CA1262069A - Photosensitive composition based on a diazonium salt polycondensation product and photosensitive recording material prepared from this composition - Google Patents
Photosensitive composition based on a diazonium salt polycondensation product and photosensitive recording material prepared from this compositionInfo
- Publication number
- CA1262069A CA1262069A CA000473490A CA473490A CA1262069A CA 1262069 A CA1262069 A CA 1262069A CA 000473490 A CA000473490 A CA 000473490A CA 473490 A CA473490 A CA 473490A CA 1262069 A CA1262069 A CA 1262069A
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- acid
- photosensitive
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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
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Paints Or Removers (AREA)
- Telescopes (AREA)
- Lenses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Photolithography (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Printing Plates And Materials Therefor (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a photosensitive composition which comprises a diazonium salt polycondensation product and, as the binder, a reaction product of an intramolecular anhydride of an organic polycarboxylic acid with a polymer containing hydroxyl groups, which does not contain any further functional groups which are capable of reaction with acid anhydrides. The composition is suitable for use in the production of printing plates and photoresists. It can be devel-oped with neutral or alkaline aqueous solutions and yields printing plates having a good ink receptivity and producing large print runs.
Disclosed is a photosensitive composition which comprises a diazonium salt polycondensation product and, as the binder, a reaction product of an intramolecular anhydride of an organic polycarboxylic acid with a polymer containing hydroxyl groups, which does not contain any further functional groups which are capable of reaction with acid anhydrides. The composition is suitable for use in the production of printing plates and photoresists. It can be devel-oped with neutral or alkaline aqueous solutions and yields printing plates having a good ink receptivity and producing large print runs.
Description
3~j~
PHOTOSENSITIVE COMPOSITION BASED ON A DIAZONIUM
SALT POLYCONDENSATION PRODUCT AND
. . . _ .
PHOTOSENSITIVE RECORDING MATERIAL
. .
PREPARED FROM THIS COMPOSITION
~ . , BACKGROUND OF THE INVENTION
The present invention relates to photosen-sitive compositions and, in particular, to such com-positions suitable for the production of printing plates7 Specifically, the invention relates to such compositions comprising diazonium salt polycondensation products and a polymeric binder.
German Offenlegungsschrift No. 2r024,244 (corresponding to U.S. Patent No. 3,867,147; disclo-ses photosensitive recording materials comprising co-condensation products of condensible diazonium saltsand other non-photosensitive condensible compounds, optionally combined with polymeric binders, which are used for producing printing plates. These photosen-sitive materials are distinguished by their high pho-tosensitivity and good print runs. The print runobtained is particularly large if water-insoluble binders, Eor example, polyvinyl formal, are used, but such layers can only be properly processed by means of developers containing a considerable amount of volatile organic solvents.
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German Offenlegungsschrift ~o. 3,130,987 describes similar compositions which comp~ise styrene-maleic anhydride copolymers as the binders and which can be developed with purely aqueous alka-line solutions. These binders usually have acid num-bers well over 100. The printing plates obtained using these compositions, howeverr yield print runs which are inferior to those of printing plates con-taining binders which are insoluble in aqueous alka-line solutions.
German Offenlegungsschrift No. 3,036,077discloses corresponding compositions which contain binders comprising polymers with alkenylsulEonyl-urethane side groups. These compositions can also be developed by means of purely aqueous solutions. How-ever, when the compositions are processed to form lithographic printing plates, they yield light cured coatings, in which ink receptivity is insufficient.
From U.S. Patent No. 2,861,058, photosen sitive polymers are known, having cinnamate and dicarboxylic acid monoester side groups. These poly~
mers contain a relatively high amount of acid groups, corresponding to acid numbers from at least 100 to about 300, in order to render the coatings soluble in aqueous alkaline solutions.
In German Offenlegungsschrift No. 2,751,060, photosensitive compositions are described which comprise a photosensitive resin and a cellulose ether dicarboxylic acid halfester. These compositions are used in the production oE photoresist coatings and have the advanta~e of a good etch resistance. Due to the strongly hydrophilic nature of the cellulose which serves as the parent substance, the oleophilic character of these polymers is, in most cases, inade-quate for use in the printing image areas of printingplates. Moreover, since the cellulose molecule has a ~2~
given molecular size and structure, it is difficult to vary its properties to a sufficient extent by substitution.
SU~ARY OF THE INVENTION
It is an object of the present invention to provide a negative-working photosensitive composition which is suitable for use in the production of print-ing plates, particularly lithographic printing plates, and which has all the advantages of the known compositions based on diazonium salt polycondensation products.
It is another object to provide such a com position which can be developed by means of prac-tically solvent-free, neutral or alkaline aqueous solutions, and which, at the same time, yields printing plates pro-ducing large print runs and having a good ink recep-tivity. Heretofore, those properties could only be achieved with printing plates requiring the addition of relatively large amounts of organic solvents in the developing process.
Still another object resides in providing an improved photosensitive recording material utilizing the compositions according to the invention. In accomplishing these objects, there has been provided according to one aspect of the present invention a photosensitive composition which comprises a diazo-nium salt polycondensation product and a non~photo-sensitive polymeric binder having carboxyl side groups, which is solubley or at least swellable, in aqueous alkaline solutions, wherein the binder comprises a reaction product of an intramolecular anhydride of an organic polycarboxylic acid with a synthetic polymer containing hydroxyl groups and having no further functional groups which are capable of reaction with acid anhydrides.
.
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In accordance with another aspect of the invention, there has been provided a photosensitive recording material comprising a support and a photo-sensitive coating comprised of the photosensitive composition described above.
Further objects, features and advantages of the invention will become apparent from the detailed description of preferred embodiments which follows.
DETAILED DESCRIPTION OF THE PREFERRED EME~ODIMENTS
The acid anhydride according to the inven-tion is preferably derived from a dicarboxylic or tricarboxylic acid, particularly from a dicarboxylic acid and may have one, two or several rings.
Particularly preferred binders are obtained by reacting with acid anhydrides corresponding to one of the formulae I, II or III
R 2 _ c --co/ t I ) x ~ ~ o ( I I ) C
/ ¦ \c~l--co\ (III) Z~ Y I o \ ¦ ~ CH--co wherein Rl and R2 individually are selected from hydrogen atoms and alkyl groups, or are intercon-nected to form an aromatic or heteroaro-matic, unsubstituted or substituted and optionally partially hydrogenated five-~ 3 membered or six-membered ring which may be ~used with up to two aromatic or cycloali-phatic rings, R3, R4 and R5 individually are selected from hydrogen atoms and alkyl groups, further, R3 and R5 can be interconnected to form an unsubsti-tuted or substituted, saturated or unsatu-rated aliphatic ring which, inclusive o X, may have five or six ring members, O R6 and R7 are selected from hydrogen atoms and alkyl groups, X is a single bond, an unsubstituted or substituted l,l-alkylene group or l,l-cycloalkylene group, an oxygen atom or a sulfur atom, Y is an oxygen atom or a sulfur atom/ a l,l-or l,2-alkylene group or a l,2-alkenylene group, which may optionally be fused with an aromatic or cycloaliphatic ring, and 20 Z is selected from ring members required for the completion of a saturated or unsatu-rated, unsubstituted or substituted ring, this ring optionally being fused with up to two aromatic or cycloaliphatic rings.
If Rl R2 R3 R4 R5, R6, or R7 stand for alkyl groups, the latter generally have from l to 4, pre-~erably 1 or 2, carbon atoms. Substituents which may be bonded to the aromatic or cycloaliphatic rings include, for example, alkyl groups, alkoxy groups, halogen atoms, nitro groups or carboxyl grou~s.
, . . .
sj~
~ xa~ples of suitable acid anhydrides include:
Maleic anhydride and derivatives thereof, for example, dimethyl maleic anhydride or citraconic anhydride;
succinic anhydride and derivatives thereof, for example, methyl succinic anhydride;
glutaric anhydride and derivatives thereof, for example, 3-methyl glutaric anhydride, 3,3-tetra-methylene glutaric anhydride, or camphoric acidanhydride;
3-oxa-glutaric anhydride and derivatives thereof; phthalic anhydride and substitution products thereof, for example, chloro, nitro, or carboxy-phthalic anhydride, partially or completely hydroge-nated phthalic anhydrides, for example, hexahydro-phthalic anhydride or cyclohexene'l, 2 dicarboxylic acid anhydride;
naphthalene-2,3-dicarboxylic acid anhydride 2Q or naphthalene-1,8-dicarboxylic acid anhydride and substitution products thereof;
pyridine-o-dicarboxylic acid anhydride and substitution products thereof;
pyrazine-o-dicarboxylic acid anhydride and 25 ~ substitution products thereof;
furan-o-dicarboxylic acid anhydride or furan-2,5-dicarboxylic acid anhydride, the substitu-tion prod~lcts thereof and the partially or completely hydrogenated derivatives thereof;
thiophene-o-dicarboxylic acid anhydride or thiophene-2,5-dicarboxylic acid anhydride, the subs-titution products thereoE and the completely or par-tially hydrogenated derivatives thereof;
dicyclic or polycyclic anhydrides Eormed by the Diels-Alder reaction of a diene with maleic anhydride, for example, the addition products from ' ~ 3S`~
furan, anthracene, cyclohexadiene-1,3 or cyclopen-tadiene with maleic anhydride.
The products obtained from the reaction with maleic an'nydride, phthalic anhydride, succinic anhydride or 3-oxa-glutaric anhydride are preferred.
Synthetic polymers containing hydroxy groups, which can be used include, in particular, polymers having vinyl alcohol units. Also useEul are epoxy resins and saponified epoxy resins, copolymers of allyl alcohol or higher molecular weight unsatu-rated alcohols, polyhydroxyalkyl acrylates and poly-hydroxyalkyl methacrylates and similar polymers.
Suitable polymers containing vinyl alcohol units include partially saponified polyvinyl esters, polyvinyl acetals having free hydroxy groups and corresponding reaction products of copolymers with vinyl ester units or vinyl acetal units or vinyl alcohol units.
The molecular weight o~ the binders con-taining carboxyl groups can vary within wide limits.
Generally, the binders used have average molecular weights in the range between 5,000 and about 200,000 or above, preferably between lO,000 and 100,000. The acid numbers of the binders can generally be in the range between 5 and 80, preferably between 10 and 70.
The acid numbers of the polymers are thus clearly lower than the acid numbers of the binders which have hitherto been used in photosensitive compositions o~
the same generic type, as far as these composltions were suitable and intended for the development with aqueous solutions.
The reaction between acid anhydride andpolymer containing hydroxy groups proceeds very smoothly and is a quantitative reaction in many cases; it is therefore very readily reproducible. As a consequence, it is possible to exactly and reprodu-'2~ 3 cibly adjust the desired acid number of the binder,for example, for the application of a particular developer.
The reaction can be run in ketones, Eor example, butanone, or tetrahydrofuran, dioxane or other ethers. As catalysts, tertiary amines are appropriately employed. In general, from 0.5 to 20 parts by weight of anhydride, from 1,000 to 3,000 parts by weight of solvent and from 0.5 to 5 parts by weight of tertiary amine are used per 100 parts by weight of polymer containing hydroxy groups.
Suitable diazonium salt polycondensation products are condensation products of condensible aromatic diazonium salts, for example, of diphenylamine-4-diazonium salts, with aldehydes, pre-ferably with formaldehyde. It is particularly advan tageous to use co-condensation products containing, in addition to the diazonium salt units, other non-photosensitive units which are derived from conden~
sible compounds, particularly from aroma~ic amines, phenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic hetero-cyclic compounds and organic acid amides. These con-densation products are described in German 25 Offenlegungsschrift No. 2,024,244. Generally, all diazonium salt polycondensation products described in German Offenlegunysschrift No. 2,739,774 are suit-able.
The diazonium salt units A-N2X are pre-ferably derived from compounds corresponding to the ~ormula (R8_R9-) RlO-N2X
wherein X is the anion of the diazonium compound, p is an integer from 1 to 3, R8 is an aromatic radical which is capable of condensation with an active car-bonyl compound, in at least one posi-tion, R10 is a phenylene group, and R9 is a single bond or one of the groups:
~(CH2)q~NR~
-O- (CH2) r-NR -, -S-(CH2)r NR~
-S--CH2CO-NRll--, _o-Rl 2_o_, --o--, -S-, or -co -NR~
wherein q is a number from 0 to 5, r is a number from
PHOTOSENSITIVE COMPOSITION BASED ON A DIAZONIUM
SALT POLYCONDENSATION PRODUCT AND
. . . _ .
PHOTOSENSITIVE RECORDING MATERIAL
. .
