CA1061156A - Lithographic plate with layer of photosensitive diazo-oxide resin - Google Patents
Lithographic plate with layer of photosensitive diazo-oxide resinInfo
- Publication number
- CA1061156A CA1061156A CA220,777A CA220777A CA1061156A CA 1061156 A CA1061156 A CA 1061156A CA 220777 A CA220777 A CA 220777A CA 1061156 A CA1061156 A CA 1061156A
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- Canada
- Prior art keywords
- group
- photosensitive
- printing plate
- lithographic printing
- quinonediazide
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/22—Oxygen
- C08F112/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Emergency Medicine (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A photosensitive lithographic printing plate comprising a support having thereon a photosensitive layer composed of a photosensitive diazo-oxide resin containing a hydroxystyrene unit and a hydroxystyrene unit having an o-quinonediazide group bonded through the oxygen of the hydroxystyrene. The photosensitive layer can contain an alkali-soluble resin. The photosensitive lithographic printing plate is stable mechanically, provides a large difference in solubility between the exposed areas and the unexposed areas of the layer, and has improved printability and sensitivity.
A photosensitive lithographic printing plate comprising a support having thereon a photosensitive layer composed of a photosensitive diazo-oxide resin containing a hydroxystyrene unit and a hydroxystyrene unit having an o-quinonediazide group bonded through the oxygen of the hydroxystyrene. The photosensitive layer can contain an alkali-soluble resin. The photosensitive lithographic printing plate is stable mechanically, provides a large difference in solubility between the exposed areas and the unexposed areas of the layer, and has improved printability and sensitivity.
Description
5~
___~ __,_ ~_________________ 1. Field of the Invention The present invention relates to a photosensitive litho-graphic printing plate and more particularly, the invention relates to a lithographic printing plate having a photosensitive layer of a novel and improved photosensitive diazo-oxide resin.
___~ __,_ ~_________________ 1. Field of the Invention The present invention relates to a photosensitive litho-graphic printing plate and more particularly, the invention relates to a lithographic printing plate having a photosensitive layer of a novel and improved photosensitive diazo-oxide resin.
2. Description of the Prior Art It is well known to use a photosensitive diazo-oxide in the production of photocopies or photoresists and also as a photosensitive rnaterial for litho~raphic printing plates. In these techniques, as the result of light exposure, due to the properties of the photosensitive diazo-oxide, a difference in soluhilit~v between the exposed areas and the unexposed areas~
results and by treating the exposed layer of such a material with an appropriate solvent, a desired image portion remains on the support while undesired portions are washed away from the support. These techniques are described in detail in the specl-fications of, e.g , U.S. Patent Nos. 3,046,1~1, 3,046,122, and
results and by treating the exposed layer of such a material with an appropriate solvent, a desired image portion remains on the support while undesired portions are washed away from the support. These techniques are described in detail in the specl-fications of, e.g , U.S. Patent Nos. 3,046,1~1, 3,046,122, and
3,046,123. In the above patents, the ester or acid amide of benzenediazo-oxide or naphthalenediazo-oxide is used as the photosensitive material for photosensitive lithographic printing plates. Other various materials for thls purpose have also been reported.
~ Iowever, almost all of these compounds are low molecular weight compounds and when such a compound is used individually for a photosensitive litho~raphic printing plate, crystallization occurs, which results in a poor film of the compound being obtained, and thus the ima~e formed has low mechanical strength~ This makes it difficult to ohtain many satisfactory copies or prints. There-fore, the aforeE;aid photosensitive materjal is frequently used ~p~
together with an alkali-soluble reslnous binder or as a compound formed by the reaction thereof with an alkali-soluble resinous material.
Such polymers are described in the specifications of United States Patent Number 3,046,120, British Patent Number 1,113,759, and United States Patent Number 3,759,711. The compounds described in these specifications are mainly polymers such as phenol resins and aminostyrene resins.
However, although these compounds may have good sensi-tivity and provide sufficient difference in solubility between the exposed areas and the unexposed areas, they have the dis-advantages that coated layers of these compounds are brittle and have a comparatively poor flexibility.
SUMMARY OF THE INVENTION
An object of this invention is, therefore, to provide a photosensitive lithographic printing plate having a layer of a photosensitive diazo-oxide resin without the above-described disadvantages.
Another object of this invention is to provide a stab]e photosensitive lithographic printing plate having a layer of a photosensitive diazo-oxide resin comprising a polymer in which a diazo-oxide compo~nd, which is a photosensitive group, is bonded, as a side chain, to the main chain of a homopolymer or copolymer of hydroxystyrene.
Still another object of this invention is to provide a photosensitive lithographic printing plate having a photosensitive layer having a large difference in solubility in a developer between the exposed portions and the unexposed portions thereof.
A further object of this invention is to provide a photosensitive lithographic printing plate having a long press life and high sensitivity.
As the results of various investigations on attaining the above-described objects of this invention, the photosensitive lithographic printing plate of this invention has been obtained.
That is to say, according to the present invention there is provided a photosensitive lithographic printing plate comprising a support having thereon a layer of a photosensitive diazo-oxide resin containing a hydroxystyrene unit and a hydroxystyrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of hydroxystyrene.
1~ Also, according to another embodiment of this invention there is provided a photosensitive lithographic printing plate comprising a support having thereon a layer of a photosensitive composition comprising a photosensitive diazo-oxide resin and an alkali-soluble resin, the photosensitive diazo-oxide resin con-taining a hydroxystyrene unit and a h~droxystyrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of hydroxystyrene.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
__,____________________________._____________. _ Figure 1 is a schematic cross sectional view showing an embodiment of the photosensitive lithographic printing plate of this invention.
Figure 2 is a cross sectional view of the photosensitive lithographic pxinting plate shown in Figure 1 after exposure.
Figure 3 is a cross sectional view of the photosensitive lithographic printing plate shown in Figure 2 after development~
DETAILED DESCRIPTION OF THE INVENTION
_____________________________________ The lithographic printing plate of this invention comprises a support ~ith a hydrophilic surface having thereon a photosensitive layer mainly comprising a specific photosensitive diazo-oxide resin.
The support used in this inven~ion is a dimensionally stable support such as a sheet or plate and various kinds of supports which have hitherto been used for printing plates can be used in this invention. Examples o~ such supports include paper, a paper coated with a polymer (such as polyethylene, polypropylene, polystyrene, etc.); a plate or a sheet of a metal such as aluminum, an aluminum alloy, zinc, copper, etc.; a film of a polymer such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, poly-~thylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc~; a paper or a polymer film having coated or vacuum deposited thereon a metal as described above.
Of these supports, an aluminum support is dimensionally stable, is inexpensive, and is particularly preferred. Further-more, a composite sheet of a polyethylene terephthalate film having an alum;num sheet bonded thereto is also preferred as a support.
Particularly,~ the surface of the support must be hydro-philic and various methods are known for rendering the surface hydrophilic.
For instance, for a support with a polymer surface, surface treatments such as a chemical treatment, a corona dis-charge treatment, a flame treatment, an ultraviolet treatment, a high frequency wave treatment, a glow discharge treatment, a laser treatmentr etc., (as described in the specifications of U.S. Patent Nos. 2,764,520, 3,497,407, 3,145,242, 3,376,208, 3,072,483, 3,475,193 and 3,360,448 and the speci~ication of 1 British Patent No. 7g8,365) can be used and a method where the surface is subjected to the aforesaid suxface treatment and then a subbing layer is formed on the treated surface of the polymer layer can be employed. A suitable subbing layer comprises a coating of a 1~ by weight acrylic acid aqueous solution or a coating of polyvinyl alcohol onto a grained aluminum plate, which, when washed, provides a hydrophilic coating. A diazo resin layer is then coated thereon. Suitable examples of subbing layers are disclosed in British Patent 918,599 and U.S. Patent 3,064,562.
Various approaches have been used for forming a subbing layer on the polymer surface. For ins-tance, a double layer method in which a hydrophobic resin layer which adheres well to the poly-mer surface and has good solubility is formed on the polymer surface as a first layer and then a h~drophilic layer is formed as a second layer and a single layer method in which a layer of a polymer havin~ a hydrophobic group and a hydrophilic group in the same molecule is formed on the polymer surface have been used.
~ lso, in the case of a support having a metallic surEace, in particular, the surface of aluminum, preferably the surface of the metallic layer or support has been subjected to a graining treatment~ an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, a phosphate, etc., or an anodic oxidation treatment. Also, an aluminum plate which is grained and immersed in an aqueous solution of sodium silicate as described in the specification of U.S. Patent No. 2,714,066 and an aluminum plate which is subjected to an anodic oxidation treatment and then immersed in an aqueous solution of an alkali metal silicate as described in the specification of U.S. Patent No. 3,181,~61 can be used appropriately in this invention~ The above-described anodic oxidation treatment can be conducted by _ 5 _ Y placing the aluminum plate in an electrolyte of an aqueous solu-tion or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., an organic acid such as oxalic acid, sulfamic acid, etc., or a salt thereof or of a combination of these solutions and an electric current is passed using the aluminum plate as the anode.
