photoinitiators, a combination of a photoreducible dye, a radiation-sensitive trihalomethyl compound and an acridine, phenazine or quinoxaline compound.
In EP-A 364 735 photopolymerizable mixtures are described which contain the same or similar binders and polymerizable compounds and also a photoinitiator com-bination of a photoreducible dye, a radiolyzabletrihalomethyl compound, and a metallocene compound.
These mixtures have a particularly high light sensitiv-ity, especially in the visible spectrum. This property makes them particularly suitable for producing printing plates on which images can be recorded with visible laser light, for example with an argon ion laser. These known mixtures generally comprise from 20 to 90 % by weight, preferably from 40 to 80% by weight of binders.
However, there is an ever-increasing need to improve the light sensitivity for the aforementioned use and also for recording images by projection irradiation.
. .
- It is an object of the present invention to provide photopolymerizable mixtures that are especially suitable for producing printing plates having the high ., .
', .
.
., ., 2~97~38 degree of efficiency described in EP-A 364 735 and whose light sensitivity in the near ultraviolet and in particular in the visible spectral region is improved still further compared to the mixtures described therein.
According to the invention a photopolymerizable mixture is proposed which comprises:
a) a polymeric binder, b) a free-radically polymerizable compound having at least one polymerizable group, and, as photoinitiators:
c) a photoreducible dye, d) a radiolyzable trihalomethyl compound, and e) a metallocene compound, wherein the binder (a) is present in an amount of from about 5 to about 25~, the polymerizable compound (b) is present in an amount of from about 60 to about 90%, and the photoinitiators (c), (d) and (e) are present in a total amount of from about 3 to about 20~, based on the weight of the nonvolatile constituents.
The metallocenes that can be used as initiator components are generally known as photoinitiators from EP-A 364 735. In the present invention, preference is given to metallocenes of elements of Group IV of the Periodic System, in particular compounds of titanium and zirconium. Of the numerous known metallocenes, especially titanocenes, preference is given to compounds of the formula I.
R1\ R3 /Me\ (I) . .
2097~3~
In this formula:
Me is a tetravalent metal atom, preferably Ti or zr, R1 and RZ are identical or different cyclopenta-dienyl radicals, which may be substitu-ted, and R3 and R4 are identical or different phenyl radi-cals, which may also be substituted.
The cyclopentadienyl groups may be substituted by alkyl radicals having 1 to 4 carbon atoms, chlorine atoms, phenyl or cyclohexyl radicals, or may be coupled to one another by alkylene groups.
R3 and R4 are preferably phenyl groups that contain at least one fluorine atom in the ortho position relative to the bond, and which may also be substituted by halogen atoms such as F, Cl or Br, alkyl or alkoxy groups having 1 to 4 carbon atoms, or a polyoxyalkylene group, which may be etherified or esterified. The polyoxyalkylene group may contain from 1 to 6 oxyalkylene units and is preferably in the 4- position of the phenyl radical, and may be etherified or esterified by an alkyl or acyl radical having 1 to 18 carbon atoms; the polyoxyalkylene group is preferably a polyoxyethylene group. Particularly preferred are phenyl radicals substituted by 4 or 5 fluorine atoms. The proportion by weight of metallocene compound is normally from about 1.5 to about 10% by weight, preferably from about 2 to about 6% by weight, based on the nonvolatile fractions of the mixture.
The mixture according to the invention comprises, as further photoinitiator constituent, a photoreducible dye. Suitable dyes include, in particular, xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine dyes.
,~
2~971)~8 Suitable xanthene and thiazine dyes are described, for example, in EP-A 287 817.
Suitable benzoxanthene and benzothioxanthene dyes are described in EP-A 321 828.
A suitable porphyrin dye is, for example, hematoporphyrin and a suitable acridine dye is, for example, acriflavinium chloride hydrochloride. Examples of xanthene dyes are Eosin B (C.I. No. 45 400), Eosin J
(C.I. No. 45 380), alcohol-soluble Eosin (C.I. No.
45 386), Cyanosin (C.I. No. 45 410), Bengal Rose, Erythrosin (C.I. No. 45 430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and Rhodamine 6 G (C.I. No.
45 160).
Examples of thiazine dyes are Thionin (C.I. No.
52 000), Azure A (C.I. No. 52 005) and Azure C (C.I.
No. 52 002).
Examples of pyronine dyes are Pyronine B (C.I. No.
45 010) and Pyronine GY (C.I. No. 45 005). The amount of photoreducible dye is normally from about 1 to about 10% by weight, preferably from about 3 to about 8% by weight, based on the nonvolatile fractions of the mixture.
In order to improve the light sensitivity, the mixtures according to the invention also comprise compounds containing photolyzable trihalomethyl groups, which are - generally known per se as free-radical-forming photoinitiators for photopolymerizable mixtures. In the present invention, as co-initiators of this type, compounds containing chlorine and bromine, especially chlorine, as halogens have proved particularly suitable. The trihalomethyl groups may be bound ~-directly or via a conjugated chain to an aromatic ~ carbocyclic or heterocyclic ring. Preference is given ; to compounds having a triazine ring in the parent 2~97038 structure, which preferably carries two trihalomethyl groups, in particular compounds such as are described in EP-A 137 452, DE-A 27 18 259 and DE-A 22 43 621.
These compounds exhibit strong light absorption in the near UV region, for example around 350-400 nm. Co-initiators that do not themselves absorb, or only slightly absorb, in the spectral range of the copying light are also suitable, for example trihalomethyltriazines, which contain substituents with shorter electron systems capable of mesomerism or aliphatic substituents. Also suitable are compounds having a different basic skeleton, that absorb in the shorter-wavelength UV range, for example phenyl trihalomethyl sulfones, or phenyl trihalomethyl ketones, for example phenyl tribromomethyl sulfone.
These halogen compounds are generally used in an amount of from about 0.05 to about 4% by weight, preferably from about 0.25 to about 1% by weight, based on the nonvolatile constituents of the mixture.
The total amount of these three necessary initiator components is from about 3 to about 20% by weight, preferably from about 6 to about 12% by weight. The proportion of titanocene compound is preferably from about 30 to about 55% by weight, that of trihalomethyl compound is from about 3 to about 15% by weight, and that of photoreducible dye is from about 40 to about 67% by weight, based on the total amount of photoinitiators (c), (d) and (e).
The mixtures according to the invention may contain an acridine, phenazine or quinoxaline compound as further initiator constituent. These compounds are generally known as photoinitiators and are described in DE-C 20 27 467 and 20 39 861. The sensitivity of the mixture, particularly in the near ultraviolet region, is increased by means of these compounds. Suitable examples of this class of compound are described in the .
aforementioned patents. The amount of this component in the mixture of the present invention is in the range from 0 to about 5% by weight, preferably from about 0.05 to about 3% by weight.