PREPARED FROM THIS COMPOSITION
~ . , BACKGROUND OF THE INVENTION
The present invention relates to photosen-sitive compositions and, in particular, to such com-positions suitable for the production of printing plates7 Specifically, the invention relates to such compositions comprising diazonium salt polycondensation products and a polymeric binder.
German Offenlegungsschrift No. 2r024,244 (corresponding to U.S. Patent No. 3,867,147; disclo-ses photosensitive recording materials comprising co-condensation products of condensible diazonium saltsand other non-photosensitive condensible compounds, optionally combined with polymeric binders, which are used for producing printing plates. These photosen-sitive materials are distinguished by their high pho-tosensitivity and good print runs. The print runobtained is particularly large if water-insoluble binders, Eor example, polyvinyl formal, are used, but such layers can only be properly processed by means of developers containing a considerable amount of volatile organic solvents.
r, ~
', ~.
' '' 3~.~
German Offenlegungsschrift ~o. 3,130,987 describes similar compositions which comp~ise styrene-maleic anhydride copolymers as the binders and which can be developed with purely aqueous alka-line solutions. These binders usually have acid num-bers well over 100. The printing plates obtained using these compositions, howeverr yield print runs which are inferior to those of printing plates con-taining binders which are insoluble in aqueous alka-line solutions.
German Offenlegungsschrift No. 3,036,077discloses corresponding compositions which contain binders comprising polymers with alkenylsulEonyl-urethane side groups. These compositions can also be developed by means of purely aqueous solutions. How-ever, when the compositions are processed to form lithographic printing plates, they yield light cured coatings, in which ink receptivity is insufficient.
From U.S. Patent No. 2,861,058, photosen sitive polymers are known, having cinnamate and dicarboxylic acid monoester side groups. These poly~
mers contain a relatively high amount of acid groups, corresponding to acid numbers from at least 100 to about 300, in order to render the coatings soluble in aqueous alkaline solutions.
In German Offenlegungsschrift No. 2,751,060, photosensitive compositions are described which comprise a photosensitive resin and a cellulose ether dicarboxylic acid halfester. These compositions are used in the production oE photoresist coatings and have the advanta~e of a good etch resistance. Due to the strongly hydrophilic nature of the cellulose which serves as the parent substance, the oleophilic character of these polymers is, in most cases, inade-quate for use in the printing image areas of printingplates. Moreover, since the cellulose molecule has a ~2~
given molecular size and structure, it is difficult to vary its properties to a sufficient extent by substitution.
SU~ARY OF THE INVENTION
It is an object of the present invention to provide a negative-working photosensitive composition which is suitable for use in the production of print-ing plates, particularly lithographic printing plates, and which has all the advantages of the known compositions based on diazonium salt polycondensation products.
It is another object to provide such a com position which can be developed by means of prac-tically solvent-free, neutral or alkaline aqueous solutions, and which, at the same time, yields printing plates pro-ducing large print runs and having a good ink recep-tivity. Heretofore, those properties could only be achieved with printing plates requiring the addition of relatively large amounts of organic solvents in the developing process.
Still another object resides in providing an improved photosensitive recording material utilizing the compositions according to the invention. In accomplishing these objects, there has been provided according to one aspect of the present invention a photosensitive composition which comprises a diazo-nium salt polycondensation product and a non~photo-sensitive polymeric binder having carboxyl side groups, which is solubley or at least swellable, in aqueous alkaline solutions, wherein the binder comprises a reaction product of an intramolecular anhydride of an organic polycarboxylic acid with a synthetic polymer containing hydroxyl groups and having no further functional groups which are capable of reaction with acid anhydrides.
.
~L,fr~ ;6 ~
In accordance with another aspect of the invention, there has been provided a photosensitive recording material comprising a support and a photo-sensitive coating comprised of the photosensitive composition described above.
Further objects, features and advantages of the invention will become apparent from the detailed description of preferred embodiments which follows.
DETAILED DESCRIPTION OF THE PREFERRED EME~ODIMENTS
The acid anhydride according to the inven-tion is preferably derived from a dicarboxylic or tricarboxylic acid, particularly from a dicarboxylic acid and may have one, two or several rings.
Particularly preferred binders are obtained by reacting with acid anhydrides corresponding to one of the formulae I, II or III
R 2 _ c --co/ t I ) x ~ ~ o ( I I ) C
/ ¦ \c~l--co\ (III) Z~ Y I o \ ¦ ~ CH--co wherein Rl and R2 individually are selected from hydrogen atoms and alkyl groups, or are intercon-nected to form an aromatic or heteroaro-matic, unsubstituted or substituted and optionally partially hydrogenated five-~ 3 membered or six-membered ring which may be ~used with up to two aromatic or cycloali-phatic rings, R3, R4 and R5 individually are selected from hydrogen atoms and alkyl groups, further, R3 and R5 can be interconnected to form an unsubsti-tuted or substituted, saturated or unsatu-rated aliphatic ring which, inclusive o X, may have five or six ring members, O R6 and R7 are selected from hydrogen atoms and alkyl groups, X is a single bond, an unsubstituted or substituted l,l-alkylene group or l,l-cycloalkylene group, an oxygen atom or a sulfur atom, Y is an oxygen atom or a sulfur atom/ a l,l-or l,2-alkylene group or a l,2-alkenylene group, which may optionally be fused with an aromatic or cycloaliphatic ring, and 20 Z is selected from ring members required for the completion of a saturated or unsatu-rated, unsubstituted or substituted ring, this ring optionally being fused with up to two aromatic or cycloaliphatic rings.
If Rl R2 R3 R4 R5, R6, or R7 stand for alkyl groups, the latter generally have from l to 4, pre-~erably 1 or 2, carbon atoms. Substituents which may be bonded to the aromatic or cycloaliphatic rings include, for example, alkyl groups, alkoxy groups, halogen atoms, nitro groups or carboxyl grou~s.
, . . .
sj~
~ xa~ples of suitable acid anhydrides include:
Maleic anhydride and derivatives thereof, for example, dimethyl maleic anhydride or citraconic anhydride;
succinic anhydride and derivatives thereof, for example, methyl succinic anhydride;
glutaric anhydride and derivatives thereof, for example, 3-methyl glutaric anhydride, 3,3-tetra-methylene glutaric anhydride, or camphoric acidanhydride;
3-oxa-glutaric anhydride and derivatives thereof; phthalic anhydride and substitution products thereof, for example, chloro, nitro, or carboxy-phthalic anhydride, partially or completely hydroge-nated phthalic anhydrides, for example, hexahydro-phthalic anhydride or cyclohexene'l, 2 dicarboxylic acid anhydride;
naphthalene-2,3-dicarboxylic acid anhydride 2Q or naphthalene-1,8-dicarboxylic acid anhydride and substitution products thereof;
pyridine-o-dicarboxylic acid anhydride and substitution products thereof;
pyrazine-o-dicarboxylic acid anhydride and 25 ~ substitution products thereof;
furan-o-dicarboxylic acid anhydride or furan-2,5-dicarboxylic acid anhydride, the substitu-tion prod~lcts thereof and the partially or completely hydrogenated derivatives thereof;
thiophene-o-dicarboxylic acid anhydride or thiophene-2,5-dicarboxylic acid anhydride, the subs-titution products thereoE and the completely or par-tially hydrogenated derivatives thereof;
dicyclic or polycyclic anhydrides Eormed by the Diels-Alder reaction of a diene with maleic anhydride, for example, the addition products from ' ~ 3S`~
furan, anthracene, cyclohexadiene-1,3 or cyclopen-tadiene with maleic anhydride.
The products obtained from the reaction with maleic an'nydride, phthalic anhydride, succinic anhydride or 3-oxa-glutaric anhydride are preferred.
Synthetic polymers containing hydroxy groups, which can be used include, in particular, polymers having vinyl alcohol units. Also useEul are epoxy resins and saponified epoxy resins, copolymers of allyl alcohol or higher molecular weight unsatu-rated alcohols, polyhydroxyalkyl acrylates and poly-hydroxyalkyl methacrylates and similar polymers.
Suitable polymers containing vinyl alcohol units include partially saponified polyvinyl esters, polyvinyl acetals having free hydroxy groups and corresponding reaction products of copolymers with vinyl ester units or vinyl acetal units or vinyl alcohol units.
The molecular weight o~ the binders con-taining carboxyl groups can vary within wide limits.
Generally, the binders used have average molecular weights in the range between 5,000 and about 200,000 or above, preferably between lO,000 and 100,000. The acid numbers of the binders can generally be in the range between 5 and 80, preferably between 10 and 70.
The acid numbers of the polymers are thus clearly lower than the acid numbers of the binders which have hitherto been used in photosensitive compositions o~
the same generic type, as far as these composltions were suitable and intended for the development with aqueous solutions.
The reaction between acid anhydride andpolymer containing hydroxy groups proceeds very smoothly and is a quantitative reaction in many cases; it is therefore very readily reproducible. As a consequence, it is possible to exactly and reprodu-'2~ 3 cibly adjust the desired acid number of the binder,for example, for the application of a particular developer.
The reaction can be run in ketones, Eor example, butanone, or tetrahydrofuran, dioxane or other ethers. As catalysts, tertiary amines are appropriately employed. In general, from 0.5 to 20 parts by weight of anhydride, from 1,000 to 3,000 parts by weight of solvent and from 0.5 to 5 parts by weight of tertiary amine are used per 100 parts by weight of polymer containing hydroxy groups.
Suitable diazonium salt polycondensation products are condensation products of condensible aromatic diazonium salts, for example, of diphenylamine-4-diazonium salts, with aldehydes, pre-ferably with formaldehyde. It is particularly advan tageous to use co-condensation products containing, in addition to the diazonium salt units, other non-photosensitive units which are derived from conden~
sible compounds, particularly from aroma~ic amines, phenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic hetero-cyclic compounds and organic acid amides. These con-densation products are described in German 25 Offenlegungsschrift No. 2,024,244. Generally, all diazonium salt polycondensation products described in German Offenlegunysschrift No. 2,739,774 are suit-able.
The diazonium salt units A-N2X are pre-ferably derived from compounds corresponding to the ~ormula (R8_R9-) RlO-N2X
wherein X is the anion of the diazonium compound, p is an integer from 1 to 3, R8 is an aromatic radical which is capable of condensation with an active car-bonyl compound, in at least one posi-tion, R10 is a phenylene group, and R9 is a single bond or one of the groups:
~(CH2)q~NR~
-O- (CH2) r-NR -, -S-(CH2)r NR~
-S--CH2CO-NRll--, _o-Rl 2_o_, --o--, -S-, or -co -NR~
wherein q is a number from 0 to 5, r is a number from
2 to 5, ~11 is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms or an aryl group having from 6 to 12 carbon atoms, and Rl~ is an arylene group having ~rom 6 to 12 carbon atoms.
The compositions according to the present invention generally comprise from 5 to 90, preEerably from 10 to 70, percent by weight oE diazonium com-pound, and ~rom 95 to 10, preferably from 90 to 30, percent by weight of polymeric binder.
To stabilize the photosensitive composition, it is advantageous to add a compound having an acid character. Compounds which can be used include min-eral acids and strong organic acids, with phosphoric acid, sulEuric acid/ perchloric acid, boric acid or _g _ .
p-toluene sulfonic acid being preEerred. Pho~phoric acid is a particularly suitable acid.
Plasticizers, adhesion promoters, dyes, pigments and color precursors can also be added to the compositions.
The types and quantities of such additions depend upon the field of application for which the photosensitive composition is intended. In principle, care must be taken that the added substances do not absorb an excessive portion of the actinic light which is required for cross-linking, because this would result in a reduction of the practical sensi-tivity to light.
In addition, the light-sensitive composi-tions can contain dyes and/or Digments which mayserve to enhance the contrast upon exposure and also to harden the layer. Suitable dyes are, for example, specified in U.S. Patents No. 3,218,167 and No.
The compositions according to the present invention generally comprise from 5 to 90, preEerably from 10 to 70, percent by weight oE diazonium com-pound, and ~rom 95 to 10, preferably from 90 to 30, percent by weight of polymeric binder.
To stabilize the photosensitive composition, it is advantageous to add a compound having an acid character. Compounds which can be used include min-eral acids and strong organic acids, with phosphoric acid, sulEuric acid/ perchloric acid, boric acid or _g _ .
p-toluene sulfonic acid being preEerred. Pho~phoric acid is a particularly suitable acid.
Plasticizers, adhesion promoters, dyes, pigments and color precursors can also be added to the compositions.
The types and quantities of such additions depend upon the field of application for which the photosensitive composition is intended. In principle, care must be taken that the added substances do not absorb an excessive portion of the actinic light which is required for cross-linking, because this would result in a reduction of the practical sensi-tivity to light.
In addition, the light-sensitive composi-tions can contain dyes and/or Digments which mayserve to enhance the contrast upon exposure and also to harden the layer. Suitable dyes are, for example, specified in U.S. Patents No. 3,218,167 and No.