Moreover, the electrodeposition of silicate as described in the specification of ~.S. Patent No. 3,658,662 can be effect-ively employed for the surface treatment of an aluminum layer or 1~ sheet.
The above-described surface treatment is employed, in addition to rendering surface of a support hydrophilic, to prevent the occurrence of any harmful reactions with the photosensitive composition formed thereon and to improve the adhe:rence between the support surface and the photosensitive layer formed thereon.
In particular, however, when aluminum is used as the support, the surface thereof has sufficient hydrophilic property without the necessity oE any surface treatment to render the surface hydrophilic and hence the surface treatment as described above is applied to the surface o the aluminum support mainly for preventing the occurrence of any harmful reactions with the photosensitive composition and improving the adherence between the support surface and the photosensitive layer formed thereon.
The photosensitive diazo-oxide resin used in this invention contains at least a hydroxystyrene unit and a hydroxy-styrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of the hydroxystyrene. Examples of such a resin are those containing therein structural units represented by the following general formulas (I) and (II) --~CH2-CH ) X ( C~2-CH~
OH
Xl 1 -~-C 2 )x ~ 2 ~
OH
Rl CH--OH
wherein X represents a connecting group such as a sulfonyl group ~ .
-~ S ~- , or a carbonyl group ( C ~--, etc.; Rl represents an o aromatic o-quinonediazide group such as 1,2-benzoquinonediazide, 1,2-naphthoquinonediazide, 3,3',4,4'-biphenyl-bis-quinonediazide, 2,3-phenanthrenequinonediazide, etc., in which the o-quinone-diazide group can have a substituent on the aromatic nucleus, for instance, an alkyl group (e.g., having generally l to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, etc.) or an alkoxy group (e.g., having generally l to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a ~V61~
1 hexyloxy group, a heptyloxy group, an octyloxy group, etc.);
and R2 represents an alkyl group (e.g., having l to 4 carbon atoms), an aryl group (e.g., a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc.3, or a substituted aryl group and further R2 can include a quinonediazide group substi~
tuted witll an alkyl or aryl group if the photodecomposition of the quinonediazide is not affected by such a substituent. Here-inafter, for brevity, the compound containing therein structural units of the general formula (I) is designated "compound of the i general formula (I)" and the compound containing therein struc-tural units of the general formula (II) is designated "compound of the general formula (II)".
The molecular weight of the compound of the general formula (I) can range from ahout l,000 to about 30(),000, pre-ferably from 3,000 to lO0,000, x and y each represents the molar proportions of the components designated and x/x+y is from about 0 05 to 0.5, preferably from 0.1 to 0.4.
The compound of the general formula (I~ can be pre-pared using, for instance, the following polymerization reaction.
That is to say, poly(p-hydroxystyrene) which becomes the main chain of the polymer and an acid halide of a diazo-o~ide to be reacted, such as, for instance, quinonediazidosulfonyl chloride, quinonediazidocarbonyl chloride, etc., are uniformly dissolved in a common solvent such as dioxane, tetrahydrofuran, acetoner etc., and then the reaction, generally at about -10C to ~0C, preferably 20C to 40C, is conducted by adding, for instance, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, pyridine, etc., to the solution as a base, generally in an amount substantially equivalent to the quinone-diazido acid halide. A suitable molax ratio of the acid halide to the poly-(p-hydroxystyren~ is about 0.1 to 1 equivalent, pre-ferably 0.2 to 0.8 equivalent, per hydroxyl group equivalent.
Then, by purifying the reaction mixture thus obtained by a re-crystallization method, the photosensitive diazo-oxide resin of this invention is obtained. The poly-(p-hydroxystyrene) can be prepared in accordance with the disclosure in J. Poly. Sci.
A-l, 7, 2175 ~ 2184 (1969~ and ibid., 7, 2405 ~ 2410 (1969).
The molecular weight of the compound shown by general formula (II) can range from about 1,000 to about 300,000, pre-ferably from 3,000 to 100,000. Also, x, y and z each represents the molar proportions of the components designated and the ratio x/xfy~z is from about 0.05 to 0.5 and the ratio y/x+y-~z is from about 0.05 to 0.2.
The compound of the general formula (II) can be prepar~d in the following manner. That is to say, poly-(p-hydroxystyrene) which is also used as a starting material in the production of the compound of general formula (I) is first reacted with a glycidyl ether such as phenylglycidyl ether in a solvent such as acetone, tetrahydrofuran, methyl ethyl ketone, dioxane, etc., preferably methyl ethyl ketone, in the presence of triethylamine, 1,4-diazabicyclo[2,2,2]octane etc., in an amount of about 0.005 to 0.1 g, preferably 0.01 to 0.2 g, per g of the poly-(p-hydroxy-styrene), e.g., at about -10C to 80C, preferably 20C to 40C, particularly preferably at reflux, to form the polymer containing therein structural units represented by the following general formula (III) _ g _ ( CH2-CH )x ( C 2 1 ~
(III) OH o Cll CH2 0 ~
I
OH
wherein x and y are as described above.
Then, by reacting the polymer of general formula (II~) thus formed with the acid halide of a diazo-oxide as in the case of producing the compound of general ormula (I) and under the conditions as described above, th~ compound of general formula ~II) is obtained. Alkyl substituted glycidyl ethers and alkyl substituted phenyl glycidyl ethers in which the alkyl moiety has 1 to 4 carbon atoms can also be used as a starting material in the above procedures.
In the above-described processes of producing the photo-sensitive diazo-oxide resin of this invention, polyhydroxystyrene is used as the starting material but in place of such a compound, a copolymer of hydroxystyrene and a monomer not having a group with which the o-quinonediazide and the photodecomposition pro-duct thereof reacts can also be used as the starting material.
Examples of such a copolymerizable comonomer for the copolymer are phthalic anhydride, styrene, acrylonitrile, an acrylic acid ester, and a methacrylic acid ester.
The photosensitive diazo-oxide compound of this inven-tion can be used individually as a photosensitive layer of the photosensitive lithographic printing plate of this invention but it is more preferable to use the compound together with an alkaline solution-soluble resin as a binder therefor. Preferred examples of such an alkali-soluble resin are phenol formaldehyde resins, cresol resins, styrene-male;c anhydride copolymers, and shellac. A suitable molecular weight range for the phenol-form-aldehyde resins and the cresol resins can ran~e from about 2,000 to 50,000, preferably 4,000 to 10,000, and for the styrene-maleic anhydride copolymer can range from about 5,000 to 20,000, pre-ferably 8,000 to 14,000. Such a resin is soluble in an alkaline solution, has high adhesivity to support, and provides desirable 1~ effects in printability. Examples of such resins are disclosed in Synthetic Resins_in Coating, H.P. Preuss Noyes Development Corp., Pearl River, New York (1965).
In using the mixture of the photosensitive diazo-oxide compound of this invention and the alkaline solution-soluble binder resin, a suitable propo~tion of the photosensitive diazo-oxide is more than about 20~ by weight. If the proportion of the photosensitive diazo-oxide is less than about 20% by weight of the mixture, difficulties in development occur providing images which are not sufficient and hence good prin-ts are not obtained.
XO Furthermore, by incorporating the various additives as described hereinafter in the photosensitive layer of the photo-sensitive lithographic printing plate of this invention, the printing plate can be provided with desired specific properties.
For instance, in order to obtain visible images by light exposure and development of the photosensitive lithographic printing plate, a dye can be incorporated in the photosensitive layer of the printing plate. Suitable examples of appropriate dyes which can be used for this purpose include C.I. 26,105 (Oil Red RR), C.I.
21,260 (Oil Scarlet ~308~, C.I. 74,350 (Oil Blue), C.I. 52,015 (Methyl Blue), C.I. 42,555 (Crystal Violet), etc. Such a dye 1 can be incorporated in the photosensitive layer in an amount which provides a suf~iciently clear contrast between the color of the hydrophilic surface of the support exposed by light-exposure and development o~ the photosensitive layer of the photosensitive lithographic printing plate and the color of the remaining portions of the photosensitive layer and, in general, it is appropriate to incorporate the dye at a level of less than about 7% by weight to the total amount of the photosensitive composition ~or forming the photosensitive layer.
