GB2029592A - Storage stable lithographic printing plates - Google Patents
Storage stable lithographic printing plates Download PDFInfo
- Publication number
- GB2029592A GB2029592A GB7927667A GB7927667A GB2029592A GB 2029592 A GB2029592 A GB 2029592A GB 7927667 A GB7927667 A GB 7927667A GB 7927667 A GB7927667 A GB 7927667A GB 2029592 A GB2029592 A GB 2029592A
- Authority
- GB
- United Kingdom
- Prior art keywords
- lithographic printing
- printing plate
- acid
- coating
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000003860 storage Methods 0.000 title abstract description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Chemical group 0.000 claims abstract description 6
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 6
- -1 methoxy, ethoxy Chemical group 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 229910052717 sulfur Chemical group 0.000 claims abstract description 5
- 239000011593 sulfur Chemical group 0.000 claims abstract description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005554 polynitrile Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 8
- 239000003504 photosensitizing agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- LHORZPMPPHTXFQ-UHFFFAOYSA-N 1-chloroethanesulfonic acid Chemical compound CC(Cl)S(O)(=O)=O LHORZPMPPHTXFQ-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 description 1
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 1
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- ACPXHHDRVABPNY-UHFFFAOYSA-N 4-acetylbenzenesulfonic acid Chemical compound CC(=O)C1=CC=C(S(O)(=O)=O)C=C1 ACPXHHDRVABPNY-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Materials For Photolithography (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
Storage stable lithographic printing plates comprising a metal sheet substrate having coated thereon a composition comprising a light sensitive, high molecular weight diazo polymers having the generic formula: <IMAGE> Where R is methyl or hydrogen X is methoxy, ethoxy or hydrogen Y is oxygen or sulfur Z is an anion of a sulfonic, carboxylic or phosphonic acid n is an integer from 8 to 970
Description
SPECIFICATION
Storage stable lithographic printing plates
This invention relates to storage stable lithographic printing plates comprising a metal substrate having coated thereon a composition comprising certain lithographic photosensitizers which are optionally blended with a suitable dye and a compatible resin in an acceptable solvent system.
It has been a problem in the past to produce commercially satisfactory lithographic printing plates which retain their ability to be effectively exposed and developed many years after their original manufacture.
Planographic printing plates must be carefully prepared so as to maintain their ability to differentiate between hydrophilic and oleophilic areas on its surface.
The prior art has described a plethora of photosensitive compositions which may be employed to produce such plates. One such example is the condensation product of paradiazo diphenyl amine with paraformaldehyde which has subsequently been reacted with a sulfonic acid. Typically, the shelf life of materials which have been used in the past to form such plates is less than two years and usually from about 1 yearto 1-1/2 years.
The present invention provides a lithographic printing plate employing certain specific photosensitizers wherein the obtained shelf life is in excess of five years.
It is known in the part to produce diazo type photosensitizers. In particular, U.S. Patent 3,373,021 discloses diazo compounds which are relatively low molecular weight monomers, whereas the instant invention uses only high molecular weight polymers.
By a selection of particular diazo type polymeric photosensitizers the present invention provides storage stable lithographic printing plates whose shelf-life is substantially extended as compared to plates coated with other photosensitizers known to the prior art. The polymeric photosensitizers used in the present invention are represented by the formula:
Where R is methyl or hydrogen
X is methoxy, ethoxy or hydrogen
Y is oxygen or sulfur
Z is an anion of a sulfonic, carboxylic or
phosphonic acid
n is an integer from 8 to 970
These photosensitizers are described and claimed in our copending patent application No. 1134/78.
Accordingly the present invention provides a lithographic printing plate which comprises a metal substrate having coated thereon a composition which comprises a light-sensitive high molecular weight diazo polymers having the general formula set forth above.