3,884,693. Particularly suitable are, for example, Victoria Pure Blue FGA, Renol Blue B2G-EI (Color Index 74,160), Crystal Violet or Rhodamine Ç GDN (C.I.
45,160). To enhance the image contrast after expo-sure, Metanil Yellow (C.I. 13,065), Methyl Orange (C.I. 13,025) or phenylazodiphenylamine can be used.
For particular purposes it can be favorable to admix the photosensitive compositions of the invention with further polymers in quantities of up to 40 percent by weight, relative to the above-described polymeric binders. Resins which contain hydroxy groups or carboxyl groups or amide or ure-thane groupings are advantageous for this purpose.
In many cases, an addition oE binders which differ from the above-described carboxyl group-con-taining binders results in an undesired deterioration of numerous properties of the photosensitive composi-tion, and this deterioration can usually be ascribed ~ 3~
to an incompatibility with the individual constitu-ents of the coating. As against this, the aforemen-tioned advantageous additional resins can, for example, lead to an improvement in abrasion resis-tance and thus to an increase in the number oE print~ed copies, if the composition is used in a litho-graphic printing plate.
Preferred additional polymers include poly-mers which contain amide groups or urethane groups.
The polyamides used according to German Offenlegungs-schrift No. 2,218,821, the polyurethanes disclosed in German Offenlegungsschrift No. 2,948,554, or the sulfonylurethanes disclosed in German Offenlegungs-schriften Nos. 2,053,363 and 2,053,364 are, for example, advantageously used for the above-mentioned purpose.
Additions of polyamides and polyurethanes which have approximately the same molecular weights as the polymers containing carboxyl groups, which are used in the photosensitive composition, have proved to be particularly suitable.
Within the scope of the present invention, the following weight proportions of the most impor-tant components of the photosensitive composition are preferred, which are, in each case, based on the con-tent of non-volatile constituents, i.e., the constit-uents of the solid photosensitive coating obtained after evaporation of the solvent:
Binder: 30 to 90 %
diazonium salt poly-condensation product: 10 to 70 acid: 0 to 10 %
dye or pigment:0 to 12 %
~ --11--dye which changes its color upon exposure: 0 to 5 % ~
The support material is coated from appro-priate organic solvents or solvent mixtures, generally by Elow-coating, spraying or dipping.
Suitable solvents include alcohols, ketones, esters, ethers, and the like. The partial ethers of glycols or oE ketoalcohols have proved to be favor-able solvents, for example, ethylene glycol mono-methyl ether.
Suitable supports are, for example, magne-sium, zinc, copper, mechanically, chemically and electrochemically roughened aluminum, anodically oxi-dized aluminum, steel, and also polyester film or cellulose acetate film, Rerlon gauze etc., the sur-face of which, optionally, may have been subjected to a pretreatment. The support material may function as the final support or as a temporary support material from which ~he photosensitive coating is transferred by lamination to the workpiece to be processed.
The recording material which is prepared using the photosensitive compositions of the inven-tion ser~es, on the one hand, to produce images on suitable supports or receptor sheets and, on the other hand, to produce reliefs which are used as printing plates, screens, resists, and the like.
In addition, it is also possible to use the photosensitive compositions for the formulation of W -hardenable printing inks or for the preparation of lacquers which are hardenable by ultraviolet radia-tion and which can be used for the protection oE sur-faces.
Primarily, the compositions are used for the production oE lithographic printing plates, in which aluminum is the preferred support material.
It is particularly preferred to pretreat the aluminum used for this purpose in the usual manner, 3~
for example, by a mechanical, chemical or electro-chemical roughening process which is, optionally, followe~ by an anodic oxidation. A further treatment of this support material, for example, with polyvinyl phosphonic acid, alkali metal silicate, phosphate, hexafluorozirconate, chromate, borate, polyacrylamide and cellulose derlvatives is advantageous.
The recording materials obtained from the compositions are processed in the conventional man-ner, by exposing imagewise and washing out the unex-posed areas of the coating with a suitable developer.
~ he recording material is exposed under an original, as is known in the art, using light sources which emit light with the highest possible spectral fraction in the near ultraviolet region. The material can also be exposed by laser irradiation~ Suitable lasers Eor irradiation are shorter-wave lasers, for example, Ar lasers, krypton ion lasers, helium/cad-mium lasers, emitting in the region between about 300 and 600 nm and, for some coatings, even CO2 lasers, which emit at about 10.6/um, or YAG lasers emitting at about 1.06/um.
As the developer solutions, substantially neutral or alkaline aqueous solutions are used,which have a pH
25 - value in the range from 6 to 14, preferably from 7.5 to 12, and which contain buffer salts, for example, water-soluble alkalimetal phosphates, silicates, boratesr carbonates, acetates or benzoates. ~dditlonal con-stituents used are wetting agents, preferably anionic wetting agents and, if appropriate, water-soluble polymers. The solution can also contain minor amounts, for example, up to 5 percent by weight, pre-ferably not more than 2 percent by weightf of water--miscible organic solvents. It is preferred to use solvents having low volatility, for example, ara-liphatic alcohols, the vapor pressure of which is of no consequence in the handling of the developer.
~ q)S~3 Development can be performed in the conven-tional manner by dipping, spraying, brushing or wiping-over with a pad.
The binders containing carboxyl groups, which are used according to the present invention~
can easily and reproducibly be prepared from inexpen-sive starting materials. They are readily compatible with other constituents of the coating and are readily combined with each other and also with other polymers to form homogeneous coatings.
The coatings produced are hardly susceptible to scratching, they are easily developed and yield an excellent differentiation between image and non-image areas and a steep grada-tion.
The large print runs and the good ink recep-tivity obtained with printing ~lates prepared using the material of the present invention are particu-larly advantageous. The printing stencils are also highly resistant to alkaline developers.
It is extremely surprising that the materials of this invention are easily developable by means of ecologically acceptable, neutral or alkaline aqueous solutions, irrespective of -the exceptionally low acid nu~bers of the binders.
In the examples which follow, the invention - is explained in detail. Parts by weight and parts by volume are related as g/cm3, percentages and quan-titative proportions refer to units by weight, unless otherwise indicated.
Example l 50 parts by weight oE a polyvinyl butyral which has a molecular weight oE about 70,000 to 80,000 and comprises 71 % of vinyl butyral units, 2 %
of vinyl acetate units and 27 % of vinyl alcohol units, and 4 parts by weight of maleic anhydride were dissolved in 725 parts by weight of methyl ethyl ketone, while heating. The clear solution produced was admixed with 1 part by weight of triethylamine and was refluxed for five hours. After cooling, the solution was filtered and added dropwise to 10,000 parts by weight of distilled water. In the process, a white fibrous product was obtained, which was drawn off by suction and dried in vacuum at 40C to constant weight.
Yield : 52 parts by weight Analysis : C 61.9~; H 9.3 %
Acid Number : 30 A coating ~lution was prepared having the fol-lowing composition: 62 parts by weight of the above-described polymer, 21 parts by weight of a diazoniumsalt polycondensation product prepared from 1 mole of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxy-methyl diphenylether in an 85 ~ strength phosphoric acid and isolated as the mesitylene sulfonate, 2.5 parts by weight of phos-phoric acid (85 % strength), 3 parts by weight of Victoria Pure Blue FGA (Color Index Basic Blue 81)~
and 0.7 part by weight of phenylazodiphenylamine in 2,570 parts by weight of ethylene glycol monomethyl ether and 780 parts by weight of tetrahydrofuran.
The coating was applied to an aluminum foil which had been roughened by brushing with an aqueous abrasive slurry and then pretreated with an 0.1 % strength aqueous solution of polyvinyl phosphonic acid, and was thereafter dried.
The photosensitive coating thus produced, which had a coating weight of 0.95 g/m2, was exposed for 30 seconds under a negative original, using a 5 kW metal halide lamp as the light source.
The exposed coating was treated with a developer solution having the Eollowing composition:
~ 3~j~3 5.0 parts by weight oE sodium octyl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1 part by weight of trisodium phosphate in 12 water, 0.5 part by weight of disodium hydrogen phosphate in 12 water, 92.0 parts by weight oE water. The solu-tion was applied with a plush pad such that the unex-posed areas of the coating were properly removed.
Development was followed by rinsing with water and drying.
10The exposed and developed plate so prepared showed a solid step 4 of a silver film continuous-tone step wedge having a density range from 0.15 to 1.50, with density increments of 0.15.
The printing plate obtained in this manner 15yielded a print run of 40,000 printed sheets, when used on a sheet-fed offset press.
Example_2 24.7 parts by weight of a copolymer of styrene and allyl alcohol, which comprises 46 % of styrene units and 54 % of allyl alcohol units and has a hydroxyl number of 192, was dissolved in 350 parts by weight of methyl ethyl ketone. One part by weight of maleic anhydride was added to the clear solution.
When the maleic anhydride had dissolved, 0~5 parts by weight of triethylamine was added and the mixture was heated to reflux temperature. After five hours, the mixture was allowed to cool and the substantially clear solution was filtered and added dropwise to 5,000 parts by weight of distilled water. The powdery, white product obtained was drawn off by suc-tion and dried as described in Example 1~
The yield amounted to 25 parts by weight of polymer having an acid number of 16.
A coating solution was prepared having the following composition: 86~5 parts by weight of the "
~ S~3 above-indicated binder, 29 par-ts by weight of t'ne di~zonium salt polycondensate described in Example 1, 3O5 parts by weight oE phosphoric acid (85 %
strength), 4.3 parts by weight of Victoria Pure Blue FGA and 1 part by weight of phenylazodiphenylamine in
45,160). To enhance the image contrast after expo-sure, Metanil Yellow (C.I. 13,065), Methyl Orange (C.I. 13,025) or phenylazodiphenylamine can be used.
For particular purposes it can be favorable to admix the photosensitive compositions of the invention with further polymers in quantities of up to 40 percent by weight, relative to the above-described polymeric binders. Resins which contain hydroxy groups or carboxyl groups or amide or ure-thane groupings are advantageous for this purpose.
In many cases, an addition oE binders which differ from the above-described carboxyl group-con-taining binders results in an undesired deterioration of numerous properties of the photosensitive composi-tion, and this deterioration can usually be ascribed ~ 3~
to an incompatibility with the individual constitu-ents of the coating. As against this, the aforemen-tioned advantageous additional resins can, for example, lead to an improvement in abrasion resis-tance and thus to an increase in the number oE print~ed copies, if the composition is used in a litho-graphic printing plate.
Preferred additional polymers include poly-mers which contain amide groups or urethane groups.
The polyamides used according to German Offenlegungs-schrift No. 2,218,821, the polyurethanes disclosed in German Offenlegungsschrift No. 2,948,554, or the sulfonylurethanes disclosed in German Offenlegungs-schriften Nos. 2,053,363 and 2,053,364 are, for example, advantageously used for the above-mentioned purpose.
Additions of polyamides and polyurethanes which have approximately the same molecular weights as the polymers containing carboxyl groups, which are used in the photosensitive composition, have proved to be particularly suitable.
Within the scope of the present invention, the following weight proportions of the most impor-tant components of the photosensitive composition are preferred, which are, in each case, based on the con-tent of non-volatile constituents, i.e., the constit-uents of the solid photosensitive coating obtained after evaporation of the solvent:
Binder: 30 to 90 %
diazonium salt poly-condensation product: 10 to 70 acid: 0 to 10 %
dye or pigment:0 to 12 %
~ --11--dye which changes its color upon exposure: 0 to 5 % ~
The support material is coated from appro-priate organic solvents or solvent mixtures, generally by Elow-coating, spraying or dipping.
Suitable solvents include alcohols, ketones, esters, ethers, and the like. The partial ethers of glycols or oE ketoalcohols have proved to be favor-able solvents, for example, ethylene glycol mono-methyl ether.
Suitable supports are, for example, magne-sium, zinc, copper, mechanically, chemically and electrochemically roughened aluminum, anodically oxi-dized aluminum, steel, and also polyester film or cellulose acetate film, Rerlon gauze etc., the sur-face of which, optionally, may have been subjected to a pretreatment. The support material may function as the final support or as a temporary support material from which ~he photosensitive coating is transferred by lamination to the workpiece to be processed.
The recording material which is prepared using the photosensitive compositions of the inven-tion ser~es, on the one hand, to produce images on suitable supports or receptor sheets and, on the other hand, to produce reliefs which are used as printing plates, screens, resists, and the like.
In addition, it is also possible to use the photosensitive compositions for the formulation of W -hardenable printing inks or for the preparation of lacquers which are hardenable by ultraviolet radia-tion and which can be used for the protection oE sur-faces.
Primarily, the compositions are used for the production oE lithographic printing plates, in which aluminum is the preferred support material.