When a further increase in sensitivity of the mixture in the visible spectrum is necessary, this is achieved by adding a compound of the dibenzalacetone or coumarin type. This addition produces a higher resolution of the copy and a continuous sensitization of the mixture for the visible spectrum up to wavelengths of about 600 nm.
Suitable examples of these compounds are 4,4'-disubstituted dibenzalacetones, for example 4-diethylamino-4'-methoxydibenzalacetone, or coumarin derivatives such as 3-acetyl-7-diethylaminocoumarin, 3-benzimidazolyl-7-diethylaminocoumarin or carbonyl-bis(7-diethylaminocoumarin). The amount of this compound is in the range from 0 to about 5% by weight, preferably from about 0.05 to about 2% by weight, based on the nonvolatile constituents of the mixture.
Suitable polymerizable compounds for the purposes of the invention are described, for example, in US
i Patents 2,760,863 and 3,060,023.
.
~` Preferred examples are acrylic and methacrylic esters of dihydric or higher alcohols, for example ethylene glycol diacrylate, polyethylene glycol dimethacrylate, acrylates and methacrylates of trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol, and of polyhydric alicyclic alcohols or N-substituted acrylic and methacrylic acid amides.
Also, the reaction products of monoisocyanates or diiosocyanates with partial esters of polyhydric alcohols are advantageously used. Such monomers are described in DE-A 20 64 079, 23 61 041 and 28 22 190.
Particularly preferred are polymerizable compounds that contain at least one photooxidizable group and, if .
2~97038 deslred, at least one urethane group in the molecule.
Suitable photooxidizable groups are in particular amino groups, urea groups, thio groups, which may also be 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. Preference is given to polymerizable compounds containing primary, secondary and, preferably, tertiary amino groups.
Examples of compounds containing photooxidizable groups are described in EP-A 287 818, 355 387 and 364 735. Of the compounds described there, preference is given to those that also contain, in addition to a tertiary amino group, a urea group and/or a urethane group.
Groups of the formula /N-CC~-N\
in which the valences on the nitrogen are saturated by unsubstituted or substituted hydrocarbon radicals, should be regarded as urea groups.
The proportion by weight of polymerizable compounds in the photopolymerizable layer is normally from about 60 to about 90% by weight, preferably from about 70 to about 85% by weight, based on the nonvolatile constituents.
Examples of binders that can be used include poly(meth)acrylic acid alkyl esters, in which the alkyl group is for example, methyl, ethyl, n-butyl, i-butyl, n-hexyl or 2-ethylhexyl, copolymers of the aforementioned (meth)acrylic acid alkyl esters with at least one monomer, such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene or butadiene;
polyvinyl acetate, vinyl acetate copolymers, , polyurethanes, methyl cellulose, ethyl cellulose, polyvinyl formal and polyvinyl butyral.
Particularly suitable are binders that are insoluble in water, but are soluble in organic solvents and are soluble, or at least swellable, in aqueous-alkaline solutions.
In particular there should be mentioned carboxyl group-containing binders, for example copolymers of (meth)-acrylic acid and/or their unsaturated homologs, for example crotonic acid, copolymers of maleic anhydride or its monoesters, reaction products of hydroxyl group-containing polymers with dicarboxylic anhydrides, or their mixtures.
The afore-described polymers are particularly suitable if they have a molecular weight from about 500 to about 200,000 or above, preferably from about 1000 to about 100,000, and either have acid numbers from about 10 to about 250, preferably from about 20 to about 200, or hydroxyl numbers from about 50 to about 750, preferably from about 100 to about 500.
Preferred alkali-soluble binders include:
copolymers of (meth)acrylic acid with alkyl (meth)acry-lates, (meth)acrylonitrile or the like, vinyl acetate copolymers, copolymers of crotonic acid with vinyl 25 acetate, alkyl (meth)acrylates (meth)acrylonitrile or the like, copolymers of vinylacetic acid, with alkyl (meth)acrylates, copolymers of maleic anhydride with unsubstituted or substituted styrenes, unsaturated hydrocarbons, unsaturated ethers or esters, esterifica-tion products of copolymers of maleic anhydride, esterification products of hydroxyl group-containing polymers with anhydrides of dicarboxylic or higher polycarboxylic acids, for example copolymers of hydroxyalkyl (meth)acrylates with alkyl (meth)acrylates, (meth)acrylonitrile or the like, ~-2097~38 g copolymers of polyurethanes, provided they contain a sufficient number of free OH-groups, of epoxy resins, polyesters, partially saponified vinyl acetate copoly-mers, polyvinyl acetals having free OH-groups, copolymers of hydroxystyrenes with alkyl (meth)acrylates or the like, and also phenol-formaldehyde resins, for example Novolaks.
The amount of the binder in the light-sensitive layer is normally from about 5 to about 25% by weight, preferably from about 10 to about 19~ by weight.
Depending on the intended use and desired properties, the photopolymerizable layers may comprise various substances as additives. Examples of such additives include inhibitors to prevent thermal polymerization of the monomers, hydrogen donors, dyes, colored and non-colored pigments, color formers, indicators, plasticizers and chain transfer agents. These constitu-ents should be conveniently selected so that they absorb as little as possible in the actinic radiation range important for the initiation process.
Actinic radiation is understood in the context of this description to be any radiation whose energy corresponds at least to that of visible light.
Particularly suitable are visible light and long-wave UV radiation, though short-wave UV radiation and laser radiation are also suitable. The light sensitivity extends from about 300 nm to 700 nm and thus covers an extremely broad range.
The combination of photoreducible dyes with photolyzable halogen compounds and metallocenes produces a synergistic initiator system that is very active especially in the long-wave spectral region at or above 455 nm. Particularly high light sensitivities are obtained in combination with polymerizable ; 35 compounds that contain photooxidizable groups. Compared ., , /
2097~38 with the known mixtures of the foregoing composition, the mixtures according to the invention, which contain substantially smaller amounts of binders and different amounts of initiators, have a further improved light sensitivity.
The following may be mentioned as possible uses of the material according to the invention: recording layers for the photomechanical production of printing plates for relief printing, planographic printing, gravure printing and screen printing, of relief copies, for example production of braille text, of individual copies, tanned images, pigmented images, etc. The mixtures may also be used for the photomechanical production of etch resists, for example for producing name plates, of printed circuits, and for chemical milling. The mixtures according to the invention are especially important as recording layers for producing planographic printing plates and for use in photoresist technology.
Suitable layer carriers for the recording material according to the invention are for example aluminum, steel, zinc, copper and plastics films, for example of polyethylene terephthalate or cellulose acetate, and also screen printing carriers such as Perlon gauze. It is convenient in many cases to pretreat (chemically or mechanically) the carrier surface, the purpose of which pretreatment is correctly to adjust the adhesion of the layer, improve the lithographic properties of the carrier surface, or reduce the reflectance of the carrier in the actinic region of the copying layer ~-(antihalation).
The light-sensitive materials are prepared in a known manner. For example, the layer constituents can be taken up in a solvent and the solution or dispersion can be applied to the intended carrier by pouring, 209703~
spraying, dipping, roller application, etc., and then dried.