~ Also, the photosensitive composition can contain a plasticizer for imparting the desired flexibility to the photo-sensitive layer formed on the support. Examples of effective plasticizers which can be used for this purpose are phthalic acid esters such as dimethyl phthalate, diethyl phthalat:e, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octylcapryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl-benzyl pht-halate, diisodecyl phthalate, diaryl phthalate, etc.;
glycol esters such as dimethylglycol phthalate, ethylphthalylethyl glycolate, meth~lphthalylethyl glycolate, butylphthalylbutyl glycolate, triethyleneglycol dicaprylic acid ester, etc.;
phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, etc.; aliphatic dicarboxylic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl maleate, etc.; polyglycidyl methacrylate; citric acid triethyl ester; glycerin triacetyl ester; and butyl laurate.
~ he plasticizer is usually employed in an amount of less than about 5% by weight to the total amount o~ the photo-sensitive composition.
Also, in order to obtain visible images i-mmediately by exposing the photosensitive lithographic printing plate of this invention, the following spiropyran compounds which are discolored by light exposure can be incorporated in the photo-sensitive compositions as described in the specification of British Patent No. 1,154,716. Suitable examples include 6-nitro-ben70indolinospiropyran, 1,3,3-trimethylindolino-8'-methoxy-6'-nitrobenzospiropyran, 6'-nitro-1,3,3-trimethy]indoline benzospiro-pyran, 1,3,3-trimethylindolinobenzospiropyran, 1,3,3-trimethyl-indolino-~-naphthospiropyran, xantho-~-benzospiropyran, 6'-nitro-1,3,3-trimethylspiro(indoline-2,2'-2'H-chromene), 6',8'-dichloro-l,313-trimethylspiro(indoline-2,2'-2'~-chromene), etc. A suitahle amount of the spiropyran compound is ahout 2 to 20% by wei~ht to the total amount of the photosensitive composition.
The photosensitive composition containing the photo-sensitive diazo-oxide compound of this invention together with, if desired, the above-described additives is coated on a support having a hydrophilic surface as a solution or a dispersion in an appropriate solvent. Examples of the solvent which can be used for this purpose are organic solvents such as ketones, e.g., methyl ethyl ketoner acetone, methyl isobutyl ketone, etc.;
ethyleneglycol monoalkyl ethers, e.g., ethyleneglycol methyl ether, ethyleneglycol monoethyl ether, etc.; ethers, e.g., dioxane, tetrahydrofuran, etc.; and a mixed solvent thereof, such as ethylene dichloride and methyl cellosolve acetate. When the photosensitive composition is coated as a solution thereof, pre-ferably the concentration of the composition in the solution is about 1 to 50~ by weight, preferably 4 to 20% by weight.
The coating composition can be coated using conventional methods such as, for instance, dip coating, air knife coating, bead coating, curtain coating, and also extrusion coating using the hopper as descrihed in the specification of U.S. Patent ~o.
2,68],294.
The amount of the photosensitive layer coated on a support generally ranges from about 0.1 g/m2 to about 5 g/m2 but the amount of the photosensitive layer suitable for obtaining from about 10 to 10,000 good copies ranyes from about 1.0 y/m2 to about 3.5 g/m . If particular care is taken, however, in making the printing plate or in printing, about 5,000 good copies can be obtained with a coated amount of as low as about 1 g/m2.
If a longer press life is required, the coating composition pre-ferably is coated in an amount of about 3.5 g/m2. In this case, a considerable amount of exposure is required at image exposure o~ the photosensitive layer.
The photosensitive lithographic printing plate of this invention is exposed to active light, such as a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, etc~, and then the exposed portions of the photosensitive layer are removed by proc~ssing the plate with a developer, whereby the hydrophilic surface of the support is uncovered at the portions removed.
Suitable developers for the photosensitive lithographic printing plate of this invention basically include conventional alkaline solutions which have hitherto been used as developers for a photosensitive layer comprising a photosensitive diazo-oxide compound. Such alkaline solutions can suitably have a pH
of about 9.5 to 12. For instance, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium tertiary phosphate, sodium primary phosphate, sodium carbonate, potasslum carbonate, etc., or an aqueous solution of a basic solvent such as ethanolamine is used. These alkaline aqueous solutions as described above can be used individually or as a mixture thereof. Furthermore, if desired, the alkaline aqueous solution can further contain ertain organic solvents, for instance, benzyl alcohol, 2-butoxy-ethanol, 2-metho~yethanol, n-propanol, etc., in an amount of less than about 10~ by weight, preferably about 1 to 2% by weight.
By using a small amount of the organic solvent as indicated above, the speed of the development can be remarkably increased.
Furthermore, if desired, the developer can contain a wetting agent (e.g., a surface active agent). Examples of pre-ferred wetting agen~s include compounds having mor~ than 6 carbon atoms, each having a hydrophilic group such as a hydroxyl group, a carboxyl group, a sodium carboxylate group, a sulfo group, a sodium sulfonate group, and an alkyleneoxy group. Such wetting agents are well known as anionic surface active agents and non-ionic surface active agents. Examples of anionic surface active agents which can be used as a wetting agent in the developer are long chain alcohol (e.g., having about 8 to 22 carbon atoms) sulfuric acid esters, aliphatic alcohol phosphoric acid esters, sulfonates of dibasic aliphatic acid esters, aliphatic amido-sulfonates, etc~
Examples of nonionic surface active agents are polyoxy-29 ethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitanalkyl estersl polyoxypropylene ethers, polyoxyethylene ethers, etc. Specific examples of these surface active agents are described in Kaimen Kasseizai Binran (Handbook of Surface~Active Agents), published by Sangyo Tosho K.K. in 1961.
Specifically preferred wetting agents used in this invention are DUPONOL ME (the trade mark of the sodium salt of lauryl alcohol sulfate made by E.I du Pont de Nemours ~ Co.), *
MONOGEN Y-100 (the trade mark of sodium lauryl sulfate made by Daiichi Kogyo Seiyaku K.K.), the sodium salt of octyl alcohol sulfuric acid ester, the ammonium salt of lauryl alcohol sulfuric * Trade Mark 1,~,, acid esterr the sodium salt of xylenol sulfuric acid Pster, DUPONOL LS (the trade mark of the sodium salt of oleyl alcohol sulfuric acid ester made by E.I. du Pont de Nemours ~ Co ~, the monosodium salt of N,N~dihydroxyethylglycine, and the like. Of these compounds, the sodium salt of lauryl alcohol sulfuric acid ester is most preferred. These surface active agents can be used individually or as a combination of two or more compounds.
Also, the amount of the surface active agent can vary but generally the surface active agent is used at about 0.005 to 30% by weight, preferably 0.5 to 10% by weight, most preferably 4 to 8~ by weight of the developer.
The development is conducted by contacting the image exposed photosensitive layer of the photosensitive lithographic printing pla~e of this invention with the developer as described above. The contact can be used in various methods such as, for instance, immersion, spraying, etc.
After contacting the photosensitive layer and the developer for 60 to 180 seconds, the surface of the printing plate is softly rubbed using an appropriate brush, absorbent cotton, etc., whereby only the exposed portions of the photo sensitive layer are removed. In order to conduct development more effectively, the exposed surface preferably is processed with a developer at a temperature higher than about room temper-ature (about 20 ~ 30C), for instance, at about 40 to 50C.
To further clarify the invention, the invention will be explained additionally by referring to the accompanying drawings.
In an embodiment of the photosensitive lithographic printing plate of this invention as illustrated in Figure l, a photosensitive layer 2 mainly consisting of the novel diazo-oxide * Trade Mark 1 compound of this invention is formed on a support 1, such as an aluminum support, having a hydrophilic surface.
By image exposing the photosensitive lithographic printing plate showh in Figure 1, the exposed portion 2a becomes alkaline solution-soluble as shown in Figure 2.
~ he state of the image exposed photosensitive layer after development is shown in Figure 3 as a cross sectional viewO
As shown in Figure 3, the exposed portions 2a of the photosensi-tive layer 2 have heen removed and the hydrophilic surface of the support 1 has been uncovered there. The uncovered surface of the support is hydrophi]ic and oleophobic. On the other hand, the unexposed portions 2b of the photosensitive layer 2 remain on the support after development and the surface thereof is oleo-philic and hydrophobic. Thus, a printing plate is obtained.
In the present invention, by using the novel photo-sensitive diazo-oxide compound, a photosensitive lithographic printing plate having high sensitivity and exhibiting excellent printability is obtained. Furthermore, the lithographic printing plate of this invention is supexior in ink-receptivity and the control of fountain solution in printing becomes quite simple in the case of using the printing plate made from the photo-sensitive lithographic printing plate of this invention. More-over, the lithographic printing plate of this invention is stable to the passage of time.
Thus, by using the lithographic prinJcing plate of this invention, very excellent copies are obtained.
The invention will be described further by reference to the following examples. Unless otherwise indicated herein, all parts, percents, ratios and the like are by weight.