It is particularly preferred to pretreat the aluminum used for this purpose in the usual manner, 3~
for example, by a mechanical, chemical or electro-chemical roughening process which is, optionally, followe~ by an anodic oxidation. A further treatment of this support material, for example, with polyvinyl phosphonic acid, alkali metal silicate, phosphate, hexafluorozirconate, chromate, borate, polyacrylamide and cellulose derlvatives is advantageous.
The recording materials obtained from the compositions are processed in the conventional man-ner, by exposing imagewise and washing out the unex-posed areas of the coating with a suitable developer.
~ he recording material is exposed under an original, as is known in the art, using light sources which emit light with the highest possible spectral fraction in the near ultraviolet region. The material can also be exposed by laser irradiation~ Suitable lasers Eor irradiation are shorter-wave lasers, for example, Ar lasers, krypton ion lasers, helium/cad-mium lasers, emitting in the region between about 300 and 600 nm and, for some coatings, even CO2 lasers, which emit at about 10.6/um, or YAG lasers emitting at about 1.06/um.
As the developer solutions, substantially neutral or alkaline aqueous solutions are used,which have a pH
25 - value in the range from 6 to 14, preferably from 7.5 to 12, and which contain buffer salts, for example, water-soluble alkalimetal phosphates, silicates, boratesr carbonates, acetates or benzoates. ~dditlonal con-stituents used are wetting agents, preferably anionic wetting agents and, if appropriate, water-soluble polymers. The solution can also contain minor amounts, for example, up to 5 percent by weight, pre-ferably not more than 2 percent by weightf of water--miscible organic solvents. It is preferred to use solvents having low volatility, for example, ara-liphatic alcohols, the vapor pressure of which is of no consequence in the handling of the developer.
~ q)S~3 Development can be performed in the conven-tional manner by dipping, spraying, brushing or wiping-over with a pad.
The binders containing carboxyl groups, which are used according to the present invention~
can easily and reproducibly be prepared from inexpen-sive starting materials. They are readily compatible with other constituents of the coating and are readily combined with each other and also with other polymers to form homogeneous coatings.
The coatings produced are hardly susceptible to scratching, they are easily developed and yield an excellent differentiation between image and non-image areas and a steep grada-tion.
The large print runs and the good ink recep-tivity obtained with printing ~lates prepared using the material of the present invention are particu-larly advantageous. The printing stencils are also highly resistant to alkaline developers.
It is extremely surprising that the materials of this invention are easily developable by means of ecologically acceptable, neutral or alkaline aqueous solutions, irrespective of -the exceptionally low acid nu~bers of the binders.
In the examples which follow, the invention - is explained in detail. Parts by weight and parts by volume are related as g/cm3, percentages and quan-titative proportions refer to units by weight, unless otherwise indicated.
Example l 50 parts by weight oE a polyvinyl butyral which has a molecular weight oE about 70,000 to 80,000 and comprises 71 % of vinyl butyral units, 2 %
of vinyl acetate units and 27 % of vinyl alcohol units, and 4 parts by weight of maleic anhydride were dissolved in 725 parts by weight of methyl ethyl ketone, while heating. The clear solution produced was admixed with 1 part by weight of triethylamine and was refluxed for five hours. After cooling, the solution was filtered and added dropwise to 10,000 parts by weight of distilled water. In the process, a white fibrous product was obtained, which was drawn off by suction and dried in vacuum at 40C to constant weight.
Yield : 52 parts by weight Analysis : C 61.9~; H 9.3 %
Acid Number : 30 A coating ~lution was prepared having the fol-lowing composition: 62 parts by weight of the above-described polymer, 21 parts by weight of a diazoniumsalt polycondensation product prepared from 1 mole of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxy-methyl diphenylether in an 85 ~ strength phosphoric acid and isolated as the mesitylene sulfonate, 2.5 parts by weight of phos-phoric acid (85 % strength), 3 parts by weight of Victoria Pure Blue FGA (Color Index Basic Blue 81)~
and 0.7 part by weight of phenylazodiphenylamine in 2,570 parts by weight of ethylene glycol monomethyl ether and 780 parts by weight of tetrahydrofuran.
The coating was applied to an aluminum foil which had been roughened by brushing with an aqueous abrasive slurry and then pretreated with an 0.1 % strength aqueous solution of polyvinyl phosphonic acid, and was thereafter dried.
The photosensitive coating thus produced, which had a coating weight of 0.95 g/m2, was exposed for 30 seconds under a negative original, using a 5 kW metal halide lamp as the light source.
The exposed coating was treated with a developer solution having the Eollowing composition:
~ 3~j~3 5.0 parts by weight oE sodium octyl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1 part by weight of trisodium phosphate in 12 water, 0.5 part by weight of disodium hydrogen phosphate in 12 water, 92.0 parts by weight oE water. The solu-tion was applied with a plush pad such that the unex-posed areas of the coating were properly removed.
Development was followed by rinsing with water and drying.
10The exposed and developed plate so prepared showed a solid step 4 of a silver film continuous-tone step wedge having a density range from 0.15 to 1.50, with density increments of 0.15.
The printing plate obtained in this manner 15yielded a print run of 40,000 printed sheets, when used on a sheet-fed offset press.
Example_2 24.7 parts by weight of a copolymer of styrene and allyl alcohol, which comprises 46 % of styrene units and 54 % of allyl alcohol units and has a hydroxyl number of 192, was dissolved in 350 parts by weight of methyl ethyl ketone. One part by weight of maleic anhydride was added to the clear solution.
When the maleic anhydride had dissolved, 0~5 parts by weight of triethylamine was added and the mixture was heated to reflux temperature. After five hours, the mixture was allowed to cool and the substantially clear solution was filtered and added dropwise to 5,000 parts by weight of distilled water. The powdery, white product obtained was drawn off by suc-tion and dried as described in Example 1~
The yield amounted to 25 parts by weight of polymer having an acid number of 16.
A coating solution was prepared having the following composition: 86~5 parts by weight of the "
~ S~3 above-indicated binder, 29 par-ts by weight of t'ne di~zonium salt polycondensate described in Example 1, 3O5 parts by weight oE phosphoric acid (85 %
strength), 4.3 parts by weight of Victoria Pure Blue FGA and 1 part by weight of phenylazodiphenylamine in
4,200 parts by weight of ethylene glycol monomethyl ether. The solution was applied to an aluminum foil which had been electrochemically roughened in nitric acid and thereafter anodically oxidi~ed and post treated with polyvinyl phosphonic acid. The dry coating weight was 1.02 g/m2.
Exposure and processing were carried out similarly to the procedures indicated in Example 1.
Upon inking, a printing plate was obtained which was readily ink-receptive and the non-image areas of which did not accept greasy printing ink.
When the printing plate was clamped on a sheet-fed offset press, it yielded thousands of good prints.
Exam~le 3 A polymer containing 61.3 ~ of C and 9.3 %
of ~I and having an acid number of 8 was prepared in a procedure similar to that described in Example 1, by reacting 100 parts by weight of the polyvlnyl butyral indicated in Example 1 with 1 part by weight maleic anhydride in 1,300 parts by weight of methyl ethyl ketone, precipitated in water and dried.
The binder so produced was used to prepare a coating solution having the composition specified in Example 1.
This coating solution was applied to alu-minum foil which had been pretreated as indicated in Example 2 and was then dried. The coating weight was about 1 g/m2.
~ 3 The p`notosensitive coating was exposed for 30 seconds under a negative original, using a 5 kW
metal halide lamp as the light source and was then developed with a developer which had the following compositions: 5.0 parts by weight of sodium octyl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1 part by weight oE trisodium phosphate in 12 water, 1 part by weight of phenoxyethanol, 91.5 parts by weight of water.
The non-image areas of the photosensitive coating were already detached after a few seconds and, after wiping over with a plush pad, the plate was rinsed with water and dried.
The exposed and developed plate thus obtained had the same properties as that described in Example 1. The plate was gummed and then clamped on a sheet-fed offset press, where it yielded 220,000 good prints.
Example 4 25 parts by weight of the polyvinyl butyral indicated in Example 1 and 10 parts by weight of maleic anhydride were dissolved in 400 parts by weight of methyl ethyl ketone, admixed with 1 part by weight of triethylamine and refluxed for 5 hours.
After precipitating in water, a polymer was obtained which contained 59.9 % of C and 8.5 % of H
and had an acid number of 70.
A coating solution was prepared having the fol-lowing composition; 34.1 parts by weight of the above-described polymer, 11.4 parts by weight of the diazonium salt polycondensation product specified in Example 1, lo 5 parts by weight of phosphoric acid (85 strength), 1.1 parts by weight of crystal violet (Color Index 42~555) and 1.1 parts by weight of phenylazodiphenylamine in 1, 600 parts by weight of ethylene glycol monomethyl ether. The solution was applled to a support as indicated in Example 2.After drying, the coating had a weigh-t of 0.98 g/m .
Processing was carried out similarly to Example 1. In this case, the printing plate was immersed in the developer for one minute after ima-gewise exposure and was then rinsed off with water.
The printing plate thus obtained was excellently developed, i.e. even very fine halftone and line ele-ments showed a differentiated reproduction, the non-image areas were free from staining or coating residues and a high resolution was attained.
When the printing plate was used for printing on a sheet-fed offset press, many prints of excellent quality were obtained~
Example 5 46 parts by weight of the polyvinyl butyral specified in Example 1 and 3.6 parts by weight of phthalic anhydride were dissolved in 690 parts by weight of methyl ethyl ketone to give a clear solu-tion and, after adding 1.1 parts by weight of triethylamine, the solution was refluxed or five hours. After cooling, the solution was added dropwise 25 to 10,000 parts by weight of water and the fibrous, white polymer which was precipitated was drawn off by suction and dried.
Yield : 49 parts by weight Analysis : C 61.9 %; ~ 9.2 %
Acid Number : 16 A coating solu-tion was prepared having the fol-lowing composition: 35~1 parts by weight of the above-described polymer, 23.4 parts by weight of a diazonium salt condensation product prepared by con-... .
densing 1 mole of 3-methoxy-dipheny~amine-4-diazonium sulfate with 1 mole of 4-methyl-4'-methoxymethyl-diphenylether and then with 1 mole of ~,4'-bis-methoxymethyl-diphenylether in an 85 % strength phosphoric acid and isolated as the mesitylene sulfonate, 2.1 parts by weight of phosphoric acid (85 ~ strength), 1.5 parts by weight oE Victoria Pure Blue FGA, and 1.1 parts by weight of phenylazodi-phenylamine in 1,900 parts by weight of ethylene gly-col monomethyl ether. The solu-tion was applied to a support as indicated in Example 2 to give a dry coat-inq weight of 0.95 g/m2.
After exposing imagewise and developing with the developer solution specified in Example 1, a printing plate was obtained showing a very high reso-lution and a steep gradation. In proof printing, the image areas very quickly accepted printing ink. The behavior upon proof printing of the cleaned printing plate was not adversely influenced by the action of various treating chemicals.
Examples 6 to 9 According to Example 5, the following acid anhydrides were reacted:
Example 6: cis-hexahydrophthalic anhydride Example 7: 4,5-dich oro-phthalic anhydride Example 8: 3-nitro-phthalic anhydride Example 9: trimellitic anhydride.
In all cases, practically quantitati~e yields of the corresponding polymers were obtained.
The coatings which were prepared with these polymers, according to Example 5 and which were applied to supports as used in Example 2could be developed with increasing ease using the developer solutions specified in Example 1 or Example 3 i3 The exposed and developed plates showing well differentiated images in all cases, yielded prints of high resolution and good quality, when they were clamped on a sheet fed offset press.
ExamPle 10 20 parts by weight of the polyvinyl butyral specified in Example l, and 1.6 parts by weight of pyridine-2,3-dicarboxylic acid anhydride, were dissolved in 280 parts by weight of methyl ethyl ketone. AEter adding 0.5 part by weight of triethyla-mine, the clear solution was refluxed for five hoursO
The solution, after being allowed to cool, was then added dropwise to 5,000 parts by weight of water and the precipitated polymer was drawn off by suction and dried. 20.5 parts by weight of a white, brittle polymerwere obtained.
Analysis : C 62.2 %; H 9.4 ~; N 0.6 Acid Number : 17.
A coating solution was prepared having the fol-lowing composition: 88.7 parts by weight of the above-described polymer, 30 parts by weight of the diazonium salt condensate specified in Example 1, 4.6 parts by weight of phosphoric acid 185 % strength), 4.3 parts by weight of Victoria Pure Blue FGA, and l.l parts by weight of phenyla~odiphenylamine, 3,675 parts by weight oE ethylene glycol monomethyl ether and 1,115 parts by weight of tetrahydrofuran. The solution was coated upon a support as indicated in Example 2 and dried. The coating weight was 1.03 g/m2.