Due to the broad spectral sensitivity of the recording material according to the invention, all light sources known to those skilled in the art may be used, for example tubular lamps, pulsed xenon lamps, metal halide-doped high-pressure mercury vapor lamps and carbon arc lamps. Furthermore, irradiation in normal projection and magnification equipment under the light from metal filament lamps and contact irradiation with normal incandescent lamp bulbs is possible with the light-sensitive mixtures according to the invention.
Irradiation can also be effected with the coherent light from a laser. Tuned lasers are suitable for the lS purposes of the present invention, for example argon ion, krypton ion, dye, helium-cadmium and helium-neon lasers, which emit in particular from about 250 to about 650 nm. The laser beam can be controlled by means of a preprogrammed linear and/or dot-like movement.
In general it is convenient to exclude as far as possible the influence of atmospheric oxygen on the mixtures during the light polymerization. In the case where the mixture is used in the form of thin copying layers it is recommended to apply a suitable cover film that is only slightly permeable to oxygen. This cover film may be self-supporting and can be removed before the copying layer is developed. Polyester films for example are suitable for this purpose. The cover film may also comprise a material that dissolves in the developer liquid or that can at least be removed during development from the non-hardened places. Suitable materials for this purpose include polyvinyl alcohol, polyphosphates, sugars, etc. Such cover layers generally have a thickness of from about 0.1 to about 10 ~m, preferably from about 1 to about 5 ~m.
" ~
20970t',8 The materials are processed further in a known manner.
A post-heating may be carried out after irradiation in order to improve the crosslinking of the layer. The materials are developed with a suitable developer solu-tion, for example with organic solvents, but preferablywith a weakly alkaline aqueous solution, the non-irradiated parts of the layer being removed and the irradiated regions of the copying layer remaining on the carrier. The developer solutions may contain a small proportion, preferably less than 5% by weight, of water-miscible organic solvents. They may also contain wetting agents, dyes, salts and other additives.
The whole cover layer together with the non-irradiated regions of the photopolymerizable layer are removed in the development process.
Embodiments of the invention are given hereinafter. In these embodiments parts by weight (pbw) and parts by volume (pbv) are in the same ratio as g to ccm. Unless otherwise stated, percentages and amounts are by weight.
Examples 1-7(Comparative examples) ~ .
Solutions of:
2.87 pbw of a polymeric binder 6.76 " of the reaction product of 1 mol of triethanolamine with 3 mol of isocyanato ethyl methacrylate, as monomer, 0.18 " alcohol-soluble Eosin (C.I. 45 386) 0.14 " 2,4-bis-trichloromethyl-6-(4-styrylphenyl)-s-triazine, and 0.05 " dicyclopentadienyl bis(pentafluorophenyl-titanium) in 85 " propylene glycol monomethyl ether and 46 " butanone ' ~, ~ . . . ... . .
were applied to electrolytically roughened and anodically oxidized aluminum plates having an oxide layer of 3 g/m2 that had been pretreated beforehand with an aqueous solution of polyvinylphosphonic acid. The layers were dried for 2 minutes at 100C in a circulating air cabinet and then had a layer weight of 2.1 g/m2. An 8% strength aqueous solution of polyvinyl alcohol (12~ residual acetyl groups, K value 4) was then applied in such a thickness that a layer weight of 2.4 g/m2 was obtained after the drying (2 minutes at 100 C) .
~he printing plates obtained were in each case irradi-ated for 20 seconds with a 60 W incandescent lamp at a distance of 80 cm under a 13-step standard stepped photometric absorption wedge with density steps of 0.15. After irradiation the plates were post-heated for one minute at 100C and then developed with a developer having the following composition:
1 pbw trisodium citrate x 2 H2O, 2 " 1-amino-2-propanol, 1.4 " benzyl alcohol, l.S " sodium cumol sulfonate (40% strength solution) 0.04 " sodium metasilicate x 5 H2O 5 0.02 " fatty alcohol polyglycol ether (non-ionogenic wetting agent) 94.04 " water In a further experiment the light-sensitive plates were treated with the developer without any image-forming irradiation. The following binders were used:
Example 1 terpolymer of styrene, n-hexyl methacrylate and methacrylic acid (10:60:30; acid number 190) 20~7~38 Example 2 copolymer of styrene and maleic acid semi-ester (acid number 185; ~Scripset 540) Example 3 copolymer of 95% vinyl acetate and 5%
crotonic acid Example 4 copolymer of 65% vinyl acetate and 35%
dibutyl maleate Example 5 copolymer of acrylic acid, styrene and a-methyl styrene, acid number 245; M~ 7000 Example 6 reaction product of a polyvinyl butyral (71%
vinylbutyral units, 2% vinyl acetate units, 27% vinyl alcohol units, M~ = 70000-80000) with maleic anhydride; acid number 30 Example 7 methylmethacrylate/methacrylic acid copolymer, acid number 117 The results are summarized in Table 1. The second column gives the number of the solid, i.e. completely . hardened wedge steps. The comparisons show, with the specified binder content, none of the layers could be satisfactorily developed in such a way that the irradiated regions of the layer remained unaffected while the non-irradiated regions were completely removed.
.
Table 1 With irradiation Without irradiation Wedge Remarks steps 1 4 _ partially delayered 2 _ not partially developed delayered 3 1 _ completely delayered 4 _ completely completely delayered delayered _ not partially developed delayered I
6 _ not not delayered developed 7 _ not partially developed delayered Exam~les 8-10 (Com~arative Examples) Printing plates were produced as described in Example l, the monomer being replaced by the same amount of monomers specified in Table 2. The further procedure was as described in Example 1; Table 2 shows the number of solid wedge steps.
~.
,~
20970~8 Table 2 Example Monomer Wedge steps ¦
I
1 as specified there 8 the reaction product of 2 mol 4 of isocyanato ethyl methacrylate and 1 mol of 2-hydroxyethylpiperidine 9 reaction product of 3 mol of 3 isocyanato ethyl methacrylate and 1 mol of diethanolamine reaction product of 2 mol of 4 hexamethylene diisocyanate, 2 mol of hydroxyethyl meth-acrylate and 1 mol of 2-hyd-roxyethylpiperidine Example 11 (Comparative ExamPle) A printing plate was produced as described in Example 1. The following coating solution was used.
2.87 pbw of the terpolymer of Example 1 6.64 " of the reaction product of 2 mol of hexamethylenediisocyanate, 2 mol of 2-hydroxyethyl methacrylate and 1 mol of 2-(2-hydroxyethyl)piperidine, as monomer 0.18 " alcohol-soluble Eosin (C.I. 45386) 0.14 " of the triazine given in Example 1 0.05 " of the titanocene given in Example 1, and 0.12 " Renol blue (C.I. 20 505) in " propylene glycol monomethyl ether and 46 " butanone.