In the above general formula the anions usable within the context of the instant invention include anions which form a stable salt with the diazo resin and which render it soluble in organic solvents. These include the anions derived from organic carboxylic acids such as, decanoic acid and benzoic acid, organic phosphonic acids such as phenylphosphonic acid, and sulfonic acids, typical examples of which include aliphatic and aromatic sulfonic acids, such as methane sulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesuifonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid. Preferred sulfonic acids are 2-hydroxy-4-methoxybensophenone-5-sulfonic acid, hydroquinonesulfonic acid, 4-acetyl-benzenesulfonic acid and dimethyl-5-sulfoisophthalate.
Generally in the production of the coating composition used in the present invention, a diazonium salt is treated with paraformaldehyde and sulfuric acid. The reaction product thus produced is then treated with a sulfonic, carboxylic or phosphonic acid to produce the desired condensation product. This light sensitive composition may optionally be blended with such oleophilic binding resins as, polyamides, polyesters, polyethers, polycarbonates, polystyrenes, polyurethanes, polyvinyl chloride and its copolymers, polyviny
Iketals, polynitriles, polysulfones. The selection of particular ingredients and reaction conditions is made and controlled by the skilled worker to achieve a composition having the desired properties including molecular weight.
In a series of preferred embodiments, it has been found beneficicial to produce the said coating composition such that in the general formula set forth hereinabove, R is methyl, X is ethoxy, Y is sulfur, Z is 2-hydroxy-4-methoxy bensophenone-5 sulfonic acid and n is selected such that the molecular weight of the polymer is from about 60,000 to about 80,000.
The following specific examples illustrate the invention and methods of producing the polymers but it is to be understood that variations and modifications can be made therein without departing from the spirit and scope of the invention.
Example
(i) 120 g of 2,5-diethoxy-4-tolymercaptodiazobenzene zinc chloride double salt was added slowly to 385 ml of 98% sulfuric acid at 25 C. and stirred for 15 minutes while hydrogen chloride evolved. 8.03 g of paraformaldehyde was added and the mixture was stirred for 4 hours at 32 + 2 C. The reaction product was poured into 2.9 liters of ice water with stirring and treated with a cold concentrated solution of 383 g of zinc chloride in water. The precipitate was recovered by suction filtration and the partially dry cake was dissolved in 3.8 liters of water, filtered, cooled with ice and treated with a solution of 96 g of 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid in water. The precipitate was recovered by filtration and air dried to obtain 175 g of brittle solid.
(ii) The light sensitive diazo resin prepared in (i) above was incorporated in a light sensitive coating solution by the following method.
To 80 ml. methylene chloride, 56 ml. methanol, 35 ml. methyl cellosolve (Registered Trade Mark) and 3.5 mi. of dimethylformamide was added 2.0 g. of the above light-sensitive diazo resin, 1.0 g. of Epon 1031 resin, 0.5 g. of Formvar (Registered Trade Mark)12/85 resin, 1.6 g. of a 60% solution of a polyester resin, 0.2 g. Basic blue due, 0.02 g. of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid available from GAF under the name MS-40, 0.03 g. methyl orange and 4 ml. of a phosphoric acid solution prepared by diluting 1 g. of concentrated phosphoric acid in 100 ml. of methyl cellosolve.
The materials were added to the solvent mixture while the mixture was stirred. Each material readily dissolved.
The photosensitive solution was whirl-coated onto a grained anodized aluminum plate having a sodium silicate interlayer at a speed 80 rpm. During whirl-coating the aluminum plate was heated with electrical heating units. The temperature of the aluminum was approximately 70 to 80 degrees C. Within one minute the plate was dry and was kept in the whirl-coater and heated for a total of 5 minutes. This coating is identified as coating A.
Coating B was prepared by the same procedure as Coating A except that only 1 g. of the light sensitive diazo resin was used.
Coating C was prepared by the same procedure as Coating A except that a different diazo sensitizer was used. That sensitizer is the commonly used diazo resin for lithographic plates and is made by the condensation of p-diazodiphenylaminebisulfate with p-formaldehyde. The water soluble resin is then further reacted with MS-40 to form a sulfonate.