The photosensitive coating thus obtained was exposed for 25 seconds under a negative original, using a 5 kW metal halide lamp as the light source.
The exposed coating was developed within a few seconds using a developer solution of the .3~
following composition: 5.0 parts by weignt of sodium octyl sulfate, 1.5 parts by weight of sodium metasi-licate in 5 water, l.0 part by weight of trisodium phosphate in 12 water, 92.5 parts by weight of water, which was applied with a plush pad.
In the exposed and developed plate, which was an excellently differentiated reproduction of the negative original, a solid step 4 of a continuous tone step wedge was obtained.
Exame~e 11 294 parts by weight oE the polyvinyl butyral specified in Example 1 and 10.3 parts ~y weight of maleic anhydride were dissolved in 4,170 parts by weight oE methyl ethyl ketone and after adding 5 parts by weight of triethylamine, the solution was refluxed for five hours. The solution, after being allowed to cool, was added dropwise to 50,000 parts by weight of water and, in the process, a fibrous, white polymer was precipitated.
20 Analysis : C 62.0 ~; H 9.4 Acid Number : 13 A caoting solution was prepared having the fol-lowing composition: 270 parts by weight of the above-described polymer, 165 parts by weight of the diazonium salt condensation product specified in Example 1, 17 parts hy weight of Victoria Pure Blue FGA, 4 parts by weight of phenylazodiphenylamine, and 15 parts by weight of phosphoric acid (85 % strength) in 10,500 parts by weight of ethylene glycol mono-methyl ether, 2,400 parts by weight of tetrahydro-furan, and 800 parts by weight of butyl acetate. The solution was applied to a support as indicated in Ex-ample 2 and dried. The coating weight was 1.03 g/m2.
The photosensitive coating was exposed imagewise as described in Example lO. It was swiftly ~ 3~
processed using the developer specified in Example lO. After development, the plate was treated with a commercially available gumming agent. When the printing plate so produced was clamped on a sheet-fed offset press,it y1elded more than 200,000 prints of excellent quality.
Example 12 The coating solution described in Example ll was applied to an aluminum foil which had been elec-trochemically roughened in hydrochloric acid, anodi-cally oxidized and post-treated as indicated in Example 2, to give a dry coating weight of 0.95 g/m2.
After exposure and development, the printing plate was clamped on a sheet-fed offset press. The printing test was stopped after printing 170,000 sheets, at which point the prints obtained still showed an excellent quality.
Example 13 The photosensitive coating described in Example 3 was applied to five aluminum foils which had been treated according to Example 2.
The five printing plates obtained were stored in a drying oven which had been heated to 100 C, for periods ranging from one to five hours.
The photosensitive coatings, after being allowed to cool, were exposed for 25 seconds under a negative original and then treated for 45 seconds with the developer solution described in Example 3.
The plates, which had been stored in the drying oven for one or two hours respectively, did not show any no~iceable extension of the stepwedge or an~ reduced speed of development, as compared with a plate processed in the usual manner~ However, in the plate stored for three hours, a slightly reduced speed of development and an extension o~ the step-wedge by about one step ~as observed. In the platestored for four hours, initial tendencies to scumming showed in non-image areas upon inking with a greasy printing ink, while the plate cured for five hours clearly accepted inlc, even in the non-image areas.
The above-indicated results show that the photosensitive coating is rather insensitive to the action of heat.
Examples 14 to 17 The maleic anhydride of Example 1 was replaced by the same quantities of -the following aliphatic dicarboxylic acid anhydrides. Polymers of similar properties were obtained, which yielded exposed and developed plates showing a high resolu-tion, a good reproduction upon printing and large print runs, when they were added to one of the coating solutions described in ~xample 1 or Example 3 and processed as indicated in these ~xamples.
Example __ Acid Anhydride _Acid Number 14 succinic anhydride 26 25 15 3,3-tetramethylene-glutaric acid anhydride 14 16 camphoric acid anhydride 12 17 3_oxa-~lutaric-anhydride_ 27 __ -~4-~ 3 Example _ A coating solution prepared Erom 35.1 parts by weight of the polymer described in Example 11, 23.4 parts by weight of the diazonium salt polycon-densate specified in Example 5, 2.3 parts by weightof phosphoric acid (85 ~ strength), 2.0 parts by weight of Renol Blue B2G-H (Color Index 74,160) and 1.1 parts by weight of phenylazodiphenylamine in 1,800 parts by weight of ehtylene glycol monomethyl ether and 480 parts by weight of butyl acetate was applied to a support as indicated ln Example 2, dried and processed as described in Example 1. The coating weight was 1.03 g/m .
The printing plate, which behaved excellent-ly in the platemaking process, was clamped on aprinting press and yielded a great number of prints showing an excellent resolution.
Example 19 50 parts by weight of the polyvinyl butyral described in Example 1 and 8 parts by weight of 3-oxa-glutaric anhydride were dissolved in 700 parts by weight of methyl ethyl ketone. Then 1 part by weight of triethylamine was added and the mixture was refluxed for five hours. Upon cooling of the mixture, precipitation was carried out in 5,000 parts by weight oE water and the fibrous product obtained was dried. Yield: 54 parts by weight of polymer having an acid number of 50.
A coatin~ solution which had the following composition: 15.7 parts by weight of the above-described polymer, 15.7 parts by weight of the diazo-niurn salt polycondensation product specified in Example 1, 1.0 part by weight of phosphoric acid ~ ~3~13~
(85 ~ strength), l.2 parts by weigh-t of Renol Blue B2G-H (Color Index 7~,160), and 0.2 part by weight of phenylazodiphenylamine in l,200 parts by weight oE
ethylene glycol monomethyl ether was applied to a support as used in Exa~ple 2. The coating weight of the photosensitive coating after drying was l.0 g/m2.
Processing was carried out as indicated in Example l. The exposed and developed plate thus obtained, which was very readily processed and showed a steep gradation and a high resolution, yielded a print run exceeding lO0,000 printed sheets without any marked wear of the plate, when it was used for printing on a sheet-fed offset press.
Examples 20 to 22 In these Examples, various hydroxyl group-containing polymers were used, which were reacted with a constant quantity of maleic anhydride. The polymers prepared as described in Example l were employed in coating solutions having compositions corresponding to the composition described in Example 18. Processing was carried out according to Example 3. In all cases, high-quality printing plates were obtained, showing exceptionally high chemical and mechanical resistances when they were used on a printing press, and which yielded large print runs.
Example 20 20 parts by weight of the polyvinyl butyral described in Example l were reacted with 8 parts by weig`nt of maleic anhydride in 350 parts by weight of methyl ethyl ketone and worked up as indicated in Example l. The acid number was 70.
S~3 Example 21 20 parts by weight of a polyvinyl butyral having a molecular weight of about 70,000 to 80,000 and comprising 79 % by weight of vinyl butyral units, 2 ~ by weigh-t of vinyl acetate units and 19 % by weight of vinyl alcohol units, were reacted with 8 parts by weight of maleic anhydride in 350 parts by weight of methyl ethyl ketone. The acid number was 73.
Example 22 20 parts by weight of a polyvinyl butyral having a molecular weight of about 70,000 to 80,000 and comprising 86 ~ by weight of vinyl butyral units, 2 % by weight of vinyl acetate units and 12 ~ by weight of vinyl alcohol units, were reacted with 8 parts by weight of maleic anhydride in 350 parts by weight of methyl ethyl ketone. The acid number was 43.
Example_23 50 parts by weight of the polyvinyl butyral described in Example 1, and 4 parts by weight of maleic anhydride were dissolved in 725 parts by weight of methyl ethyl ketone while heating and, after adding 1 part by weight of triethylamine, the solution wa.s refluxed for five hours. A 7.42 %
strength solution of the polymer in methyl ethyl ketone was thus obtained.
15 parts by weight of this solution were added dropwise to water. The polymer so produced had the composition indicated in Example lo ~ 3~3 A caoting solution was prepared having the Eol-lowing composition: 50.5 parts by weight of a 7.42 ~
strength solution of the above-described polymer in methyl ethyl ketone, 1.26 parts by weight of the diazo polycondensate specified in Example 1, 0.15 part by weight of phosphoric acid (85 % strength), 0.18 part by weight of Victoria Pure Blue FGA and 0.04 part by weight of phenylazodiphenylamine in 154 parts by weight of ethylene glycol monomethyl ether The solution was processed according to Example 1.
As the present formulation corresponded to the composition indicated in Example 1, with the exception that methyl ethyl ketone had been substi-tuted for tetrahydroEuran, it was found, as expected, that the photosensitive coating obtained was substan-tially indentical with the photosensitive coating described in Example 1 regarding its technical pro-perties for platemaking and printing.
Example 24 According to Example 11, a polymer con~
taining 62.2 ~ of C and 9.4 % of H and having an acid number of 12.2 was prepared in the form of a 6.8 strength solution in methyl ethyl ketone. The polymer produced was not isolated from the reaction medium~
A coating solution was prepared having the following composition: 258 parts by weight of the above-described 6.8 % strength soiution of the polymer in methyl ethyl ketone, 16.7 parts by weight of the diazonium salt polycondensate specified in Example 5, 1.2 parts by weight of phosphoric acid (85 strength) 1.0 part by weight of Renol Blue B2G-H
and 0.55 part by weight of phenylazodiphenylamine in 600 parts by weight of ethylene glycol monomethyl ether. 'I'h~ s:Dlu-tion was applied and processeclaccording to ExaTple 18. The printing plate obtained corresponded to that described in Example 18, i.e. the use of the reac-tion solution including triethylamine did not have any adverse influence on storability and technical properties for printing and platemaking. After clamping on the printing press, a print run of well over 150,000 sheets was obtained.
Example 25 The coating solution described in Example 24 was varied in such a way that 206 parts by weight of the 6.8 % strength polymer solution therein described and 3.5 parts by weight of the polyurethane specified below were used. The polyurethane was prepared by reacting l mole of a prepolymer, obtained from toly-lene diisocyanate and l,l,l-trimethylol propane, in a molecular ratio o~ 3:19 with about 2.5 moles of hexane diol-1,6 in tetrahydrofuran. The product was precipitated in water and thereafter dried.
After processing of the solution as indi-cated in Example 24, a hardly noticeable reduction of developing speed was observed.
When the printing plate produced was clamped on a printing press and used for printing under iden-tical conditionsr a print run was attained which exceeded that of the preceding example by about 20~.
An evaluation of the printing result showed, however, that this printing plate tended to a slight dot gain, compared with the printing plate of Example 24.
Example 26 parts by weight of a terpolymer com-prising 31 ~ of vinyl chloride, 3 % of vinyl acetate and 6 % o~ vinyl alcohol and having an average mole-cular weight of 15,500 and a softening point of 77Cwas reacted with 2 parts by weight of 3-oxaglutaric anhydride, as described in Example 1. The polymer obtained had an acid number of 24.
A coating solution was prepared having the fol-lowing composition: 55 parts by weight of a 6.4 %
strength solution of the above-described reaction product in methyl ethyl ketone, 1.79 parts by weight oE the diazonium salt polycondensate specified in Example 1, 0.18 part by weight of phosphoric acid (85 % strength), 0.06 part by weight of phenylazodi-phenylamine and 0.13 part by weight of crystal violet in 140 parts by weight of ethylene glycol monomethyl ether was applied to an aluminum foil which had been mechanically roughened and post-treated with an 0.1 %
strength aqueous solution of polyvinyl phosphonic acid and was dried to give a coating weight of 0.8 g/m2 .
After exposure and development as indicated in Example 1, a printing plate was obtained which yielded several thousand good prints, when clamped on a printing press.
Exam~le 27 parts by weight of a polyvinyl formal having a molecular weight oE about 25,000 to 30,000 and comprising 68 % by weight of vinylformal units, 25 % by weight of vinyl acetate units and 7 % by weight of vinyl alcohol units (hydroxyl number 85), and 4 parts by weight of maleic anhydride were ~ i¢3 dissolved in 500 parts by weight of tetrahydrofuran to give a clear solution. This solution was admixed with 10 parts by weig`nt of triethylamine, and the exothermic solution was refluxed Eor eight hours.
After cooling, the solution was filtered and added dropwise to 8,000 parts by weight of water to produce a white, comparatively brittle product which was drawn oEf by suction and dried.
The yield amounted to 51 parts by weight of polymer having an acid number of 28.
A coating solution was prepared having the fol-lowing composition: 20 parts by weight of the above-described polymer, 8 parts by weight of the diazonium salt polycondensation product specified in Example 1, 0.9 part by weight of phosphoric acid (85 strength), 1.1 parts by weight of Victoria Pure Blue FGA and 0.3 part by weight of phenylazodiphenylamine in 1,100 parts by weight of ethylene glycol mono-methyl ether. The solution was applied to a support as described in Example 2 and dried. The coating weight was 0.99 g/m .
The photosensitive coating was exposed under a negative original, as indicated in Example 3, and was treated with the developer mixture described in 25- Example 3 The offset printing plate so produced had a coatin9 which exhibited an exceptionally high mecha-nical resistance and yielded several thousand excellent quality prints, when use~d for printing on a sheet-~ed offset press.
ExamPle 28 (ComParatlve Example) A coating solution A comprising the follow-ing components was prepared in accordance with -~ ;t3 E~ample 6 of German Offenlegungsschrift No.3,130,987: 15.0 parts by weight of a styrene-maleic acid ester copolymer, softening range from 190 to 205 C, acid number about 200, average molecular weight about 10,000, 15.0 parts by weight of the diazonium salt cocondensate specified in Example 1, 0.8 part by weight of Victoria Pure Blue FGA, 0.5 part by weight of phenylazodiphenylamine and 1.2 parts by weight of phosphoric acid (85 ~ strength) in 900 parts by weight of ethylene glycol monomethyl ether.
An additional coating solution B was pre-pared b~r substituting the same quantity of the polymer described in Example 4 for the above-indicated copolym er.
The two solutions were applied to an alumi-num foil which had been pretreated according to Example 2, to produce a coating weight of l g/m2.
The two photosensitive coatings were exposed for 22 seconds under a negative original and deve-loped wi-th a developer mixture having the following composition: 5.0 parts by weight of sodium lauryl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1~5 parts by weight of trisodium 25- phosphate in 12 water, 92 parts by weight of water.
The results obtained were as follows:
The photosensitivities of the two photosen-sitive coatings A and B were almost identical.
The contrast of the exposed, still undeve-loped plate B was clearly better and more pleasant tothe eye than the contrast of plate A.
After development, which proceeded swiftly in both cases, printing plates were obtained which were, on the whole, comparable. However, the grada-tion of plate B was somewhat steeper than that ofplate A. The two plates were clamped on a printing press for the purpose of comparlson.
' -, The ~ollowing results were obtained:
In proof printing, plate B accepted ink definitely more rapidly (by a factor of 2-3) than plate A. If an al'~aline dampening solution was used, this effect was even more pronounced.
When running on, it was found that plate B
clearly printed more open screen areas than plate A~
Moreover, plate A showed irregularities in the screen. After only 80,000 printed copies, the reproduction of the continuous-tone stepwedge was reduced by two steps. After printing the same number of copies, plate B did not show any irregularity in the screen. The reproduction of the continuous-tone stepwedge was reduced by about one step.
After 100,000 printed copies, plate A showed the first coating damage, while the screen and solid areas of plate B did not exhibit any damage, even after 150,000 printed copies.
On the whole, it can thus be stated that printing plate B, made according to the present invention, is superior t~ the prior art printing plate A in substantial criteria.
Example 29 (Com~ative Example) According to Example 28, two coating solu-tions A 1 (German Offenlegungsschrift No. 3,130,987) and B 1 (according to this invention) were prepared, in which Renol Blue B2G-H was substi-tuted for the Victoria Pure Blue FGA dye.
Coating, exposure and development were carried out as indicated in Example 28.
It was ound that the dye used was incom-patible with the binder of plate Al and agglomerated.
The exposed plate showed a pale gray color and even . .
-~, ....
.
~ 3~
after development, contrast was insufficient. The gradation of printing plate B 1 was much steeper than that o~ printing plateAl. When plates A 1 and B 1 were used in a press run, the above-described results were basically repeated.
Exposure and processing were carried out similarly to the procedures indicated in Example 1.
Upon inking, a printing plate was obtained which was readily ink-receptive and the non-image areas of which did not accept greasy printing ink.
When the printing plate was clamped on a sheet-fed offset press, it yielded thousands of good prints.
Exam~le 3 A polymer containing 61.3 ~ of C and 9.3 %
of ~I and having an acid number of 8 was prepared in a procedure similar to that described in Example 1, by reacting 100 parts by weight of the polyvlnyl butyral indicated in Example 1 with 1 part by weight maleic anhydride in 1,300 parts by weight of methyl ethyl ketone, precipitated in water and dried.
The binder so produced was used to prepare a coating solution having the composition specified in Example 1.
This coating solution was applied to alu-minum foil which had been pretreated as indicated in Example 2 and was then dried. The coating weight was about 1 g/m2.
~ 3 The p`notosensitive coating was exposed for 30 seconds under a negative original, using a 5 kW
metal halide lamp as the light source and was then developed with a developer which had the following compositions: 5.0 parts by weight of sodium octyl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1 part by weight oE trisodium phosphate in 12 water, 1 part by weight of phenoxyethanol, 91.5 parts by weight of water.
The non-image areas of the photosensitive coating were already detached after a few seconds and, after wiping over with a plush pad, the plate was rinsed with water and dried.
The exposed and developed plate thus obtained had the same properties as that described in Example 1. The plate was gummed and then clamped on a sheet-fed offset press, where it yielded 220,000 good prints.
Example 4 25 parts by weight of the polyvinyl butyral indicated in Example 1 and 10 parts by weight of maleic anhydride were dissolved in 400 parts by weight of methyl ethyl ketone, admixed with 1 part by weight of triethylamine and refluxed for 5 hours.
After precipitating in water, a polymer was obtained which contained 59.9 % of C and 8.5 % of H
and had an acid number of 70.
A coating solution was prepared having the fol-lowing composition; 34.1 parts by weight of the above-described polymer, 11.4 parts by weight of the diazonium salt polycondensation product specified in Example 1, lo 5 parts by weight of phosphoric acid (85 strength), 1.1 parts by weight of crystal violet (Color Index 42~555) and 1.1 parts by weight of phenylazodiphenylamine in 1, 600 parts by weight of ethylene glycol monomethyl ether. The solution was applled to a support as indicated in Example 2.After drying, the coating had a weigh-t of 0.98 g/m .
Processing was carried out similarly to Example 1. In this case, the printing plate was immersed in the developer for one minute after ima-gewise exposure and was then rinsed off with water.
The printing plate thus obtained was excellently developed, i.e. even very fine halftone and line ele-ments showed a differentiated reproduction, the non-image areas were free from staining or coating residues and a high resolution was attained.
When the printing plate was used for printing on a sheet-fed offset press, many prints of excellent quality were obtained~
Example 5 46 parts by weight of the polyvinyl butyral specified in Example 1 and 3.6 parts by weight of phthalic anhydride were dissolved in 690 parts by weight of methyl ethyl ketone to give a clear solu-tion and, after adding 1.1 parts by weight of triethylamine, the solution was refluxed or five hours. After cooling, the solution was added dropwise 25 to 10,000 parts by weight of water and the fibrous, white polymer which was precipitated was drawn off by suction and dried.
Yield : 49 parts by weight Analysis : C 61.9 %; ~ 9.2 %
Acid Number : 16 A coating solu-tion was prepared having the fol-lowing composition: 35~1 parts by weight of the above-described polymer, 23.4 parts by weight of a diazonium salt condensation product prepared by con-... .
densing 1 mole of 3-methoxy-dipheny~amine-4-diazonium sulfate with 1 mole of 4-methyl-4'-methoxymethyl-diphenylether and then with 1 mole of ~,4'-bis-methoxymethyl-diphenylether in an 85 % strength phosphoric acid and isolated as the mesitylene sulfonate, 2.1 parts by weight of phosphoric acid (85 ~ strength), 1.5 parts by weight oE Victoria Pure Blue FGA, and 1.1 parts by weight of phenylazodi-phenylamine in 1,900 parts by weight of ethylene gly-col monomethyl ether. The solu-tion was applied to a support as indicated in Example 2 to give a dry coat-inq weight of 0.95 g/m2.
After exposing imagewise and developing with the developer solution specified in Example 1, a printing plate was obtained showing a very high reso-lution and a steep gradation. In proof printing, the image areas very quickly accepted printing ink. The behavior upon proof printing of the cleaned printing plate was not adversely influenced by the action of various treating chemicals.
Examples 6 to 9 According to Example 5, the following acid anhydrides were reacted:
Example 6: cis-hexahydrophthalic anhydride Example 7: 4,5-dich oro-phthalic anhydride Example 8: 3-nitro-phthalic anhydride Example 9: trimellitic anhydride.
In all cases, practically quantitati~e yields of the corresponding polymers were obtained.
The coatings which were prepared with these polymers, according to Example 5 and which were applied to supports as used in Example 2could be developed with increasing ease using the developer solutions specified in Example 1 or Example 3 i3 The exposed and developed plates showing well differentiated images in all cases, yielded prints of high resolution and good quality, when they were clamped on a sheet fed offset press.
ExamPle 10 20 parts by weight of the polyvinyl butyral specified in Example l, and 1.6 parts by weight of pyridine-2,3-dicarboxylic acid anhydride, were dissolved in 280 parts by weight of methyl ethyl ketone. AEter adding 0.5 part by weight of triethyla-mine, the clear solution was refluxed for five hoursO
The solution, after being allowed to cool, was then added dropwise to 5,000 parts by weight of water and the precipitated polymer was drawn off by suction and dried. 20.5 parts by weight of a white, brittle polymerwere obtained.
Analysis : C 62.2 %; H 9.4 ~; N 0.6 Acid Number : 17.
A coating solution was prepared having the fol-lowing composition: 88.7 parts by weight of the above-described polymer, 30 parts by weight of the diazonium salt condensate specified in Example 1, 4.6 parts by weight of phosphoric acid 185 % strength), 4.3 parts by weight of Victoria Pure Blue FGA, and l.l parts by weight of phenyla~odiphenylamine, 3,675 parts by weight oE ethylene glycol monomethyl ether and 1,115 parts by weight of tetrahydrofuran. The solution was coated upon a support as indicated in Example 2 and dried. The coating weight was 1.03 g/m2.
The photosensitive coating thus obtained was exposed for 25 seconds under a negative original, using a 5 kW metal halide lamp as the light source.
The exposed coating was developed within a few seconds using a developer solution of the .3~
following composition: 5.0 parts by weignt of sodium octyl sulfate, 1.5 parts by weight of sodium metasi-licate in 5 water, l.0 part by weight of trisodium phosphate in 12 water, 92.5 parts by weight of water, which was applied with a plush pad.
In the exposed and developed plate, which was an excellently differentiated reproduction of the negative original, a solid step 4 of a continuous tone step wedge was obtained.
Exame~e 11 294 parts by weight oE the polyvinyl butyral specified in Example 1 and 10.3 parts ~y weight of maleic anhydride were dissolved in 4,170 parts by weight oE methyl ethyl ketone and after adding 5 parts by weight of triethylamine, the solution was refluxed for five hours. The solution, after being allowed to cool, was added dropwise to 50,000 parts by weight of water and, in the process, a fibrous, white polymer was precipitated.
20 Analysis : C 62.0 ~; H 9.4 Acid Number : 13 A caoting solution was prepared having the fol-lowing composition: 270 parts by weight of the above-described polymer, 165 parts by weight of the diazonium salt condensation product specified in Example 1, 17 parts hy weight of Victoria Pure Blue FGA, 4 parts by weight of phenylazodiphenylamine, and 15 parts by weight of phosphoric acid (85 % strength) in 10,500 parts by weight of ethylene glycol mono-methyl ether, 2,400 parts by weight of tetrahydro-furan, and 800 parts by weight of butyl acetate. The solution was applied to a support as indicated in Ex-ample 2 and dried. The coating weight was 1.03 g/m2.
The photosensitive coating was exposed imagewise as described in Example lO. It was swiftly ~ 3~
processed using the developer specified in Example lO. After development, the plate was treated with a commercially available gumming agent. When the printing plate so produced was clamped on a sheet-fed offset press,it y1elded more than 200,000 prints of excellent quality.
Example 12 The coating solution described in Example ll was applied to an aluminum foil which had been elec-trochemically roughened in hydrochloric acid, anodi-cally oxidized and post-treated as indicated in Example 2, to give a dry coating weight of 0.95 g/m2.
After exposure and development, the printing plate was clamped on a sheet-fed offset press. The printing test was stopped after printing 170,000 sheets, at which point the prints obtained still showed an excellent quality.
Example 13 The photosensitive coating described in Example 3 was applied to five aluminum foils which had been treated according to Example 2.
The five printing plates obtained were stored in a drying oven which had been heated to 100 C, for periods ranging from one to five hours.
The photosensitive coatings, after being allowed to cool, were exposed for 25 seconds under a negative original and then treated for 45 seconds with the developer solution described in Example 3.
The plates, which had been stored in the drying oven for one or two hours respectively, did not show any no~iceable extension of the stepwedge or an~ reduced speed of development, as compared with a plate processed in the usual manner~ However, in the plate stored for three hours, a slightly reduced speed of development and an extension o~ the step-wedge by about one step ~as observed. In the platestored for four hours, initial tendencies to scumming showed in non-image areas upon inking with a greasy printing ink, while the plate cured for five hours clearly accepted inlc, even in the non-image areas.
The above-indicated results show that the photosensitive coating is rather insensitive to the action of heat.
Examples 14 to 17 The maleic anhydride of Example 1 was replaced by the same quantities of -the following aliphatic dicarboxylic acid anhydrides. Polymers of similar properties were obtained, which yielded exposed and developed plates showing a high resolu-tion, a good reproduction upon printing and large print runs, when they were added to one of the coating solutions described in ~xample 1 or Example 3 and processed as indicated in these ~xamples.
Example __ Acid Anhydride _Acid Number 14 succinic anhydride 26 25 15 3,3-tetramethylene-glutaric acid anhydride 14 16 camphoric acid anhydride 12 17 3_oxa-~lutaric-anhydride_ 27 __ -~4-~ 3 Example _ A coating solution prepared Erom 35.1 parts by weight of the polymer described in Example 11, 23.4 parts by weight of the diazonium salt polycon-densate specified in Example 5, 2.3 parts by weightof phosphoric acid (85 ~ strength), 2.0 parts by weight of Renol Blue B2G-H (Color Index 74,160) and 1.1 parts by weight of phenylazodiphenylamine in 1,800 parts by weight of ehtylene glycol monomethyl ether and 480 parts by weight of butyl acetate was applied to a support as indicated ln Example 2, dried and processed as described in Example 1. The coating weight was 1.03 g/m .
The printing plate, which behaved excellent-ly in the platemaking process, was clamped on aprinting press and yielded a great number of prints showing an excellent resolution.
Example 19 50 parts by weight of the polyvinyl butyral described in Example 1 and 8 parts by weight of 3-oxa-glutaric anhydride were dissolved in 700 parts by weight of methyl ethyl ketone. Then 1 part by weight of triethylamine was added and the mixture was refluxed for five hours. Upon cooling of the mixture, precipitation was carried out in 5,000 parts by weight oE water and the fibrous product obtained was dried. Yield: 54 parts by weight of polymer having an acid number of 50.
A coatin~ solution which had the following composition: 15.7 parts by weight of the above-described polymer, 15.7 parts by weight of the diazo-niurn salt polycondensation product specified in Example 1, 1.0 part by weight of phosphoric acid ~ ~3~13~
(85 ~ strength), l.2 parts by weigh-t of Renol Blue B2G-H (Color Index 7~,160), and 0.2 part by weight of phenylazodiphenylamine in l,200 parts by weight oE
ethylene glycol monomethyl ether was applied to a support as used in Exa~ple 2. The coating weight of the photosensitive coating after drying was l.0 g/m2.
Processing was carried out as indicated in Example l. The exposed and developed plate thus obtained, which was very readily processed and showed a steep gradation and a high resolution, yielded a print run exceeding lO0,000 printed sheets without any marked wear of the plate, when it was used for printing on a sheet-fed offset press.
Examples 20 to 22 In these Examples, various hydroxyl group-containing polymers were used, which were reacted with a constant quantity of maleic anhydride. The polymers prepared as described in Example l were employed in coating solutions having compositions corresponding to the composition described in Example 18. Processing was carried out according to Example 3. In all cases, high-quality printing plates were obtained, showing exceptionally high chemical and mechanical resistances when they were used on a printing press, and which yielded large print runs.
Example 20 20 parts by weight of the polyvinyl butyral described in Example l were reacted with 8 parts by weig`nt of maleic anhydride in 350 parts by weight of methyl ethyl ketone and worked up as indicated in Example l. The acid number was 70.
S~3 Example 21 20 parts by weight of a polyvinyl butyral having a molecular weight of about 70,000 to 80,000 and comprising 79 % by weight of vinyl butyral units, 2 ~ by weigh-t of vinyl acetate units and 19 % by weight of vinyl alcohol units, were reacted with 8 parts by weight of maleic anhydride in 350 parts by weight of methyl ethyl ketone. The acid number was 73.
Example 22 20 parts by weight of a polyvinyl butyral having a molecular weight of about 70,000 to 80,000 and comprising 86 ~ by weight of vinyl butyral units, 2 % by weight of vinyl acetate units and 12 ~ by weight of vinyl alcohol units, were reacted with 8 parts by weight of maleic anhydride in 350 parts by weight of methyl ethyl ketone. The acid number was 43.
Example_23 50 parts by weight of the polyvinyl butyral described in Example 1, and 4 parts by weight of maleic anhydride were dissolved in 725 parts by weight of methyl ethyl ketone while heating and, after adding 1 part by weight of triethylamine, the solution wa.s refluxed for five hours. A 7.42 %
strength solution of the polymer in methyl ethyl ketone was thus obtained.
15 parts by weight of this solution were added dropwise to water. The polymer so produced had the composition indicated in Example lo ~ 3~3 A caoting solution was prepared having the Eol-lowing composition: 50.5 parts by weight of a 7.42 ~
strength solution of the above-described polymer in methyl ethyl ketone, 1.26 parts by weight of the diazo polycondensate specified in Example 1, 0.15 part by weight of phosphoric acid (85 % strength), 0.18 part by weight of Victoria Pure Blue FGA and 0.04 part by weight of phenylazodiphenylamine in 154 parts by weight of ethylene glycol monomethyl ether The solution was processed according to Example 1.
As the present formulation corresponded to the composition indicated in Example 1, with the exception that methyl ethyl ketone had been substi-tuted for tetrahydroEuran, it was found, as expected, that the photosensitive coating obtained was substan-tially indentical with the photosensitive coating described in Example 1 regarding its technical pro-perties for platemaking and printing.
Example 24 According to Example 11, a polymer con~
taining 62.2 ~ of C and 9.4 % of H and having an acid number of 12.2 was prepared in the form of a 6.8 strength solution in methyl ethyl ketone. The polymer produced was not isolated from the reaction medium~
A coating solution was prepared having the following composition: 258 parts by weight of the above-described 6.8 % strength soiution of the polymer in methyl ethyl ketone, 16.7 parts by weight of the diazonium salt polycondensate specified in Example 5, 1.2 parts by weight of phosphoric acid (85 strength) 1.0 part by weight of Renol Blue B2G-H
and 0.55 part by weight of phenylazodiphenylamine in 600 parts by weight of ethylene glycol monomethyl ether. 'I'h~ s:Dlu-tion was applied and processeclaccording to ExaTple 18. The printing plate obtained corresponded to that described in Example 18, i.e. the use of the reac-tion solution including triethylamine did not have any adverse influence on storability and technical properties for printing and platemaking. After clamping on the printing press, a print run of well over 150,000 sheets was obtained.
Example 25 The coating solution described in Example 24 was varied in such a way that 206 parts by weight of the 6.8 % strength polymer solution therein described and 3.5 parts by weight of the polyurethane specified below were used. The polyurethane was prepared by reacting l mole of a prepolymer, obtained from toly-lene diisocyanate and l,l,l-trimethylol propane, in a molecular ratio o~ 3:19 with about 2.5 moles of hexane diol-1,6 in tetrahydrofuran. The product was precipitated in water and thereafter dried.
After processing of the solution as indi-cated in Example 24, a hardly noticeable reduction of developing speed was observed.
When the printing plate produced was clamped on a printing press and used for printing under iden-tical conditionsr a print run was attained which exceeded that of the preceding example by about 20~.
An evaluation of the printing result showed, however, that this printing plate tended to a slight dot gain, compared with the printing plate of Example 24.
Example 26 parts by weight of a terpolymer com-prising 31 ~ of vinyl chloride, 3 % of vinyl acetate and 6 % o~ vinyl alcohol and having an average mole-cular weight of 15,500 and a softening point of 77Cwas reacted with 2 parts by weight of 3-oxaglutaric anhydride, as described in Example 1. The polymer obtained had an acid number of 24.
A coating solution was prepared having the fol-lowing composition: 55 parts by weight of a 6.4 %
strength solution of the above-described reaction product in methyl ethyl ketone, 1.79 parts by weight oE the diazonium salt polycondensate specified in Example 1, 0.18 part by weight of phosphoric acid (85 % strength), 0.06 part by weight of phenylazodi-phenylamine and 0.13 part by weight of crystal violet in 140 parts by weight of ethylene glycol monomethyl ether was applied to an aluminum foil which had been mechanically roughened and post-treated with an 0.1 %
strength aqueous solution of polyvinyl phosphonic acid and was dried to give a coating weight of 0.8 g/m2 .
After exposure and development as indicated in Example 1, a printing plate was obtained which yielded several thousand good prints, when clamped on a printing press.
Exam~le 27 parts by weight of a polyvinyl formal having a molecular weight oE about 25,000 to 30,000 and comprising 68 % by weight of vinylformal units, 25 % by weight of vinyl acetate units and 7 % by weight of vinyl alcohol units (hydroxyl number 85), and 4 parts by weight of maleic anhydride were ~ i¢3 dissolved in 500 parts by weight of tetrahydrofuran to give a clear solution. This solution was admixed with 10 parts by weig`nt of triethylamine, and the exothermic solution was refluxed Eor eight hours.
After cooling, the solution was filtered and added dropwise to 8,000 parts by weight of water to produce a white, comparatively brittle product which was drawn oEf by suction and dried.
The yield amounted to 51 parts by weight of polymer having an acid number of 28.
A coating solution was prepared having the fol-lowing composition: 20 parts by weight of the above-described polymer, 8 parts by weight of the diazonium salt polycondensation product specified in Example 1, 0.9 part by weight of phosphoric acid (85 strength), 1.1 parts by weight of Victoria Pure Blue FGA and 0.3 part by weight of phenylazodiphenylamine in 1,100 parts by weight of ethylene glycol mono-methyl ether. The solution was applied to a support as described in Example 2 and dried. The coating weight was 0.99 g/m .
The photosensitive coating was exposed under a negative original, as indicated in Example 3, and was treated with the developer mixture described in 25- Example 3 The offset printing plate so produced had a coatin9 which exhibited an exceptionally high mecha-nical resistance and yielded several thousand excellent quality prints, when use~d for printing on a sheet-~ed offset press.
ExamPle 28 (ComParatlve Example) A coating solution A comprising the follow-ing components was prepared in accordance with -~ ;t3 E~ample 6 of German Offenlegungsschrift No.3,130,987: 15.0 parts by weight of a styrene-maleic acid ester copolymer, softening range from 190 to 205 C, acid number about 200, average molecular weight about 10,000, 15.0 parts by weight of the diazonium salt cocondensate specified in Example 1, 0.8 part by weight of Victoria Pure Blue FGA, 0.5 part by weight of phenylazodiphenylamine and 1.2 parts by weight of phosphoric acid (85 ~ strength) in 900 parts by weight of ethylene glycol monomethyl ether.
An additional coating solution B was pre-pared b~r substituting the same quantity of the polymer described in Example 4 for the above-indicated copolym er.
The two solutions were applied to an alumi-num foil which had been pretreated according to Example 2, to produce a coating weight of l g/m2.
The two photosensitive coatings were exposed for 22 seconds under a negative original and deve-loped wi-th a developer mixture having the following composition: 5.0 parts by weight of sodium lauryl sulfate, 1.5 parts by weight of sodium metasilicate in 5 water, 1~5 parts by weight of trisodium 25- phosphate in 12 water, 92 parts by weight of water.
The results obtained were as follows:
The photosensitivities of the two photosen-sitive coatings A and B were almost identical.
The contrast of the exposed, still undeve-loped plate B was clearly better and more pleasant tothe eye than the contrast of plate A.
After development, which proceeded swiftly in both cases, printing plates were obtained which were, on the whole, comparable. However, the grada-tion of plate B was somewhat steeper than that ofplate A. The two plates were clamped on a printing press for the purpose of comparlson.
' -, The ~ollowing results were obtained:
In proof printing, plate B accepted ink definitely more rapidly (by a factor of 2-3) than plate A. If an al'~aline dampening solution was used, this effect was even more pronounced.
When running on, it was found that plate B
clearly printed more open screen areas than plate A~
Moreover, plate A showed irregularities in the screen. After only 80,000 printed copies, the reproduction of the continuous-tone stepwedge was reduced by two steps. After printing the same number of copies, plate B did not show any irregularity in the screen. The reproduction of the continuous-tone stepwedge was reduced by about one step.
After 100,000 printed copies, plate A showed the first coating damage, while the screen and solid areas of plate B did not exhibit any damage, even after 150,000 printed copies.
On the whole, it can thus be stated that printing plate B, made according to the present invention, is superior t~ the prior art printing plate A in substantial criteria.
Example 29 (Com~ative Example) According to Example 28, two coating solu-tions A 1 (German Offenlegungsschrift No. 3,130,987) and B 1 (according to this invention) were prepared, in which Renol Blue B2G-H was substi-tuted for the Victoria Pure Blue FGA dye.
Coating, exposure and development were carried out as indicated in Example 28.
It was ound that the dye used was incom-patible with the binder of plate Al and agglomerated.
The exposed plate showed a pale gray color and even . .
-~, ....
.
~ 3~
after development, contrast was insufficient. The gradation of printing plate B 1 was much steeper than that o~ printing plateAl. When plates A 1 and B 1 were used in a press run, the above-described results were basically repeated.
Claims (10)
1. A photosensitive composition, compri-sing: a diazonium salt polycondensation product and a non-photosensitive polymeric binder having carboxyl side groups, said binder being soluble or at least swellable in aqueous-alkaline solutions, the binder comprising the reaction product of an intramo-lecular anhydride of an organic polycarboxylic acid and a synthetic polymer containing hydroxyl groups and having no further functional groups capable of reaction with acid anhydrides.
2. A photosensitive composition as claimed in claim 1, wherein the organic polycarboxylic acid comprises a dicarboxylic acid or a tricarboxylic acid.
3. A photosensitive composition as claimed in claim 2, wherein the acid anhydride comprises a compound corresponding to one of the formulae I, II
or III
(I) (III) (II) wherein R1 and R2 individually are selected from hydrogen atoms and alkyl groups and, further, can be interconnected to form an aromatic or heteroaromatic, unsubstituted or substi-tuted and optionally partially hydro-genated five-membered or six-membered ring which may be fused with up to two aromatic or cycloaliphatic rings, R3, R4 and R5 individually are selected from hydrogen atoms and alkyl groups, further, R3 and R5 can be interconnected to form an unsubsti-tuted or substituted saturated or unsa-turated aliphatic ring which, inclusive of X, may have five or six ring members, R6 and R7 are selected from hydrogen atoms and alkyl groups, X is a single bond, an unsubstituted or substituted 1,1-alkylene group or 1,1-cycloalkylene group, an oxygen atom or a sulfur atom, Y is an oxygen atom or a sulfur atom, a 1,1-or 1,2-alkylene group or a 1,2-alkenylene group, which may optionally be fused with an aromatic or cycloaliphatic ring, and Z is selected from ring members required for the completion of a saturated or unsa-turated, unsubstituted or substituted ring, this ring optionally being fused with up to two aromatic or cycloaliphatic rings.
or III
(I) (III) (II) wherein R1 and R2 individually are selected from hydrogen atoms and alkyl groups and, further, can be interconnected to form an aromatic or heteroaromatic, unsubstituted or substi-tuted and optionally partially hydro-genated five-membered or six-membered ring which may be fused with up to two aromatic or cycloaliphatic rings, R3, R4 and R5 individually are selected from hydrogen atoms and alkyl groups, further, R3 and R5 can be interconnected to form an unsubsti-tuted or substituted saturated or unsa-turated aliphatic ring which, inclusive of X, may have five or six ring members, R6 and R7 are selected from hydrogen atoms and alkyl groups, X is a single bond, an unsubstituted or substituted 1,1-alkylene group or 1,1-cycloalkylene group, an oxygen atom or a sulfur atom, Y is an oxygen atom or a sulfur atom, a 1,1-or 1,2-alkylene group or a 1,2-alkenylene group, which may optionally be fused with an aromatic or cycloaliphatic ring, and Z is selected from ring members required for the completion of a saturated or unsa-turated, unsubstituted or substituted ring, this ring optionally being fused with up to two aromatic or cycloaliphatic rings.
4. A photosensitive composition as.claimed in claim 3, wherein the acid anhydride comprises maleic anhydride, phthalic anhydride, succinic anhydride or 3-oxa-glutaric anhydride.
5. A photosensitive composition as claimed in claim 3, wherein the acid anhydride comprises the product formed in the Diels-Alder reaction of a diene with maleic anhydride.
6. A photosensitive composition as claimed in claim 1, wherein the synthetic polymer containing hydroxyl groups comprises a polyvinyl acetal or a polyvinyl acetate, having free hydroxyl groups.
7. A photosensitive composition as claimed in claim 1, wherein the diazonium salt polycondensa-tion product comprises recurring units of A-N2X and B, linked by intermediate members, A being a radical of a diazonium compound capable of condensation with formaldehyde, and B being the radical of a compound free of diazonium groups and capable of condensation with formaldehyde and selected from aromatic amines, phenols, phenol ethers, aromatic thio-ethers, aromatic hydrocarbons, aromatic heterecyclic compounds and organic acid amides.
8. A photosensitive composition as claimed in claim 7, wherein the diazonium salt polyconden-sation product comprises a product having recurrent units A-N2X and B, which are linked by bivalent intermediate members derived from a carbonyl compound capable of condensation, the units A-N2X being derived from compounds corresponding to the general formula (R8-R9-) pR10-N2X
wherein X is the anion of the diazonium compound, p is an integer from 1 to 3, R8 is an aromatic radical which is capable of condensation with an active carbonyl com-pound, in at least one position, R10 is a phenylene group, and R9 is a single bond or one of the groups:
-(CH2)q-NR11-, -O-(CH2)r-NR11-, -S-(CH2)r-NR11-, -S-CH2CO-NR11-, -O-R12-O-, -O-, -S-, or -CO-NR11-, wherein q is a number from 0 to 5, r is a number from 2 to 5, R11 is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms or an aryl group having from 6 to 12 carbon atoms, and R12 is an arylene group having from 6 to 12 carbon atoms, and B is a radical of an aromatic amine, phenol, thiophenol, phenol ether, aromatic thioether, aromatic hydrocarbon, an aromatic hetero-cyclic compound, or an organic acid amide, which is free of diazonium groups.
wherein X is the anion of the diazonium compound, p is an integer from 1 to 3, R8 is an aromatic radical which is capable of condensation with an active carbonyl com-pound, in at least one position, R10 is a phenylene group, and R9 is a single bond or one of the groups:
-(CH2)q-NR11-, -O-(CH2)r-NR11-, -S-(CH2)r-NR11-, -S-CH2CO-NR11-, -O-R12-O-, -O-, -S-, or -CO-NR11-, wherein q is a number from 0 to 5, r is a number from 2 to 5, R11 is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms or an aryl group having from 6 to 12 carbon atoms, and R12 is an arylene group having from 6 to 12 carbon atoms, and B is a radical of an aromatic amine, phenol, thiophenol, phenol ether, aromatic thioether, aromatic hydrocarbon, an aromatic hetero-cyclic compound, or an organic acid amide, which is free of diazonium groups.
9. A photosensitive composition as claimed in claim 1, which additionally contains a polyamide or a polyurethane in an amount of up to 40 percent by weight, based on the weight of the binder having car-boxyl side groups.
10. A photosensitive recording material comprising a support and a photosensitive coating, wherein the photosensitive coating comprises a com-position as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3404366.7 | 1984-02-08 | ||
| DE19843404366 DE3404366A1 (en) | 1984-02-08 | 1984-02-08 | LIGHT SENSITIVE MIXTURE BASED ON A DIAZONIUM SALT POLYCONDENSATION PRODUCT AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1262069A true CA1262069A (en) | 1989-10-03 |
Family
ID=6227084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473490A Expired CA1262069A (en) | 1984-02-08 | 1985-02-04 | Photosensitive composition based on a diazonium salt polycondensation product and photosensitive recording material prepared from this composition |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4631245A (en) |
| EP (1) | EP0152819B1 (en) |
| JP (1) | JPH0642072B2 (en) |
| AT (1) | ATE51087T1 (en) |
| AU (1) | AU571814B2 (en) |
| BR (1) | BR8500562A (en) |
| CA (1) | CA1262069A (en) |
| DE (2) | DE3404366A1 (en) |
| ES (1) | ES8603092A1 (en) |
| FI (1) | FI80156C (en) |
| IL (1) | IL73976A (en) |
| ZA (1) | ZA85860B (en) |
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| JPH0693116B2 (en) * | 1986-01-21 | 1994-11-16 | 富士写真フイルム株式会社 | Photosensitive composition |
| DE3617499A1 (en) * | 1986-05-24 | 1987-11-26 | Hoechst Ag | LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
| DE3644161A1 (en) * | 1986-12-23 | 1988-07-07 | Hoechst Ag | LIGHT SENSITIVE MIXTURE BASED ON A DIAZONIUM SALT POLYCONDENSATION PRODUCT AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
| DE3644162A1 (en) * | 1986-12-23 | 1988-07-07 | Hoechst Ag | POLYVINYL ACETAL, THIS CONTAINING LIGHT SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREOF |
| DE3644160A1 (en) * | 1986-12-23 | 1988-07-14 | Hoechst Ag | LIGHT-SENSITIVE RECORDING MATERIAL WITH A LIGHT-SENSITIVE INTERLAYER |
| DE3644163A1 (en) * | 1986-12-23 | 1988-07-07 | Hoechst Ag | LIGHT SENSITIVE MIXTURE BASED ON A DIAZONIUM SALT POLYCONDENSATION PRODUCT AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
| JPH0727208B2 (en) * | 1987-04-20 | 1995-03-29 | 富士写真フイルム株式会社 | Photosensitive composition |
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| JP2547607B2 (en) * | 1988-04-06 | 1996-10-23 | 富士写真フイルム株式会社 | Photosensitive composition |
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| US5242779A (en) * | 1989-06-21 | 1993-09-07 | Hoechst Aktiengesellschaft | Photosensitive mixture containing photocurable compound and polyurethane binder with grafted vinyl alcohol units, carboxylic acid vinyl ester units and vinyl acetal units |
| US5238772A (en) * | 1989-06-21 | 1993-08-24 | Hoechst Aktiengesellschaft | Photopolymerizable mixture and recording material containing free-radically polymerizable compound, photosensitive polymerization initiator and polyurethane binder grafted with vinyl alcohol and vinyl acetal units |
| DE3920230A1 (en) * | 1989-06-21 | 1991-01-24 | Hoechst Ag | LIGHT-SENSITIVE MIXTURE AND LIGHT-SENSITIVE RECORDING MATERIAL MANUFACTURED THEREFROM |
| DE3938788A1 (en) * | 1989-11-23 | 1991-05-29 | Hoechst Ag | METHOD FOR PRODUCING A NEGATIVE WORKING LIGHT SENSITIVE PRINTING FORM |
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-
1984
- 1984-02-08 DE DE19843404366 patent/DE3404366A1/en not_active Withdrawn
- 1984-12-31 IL IL73976A patent/IL73976A/en not_active IP Right Cessation
-
1985
- 1985-01-29 EP EP85100889A patent/EP0152819B1/en not_active Expired - Lifetime
- 1985-01-29 DE DE8585100889T patent/DE3576582D1/en not_active Expired - Fee Related
- 1985-01-29 AT AT85100889T patent/ATE51087T1/en not_active IP Right Cessation
- 1985-02-04 CA CA000473490A patent/CA1262069A/en not_active Expired
- 1985-02-04 US US06/697,925 patent/US4631245A/en not_active Expired - Lifetime
- 1985-02-05 ZA ZA85860A patent/ZA85860B/en unknown
- 1985-02-06 ES ES540184A patent/ES8603092A1/en not_active Expired
- 1985-02-06 FI FI850490A patent/FI80156C/en not_active IP Right Cessation
- 1985-02-07 BR BR8500562A patent/BR8500562A/en not_active IP Right Cessation
- 1985-02-07 AU AU38534/85A patent/AU571814B2/en not_active Ceased
- 1985-02-08 JP JP60022103A patent/JPH0642072B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FI80156B (en) | 1989-12-29 |
| DE3576582D1 (en) | 1990-04-19 |
| IL73976A0 (en) | 1985-03-31 |
| AU3853485A (en) | 1985-08-15 |
| US4631245A (en) | 1986-12-23 |
| ES540184A0 (en) | 1985-12-01 |
| FI850490A0 (en) | 1985-02-06 |
| JPH0642072B2 (en) | 1994-06-01 |
| AU571814B2 (en) | 1988-04-21 |
| BR8500562A (en) | 1985-09-24 |
| FI850490L (en) | 1985-08-09 |
| IL73976A (en) | 1989-01-31 |
| JPS60182437A (en) | 1985-09-18 |
| DE3404366A1 (en) | 1985-08-14 |
| ES8603092A1 (en) | 1985-12-01 |
| ATE51087T1 (en) | 1990-03-15 |
| EP0152819B1 (en) | 1990-03-14 |
| EP0152819A1 (en) | 1985-08-28 |
| FI80156C (en) | 1990-04-10 |
| ZA85860B (en) | 1985-09-25 |
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