After irradiation and development as described in Example 1, 4-5 solid wedge steps were obtained.
Example 12 (Comparative Example) The same procedure as in Example 11 was adopted, though the compound specified in Example 1 was used, in the same amount as in Example 11, as monomer. Four solid wedge steps were obtained.
Example 13 (Comparative Example) The same procedure as in Example 11 was adopted, though the reaction product of 2 mol of isocyanato ethyl meth-acrylate and 1 mol of 2-(2-hydroxyethyl)piperidine was used, in the same amount as in Example 11, as monomer.
Four solid wedge steps were obtained.
Example 14 (Comparative ExamPle) The same procedure as in Example 11 was adopted, though the reaction product of 3 mol of isocyanato ethyl methacrylate and 1 mol of diethanolamine was used, in the same amount as in Example 11, as monomer. Three solid wedge steps were obtained.
Example 15 (Comparative Exam~le~
Printing plates were produced as described in Example 11! the amounts of the constituents being altered in each case as follows:
a) 6.36 pbw monomer (- 0.28) 0.46 " Eosin (+ 0.28) b) 6.74 pbw monomer (+ 0.1) 0.04 " triazine (- 0.1) c) 6.4 pbw monomer (- 0.24) 0.29 " titanocene (+ 0.24) ;
d) 3 03 pbw terpolymer (+ 0.16) 6.48 " monomer (- 0.16) e) changes (a) and (d) f) changes (a), (b) and (d) g) changes (a), (b), (c) and (d) , ., ., ~0370c,~
The multiple changes (e), (f) and (g) were made so that the total amount remained constant in each case. The plates were otherwise produced and processed as in Example 11. The following numbers of completely solid wedge steps were obtained:
Example Wedqe steps 15 a 4-5 15 b 4 15 c 6-7 15 d 4 15 e 4 15 f 4 15 g 7-8 Exam~les 16-22 (Comparative Examples) Printing plates were coated as described in Example 1 with the following solution:
3.04 pbw binder 6.06 " of the monomer given in Example 11, 0.46 " alcohol-soluble Eosin 0.04 " of the triazine given in Example 1, 0.29 " of the titanocene given in Example 1, and 0.12 " Renol blue in : 85 " propylene glycol monomethyl ether and 46 " butanone The plates were produced and processed as described in Example 1. The following table shows the numbers of solid wedge steps obtained with irradiation times of 20 and Z seconds under the conditions specified in Example 1.
,. ~ . ,.. ., , . -, . : -2097~38 Example BinderWedge steps according to 16 Example~0 C~-3 ~ 1 ~
7_8 Examples 23-31 (including Comparative Examples 24, 25, 27, 28, 30 and 31) Coating solutions according to the formulation given in Example 16 were used to prepare printing plates, the nature and amount of the binder and also the amount of the monomer being specified in the following table. The table also shows the number of solid wedge steps after 6 seconds' irrsdiation.
(j ~ ' ., - 20 - 2 0 9 7 0 3 ~
Example Binder Amount Amount of Wedge according pbw monomer, steps to Example pbw 23 7 1.5 7.6 5-6 24 7 3.0 6.1 4 7 4.5 4.6 26 1 1.5 7.6 5-6 27 1 3.0 6.1 3 28 4.5 4.6 29 1.5 7.6 5-6 2 3.0 6.1 3 31 2 4.5 4.6 _
Photopolymerizable mixtures of the aforementioned general type are known.
Examples of such photopolymerizable mixtures are described in EP-A 287 817, which comprise (meth)acrylic acid esters having urethane groups, tertiary amino i groups and, if desired, urea groups in the molecule, polymeric binders and, as photoinitiators, a combination of a photoreducible dye, a radiation-sensitive trihalomethyl compound and an acridine, phenazine or quinoxaline compound.
In EP-A 364 735 photopolymerizable mixtures are described which contain the same or similar binders and polymerizable compounds and also a photoinitiator com-bination of a photoreducible dye, a radiolyzabletrihalomethyl compound, and a metallocene compound.
These mixtures have a particularly high light sensitiv-ity, especially in the visible spectrum. This property makes them particularly suitable for producing printing plates on which images can be recorded with visible laser light, for example with an argon ion laser. These known mixtures generally comprise from 20 to 90 % by weight, preferably from 40 to 80% by weight of binders.
However, there is an ever-increasing need to improve the light sensitivity for the aforementioned use and also for recording images by projection irradiation.
. .
- It is an object of the present invention to provide photopolymerizable mixtures that are especially suitable for producing printing plates having the high ., .
', .
.
., ., 2~97~38 degree of efficiency described in EP-A 364 735 and whose light sensitivity in the near ultraviolet and in particular in the visible spectral region is improved still further compared to the mixtures described therein.
According to the invention a photopolymerizable mixture is proposed which comprises:
a) a polymeric binder, b) a free-radically polymerizable compound having at least one polymerizable group, and, as photoinitiators:
c) a photoreducible dye, d) a radiolyzable trihalomethyl compound, and e) a metallocene compound, wherein the binder (a) is present in an amount of from about 5 to about 25~, the polymerizable compound (b) is present in an amount of from about 60 to about 90%, and the photoinitiators (c), (d) and (e) are present in a total amount of from about 3 to about 20~, based on the weight of the nonvolatile constituents.
The metallocenes that can be used as initiator components are generally known as photoinitiators from EP-A 364 735. In the present invention, preference is given to metallocenes of elements of Group IV of the Periodic System, in particular compounds of titanium and zirconium. Of the numerous known metallocenes, especially titanocenes, preference is given to compounds of the formula I.
R1\ R3 /Me\ (I) . .
2097~3~
In this formula:
Me is a tetravalent metal atom, preferably Ti or zr, R1 and RZ are identical or different cyclopenta-dienyl radicals, which may be substitu-ted, and R3 and R4 are identical or different phenyl radi-cals, which may also be substituted.
The cyclopentadienyl groups may be substituted by alkyl radicals having 1 to 4 carbon atoms, chlorine atoms, phenyl or cyclohexyl radicals, or may be coupled to one another by alkylene groups.
R3 and R4 are preferably phenyl groups that contain at least one fluorine atom in the ortho position relative to the bond, and which may also be substituted by halogen atoms such as F, Cl or Br, alkyl or alkoxy groups having 1 to 4 carbon atoms, or a polyoxyalkylene group, which may be etherified or esterified. The polyoxyalkylene group may contain from 1 to 6 oxyalkylene units and is preferably in the 4- position of the phenyl radical, and may be etherified or esterified by an alkyl or acyl radical having 1 to 18 carbon atoms; the polyoxyalkylene group is preferably a polyoxyethylene group. Particularly preferred are phenyl radicals substituted by 4 or 5 fluorine atoms. The proportion by weight of metallocene compound is normally from about 1.5 to about 10% by weight, preferably from about 2 to about 6% by weight, based on the nonvolatile fractions of the mixture.
The mixture according to the invention comprises, as further photoinitiator constituent, a photoreducible dye. Suitable dyes include, in particular, xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine dyes.
,~
2~971)~8 Suitable xanthene and thiazine dyes are described, for example, in EP-A 287 817.
Suitable benzoxanthene and benzothioxanthene dyes are described in EP-A 321 828.
A suitable porphyrin dye is, for example, hematoporphyrin and a suitable acridine dye is, for example, acriflavinium chloride hydrochloride. Examples of xanthene dyes are Eosin B (C.I. No. 45 400), Eosin J
(C.I. No. 45 380), alcohol-soluble Eosin (C.I. No.
45 386), Cyanosin (C.I. No. 45 410), Bengal Rose, Erythrosin (C.I. No. 45 430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and Rhodamine 6 G (C.I. No.
45 160).
Examples of thiazine dyes are Thionin (C.I. No.
52 000), Azure A (C.I. No. 52 005) and Azure C (C.I.
No. 52 002).
Examples of pyronine dyes are Pyronine B (C.I. No.
45 010) and Pyronine GY (C.I. No. 45 005). The amount of photoreducible dye is normally from about 1 to about 10% by weight, preferably from about 3 to about 8% by weight, based on the nonvolatile fractions of the mixture.
In order to improve the light sensitivity, the mixtures according to the invention also comprise compounds containing photolyzable trihalomethyl groups, which are - generally known per se as free-radical-forming photoinitiators for photopolymerizable mixtures. In the present invention, as co-initiators of this type, compounds containing chlorine and bromine, especially chlorine, as halogens have proved particularly suitable. The trihalomethyl groups may be bound ~-directly or via a conjugated chain to an aromatic ~ carbocyclic or heterocyclic ring. Preference is given ; to compounds having a triazine ring in the parent 2~97038 structure, which preferably carries two trihalomethyl groups, in particular compounds such as are described in EP-A 137 452, DE-A 27 18 259 and DE-A 22 43 621.
These compounds exhibit strong light absorption in the near UV region, for example around 350-400 nm. Co-initiators that do not themselves absorb, or only slightly absorb, in the spectral range of the copying light are also suitable, for example trihalomethyltriazines, which contain substituents with shorter electron systems capable of mesomerism or aliphatic substituents. Also suitable are compounds having a different basic skeleton, that absorb in the shorter-wavelength UV range, for example phenyl trihalomethyl sulfones, or phenyl trihalomethyl ketones, for example phenyl tribromomethyl sulfone.
These halogen compounds are generally used in an amount of from about 0.05 to about 4% by weight, preferably from about 0.25 to about 1% by weight, based on the nonvolatile constituents of the mixture.
The total amount of these three necessary initiator components is from about 3 to about 20% by weight, preferably from about 6 to about 12% by weight. The proportion of titanocene compound is preferably from about 30 to about 55% by weight, that of trihalomethyl compound is from about 3 to about 15% by weight, and that of photoreducible dye is from about 40 to about 67% by weight, based on the total amount of photoinitiators (c), (d) and (e).
The mixtures according to the invention may contain an acridine, phenazine or quinoxaline compound as further initiator constituent. These compounds are generally known as photoinitiators and are described in DE-C 20 27 467 and 20 39 861. The sensitivity of the mixture, particularly in the near ultraviolet region, is increased by means of these compounds. Suitable examples of this class of compound are described in the .
aforementioned patents. The amount of this component in the mixture of the present invention is in the range from 0 to about 5% by weight, preferably from about 0.05 to about 3% by weight.
When a further increase in sensitivity of the mixture in the visible spectrum is necessary, this is achieved by adding a compound of the dibenzalacetone or coumarin type. This addition produces a higher resolution of the copy and a continuous sensitization of the mixture for the visible spectrum up to wavelengths of about 600 nm.
Suitable examples of these compounds are 4,4'-disubstituted dibenzalacetones, for example 4-diethylamino-4'-methoxydibenzalacetone, or coumarin derivatives such as 3-acetyl-7-diethylaminocoumarin, 3-benzimidazolyl-7-diethylaminocoumarin or carbonyl-bis(7-diethylaminocoumarin). The amount of this compound is in the range from 0 to about 5% by weight, preferably from about 0.05 to about 2% by weight, based on the nonvolatile constituents of the mixture.
Suitable polymerizable compounds for the purposes of the invention are described, for example, in US
i Patents 2,760,863 and 3,060,023.
.
~` Preferred examples are acrylic and methacrylic esters of dihydric or higher alcohols, for example ethylene glycol diacrylate, polyethylene glycol dimethacrylate, acrylates and methacrylates of trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol, and of polyhydric alicyclic alcohols or N-substituted acrylic and methacrylic acid amides.
Also, the reaction products of monoisocyanates or diiosocyanates with partial esters of polyhydric alcohols are advantageously used. Such monomers are described in DE-A 20 64 079, 23 61 041 and 28 22 190.
Particularly preferred are polymerizable compounds that contain at least one photooxidizable group and, if .
2~97038 deslred, at least one urethane group in the molecule.
Suitable photooxidizable groups are in particular amino groups, urea groups, thio groups, which may also be 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. Preference is given to polymerizable compounds containing primary, secondary and, preferably, tertiary amino groups.
Examples of compounds containing photooxidizable groups are described in EP-A 287 818, 355 387 and 364 735. Of the compounds described there, preference is given to those that also contain, in addition to a tertiary amino group, a urea group and/or a urethane group.
Groups of the formula /N-CC~-N\
in which the valences on the nitrogen are saturated by unsubstituted or substituted hydrocarbon radicals, should be regarded as urea groups.
The proportion by weight of polymerizable compounds in the photopolymerizable layer is normally from about 60 to about 90% by weight, preferably from about 70 to about 85% by weight, based on the nonvolatile constituents.
Examples of binders that can be used include poly(meth)acrylic acid alkyl esters, in which the alkyl group is for example, methyl, ethyl, n-butyl, i-butyl, n-hexyl or 2-ethylhexyl, copolymers of the aforementioned (meth)acrylic acid alkyl esters with at least one monomer, such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene or butadiene;
polyvinyl acetate, vinyl acetate copolymers, , polyurethanes, methyl cellulose, ethyl cellulose, polyvinyl formal and polyvinyl butyral.
Particularly suitable are binders that are insoluble in water, but are soluble in organic solvents and are soluble, or at least swellable, in aqueous-alkaline solutions.
In particular there should be mentioned carboxyl group-containing binders, for example copolymers of (meth)-acrylic acid and/or their unsaturated homologs, for example crotonic acid, copolymers of maleic anhydride or its monoesters, reaction products of hydroxyl group-containing polymers with dicarboxylic anhydrides, or their mixtures.
The afore-described polymers are particularly suitable if they have a molecular weight from about 500 to about 200,000 or above, preferably from about 1000 to about 100,000, and either have acid numbers from about 10 to about 250, preferably from about 20 to about 200, or hydroxyl numbers from about 50 to about 750, preferably from about 100 to about 500.
Preferred alkali-soluble binders include:
copolymers of (meth)acrylic acid with alkyl (meth)acry-lates, (meth)acrylonitrile or the like, vinyl acetate copolymers, copolymers of crotonic acid with vinyl 25 acetate, alkyl (meth)acrylates (meth)acrylonitrile or the like, copolymers of vinylacetic acid, with alkyl (meth)acrylates, copolymers of maleic anhydride with unsubstituted or substituted styrenes, unsaturated hydrocarbons, unsaturated ethers or esters, esterifica-tion products of copolymers of maleic anhydride, esterification products of hydroxyl group-containing polymers with anhydrides of dicarboxylic or higher polycarboxylic acids, for example copolymers of hydroxyalkyl (meth)acrylates with alkyl (meth)acrylates, (meth)acrylonitrile or the like, ~-2097~38 g copolymers of polyurethanes, provided they contain a sufficient number of free OH-groups, of epoxy resins, polyesters, partially saponified vinyl acetate copoly-mers, polyvinyl acetals having free OH-groups, copolymers of hydroxystyrenes with alkyl (meth)acrylates or the like, and also phenol-formaldehyde resins, for example Novolaks.
The amount of the binder in the light-sensitive layer is normally from about 5 to about 25% by weight, preferably from about 10 to about 19~ by weight.
Depending on the intended use and desired properties, the photopolymerizable layers may comprise various substances as additives. Examples of such additives include inhibitors to prevent thermal polymerization of the monomers, hydrogen donors, dyes, colored and non-colored pigments, color formers, indicators, plasticizers and chain transfer agents. These constitu-ents should be conveniently selected so that they absorb as little as possible in the actinic radiation range important for the initiation process.
Actinic radiation is understood in the context of this description to be any radiation whose energy corresponds at least to that of visible light.
Particularly suitable are visible light and long-wave UV radiation, though short-wave UV radiation and laser radiation are also suitable. The light sensitivity extends from about 300 nm to 700 nm and thus covers an extremely broad range.
The combination of photoreducible dyes with photolyzable halogen compounds and metallocenes produces a synergistic initiator system that is very active especially in the long-wave spectral region at or above 455 nm. Particularly high light sensitivities are obtained in combination with polymerizable ; 35 compounds that contain photooxidizable groups. Compared ., , /
2097~38 with the known mixtures of the foregoing composition, the mixtures according to the invention, which contain substantially smaller amounts of binders and different amounts of initiators, have a further improved light sensitivity.
The following may be mentioned as possible uses of the material according to the invention: recording layers for the photomechanical production of printing plates for relief printing, planographic printing, gravure printing and screen printing, of relief copies, for example production of braille text, of individual copies, tanned images, pigmented images, etc. The mixtures may also be used for the photomechanical production of etch resists, for example for producing name plates, of printed circuits, and for chemical milling. The mixtures according to the invention are especially important as recording layers for producing planographic printing plates and for use in photoresist technology.
Suitable layer carriers for the recording material according to the invention are for example aluminum, steel, zinc, copper and plastics films, for example of polyethylene terephthalate or cellulose acetate, and also screen printing carriers such as Perlon gauze. It is convenient in many cases to pretreat (chemically or mechanically) the carrier surface, the purpose of which pretreatment is correctly to adjust the adhesion of the layer, improve the lithographic properties of the carrier surface, or reduce the reflectance of the carrier in the actinic region of the copying layer ~-(antihalation).
The light-sensitive materials are prepared in a known manner. For example, the layer constituents can be taken up in a solvent and the solution or dispersion can be applied to the intended carrier by pouring, 209703~
spraying, dipping, roller application, etc., and then dried.
Due to the broad spectral sensitivity of the recording material according to the invention, all light sources known to those skilled in the art may be used, for example tubular lamps, pulsed xenon lamps, metal halide-doped high-pressure mercury vapor lamps and carbon arc lamps. Furthermore, irradiation in normal projection and magnification equipment under the light from metal filament lamps and contact irradiation with normal incandescent lamp bulbs is possible with the light-sensitive mixtures according to the invention.
Irradiation can also be effected with the coherent light from a laser. Tuned lasers are suitable for the lS purposes of the present invention, for example argon ion, krypton ion, dye, helium-cadmium and helium-neon lasers, which emit in particular from about 250 to about 650 nm. The laser beam can be controlled by means of a preprogrammed linear and/or dot-like movement.
In general it is convenient to exclude as far as possible the influence of atmospheric oxygen on the mixtures during the light polymerization. In the case where the mixture is used in the form of thin copying layers it is recommended to apply a suitable cover film that is only slightly permeable to oxygen. This cover film may be self-supporting and can be removed before the copying layer is developed. Polyester films for example are suitable for this purpose. The cover film may also comprise a material that dissolves in the developer liquid or that can at least be removed during development from the non-hardened places. Suitable materials for this purpose include polyvinyl alcohol, polyphosphates, sugars, etc. Such cover layers generally have a thickness of from about 0.1 to about 10 ~m, preferably from about 1 to about 5 ~m.
" ~
20970t',8 The materials are processed further in a known manner.
A post-heating may be carried out after irradiation in order to improve the crosslinking of the layer. The materials are developed with a suitable developer solu-tion, for example with organic solvents, but preferablywith a weakly alkaline aqueous solution, the non-irradiated parts of the layer being removed and the irradiated regions of the copying layer remaining on the carrier. The developer solutions may contain a small proportion, preferably less than 5% by weight, of water-miscible organic solvents. They may also contain wetting agents, dyes, salts and other additives.
The whole cover layer together with the non-irradiated regions of the photopolymerizable layer are removed in the development process.
Embodiments of the invention are given hereinafter. In these embodiments parts by weight (pbw) and parts by volume (pbv) are in the same ratio as g to ccm. Unless otherwise stated, percentages and amounts are by weight.
Examples 1-7(Comparative examples) ~ .
Solutions of:
2.87 pbw of a polymeric binder 6.76 " of the reaction product of 1 mol of triethanolamine with 3 mol of isocyanato ethyl methacrylate, as monomer, 0.18 " alcohol-soluble Eosin (C.I. 45 386) 0.14 " 2,4-bis-trichloromethyl-6-(4-styrylphenyl)-s-triazine, and 0.05 " dicyclopentadienyl bis(pentafluorophenyl-titanium) in 85 " propylene glycol monomethyl ether and 46 " butanone ' ~, ~ . . . ... . .
were applied to electrolytically roughened and anodically oxidized aluminum plates having an oxide layer of 3 g/m2 that had been pretreated beforehand with an aqueous solution of polyvinylphosphonic acid. The layers were dried for 2 minutes at 100C in a circulating air cabinet and then had a layer weight of 2.1 g/m2. An 8% strength aqueous solution of polyvinyl alcohol (12~ residual acetyl groups, K value 4) was then applied in such a thickness that a layer weight of 2.4 g/m2 was obtained after the drying (2 minutes at 100 C) .
~he printing plates obtained were in each case irradi-ated for 20 seconds with a 60 W incandescent lamp at a distance of 80 cm under a 13-step standard stepped photometric absorption wedge with density steps of 0.15. After irradiation the plates were post-heated for one minute at 100C and then developed with a developer having the following composition:
1 pbw trisodium citrate x 2 H2O, 2 " 1-amino-2-propanol, 1.4 " benzyl alcohol, l.S " sodium cumol sulfonate (40% strength solution) 0.04 " sodium metasilicate x 5 H2O 5 0.02 " fatty alcohol polyglycol ether (non-ionogenic wetting agent) 94.04 " water In a further experiment the light-sensitive plates were treated with the developer without any image-forming irradiation. The following binders were used:
Example 1 terpolymer of styrene, n-hexyl methacrylate and methacrylic acid (10:60:30; acid number 190) 20~7~38 Example 2 copolymer of styrene and maleic acid semi-ester (acid number 185; ~Scripset 540) Example 3 copolymer of 95% vinyl acetate and 5%
crotonic acid Example 4 copolymer of 65% vinyl acetate and 35%
dibutyl maleate Example 5 copolymer of acrylic acid, styrene and a-methyl styrene, acid number 245; M~ 7000 Example 6 reaction product of a polyvinyl butyral (71%
vinylbutyral units, 2% vinyl acetate units, 27% vinyl alcohol units, M~ = 70000-80000) with maleic anhydride; acid number 30 Example 7 methylmethacrylate/methacrylic acid copolymer, acid number 117 The results are summarized in Table 1. The second column gives the number of the solid, i.e. completely . hardened wedge steps. The comparisons show, with the specified binder content, none of the layers could be satisfactorily developed in such a way that the irradiated regions of the layer remained unaffected while the non-irradiated regions were completely removed.
.
Table 1 With irradiation Without irradiation Wedge Remarks steps 1 4 _ partially delayered 2 _ not partially developed delayered 3 1 _ completely delayered 4 _ completely completely delayered delayered _ not partially developed delayered I
6 _ not not delayered developed 7 _ not partially developed delayered Exam~les 8-10 (Com~arative Examples) Printing plates were produced as described in Example l, the monomer being replaced by the same amount of monomers specified in Table 2. The further procedure was as described in Example 1; Table 2 shows the number of solid wedge steps.
~.
,~
20970~8 Table 2 Example Monomer Wedge steps ¦
I
1 as specified there 8 the reaction product of 2 mol 4 of isocyanato ethyl methacrylate and 1 mol of 2-hydroxyethylpiperidine 9 reaction product of 3 mol of 3 isocyanato ethyl methacrylate and 1 mol of diethanolamine reaction product of 2 mol of 4 hexamethylene diisocyanate, 2 mol of hydroxyethyl meth-acrylate and 1 mol of 2-hyd-roxyethylpiperidine Example 11 (Comparative ExamPle) A printing plate was produced as described in Example 1. The following coating solution was used.
2.87 pbw of the terpolymer of Example 1 6.64 " of the reaction product of 2 mol of hexamethylenediisocyanate, 2 mol of 2-hydroxyethyl methacrylate and 1 mol of 2-(2-hydroxyethyl)piperidine, as monomer 0.18 " alcohol-soluble Eosin (C.I. 45386) 0.14 " of the triazine given in Example 1 0.05 " of the titanocene given in Example 1, and 0.12 " Renol blue (C.I. 20 505) in " propylene glycol monomethyl ether and 46 " butanone.
After irradiation and development as described in Example 1, 4-5 solid wedge steps were obtained.
Example 12 (Comparative Example) The same procedure as in Example 11 was adopted, though the compound specified in Example 1 was used, in the same amount as in Example 11, as monomer. Four solid wedge steps were obtained.
Example 13 (Comparative Example) The same procedure as in Example 11 was adopted, though the reaction product of 2 mol of isocyanato ethyl meth-acrylate and 1 mol of 2-(2-hydroxyethyl)piperidine was used, in the same amount as in Example 11, as monomer.
Four solid wedge steps were obtained.
Example 14 (Comparative ExamPle) The same procedure as in Example 11 was adopted, though the reaction product of 3 mol of isocyanato ethyl methacrylate and 1 mol of diethanolamine was used, in the same amount as in Example 11, as monomer. Three solid wedge steps were obtained.
Example 15 (Comparative Exam~le~
Printing plates were produced as described in Example 11! the amounts of the constituents being altered in each case as follows:
a) 6.36 pbw monomer (- 0.28) 0.46 " Eosin (+ 0.28) b) 6.74 pbw monomer (+ 0.1) 0.04 " triazine (- 0.1) c) 6.4 pbw monomer (- 0.24) 0.29 " titanocene (+ 0.24) ;
d) 3 03 pbw terpolymer (+ 0.16) 6.48 " monomer (- 0.16) e) changes (a) and (d) f) changes (a), (b) and (d) g) changes (a), (b), (c) and (d) , ., ., ~0370c,~
The multiple changes (e), (f) and (g) were made so that the total amount remained constant in each case. The plates were otherwise produced and processed as in Example 11. The following numbers of completely solid wedge steps were obtained:
Example Wedqe steps 15 a 4-5 15 b 4 15 c 6-7 15 d 4 15 e 4 15 f 4 15 g 7-8 Exam~les 16-22 (Comparative Examples) Printing plates were coated as described in Example 1 with the following solution:
3.04 pbw binder 6.06 " of the monomer given in Example 11, 0.46 " alcohol-soluble Eosin 0.04 " of the triazine given in Example 1, 0.29 " of the titanocene given in Example 1, and 0.12 " Renol blue in : 85 " propylene glycol monomethyl ether and 46 " butanone The plates were produced and processed as described in Example 1. The following table shows the numbers of solid wedge steps obtained with irradiation times of 20 and Z seconds under the conditions specified in Example 1.
,. ~ . ,.. ., , . -, . : -2097~38 Example BinderWedge steps according to 16 Example~0 C~-3 ~ 1 ~
7_8 Examples 23-31 (including Comparative Examples 24, 25, 27, 28, 30 and 31) Coating solutions according to the formulation given in Example 16 were used to prepare printing plates, the nature and amount of the binder and also the amount of the monomer being specified in the following table. The table also shows the number of solid wedge steps after 6 seconds' irrsdiation.
(j ~ ' ., - 20 - 2 0 9 7 0 3 ~
Example Binder Amount Amount of Wedge according pbw monomer, steps to Example pbw 23 7 1.5 7.6 5-6 24 7 3.0 6.1 4 7 4.5 4.6 26 1 1.5 7.6 5-6 27 1 3.0 6.1 3 28 4.5 4.6 29 1.5 7.6 5-6 2 3.0 6.1 3 31 2 4.5 4.6 _
Claims (13)
1. A photopolymerizable mixture that comprises:
a) a polymeric binder, b) a free-radically polymerizable compound having at least one polymerizable group, and, as photoinitiators:
c) a photoreducible dye d) a radiolyzable trihalomethyl compound, and e) a metallocene compound, wherein the binder (a) is present in an amount of from about 5 to about 25%, the polymerizable compound (b) is present in an amount of from about 60 to about 90%, and the photoinitiators (c), (d) and (e) are present in a total amount of from about 3 to about 20%, based on the weight of the nonvolatile constituents.
a) a polymeric binder, b) a free-radically polymerizable compound having at least one polymerizable group, and, as photoinitiators:
c) a photoreducible dye d) a radiolyzable trihalomethyl compound, and e) a metallocene compound, wherein the binder (a) is present in an amount of from about 5 to about 25%, the polymerizable compound (b) is present in an amount of from about 60 to about 90%, and the photoinitiators (c), (d) and (e) are present in a total amount of from about 3 to about 20%, based on the weight of the nonvolatile constituents.
2. A mixture as claimed in claim 1, wherein the metallocene compound is a titanocene or zirconocene.
3. A mixture as claimed in claim 1, wherein the binder (a) is present in an amount of from about 10 to about 19%.
4. A mixture as claimed in claim 1, wherein the photoinitiators (c), (d) and (e) are present in a total amount of from about 6 to about 12%.
5. A mixture as claimed in claim 1, wherein the metallocene compound (e) is present in an amount of from about 30 to about 55%, based on the total amount of (c), (d) and (e).
6. A mixture as claimed in claim 1, wherein the free-radically polymerizable compound is an acrylic or alkylacrylic acid ester having at least one group that is photooxidizable on irradiation in the presence of the photoreducible dye.
7. A mixture as claimed in claim 6, wherein the photooxidizable group is an amino, urea, thio or enol group.
8. A mixture as claimed in claim 1, wherein the photoreducible dye is a xanthene, thiazine, pyronine, porphyrin or acridine dye.
9. A mixture as claimed in claim 1, wherein the radiolyzable trihalomethyl compound is an s-triazine which is substituted by at least one trihalomethyl group or is an aryltrihalomethyl sulfone.
10. A mixture as claimed in claim 1, which also contains as photoinitiator an acridine, phenazine or quinoxaline compound that acts as a photoinitiator.
11. A mixture as claimed in claim 1, wherein the binder is insoluble in water but is soluble in aqueous-alkaline solutions.
12. A photopolymerizable recording material having a layer carrier and a photopolymerizable layer, wherein the photopolymerizable layer comprises a mixture as claimed in claim 1.
13. A recording material as claimed in claim 12, which comprises, on the photopolymerizable layer, a further transparent layer that is only slightly permeable to atmospheric oxygen, which further layer is soluble in a developer liquid for the photopolymerizable layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924217495 DE4217495A1 (en) | 1992-05-27 | 1992-05-27 | Photopolymerizable mixture and recording material produced therefrom |
| DEP4217495.3 | 1992-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2097038A1 true CA2097038A1 (en) | 1993-11-28 |
Family
ID=6459811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2097038 Abandoned CA2097038A1 (en) | 1992-05-27 | 1993-05-26 | Photopolymerizable mixture and recording material prepared therefrom |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0573805A1 (en) |
| JP (1) | JPH0635189A (en) |
| CA (1) | CA2097038A1 (en) |
| DE (1) | DE4217495A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051366A (en) * | 1994-05-27 | 2000-04-18 | Kodak Polychrome Graphics Llc | Visible radiation sensitive composition and recording material producible therefrom |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2158915A1 (en) † | 1994-09-30 | 1996-03-31 | Dekai Loo | Liquid photoimageable resist |
| TW369554B (en) * | 1995-10-19 | 1999-09-11 | Three Bond Co Ltd | Photocurable composition |
| US5824180A (en) * | 1995-10-19 | 1998-10-20 | Three Bond Co., Ltd. | Method of bonding or decorating artificial nail |
| CA2243381A1 (en) * | 1996-11-20 | 1998-05-28 | Polaroid Corporation | Protective overcoat useful for enhancing an article's resistance to ambient humidity |
| DE19729067A1 (en) | 1997-07-08 | 1999-01-14 | Agfa Gevaert Ag | Infrared imageable recording material and offset printing plate made therefrom |
| DE19739299A1 (en) * | 1997-09-08 | 1999-03-11 | Agfa Gevaert Ag | White light-insensitive, thermally imageable material and process for the production of printing forms for offset printing |
| DE19845605A1 (en) | 1998-10-05 | 2000-04-06 | Agfa Gevaert Ag | Concentrate and aqueous developer made therefrom for imagewise irradiated recording materials |
| DE19940921A1 (en) | 1999-08-27 | 2001-03-01 | Agfa Gevaert Ag | Photopolymerizable mixture and recording material produced therewith |
| EP1199606A1 (en) | 2000-10-16 | 2002-04-24 | Fuji Photo Film Co., Ltd. | Plate-making method of lithographic printing plate |
| US6936384B2 (en) | 2002-08-01 | 2005-08-30 | Kodak Polychrome Graphics Llc | Infrared-sensitive composition containing a metallocene derivative |
| DE10255667B4 (en) | 2002-11-28 | 2006-05-11 | Kodak Polychrome Graphics Gmbh | Radiation-sensitive elements with excellent storage stability |
| JP4127156B2 (en) * | 2003-08-08 | 2008-07-30 | ヤマハ株式会社 | Audio playback device, line array speaker unit, and audio playback method |
| DE10356847B4 (en) | 2003-12-05 | 2005-10-06 | Kodak Polychrome Graphics Gmbh | Radiation sensitive compositions and imageable elements based thereon |
| JP2011090294A (en) | 2009-09-24 | 2011-05-06 | Fujifilm Corp | Method of preparing lithographic printing plate |
| DE102021006273B4 (en) | 2021-12-21 | 2024-06-13 | Lohmann Gmbh & Co. Kg | Indicator mixture |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3832032A1 (en) * | 1988-09-21 | 1990-03-22 | Hoechst Ag | PHOTOPOLYMERIZABLE MIXTURE AND RECORDING MATERIAL MANUFACTURED THEREOF |
-
1992
- 1992-05-27 DE DE19924217495 patent/DE4217495A1/en not_active Withdrawn
-
1993
- 1993-05-13 EP EP93107786A patent/EP0573805A1/en not_active Withdrawn
- 1993-05-26 CA CA 2097038 patent/CA2097038A1/en not_active Abandoned
- 1993-05-27 JP JP14844393A patent/JPH0635189A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051366A (en) * | 1994-05-27 | 2000-04-18 | Kodak Polychrome Graphics Llc | Visible radiation sensitive composition and recording material producible therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0635189A (en) | 1994-02-10 |
| DE4217495A1 (en) | 1993-12-02 |
| EP0573805A1 (en) | 1993-12-15 |
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