3~
27 g of naphthoquinone-1,2-diazido-5-sulfonyl chloride and 12 g of poly-(p-hydroxystyrene) haviny a mean molecular weight of 4,770 were dissolved in 100 mQ of tetrahydrofuran at room temperature. While stirring the solution, ~0 g of an aqucous solution of 13% by weight sodium carbonate was added dropwise to the solution at 30C over a period of 45 minutes. After distil-ling off excess tetrahydrofuran under reduced pressure, 100 mQ
of the reaction mixture was added to about 1 Q of water followed by stirring vigorously, whereby yellow precipitates were formed.
The precipitates were recovered by filtration, washed with water several times, and dried at room temperature under reduced pressure to provide 21 g of the photosensitive diazo-oxide resin.
SYNTHESIS EXA~IPLE 2 .
18 g of poly-(p-hydroxystyrene), 1 mQ of triethylamine, and 2.3 g of phenylglycidyl ether were reacted in 120 mQ of methyl ethyl ketone under refluxing for 8.5 hours. Thereafter, methyl ethyl ketone was distilled off under reduced pressure, the solid obtained was recovered and dissolved in about 100 mQ of methanol.
Then, the solution was added to about 750 mQ of water, whereby precipitates were formed. The precipitates were reco~ered by filtration and dried under a reduced pressure to obtain 17 g of a resin. 15 g of this resin was reacted with 27 g of naphtho-quinone-1,2-diazo-5-sulfonyl chloride in the same manner as described in Synthesis Example 1 to provide 22 g of the photo-sensitive diazo-oxide resin.
~ ne part by weight of the photosensitive diazo-oxide resin prepared in Synthesis Example 1 described above, 2 parts 1 by weight of a novolak-type phenol resin (a phenol-formaldehyde (1:0~8 molar ratio) condensation product obtained under acid conditions; molecular weight about 1,200 to 1,500), and 0.02 parts by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate. The coating composition thus prepared was coated on an aluminum plate of a thickness of 0.24 mm, the surface of which had been grained using a rotary coating machine and dried. The 1~ coated amount was 3.1 g/m~ on a dry basis.
The photosensitive lithographic printing plate thus obtained was exposed behind a transparent positive image to a Plano PS light (3.5 amperes, using a metal halide lamp) made by Fuji Photo Film Co., Ltd., at a distance of 1 meter from the light source for 40 seconds and after immersing the exposed plate in a developer containing 5~ by weight anhydrous sodium silicate for one minute at 25C, the surface of the lithographic printing plate was softly rubbed, whereby the exposed portions were removed and a positive image of the original was obtained.
When the pxinting plate thus obtained was mounted on a rotary printer and used for printing, 50,000 good copies were obtained.
Three parts by weight of the photosensitive lithographic printing plate prepared in Synthesis E~ample 1 and 0.02 parts by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate.
The coating composition was coated on an aluminum plate of a thickness of 0.3 mm, which had been subjected to graining using - 19 ~
a rotary coatin~ machine. In this case the coated amount was 2.6 g/m2 on a dry basis.
The photosensitive lithographic printing plate thus obtained was exposed behind a transparent positive image to a Plano P5 Light made by Fuji Photo Film Co., Ltd., as a light source for 3 minutes with a distance of 1 meter from the light source as in Example 1 and after immersing the exposed plate in a developer containing 5% by weight anhydrous sodium silicate for one minute at 25C, the surface of the plate was softly 1~ rubbed, whereby the exposed portions were removed and a good printing plate was obtained.
When the printing plate was mounted on a rotary printer and used for printing, 45,000 good copies were obtained.
One part by weight of the photosensitive diazo-oxide resin prepared in Example 2, 2 parts by weight of a novolak-type phenol resin, and 0.02 part by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 pcrts by weight of methyl cellosolve acetate. The coating composition thus pre-pared was coated on an aluminum plate of a thi~kness of 0.3 rnm, which had been subjected to graining using a rotary coating machine and dried. The coated amount was 2.4 g/m2 on a dry basis.
The photosensitive lithographic printing plate was exposed behind a transparent positive image to the light source as described in Example 1 with a distance of 1 meter from the light source for 40 seconds and after irnmersing the exposed plate for one minute in a developer of 15 parts by weight of butyl cellosolve, 1 part by weight of sodium primary phosphate, 7.5 parts by weight of sodiurn tertiary phosphate, 10 parts by weight of polyvinyl pyrrolidone K-15 (made by General Aniline and Film Corp.), 2 parts by weight of Monogen Y-100 ~trade name, made by Daiichi Kogyo Seiyaku K.K.), and 200 parts by weight of water, the surface of the plate was softly rubbed to provide a printing plate having excellent positive image.
When the printing plate thus obtained was used for printing on a rotary printer, 50,000 good copies were obtained.
_ Three parts by weight of the photosensitive diazo-oxide resin prepared in Example 2 and 0.02 part by weight of a dye, Oil Blue, were dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate and the coating composition was coated on an aluminum plate, which had been subjected to graining using a rotary coating machine so that the coated amount was 2.3 g/m on a dry basis.
The photosensitive lithographic printing plate was exposed behind a transparent positive image to a Plano PS Light made by Fuji Photo Film Co., Ltd. with a distance of 1 meter from the light source for 3 minutes and after immersing the exposed plate for 1 minute in a developer having the same compo-siticn as described in Example 3, the plate was softly rubbed to provide a printing plate having a good positive image.
When the printing plate thus obtained was used for printing on a rotary printer, 50,000 good copies were obtained.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
~ Iowever, almost all of these compounds are low molecular weight compounds and when such a compound is used individually for a photosensitive litho~raphic printing plate, crystallization occurs, which results in a poor film of the compound being obtained, and thus the ima~e formed has low mechanical strength~ This makes it difficult to ohtain many satisfactory copies or prints. There-fore, the aforeE;aid photosensitive materjal is frequently used ~p~
together with an alkali-soluble reslnous binder or as a compound formed by the reaction thereof with an alkali-soluble resinous material.
Such polymers are described in the specifications of United States Patent Number 3,046,120, British Patent Number 1,113,759, and United States Patent Number 3,759,711. The compounds described in these specifications are mainly polymers such as phenol resins and aminostyrene resins.
However, although these compounds may have good sensi-tivity and provide sufficient difference in solubility between the exposed areas and the unexposed areas, they have the dis-advantages that coated layers of these compounds are brittle and have a comparatively poor flexibility.
SUMMARY OF THE INVENTION
An object of this invention is, therefore, to provide a photosensitive lithographic printing plate having a layer of a photosensitive diazo-oxide resin without the above-described disadvantages.
Another object of this invention is to provide a stab]e photosensitive lithographic printing plate having a layer of a photosensitive diazo-oxide resin comprising a polymer in which a diazo-oxide compo~nd, which is a photosensitive group, is bonded, as a side chain, to the main chain of a homopolymer or copolymer of hydroxystyrene.
Still another object of this invention is to provide a photosensitive lithographic printing plate having a photosensitive layer having a large difference in solubility in a developer between the exposed portions and the unexposed portions thereof.
A further object of this invention is to provide a photosensitive lithographic printing plate having a long press life and high sensitivity.
As the results of various investigations on attaining the above-described objects of this invention, the photosensitive lithographic printing plate of this invention has been obtained.
That is to say, according to the present invention there is provided a photosensitive lithographic printing plate comprising a support having thereon a layer of a photosensitive diazo-oxide resin containing a hydroxystyrene unit and a hydroxystyrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of hydroxystyrene.
1~ Also, according to another embodiment of this invention there is provided a photosensitive lithographic printing plate comprising a support having thereon a layer of a photosensitive composition comprising a photosensitive diazo-oxide resin and an alkali-soluble resin, the photosensitive diazo-oxide resin con-taining a hydroxystyrene unit and a h~droxystyrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of hydroxystyrene.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
__,____________________________._____________. _ Figure 1 is a schematic cross sectional view showing an embodiment of the photosensitive lithographic printing plate of this invention.
Figure 2 is a cross sectional view of the photosensitive lithographic pxinting plate shown in Figure 1 after exposure.
Figure 3 is a cross sectional view of the photosensitive lithographic printing plate shown in Figure 2 after development~
DETAILED DESCRIPTION OF THE INVENTION
_____________________________________ The lithographic printing plate of this invention comprises a support ~ith a hydrophilic surface having thereon a photosensitive layer mainly comprising a specific photosensitive diazo-oxide resin.
The support used in this inven~ion is a dimensionally stable support such as a sheet or plate and various kinds of supports which have hitherto been used for printing plates can be used in this invention. Examples o~ such supports include paper, a paper coated with a polymer (such as polyethylene, polypropylene, polystyrene, etc.); a plate or a sheet of a metal such as aluminum, an aluminum alloy, zinc, copper, etc.; a film of a polymer such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, poly-~thylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc~; a paper or a polymer film having coated or vacuum deposited thereon a metal as described above.
Of these supports, an aluminum support is dimensionally stable, is inexpensive, and is particularly preferred. Further-more, a composite sheet of a polyethylene terephthalate film having an alum;num sheet bonded thereto is also preferred as a support.
Particularly,~ the surface of the support must be hydro-philic and various methods are known for rendering the surface hydrophilic.
For instance, for a support with a polymer surface, surface treatments such as a chemical treatment, a corona dis-charge treatment, a flame treatment, an ultraviolet treatment, a high frequency wave treatment, a glow discharge treatment, a laser treatmentr etc., (as described in the specifications of U.S. Patent Nos. 2,764,520, 3,497,407, 3,145,242, 3,376,208, 3,072,483, 3,475,193 and 3,360,448 and the speci~ication of 1 British Patent No. 7g8,365) can be used and a method where the surface is subjected to the aforesaid suxface treatment and then a subbing layer is formed on the treated surface of the polymer layer can be employed. A suitable subbing layer comprises a coating of a 1~ by weight acrylic acid aqueous solution or a coating of polyvinyl alcohol onto a grained aluminum plate, which, when washed, provides a hydrophilic coating. A diazo resin layer is then coated thereon. Suitable examples of subbing layers are disclosed in British Patent 918,599 and U.S. Patent 3,064,562.
Various approaches have been used for forming a subbing layer on the polymer surface. For ins-tance, a double layer method in which a hydrophobic resin layer which adheres well to the poly-mer surface and has good solubility is formed on the polymer surface as a first layer and then a h~drophilic layer is formed as a second layer and a single layer method in which a layer of a polymer havin~ a hydrophobic group and a hydrophilic group in the same molecule is formed on the polymer surface have been used.
~ lso, in the case of a support having a metallic surEace, in particular, the surface of aluminum, preferably the surface of the metallic layer or support has been subjected to a graining treatment~ an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, a phosphate, etc., or an anodic oxidation treatment. Also, an aluminum plate which is grained and immersed in an aqueous solution of sodium silicate as described in the specification of U.S. Patent No. 2,714,066 and an aluminum plate which is subjected to an anodic oxidation treatment and then immersed in an aqueous solution of an alkali metal silicate as described in the specification of U.S. Patent No. 3,181,~61 can be used appropriately in this invention~ The above-described anodic oxidation treatment can be conducted by _ 5 _ Y placing the aluminum plate in an electrolyte of an aqueous solu-tion or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., an organic acid such as oxalic acid, sulfamic acid, etc., or a salt thereof or of a combination of these solutions and an electric current is passed using the aluminum plate as the anode.
Moreover, the electrodeposition of silicate as described in the specification of ~.S. Patent No. 3,658,662 can be effect-ively employed for the surface treatment of an aluminum layer or 1~ sheet.
The above-described surface treatment is employed, in addition to rendering surface of a support hydrophilic, to prevent the occurrence of any harmful reactions with the photosensitive composition formed thereon and to improve the adhe:rence between the support surface and the photosensitive layer formed thereon.
In particular, however, when aluminum is used as the support, the surface thereof has sufficient hydrophilic property without the necessity oE any surface treatment to render the surface hydrophilic and hence the surface treatment as described above is applied to the surface o the aluminum support mainly for preventing the occurrence of any harmful reactions with the photosensitive composition and improving the adherence between the support surface and the photosensitive layer formed thereon.
The photosensitive diazo-oxide resin used in this invention contains at least a hydroxystyrene unit and a hydroxy-styrene unit having an o-quinonediazide group bonded thereto through the oxygen atom of the hydroxystyrene. Examples of such a resin are those containing therein structural units represented by the following general formulas (I) and (II) --~CH2-CH ) X ( C~2-CH~
OH
Xl 1 -~-C 2 )x ~ 2 ~
OH
Rl CH--OH
wherein X represents a connecting group such as a sulfonyl group ~ .
-~ S ~- , or a carbonyl group ( C ~--, etc.; Rl represents an o aromatic o-quinonediazide group such as 1,2-benzoquinonediazide, 1,2-naphthoquinonediazide, 3,3',4,4'-biphenyl-bis-quinonediazide, 2,3-phenanthrenequinonediazide, etc., in which the o-quinone-diazide group can have a substituent on the aromatic nucleus, for instance, an alkyl group (e.g., having generally l to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, etc.) or an alkoxy group (e.g., having generally l to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a ~V61~
1 hexyloxy group, a heptyloxy group, an octyloxy group, etc.);
and R2 represents an alkyl group (e.g., having l to 4 carbon atoms), an aryl group (e.g., a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc.3, or a substituted aryl group and further R2 can include a quinonediazide group substi~
tuted witll an alkyl or aryl group if the photodecomposition of the quinonediazide is not affected by such a substituent. Here-inafter, for brevity, the compound containing therein structural units of the general formula (I) is designated "compound of the i general formula (I)" and the compound containing therein struc-tural units of the general formula (II) is designated "compound of the general formula (II)".
The molecular weight of the compound of the general formula (I) can range from ahout l,000 to about 30(),000, pre-ferably from 3,000 to lO0,000, x and y each represents the molar proportions of the components designated and x/x+y is from about 0 05 to 0.5, preferably from 0.1 to 0.4.
The compound of the general formula (I~ can be pre-pared using, for instance, the following polymerization reaction.
That is to say, poly(p-hydroxystyrene) which becomes the main chain of the polymer and an acid halide of a diazo-o~ide to be reacted, such as, for instance, quinonediazidosulfonyl chloride, quinonediazidocarbonyl chloride, etc., are uniformly dissolved in a common solvent such as dioxane, tetrahydrofuran, acetoner etc., and then the reaction, generally at about -10C to ~0C, preferably 20C to 40C, is conducted by adding, for instance, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, pyridine, etc., to the solution as a base, generally in an amount substantially equivalent to the quinone-diazido acid halide. A suitable molax ratio of the acid halide to the poly-(p-hydroxystyren~ is about 0.1 to 1 equivalent, pre-ferably 0.2 to 0.8 equivalent, per hydroxyl group equivalent.
Then, by purifying the reaction mixture thus obtained by a re-crystallization method, the photosensitive diazo-oxide resin of this invention is obtained. The poly-(p-hydroxystyrene) can be prepared in accordance with the disclosure in J. Poly. Sci.
A-l, 7, 2175 ~ 2184 (1969~ and ibid., 7, 2405 ~ 2410 (1969).
The molecular weight of the compound shown by general formula (II) can range from about 1,000 to about 300,000, pre-ferably from 3,000 to 100,000. Also, x, y and z each represents the molar proportions of the components designated and the ratio x/xfy~z is from about 0.05 to 0.5 and the ratio y/x+y-~z is from about 0.05 to 0.2.
The compound of the general formula (II) can be prepar~d in the following manner. That is to say, poly-(p-hydroxystyrene) which is also used as a starting material in the production of the compound of general formula (I) is first reacted with a glycidyl ether such as phenylglycidyl ether in a solvent such as acetone, tetrahydrofuran, methyl ethyl ketone, dioxane, etc., preferably methyl ethyl ketone, in the presence of triethylamine, 1,4-diazabicyclo[2,2,2]octane etc., in an amount of about 0.005 to 0.1 g, preferably 0.01 to 0.2 g, per g of the poly-(p-hydroxy-styrene), e.g., at about -10C to 80C, preferably 20C to 40C, particularly preferably at reflux, to form the polymer containing therein structural units represented by the following general formula (III) _ g _ ( CH2-CH )x ( C 2 1 ~
(III) OH o Cll CH2 0 ~
I
OH
wherein x and y are as described above.
Then, by reacting the polymer of general formula (II~) thus formed with the acid halide of a diazo-oxide as in the case of producing the compound of general ormula (I) and under the conditions as described above, th~ compound of general formula ~II) is obtained. Alkyl substituted glycidyl ethers and alkyl substituted phenyl glycidyl ethers in which the alkyl moiety has 1 to 4 carbon atoms can also be used as a starting material in the above procedures.
In the above-described processes of producing the photo-sensitive diazo-oxide resin of this invention, polyhydroxystyrene is used as the starting material but in place of such a compound, a copolymer of hydroxystyrene and a monomer not having a group with which the o-quinonediazide and the photodecomposition pro-duct thereof reacts can also be used as the starting material.
Examples of such a copolymerizable comonomer for the copolymer are phthalic anhydride, styrene, acrylonitrile, an acrylic acid ester, and a methacrylic acid ester.