All three coatings as soon as they were prepared were imaged through a negative in a Berkey Exposure
Unit by a method well known in the art. After light exposure they were developed with a developer. The plates are negative-working and the non-exposed areas were removed. The three coatings all produced satisfactory images and were totally developed. The non-image areas were all hydrophilic. No coating remained on the aluminum in the non-light exposed areas.
The developer used in this test was made according to the following formula.
Water 998 ml.
Lithium benzoate 963 ml.
Cyna-SO (Surfactant available from
Mona Industries) 860 ml.
Sodium Lauryl Sulfate 247 g.
Sodium Citrate 247 g.
n-Propanol 482 ml.
Benzyl Alcohol 136 ml.
In developing the exposed coating a sufficient amount of developer is used to cover the entire plate. The developer is kept in contact with the plate for 30 seconds before the developer is rubbed into the plate gently by the use of a cotton swab or pad. The developer is then removed from the plate by the use of squeegee. A second application of developer is applied to the plate and the process is repeated.
After the development process, it is usually apparent if part of the coating remains in the unexposed areas.
If any part of the coating remains, it would be colored. As a further test, in determining if the unexposed areas are totally removed the process of printing on a printing press is simulated. The plate is first treated with water and the excess water is removed by a squeegee. The wet plate is then rubbed gently with a cotton swab that contains a blotch of a typical lithographic ink. The image will accept the ink while the non-image areas will not accept ink. All three coatings did not accept ink in the non-light exposed areas. The coatings in these areas are therefore totally removed.
One problem in the preparation of lithographic plates is that the light sensitive coatings are not sufficiently stable and when stored for an extended period of time at room temperature will undergo chemical changes.
These changes manifest themselves by changing the solubility characteristics of the coating in the developer which is obviously undesirable and cause the coatings to be unuseable.
To predict the long term stability properties of the 3 coatings, they were heated in an oven at 60 degrees C.
for periods ranging from 5 days to 3 weeks. The coatings were then exposed and developed as previously described. The results are summarized in the table below.
DAYS OF OVEN AGING AT 60 DEGREES C.
5Days 7Days 14 Days 21 Days
Coating A Stable Stable Stable Stable
Coating B Stable Stable Stable Stable
Coating C Stable Unstable Unstable Unstable
A simulated oven aging of one day at 60 degrees C translates to a 3 month shelf life. It can readily be seen that Coating C, which is known in the art, is stable for an estimated 1-1/4 year shelf life and unstable by 1-3/4 years. However, the sensitizer of the present invention has been shown to be stable for over 5-1/4 years.
As a series of preferred embodiments, a composition produced according to the present invention is applied at a coating weight of from about 10 mg/sq. ft. to about 200 mg/sq. ft. on an aluminum sheet and dried. The thus formed coated film may then be exposed to ultraviolet radiation through a transparency in a manner well known to the art and developed using a suitable developer such as Polychrome's 922 developer.
Claims (8)
1. A lithographic printing plate which comprises a metal sheet substrate having coated thereon a composition which is comprised of a light sensitive, high molecular weight diazo polymer having the formula:
Where R is methyl or hydrogen
X is methoxy, ethoxy or hydrogen
Y is oxygen or sulfur
Z is an anion of a sulfonic, carboxylic or
phosphonic acid
n is an integer from 8 to 970
2. A lithographic printing plate as claimed in claim 1 wherein said coated composition further comprises an oleophilic binding resin.
3. A lithographic printing plate as claimed in claim 2 wherein the binding resin is a substance selected form the group consisting of polyamides, polyesters, polyethers, polycarbonates, polystyrenes, polyurethanes, polyvinyl chloride and its copolymers, polyvinylketals, polynitriles, polysulfones.
4. A lithographic printing plate as claimed in any of claims 1 to 3 wherein said metal sheet substrate is comprised of aluminium or the alloys of aluminium.
5. A lithographic printing plate as claimed in any of claims 1 to 4 wherein R is methyl, X is ethoxy, Y is sulfur and Z is an anion of a sulfonic acid.