The photosensitive diazo-oxide compound of this inven-tion can be used individually as a photosensitive layer of the photosensitive lithographic printing plate of this invention but it is more preferable to use the compound together with an alkaline solution-soluble resin as a binder therefor. Preferred examples of such an alkali-soluble resin are phenol formaldehyde resins, cresol resins, styrene-male;c anhydride copolymers, and shellac. A suitable molecular weight range for the phenol-form-aldehyde resins and the cresol resins can ran~e from about 2,000 to 50,000, preferably 4,000 to 10,000, and for the styrene-maleic anhydride copolymer can range from about 5,000 to 20,000, pre-ferably 8,000 to 14,000. Such a resin is soluble in an alkaline solution, has high adhesivity to support, and provides desirable 1~ effects in printability. Examples of such resins are disclosed in Synthetic Resins_in Coating, H.P. Preuss Noyes Development Corp., Pearl River, New York (1965).
In using the mixture of the photosensitive diazo-oxide compound of this invention and the alkaline solution-soluble binder resin, a suitable propo~tion of the photosensitive diazo-oxide is more than about 20~ by weight. If the proportion of the photosensitive diazo-oxide is less than about 20% by weight of the mixture, difficulties in development occur providing images which are not sufficient and hence good prin-ts are not obtained.
XO Furthermore, by incorporating the various additives as described hereinafter in the photosensitive layer of the photo-sensitive lithographic printing plate of this invention, the printing plate can be provided with desired specific properties.
For instance, in order to obtain visible images by light exposure and development of the photosensitive lithographic printing plate, a dye can be incorporated in the photosensitive layer of the printing plate. Suitable examples of appropriate dyes which can be used for this purpose include C.I. 26,105 (Oil Red RR), C.I.
21,260 (Oil Scarlet ~308~, C.I. 74,350 (Oil Blue), C.I. 52,015 (Methyl Blue), C.I. 42,555 (Crystal Violet), etc. Such a dye 1 can be incorporated in the photosensitive layer in an amount which provides a suf~iciently clear contrast between the color of the hydrophilic surface of the support exposed by light-exposure and development o~ the photosensitive layer of the photosensitive lithographic printing plate and the color of the remaining portions of the photosensitive layer and, in general, it is appropriate to incorporate the dye at a level of less than about 7% by weight to the total amount of the photosensitive composition ~or forming the photosensitive layer.
~ Also, the photosensitive composition can contain a plasticizer for imparting the desired flexibility to the photo-sensitive layer formed on the support. Examples of effective plasticizers which can be used for this purpose are phthalic acid esters such as dimethyl phthalate, diethyl phthalat:e, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octylcapryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl-benzyl pht-halate, diisodecyl phthalate, diaryl phthalate, etc.;
glycol esters such as dimethylglycol phthalate, ethylphthalylethyl glycolate, meth~lphthalylethyl glycolate, butylphthalylbutyl glycolate, triethyleneglycol dicaprylic acid ester, etc.;
phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, etc.; aliphatic dicarboxylic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl maleate, etc.; polyglycidyl methacrylate; citric acid triethyl ester; glycerin triacetyl ester; and butyl laurate.
~ he plasticizer is usually employed in an amount of less than about 5% by weight to the total amount o~ the photo-sensitive composition.
Also, in order to obtain visible images i-mmediately by exposing the photosensitive lithographic printing plate of this invention, the following spiropyran compounds which are discolored by light exposure can be incorporated in the photo-sensitive compositions as described in the specification of British Patent No. 1,154,716. Suitable examples include 6-nitro-ben70indolinospiropyran, 1,3,3-trimethylindolino-8'-methoxy-6'-nitrobenzospiropyran, 6'-nitro-1,3,3-trimethy]indoline benzospiro-pyran, 1,3,3-trimethylindolinobenzospiropyran, 1,3,3-trimethyl-indolino-~-naphthospiropyran, xantho-~-benzospiropyran, 6'-nitro-1,3,3-trimethylspiro(indoline-2,2'-2'H-chromene), 6',8'-dichloro-l,313-trimethylspiro(indoline-2,2'-2'~-chromene), etc. A suitahle amount of the spiropyran compound is ahout 2 to 20% by wei~ht to the total amount of the photosensitive composition.
The photosensitive composition containing the photo-sensitive diazo-oxide compound of this invention together with, if desired, the above-described additives is coated on a support having a hydrophilic surface as a solution or a dispersion in an appropriate solvent. Examples of the solvent which can be used for this purpose are organic solvents such as ketones, e.g., methyl ethyl ketoner acetone, methyl isobutyl ketone, etc.;
ethyleneglycol monoalkyl ethers, e.g., ethyleneglycol methyl ether, ethyleneglycol monoethyl ether, etc.; ethers, e.g., dioxane, tetrahydrofuran, etc.; and a mixed solvent thereof, such as ethylene dichloride and methyl cellosolve acetate. When the photosensitive composition is coated as a solution thereof, pre-ferably the concentration of the composition in the solution is about 1 to 50~ by weight, preferably 4 to 20% by weight.
The coating composition can be coated using conventional methods such as, for instance, dip coating, air knife coating, bead coating, curtain coating, and also extrusion coating using the hopper as descrihed in the specification of U.S. Patent ~o.
2,68],294.
The amount of the photosensitive layer coated on a support generally ranges from about 0.1 g/m2 to about 5 g/m2 but the amount of the photosensitive layer suitable for obtaining from about 10 to 10,000 good copies ranyes from about 1.0 y/m2 to about 3.5 g/m . If particular care is taken, however, in making the printing plate or in printing, about 5,000 good copies can be obtained with a coated amount of as low as about 1 g/m2.
If a longer press life is required, the coating composition pre-ferably is coated in an amount of about 3.5 g/m2. In this case, a considerable amount of exposure is required at image exposure o~ the photosensitive layer.
The photosensitive lithographic printing plate of this invention is exposed to active light, such as a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, etc~, and then the exposed portions of the photosensitive layer are removed by proc~ssing the plate with a developer, whereby the hydrophilic surface of the support is uncovered at the portions removed.
Suitable developers for the photosensitive lithographic printing plate of this invention basically include conventional alkaline solutions which have hitherto been used as developers for a photosensitive layer comprising a photosensitive diazo-oxide compound. Such alkaline solutions can suitably have a pH
of about 9.5 to 12. For instance, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium tertiary phosphate, sodium primary phosphate, sodium carbonate, potasslum carbonate, etc., or an aqueous solution of a basic solvent such as ethanolamine is used. These alkaline aqueous solutions as described above can be used individually or as a mixture thereof. Furthermore, if desired, the alkaline aqueous solution can further contain ertain organic solvents, for instance, benzyl alcohol, 2-butoxy-ethanol, 2-metho~yethanol, n-propanol, etc., in an amount of less than about 10~ by weight, preferably about 1 to 2% by weight.
By using a small amount of the organic solvent as indicated above, the speed of the development can be remarkably increased.
Furthermore, if desired, the developer can contain a wetting agent (e.g., a surface active agent). Examples of pre-ferred wetting agen~s include compounds having mor~ than 6 carbon atoms, each having a hydrophilic group such as a hydroxyl group, a carboxyl group, a sodium carboxylate group, a sulfo group, a sodium sulfonate group, and an alkyleneoxy group. Such wetting agents are well known as anionic surface active agents and non-ionic surface active agents. Examples of anionic surface active agents which can be used as a wetting agent in the developer are long chain alcohol (e.g., having about 8 to 22 carbon atoms) sulfuric acid esters, aliphatic alcohol phosphoric acid esters, sulfonates of dibasic aliphatic acid esters, aliphatic amido-sulfonates, etc~
Examples of nonionic surface active agents are polyoxy-29 ethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitanalkyl estersl polyoxypropylene ethers, polyoxyethylene ethers, etc. Specific examples of these surface active agents are described in Kaimen Kasseizai Binran (Handbook of Surface~Active Agents), published by Sangyo Tosho K.K. in 1961.
Specifically preferred wetting agents used in this invention are DUPONOL ME (the trade mark of the sodium salt of lauryl alcohol sulfate made by E.I du Pont de Nemours ~ Co.), *
MONOGEN Y-100 (the trade mark of sodium lauryl sulfate made by Daiichi Kogyo Seiyaku K.K.), the sodium salt of octyl alcohol sulfuric acid ester, the ammonium salt of lauryl alcohol sulfuric * Trade Mark 1,~,, acid esterr the sodium salt of xylenol sulfuric acid Pster, DUPONOL LS (the trade mark of the sodium salt of oleyl alcohol sulfuric acid ester made by E.I. du Pont de Nemours ~ Co ~, the monosodium salt of N,N~dihydroxyethylglycine, and the like. Of these compounds, the sodium salt of lauryl alcohol sulfuric acid ester is most preferred. These surface active agents can be used individually or as a combination of two or more compounds.
Also, the amount of the surface active agent can vary but generally the surface active agent is used at about 0.005 to 30% by weight, preferably 0.5 to 10% by weight, most preferably 4 to 8~ by weight of the developer.
The development is conducted by contacting the image exposed photosensitive layer of the photosensitive lithographic printing pla~e of this invention with the developer as described above. The contact can be used in various methods such as, for instance, immersion, spraying, etc.
After contacting the photosensitive layer and the developer for 60 to 180 seconds, the surface of the printing plate is softly rubbed using an appropriate brush, absorbent cotton, etc., whereby only the exposed portions of the photo sensitive layer are removed. In order to conduct development more effectively, the exposed surface preferably is processed with a developer at a temperature higher than about room temper-ature (about 20 ~ 30C), for instance, at about 40 to 50C.
To further clarify the invention, the invention will be explained additionally by referring to the accompanying drawings.
In an embodiment of the photosensitive lithographic printing plate of this invention as illustrated in Figure l, a photosensitive layer 2 mainly consisting of the novel diazo-oxide * Trade Mark 1 compound of this invention is formed on a support 1, such as an aluminum support, having a hydrophilic surface.
By image exposing the photosensitive lithographic printing plate showh in Figure 1, the exposed portion 2a becomes alkaline solution-soluble as shown in Figure 2.
~ he state of the image exposed photosensitive layer after development is shown in Figure 3 as a cross sectional viewO
As shown in Figure 3, the exposed portions 2a of the photosensi-tive layer 2 have heen removed and the hydrophilic surface of the support 1 has been uncovered there. The uncovered surface of the support is hydrophi]ic and oleophobic. On the other hand, the unexposed portions 2b of the photosensitive layer 2 remain on the support after development and the surface thereof is oleo-philic and hydrophobic. Thus, a printing plate is obtained.
In the present invention, by using the novel photo-sensitive diazo-oxide compound, a photosensitive lithographic printing plate having high sensitivity and exhibiting excellent printability is obtained. Furthermore, the lithographic printing plate of this invention is supexior in ink-receptivity and the control of fountain solution in printing becomes quite simple in the case of using the printing plate made from the photo-sensitive lithographic printing plate of this invention. More-over, the lithographic printing plate of this invention is stable to the passage of time.
Thus, by using the lithographic prinJcing plate of this invention, very excellent copies are obtained.
The invention will be described further by reference to the following examples. Unless otherwise indicated herein, all parts, percents, ratios and the like are by weight.
3~
27 g of naphthoquinone-1,2-diazido-5-sulfonyl chloride and 12 g of poly-(p-hydroxystyrene) haviny a mean molecular weight of 4,770 were dissolved in 100 mQ of tetrahydrofuran at room temperature. While stirring the solution, ~0 g of an aqucous solution of 13% by weight sodium carbonate was added dropwise to the solution at 30C over a period of 45 minutes. After distil-ling off excess tetrahydrofuran under reduced pressure, 100 mQ
of the reaction mixture was added to about 1 Q of water followed by stirring vigorously, whereby yellow precipitates were formed.
The precipitates were recovered by filtration, washed with water several times, and dried at room temperature under reduced pressure to provide 21 g of the photosensitive diazo-oxide resin.
SYNTHESIS EXA~IPLE 2 .
18 g of poly-(p-hydroxystyrene), 1 mQ of triethylamine, and 2.3 g of phenylglycidyl ether were reacted in 120 mQ of methyl ethyl ketone under refluxing for 8.5 hours. Thereafter, methyl ethyl ketone was distilled off under reduced pressure, the solid obtained was recovered and dissolved in about 100 mQ of methanol.
Then, the solution was added to about 750 mQ of water, whereby precipitates were formed. The precipitates were reco~ered by filtration and dried under a reduced pressure to obtain 17 g of a resin. 15 g of this resin was reacted with 27 g of naphtho-quinone-1,2-diazo-5-sulfonyl chloride in the same manner as described in Synthesis Example 1 to provide 22 g of the photo-sensitive diazo-oxide resin.
~ ne part by weight of the photosensitive diazo-oxide resin prepared in Synthesis Example 1 described above, 2 parts 1 by weight of a novolak-type phenol resin (a phenol-formaldehyde (1:0~8 molar ratio) condensation product obtained under acid conditions; molecular weight about 1,200 to 1,500), and 0.02 parts by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate. The coating composition thus prepared was coated on an aluminum plate of a thickness of 0.24 mm, the surface of which had been grained using a rotary coating machine and dried. The 1~ coated amount was 3.1 g/m~ on a dry basis.
The photosensitive lithographic printing plate thus obtained was exposed behind a transparent positive image to a Plano PS light (3.5 amperes, using a metal halide lamp) made by Fuji Photo Film Co., Ltd., at a distance of 1 meter from the light source for 40 seconds and after immersing the exposed plate in a developer containing 5~ by weight anhydrous sodium silicate for one minute at 25C, the surface of the lithographic printing plate was softly rubbed, whereby the exposed portions were removed and a positive image of the original was obtained.
When the pxinting plate thus obtained was mounted on a rotary printer and used for printing, 50,000 good copies were obtained.
Three parts by weight of the photosensitive lithographic printing plate prepared in Synthesis E~ample 1 and 0.02 parts by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate.
The coating composition was coated on an aluminum plate of a thickness of 0.3 mm, which had been subjected to graining using - 19 ~
a rotary coatin~ machine. In this case the coated amount was 2.6 g/m2 on a dry basis.
The photosensitive lithographic printing plate thus obtained was exposed behind a transparent positive image to a Plano P5 Light made by Fuji Photo Film Co., Ltd., as a light source for 3 minutes with a distance of 1 meter from the light source as in Example 1 and after immersing the exposed plate in a developer containing 5% by weight anhydrous sodium silicate for one minute at 25C, the surface of the plate was softly 1~ rubbed, whereby the exposed portions were removed and a good printing plate was obtained.
When the printing plate was mounted on a rotary printer and used for printing, 45,000 good copies were obtained.
One part by weight of the photosensitive diazo-oxide resin prepared in Example 2, 2 parts by weight of a novolak-type phenol resin, and 0.02 part by weight of a dye, Oil Blue, were uniformly dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 pcrts by weight of methyl cellosolve acetate. The coating composition thus pre-pared was coated on an aluminum plate of a thi~kness of 0.3 rnm, which had been subjected to graining using a rotary coating machine and dried. The coated amount was 2.4 g/m2 on a dry basis.
The photosensitive lithographic printing plate was exposed behind a transparent positive image to the light source as described in Example 1 with a distance of 1 meter from the light source for 40 seconds and after irnmersing the exposed plate for one minute in a developer of 15 parts by weight of butyl cellosolve, 1 part by weight of sodium primary phosphate, 7.5 parts by weight of sodiurn tertiary phosphate, 10 parts by weight of polyvinyl pyrrolidone K-15 (made by General Aniline and Film Corp.), 2 parts by weight of Monogen Y-100 ~trade name, made by Daiichi Kogyo Seiyaku K.K.), and 200 parts by weight of water, the surface of the plate was softly rubbed to provide a printing plate having excellent positive image.
When the printing plate thus obtained was used for printing on a rotary printer, 50,000 good copies were obtained.
_ Three parts by weight of the photosensitive diazo-oxide resin prepared in Example 2 and 0.02 part by weight of a dye, Oil Blue, were dissolved in 30 parts by weight of a mixed solvent of 12 parts by weight of ethylene dichloride and 18 parts by weight of methyl cellosolve acetate and the coating composition was coated on an aluminum plate, which had been subjected to graining using a rotary coating machine so that the coated amount was 2.3 g/m on a dry basis.
The photosensitive lithographic printing plate was exposed behind a transparent positive image to a Plano PS Light made by Fuji Photo Film Co., Ltd. with a distance of 1 meter from the light source for 3 minutes and after immersing the exposed plate for 1 minute in a developer having the same compo-siticn as described in Example 3, the plate was softly rubbed to provide a printing plate having a good positive image.
When the printing plate thus obtained was used for printing on a rotary printer, 50,000 good copies were obtained.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (12)
1. A photosensitive lithographic printing plate which comprises a support having thereon a photosensitive layer com-prising an o-quinonediazide group containing photosensitive poly-mer, said polymer containing, as essential components, monomer repeating units represented by the following general formulae (A) and (B), and having a molecular weight of 1,000 to 300,000;
General Formula (A) Wherein X represents a sulfonyl group or a carbonyl group, and R1 represents an aromatic o-quinonediazide group, with the aromatic group of the o-quinone-diazide group being unsubstituted or substituted with an alkyl group or an alkoxy group;
General Formula (B) 2. A photosensitive lighographic printing plate as claimed in claim 1, in which said photosensitive diazo-oxide resin is a compound containing therein a structural unit represented by the general formula (I)
General Formula (A) Wherein X represents a sulfonyl group or a carbonyl group, and R1 represents an aromatic o-quinonediazide group, with the aromatic group of the o-quinone-diazide group being unsubstituted or substituted with an alkyl group or an alkoxy group;
General Formula (B) 2. A photosensitive lighographic printing plate as claimed in claim 1, in which said photosensitive diazo-oxide resin is a compound containing therein a structural unit represented by the general formula (I)
Claim 2 continued....
(I) wherein X represents a sulfonyl group or a carbonyl group, R1 represents an aromatic o-quinonediazide group, with the aromatic group of the o-quinonediazide group being unsubstituted or substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms, x and y each represents the molar proportions of the components designated and x/x + y ranges from about 0.05 to 0.5.
3. A photosensitive lithographic printing plate as claim-ed in claim 1, in which said photosensitive diazo-oxide resin is a compound containing therein a structural unit represented by the general formula (II) (II) wherein X represents a sulfonyl group or a carbonyl group; R1 represents an aromatic o-quinonediazide group, with the aroma-tic ring of the o-quinonediazide group being unsubstituted or
(I) wherein X represents a sulfonyl group or a carbonyl group, R1 represents an aromatic o-quinonediazide group, with the aromatic group of the o-quinonediazide group being unsubstituted or substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms, x and y each represents the molar proportions of the components designated and x/x + y ranges from about 0.05 to 0.5.
3. A photosensitive lithographic printing plate as claim-ed in claim 1, in which said photosensitive diazo-oxide resin is a compound containing therein a structural unit represented by the general formula (II) (II) wherein X represents a sulfonyl group or a carbonyl group; R1 represents an aromatic o-quinonediazide group, with the aroma-tic ring of the o-quinonediazide group being unsubstituted or
Claim 3 continued....
substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms; R2 represents an alkyl group having 1 to 4 carbon atoms, an aryl group or a substituted aryl group or R2 may represent a quinonediazide group substituted with an alkyl or aryl group; and x, y and z each represents the molar pro-portions of the components designated and x/x+y+z ranges from about 0.05 to 0.5 and y/x+y+z ranges from about 0.05 to 0.2.
substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms; R2 represents an alkyl group having 1 to 4 carbon atoms, an aryl group or a substituted aryl group or R2 may represent a quinonediazide group substituted with an alkyl or aryl group; and x, y and z each represents the molar pro-portions of the components designated and x/x+y+z ranges from about 0.05 to 0.5 and y/x+y+z ranges from about 0.05 to 0.2.
4. A photosensitive lithographic printing plate as claimed in claim 2, wherein said aromatic o-quinonediazide group is a 1,2-benzoquinonediazide group, a 1,2-naphthoquinonediazide group and 3,3',4,4'-biphenyl-bis-quinonediazide group or a 2,3-phenanthrenequinonediazide group.
5. A photosensitive lithographic printing plate as claimed in claim 3, wherein said aromatic o-quinonediazide group is a 1,2-benzoquinonediazide group, a 1,2-naphthoquinonediazide group, a 3,3'4,4'-biphenyl-bis-quinonediazide group or a 2,3-phenanthrene-quinonediazide group.
6. A photosensitive lithographic printing plate as claimed in claim 2, wherein said x/x+y ranges from 0.1 to 0.4.
7. A photosensitive lithographic printing plate as claimed in claim 1, wherein said photosensitive layer includes an alkaline solution-soluble resin as a binder and said photo-sensitive diazo-oxide resin is present in an amount of more than about 20% by weight to the total weight of the mixture of the photosensitive diazo-oxide and the alkaline solution-soluble binder resin.
8. A photosensitive lithographic printing plate as claimed in claim 7 wherein said alkaline solution-soluble resin is a phenol-formaldehyde resin, a cresol resin, a styrenemaleic anhydride copolymer or shellac.
9. A photosensitive lithographic printing plate as claimed in claim 1, wherein said photosensitive layer includes at least one of a dye, a plasticizer, and a spiropyran com-pound.
10. A photosensitive lithographic printing plate as claimed in claim 1, wherein said support is an aluminum support.
11. A photosensitive lithographic printing plate as claimed in claim 1, wherein said photosensitive layer is coated in an amount ranging from about 0.1 g/m2 to about 5 g/m2 of the support.
12. A method of forming images comprising exposing the photosensitive lithographic printing plate as claimed in claim 1 to actinic radiation and developing said exposed photosensi-tive lithographic printing plate in an alkaline solution developer.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49020925A JPS5236043B2 (en) | 1974-02-21 | 1974-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061156A true CA1061156A (en) | 1979-08-28 |
Family
ID=12040784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,777A Expired CA1061156A (en) | 1974-02-21 | 1975-02-21 | Lithographic plate with layer of photosensitive diazo-oxide resin |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5236043B2 (en) |
| CA (1) | CA1061156A (en) |
| DE (1) | DE2507548C2 (en) |
| FR (1) | FR2262329B1 (en) |
| GB (1) | GB1494043A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439516A (en) * | 1982-03-15 | 1984-03-27 | Shipley Company Inc. | High temperature positive diazo photoresist processing using polyvinyl phenol |
| JPS58205147A (en) * | 1982-05-25 | 1983-11-30 | Sumitomo Chem Co Ltd | Positive type photoresist composition |
| JPS62227143A (en) * | 1986-03-28 | 1987-10-06 | Toshiba Corp | Photosensitive composition |
| FR2648468B1 (en) * | 1989-05-30 | 1992-12-04 | Commissariat Energie Atomique | RESIN COMPOSITION SENSITIVE TO UV RADIATION AND ELECTRON |
| JP2567282B2 (en) * | 1989-10-02 | 1996-12-25 | 日本ゼオン株式会社 | Positive resist composition |
| DE4106356A1 (en) * | 1991-02-28 | 1992-09-03 | Hoechst Ag | RADIATION-SENSITIVE POLYMERS WITH NAPHTHOQUINONE-2-DIAZIDE-4-SULFONYL GROUPS AND THEIR USE IN A POSITIVE WORKING RECORDING MATERIAL |
| JP3290316B2 (en) | 1994-11-18 | 2002-06-10 | 富士写真フイルム株式会社 | Photosensitive lithographic printing plate |
| JP3506295B2 (en) | 1995-12-22 | 2004-03-15 | 富士写真フイルム株式会社 | Positive photosensitive lithographic printing plate |
| KR100363695B1 (en) * | 1998-12-31 | 2003-04-11 | 주식회사 하이닉스반도체 | Organic diffuse reflection prevention polymer and its manufacturing method |
| US6528228B2 (en) | 1999-12-22 | 2003-03-04 | Kodak Polychrome Graphics, Llc | Chemical resistant underlayer for positive-working printing plates |
| DE602006009919D1 (en) | 2006-08-03 | 2009-12-03 | Agfa Graphics Nv | Lithographic printing plate support |
| EP2065211B1 (en) | 2007-11-30 | 2010-05-26 | Agfa Graphics N.V. | A method for treating a lithographic printing plate |
| EP2098376B1 (en) | 2008-03-04 | 2013-09-18 | Agfa Graphics N.V. | A method for making a lithographic printing plate support |
| ES2365885T3 (en) | 2008-03-31 | 2011-10-13 | Agfa Graphics N.V. | A METHOD TO TREAT A LITHOGRAPHIC PRINT IRON. |
| ES2655798T3 (en) | 2014-12-08 | 2018-02-21 | Agfa Nv | System to reduce ablation waste |
| BR112018068753A2 (en) | 2016-03-16 | 2019-01-22 | Agfa Nv | method for processing a lithographic printing plate |
| EP3637188A1 (en) | 2018-10-08 | 2020-04-15 | Agfa Nv | An effervescent developer precursor for processing a lithographic printing plate precursor |
| CN112650023B (en) * | 2020-12-23 | 2023-07-14 | 上海彤程电子材料有限公司 | High-resolution photoresist composition and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1375461A (en) * | 1972-05-05 | 1974-11-27 |
-
1974
- 1974-02-21 JP JP49020925A patent/JPS5236043B2/ja not_active Expired
-
1975
- 1975-02-20 GB GB7230/75A patent/GB1494043A/en not_active Expired
- 1975-02-20 FR FR7505313A patent/FR2262329B1/fr not_active Expired
- 1975-02-21 DE DE2507548A patent/DE2507548C2/en not_active Expired
- 1975-02-21 CA CA220,777A patent/CA1061156A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2262329B1 (en) | 1977-04-15 |
| DE2507548A1 (en) | 1975-09-04 |
| GB1494043A (en) | 1977-12-07 |
| JPS50113305A (en) | 1975-09-05 |
| FR2262329A1 (en) | 1975-09-19 |
| DE2507548C2 (en) | 1984-10-11 |
| JPS5236043B2 (en) | 1977-09-13 |
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