6. A lithographic printing plate as claimed in claim 5 wherein said sulfonic acid is 2-hydroxy-4methoxybenzophenone-5-sulfonic acid.
7. A lithographic printing plate as claimed in claim 6 wherein the molecular weight of the polymer is in the range of from about 60,000 to about 80,000.
8. A lithographic printing plate as claimed in claim 1 substantially as hereinbefore described in the
Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93274078A | 1978-08-10 | 1978-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2029592A true GB2029592A (en) | 1980-03-19 |
| GB2029592B GB2029592B (en) | 1982-10-20 |
Family
ID=25462832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7927667A Expired GB2029592B (en) | 1978-08-10 | 1979-08-08 | Storage stable lithographic printing plates |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5525093A (en) |
| DE (1) | DE2932377A1 (en) |
| GB (1) | GB2029592B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135616A3 (en) * | 1983-08-02 | 1987-01-28 | American Hoechst Corporation | Mixed photosensitive condensate and photosensitive registration material prepared therefrom |
| EP0194587A3 (en) * | 1985-03-15 | 1988-01-13 | Hoechst Aktiengesellschaft | Light-sensitive diazonium salt polycondensation product, and light-sensitive registration material prepared therewith |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938746A (en) * | 1982-08-27 | 1984-03-02 | Okamoto Kagaku Kogyo Kk | Photosensitive lithographic plate |
| JPS5938747A (en) * | 1982-08-27 | 1984-03-02 | Okamoto Kagaku Kogyo Kk | Photosensitive lithographic plate |
| JPS5978340A (en) * | 1982-10-28 | 1984-05-07 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JP2571354B2 (en) * | 1983-06-01 | 1997-01-16 | 富士写真フイルム株式会社 | Photosensitive composition |
| US4785062A (en) * | 1984-07-31 | 1988-11-15 | W. R. Grace & Co.-Conn. | Reaction product of O-epoxyalkylated tetrakis(hydroxyphenyl)ethane resin and phenol with product having no remaining epoxy groups |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB712606A (en) * | 1949-05-05 | 1954-07-28 | Kalle & Co Ag | Improvements in or relating to photolithographic diazotype printing materials and processes |
| GB728205A (en) * | 1953-05-22 | 1955-04-13 | Warren S D Co | Photo-sensitive diazotype coated paper plate for photo-lithography |
| GB880051A (en) * | 1958-12-10 | 1961-10-18 | Gen Aniline & Film Corp | Negative working offset photomechanical plates |
| GB1129407A (en) * | 1966-04-29 | 1968-10-02 | Oce Van Der Grinten Nv | Light-sensitive material for the production of printing plates |
-
1979
- 1979-07-13 JP JP8920579A patent/JPS5525093A/en active Pending
- 1979-08-08 GB GB7927667A patent/GB2029592B/en not_active Expired
- 1979-08-09 DE DE19792932377 patent/DE2932377A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB712606A (en) * | 1949-05-05 | 1954-07-28 | Kalle & Co Ag | Improvements in or relating to photolithographic diazotype printing materials and processes |
| GB728205A (en) * | 1953-05-22 | 1955-04-13 | Warren S D Co | Photo-sensitive diazotype coated paper plate for photo-lithography |
| GB880051A (en) * | 1958-12-10 | 1961-10-18 | Gen Aniline & Film Corp | Negative working offset photomechanical plates |
| GB1129407A (en) * | 1966-04-29 | 1968-10-02 | Oce Van Der Grinten Nv | Light-sensitive material for the production of printing plates |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135616A3 (en) * | 1983-08-02 | 1987-01-28 | American Hoechst Corporation | Mixed photosensitive condensate and photosensitive registration material prepared therefrom |
| EP0194587A3 (en) * | 1985-03-15 | 1988-01-13 | Hoechst Aktiengesellschaft | Light-sensitive diazonium salt polycondensation product, and light-sensitive registration material prepared therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2932377A1 (en) | 1980-02-28 |
| JPS5525093A (en) | 1980-02-22 |
| GB2029592B (en) | 1982-10-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |