CA1213600A - Light-sensitive mixture based on o- naphthoquinonediazides, and light-sensitive copying material prepared therefrom - Google Patents
Light-sensitive mixture based on o- naphthoquinonediazides, and light-sensitive copying material prepared therefromInfo
- Publication number
- CA1213600A CA1213600A CA000404463A CA404463A CA1213600A CA 1213600 A CA1213600 A CA 1213600A CA 000404463 A CA000404463 A CA 000404463A CA 404463 A CA404463 A CA 404463A CA 1213600 A CA1213600 A CA 1213600A
- Authority
- CA
- Canada
- Prior art keywords
- naphthoquinone
- light
- diazide
- sensitive
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
Abstract
Abstract of the Disclosure A light-sensitive mixture is described, which is specially intended for the production of planographic printing plates and which contains, as the light-sensitive compound, a naphthoqui-nonediazide sulfonic acid ester of the general formula I
Description
Hoe ~1/K 034 LIGHT-SENSITIVE MIXrURE BASED ON O-NAPHTHOQUINONE-DIAZIDES, AND LIGHT-SENSITIVE CO YING MATERIAL
PREPARED THEREFROM
The invention relates to a positive-working light-sensitive mixture which contains, as the light-sensitive compound , a 1, 2-naphthoquinone-2-diazide sulfonic acid ester of a bis-hydroxy-phenylalkane and which îs intended, in particular, for the produc-tion of planographic printing plates.
Light-sensitive compounds of the type indicated are known from Germ~n Patent No. 872,154. These are 2,2-bis-(4-hydroxy-phenyl)-propane or bis-(4-hydroxyphenyl)-methane which are esterified with naphthoquinonediazide sulfonic ac:ids. These com-pounds exhibit a relatlvely high sensitivity to llght and produce good printing runs, but they have the disadvantaqe of having too low a solubility for many purposes in the organic solvents which are customarily used for coating printing plates, such as glycol partial ethers or carboxylic acid alkyl esters, such as butyl ace-tate. Furthermore, in combination with the preferred binders, which are insoluble in water, but soluble in aqueous alkaline solvents, for example novolaks, they produce layers which, in the unexposed state, are insufficlently resistant to the customary alkaline developer solutions. These layers are also attacked to a certain extent during printing in offset printing machines, if fountain solutions containing alcohol are used.
Mixtures containing naphthoquinonediazide sulfonic acid esters of certain bis-phenol derivatives in which two benzene rings are linked via a methylene bridge having aliphatic 3~ Hoe 81/ K034 substitutents are known from German Offenlegungsschrift No.
PREPARED THEREFROM
The invention relates to a positive-working light-sensitive mixture which contains, as the light-sensitive compound , a 1, 2-naphthoquinone-2-diazide sulfonic acid ester of a bis-hydroxy-phenylalkane and which îs intended, in particular, for the produc-tion of planographic printing plates.
Light-sensitive compounds of the type indicated are known from Germ~n Patent No. 872,154. These are 2,2-bis-(4-hydroxy-phenyl)-propane or bis-(4-hydroxyphenyl)-methane which are esterified with naphthoquinonediazide sulfonic ac:ids. These com-pounds exhibit a relatlvely high sensitivity to llght and produce good printing runs, but they have the disadvantaqe of having too low a solubility for many purposes in the organic solvents which are customarily used for coating printing plates, such as glycol partial ethers or carboxylic acid alkyl esters, such as butyl ace-tate. Furthermore, in combination with the preferred binders, which are insoluble in water, but soluble in aqueous alkaline solvents, for example novolaks, they produce layers which, in the unexposed state, are insufficlently resistant to the customary alkaline developer solutions. These layers are also attacked to a certain extent during printing in offset printing machines, if fountain solutions containing alcohol are used.
Mixtures containing naphthoquinonediazide sulfonic acid esters of certain bis-phenol derivatives in which two benzene rings are linked via a methylene bridge having aliphatic 3~ Hoe 81/ K034 substitutents are known from German Offenlegungsschrift No.
2,828,037. The solubili-ty of thes0 compounds in organic solvents is high, However, their resistance to alkaline developer solutions and fountain solutions containing alcohol is still not optimum, It is the object of the invention to provide a light-sensitive, positive-working mixture which contains, as the light-sensitive compound, a novel 1, 2-naphthoquinone-2-diazide sulfonic acid ester and which ls at least comparable in its t~chnical propertles, for printlng and copyinq, with the best mixtur~s of this type hitherto lcnown, but which has a higher resistance to aqueous alkaline developer solutLons and to the fountain solutions, con-taining alcohol, used in offset printing, has a hard gradation, a high solubility in organic solvents and a good oleophilic character, and can be prepared in a simple manner as a single chemical sub stance .
The invention relates to a light-sensitive mixture which contains, as the light-sensitive compound, a 1, 2-naphthoquinone-2-diazide-4-sulfonic or 1, 2-naphthoquinone-2-diazide-5-sulfonic acid ester of a bis-hydroxyphenylalkane.
The mixture according to ~he invention contains a naphtho-quinonediazLde sulfonic acid ester which corresponds to the general formula I
DO ~ CnH2n ~-OD
R R' in which D is the 1, 2-naphthoquinone-2-diazide-5-sulfcnyl radical 6YiV Hoe 81/K 034 or the 1 ,2-naphthoquinone-2-diazide-4-sulfonyl radical, preferably the 1, 2-naphthoquinone-2-d;azide-5-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radi-cals of the formula DO, and n denotes an integer ~om 6 to 18, preferably ~om 8 to 14.
Preferably, at least one of the radicals R and R' is a DO
group and, in general, R and R' are preferably identical.
The quinone diazides contained in the mixture according to the invention are novel. They are prepared analogously to known processes by esterifying the phenolic OH groups of the parent polyhydric phenols with o-quinonediazide sulfonic acids or reac-tive derivatives thereof, for example the sulfonyl chlorides.
The corresponding precursors, for example the polymethyl-ene bisphenols, are prepared by heating long-chain aliphatic diols with 2 moles of the phenol in the presence of dehydrating compounds, such as boron trifluoride or zinc chloride, for 3 to 7 hours at 120 to 170 C. Compounds of this type are described in U. S. Patent No. 2 ,321, 620 and in J. Am. Chem. Soc. 62 (1940), page 413. The corresponding alkylene bisphenols also can be advantageously obtained by a Clemmensen reduction of the two keto groups of polymethylene diketophenols, which can be prepared by reacting higher paraffin dicarboxylic acids -with phenols (Chem. Ber. 74 (1941), page 1,772). 1,1-bis-(4-hydroxyphenyl)~alkanes are prepared by subjecting 2 moles of the phenol to a condensation reaction with 1 mole of a higher ali-phatic aldehyde, in the presence of hydrochloric acid. Corre-sponding compounds are described in J. Am. Chem. Soc. 54 (1932), page 4,325.
Hoe 81/K 034 The concentration of the novel naphthoquinonediazide sulfonic acid esters in the light-sensitive layer can vary within relatively wide limits . In general, the proportion is 3 to 5 0, preferably between 7 and 25 percent, based upon the weight of the solids content of the light~sensitive mix~ure, The light-sensitive mixtures according to the invention also preferably contain a polymeric, water-insoluble, resin-like blnder which is soluble in the solvents used for the mixture according to the invention and which is also soluble, or can at least be s-welled, in aqueous alkalies.
The novolak condensation resins which have proved suit-able in many positive copying materials based on naphthoquinone diazides also are particularLy useful and advantageous as an additive in the mixtures, according to the invention, containing the new naphthoquinonediazide sulfonic acid esters. They pro-mote the strong differentiation between the exposed and unexposed areas of the layer when the layer is developed, which is especi-ally true of the more highly condensed resins containing substi-tuted phenols, for example cresols, as the partner with formalde-hyde in the condensation reaction. Other binders which are soluble in alkali or can be swelled in alkali are natural resins, such as shellac and colophony, and synthetic resins, such as copolymers formed from styrene and maleic anhydride or cop~lymers of acrylic acld or methacrylic acid, particularly with acrylic or methacrylic acid esters.
The nature and amount of the alkali-soluble resin can vary, depending upon the end use; the amount is preferably between 95 12~L;~ 0 Hoe 81/K 034 and 50, particularly preferably between 90 and 65 percent by weight, based upon the total solids content, In addition, it is also possible to use concomitantly numerous other resins, prefer-ably epoxides and vinyl polymers, such as polyvinyl acetates, polyacrylates, polyvinyl acetals, polyvinyl ethers and polyvinyl pyrrolidone, and the copolymers of the monomers on which the latter are based. The most advantageous proportion of these resins depends upon the requirements of technical performance in use and upon the effect on the conditions of development and, in general, is not more than 20 percent by weight of the alkali soluble resin. For special requirements, such as flexibility, adhesion, gloss, coloration, color change, and the like, the light sensltive mixture also can contain small quantities of sub-stances such as polyglycols, cellulose derivatives, such as ethylcellulose, wetting agents, dyestuffs, adhesion promoters and finely divided pigments, and, if required, UV absorbers.
The mixtures are generally dissolved in a solvent in order to coat a suitable layer support. The choice of solvents must be such as to suit the coating process envisaged, the layer thickness and the drying conditions, Suitable solvents for the mixture according to the invention are ketones, such as methyl ethyl ketone, chlorinated hydrocarbons, such as trichloroethylene and 1 ,1,1 trichloroethane, alcohols, such as n-propanol, ethers, such as tetrahydrofuran, alcohol-ethers, such as ethyleneglycol monoethyl ether and esters, such as butyl acetate. It is also possible to use mixtures which additionally can contain, for special purposes, solvents such as acetonitrile, dloxane or o Hoe 81/K 034 dimethylformamide. In principle, it is possible to use any solvent which does not react irreversibly with the components in the layer. Partial ethers of glycols, in particular ethylene glycol monomethyl ether, are particularly preferred, In most cases, metals are used as layer supports for layer thiclcnesses below approximately 10 p~m. The following can be employed for offset printing plates: bright-rolled, mechanically or electrochemically roughened and, if appropriate, anodized alumi-num which can, additionally, be pretreated chemically, for exam-ple with polyvinyl phosphonic acid, silicates, phosphates, hexa-fluorozirconates or hydrolyzed tetraethyl orthosilicate, and also multi-metal plates composed, for example, of Al/Cu/Cr or of brass/chromium. For the production of relief printing plates, the mixture s according to the invention can be applied to zinc or magnesium plates and to commercially available microcrystalline alloys thereof for single-stage etching processes, and also to etchable plastics, such as polyoxymethylene. The mixtures according to the invention are suitable for gravure printing forms or screen printing forms because of their good adhesion and resis-tance to etching on copper and nickel surfaces. The mixtures according to the invention also can be used as photoresists in the production of printed circuit boards and in chemical milling.
Other supports, such as wood, paper, ceramics, textiles and other metals are also suitable for further applications.
Supports which are preferred for layers which are ovèr 10 ~m thick are plastic films, which are then used as temporary supports for ~ansfer layers. Polyester films, for example films 12~3~0 Hoe 81/K 034 composed of polyethylene terephthalate, are preferred for this purpose and for color test films. Polyolefin films, such as polypropylene, are also suitable, however.
The support material is coated in a known manner by spin-coating, spraying, dipping or application by means of rollers, slot dies or doctor blades or by slot-die coating. Finally, the coating of, for example, printed circuit boards, glass or ceramics and silicon disks also can be effected by transferring a layer from a temporary support. Exposure is carried out using the light sources which are customary in the art. IrradiatLon with electrons or lasers also constitutes a possible means of forming an image.
The aqueous alkaline solutions of graded alkalinity which are used for developing, which preferably have a pH within the range from 10 to 14 and which also can contain minor quantities of organic solvents or wetting agents, remove the areas of the copying layer which have been affected by llght, and thus pro-duce a positive image of the orlginal.
The light-sensitive mixtures according to the invention are preferably used in the production of printing forms, i.e., in par-ticular, offset forms and auto-type relief printing and screen printing forms, and in photoresist compositions and dry resists.
The printing plates which are produced using the new com-pounds possess a high practical sensitlvity to light and also an improved resLstance to alkaline developers. The preferred com-pounds themselves are distinguished by very good solubllity in the customary solvents, by a strongly oleophilic character and resis-tance to alcohol and by good compatibility with the remaining constituents of the copying layer.
lZ~3~ 0 Hoe 81/K 034 The invention is illustrated in greater detail by means of the examples which follow, in which parts by weight and parts by volume are in the same relationship as g to ml. Unless otherwise specified, percentages are percentages by weight.
Example 1 An electrolytically roughened and anodized aluminum plate having an oxide layer weighing 3.0 g/m was coated with a solu-tion of:
1 .1 0 parts by weight of the esterification product form~d from 1 mole of 1 ,10-bis-(4-hydroxyphenyl)-decane and 2 moles of 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride, 6.10 parts by weight of a cresol/formaldehyde novolak 'slav-lng a softening point of 10S - 120 C as specified in DIN 53 ,181, 0.12 part by wei~ht of 4-(p-tolylmercapto)-2,5-diethoxy-benzenediazonium hexafluorophosphate and 0. 06 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether and 2 0 5 0 parts by weight of tetrahydrofuran .
Before the application of the light-sensitive copying layer, the anodized aluminum support was treated with an aqueous solution of polyvinylphosphonic acid, as described in German Patent No.
1 , 621 , 478 O
The presensitized material thus prepared, which had a light-sen sitive layer weighing 2, 00 g/m2, was exposed imagewise under a transparent positive original and was then developed with -` 12~3~C.0 Hoe 81/K 03D~
the following solution:
5 . 3 parts by weight of sodium metasilicate x 9 H2O,
The invention relates to a light-sensitive mixture which contains, as the light-sensitive compound, a 1, 2-naphthoquinone-2-diazide-4-sulfonic or 1, 2-naphthoquinone-2-diazide-5-sulfonic acid ester of a bis-hydroxyphenylalkane.
The mixture according to ~he invention contains a naphtho-quinonediazLde sulfonic acid ester which corresponds to the general formula I
DO ~ CnH2n ~-OD
R R' in which D is the 1, 2-naphthoquinone-2-diazide-5-sulfcnyl radical 6YiV Hoe 81/K 034 or the 1 ,2-naphthoquinone-2-diazide-4-sulfonyl radical, preferably the 1, 2-naphthoquinone-2-d;azide-5-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radi-cals of the formula DO, and n denotes an integer ~om 6 to 18, preferably ~om 8 to 14.
Preferably, at least one of the radicals R and R' is a DO
group and, in general, R and R' are preferably identical.
The quinone diazides contained in the mixture according to the invention are novel. They are prepared analogously to known processes by esterifying the phenolic OH groups of the parent polyhydric phenols with o-quinonediazide sulfonic acids or reac-tive derivatives thereof, for example the sulfonyl chlorides.
The corresponding precursors, for example the polymethyl-ene bisphenols, are prepared by heating long-chain aliphatic diols with 2 moles of the phenol in the presence of dehydrating compounds, such as boron trifluoride or zinc chloride, for 3 to 7 hours at 120 to 170 C. Compounds of this type are described in U. S. Patent No. 2 ,321, 620 and in J. Am. Chem. Soc. 62 (1940), page 413. The corresponding alkylene bisphenols also can be advantageously obtained by a Clemmensen reduction of the two keto groups of polymethylene diketophenols, which can be prepared by reacting higher paraffin dicarboxylic acids -with phenols (Chem. Ber. 74 (1941), page 1,772). 1,1-bis-(4-hydroxyphenyl)~alkanes are prepared by subjecting 2 moles of the phenol to a condensation reaction with 1 mole of a higher ali-phatic aldehyde, in the presence of hydrochloric acid. Corre-sponding compounds are described in J. Am. Chem. Soc. 54 (1932), page 4,325.
Hoe 81/K 034 The concentration of the novel naphthoquinonediazide sulfonic acid esters in the light-sensitive layer can vary within relatively wide limits . In general, the proportion is 3 to 5 0, preferably between 7 and 25 percent, based upon the weight of the solids content of the light~sensitive mix~ure, The light-sensitive mixtures according to the invention also preferably contain a polymeric, water-insoluble, resin-like blnder which is soluble in the solvents used for the mixture according to the invention and which is also soluble, or can at least be s-welled, in aqueous alkalies.
The novolak condensation resins which have proved suit-able in many positive copying materials based on naphthoquinone diazides also are particularLy useful and advantageous as an additive in the mixtures, according to the invention, containing the new naphthoquinonediazide sulfonic acid esters. They pro-mote the strong differentiation between the exposed and unexposed areas of the layer when the layer is developed, which is especi-ally true of the more highly condensed resins containing substi-tuted phenols, for example cresols, as the partner with formalde-hyde in the condensation reaction. Other binders which are soluble in alkali or can be swelled in alkali are natural resins, such as shellac and colophony, and synthetic resins, such as copolymers formed from styrene and maleic anhydride or cop~lymers of acrylic acld or methacrylic acid, particularly with acrylic or methacrylic acid esters.
The nature and amount of the alkali-soluble resin can vary, depending upon the end use; the amount is preferably between 95 12~L;~ 0 Hoe 81/K 034 and 50, particularly preferably between 90 and 65 percent by weight, based upon the total solids content, In addition, it is also possible to use concomitantly numerous other resins, prefer-ably epoxides and vinyl polymers, such as polyvinyl acetates, polyacrylates, polyvinyl acetals, polyvinyl ethers and polyvinyl pyrrolidone, and the copolymers of the monomers on which the latter are based. The most advantageous proportion of these resins depends upon the requirements of technical performance in use and upon the effect on the conditions of development and, in general, is not more than 20 percent by weight of the alkali soluble resin. For special requirements, such as flexibility, adhesion, gloss, coloration, color change, and the like, the light sensltive mixture also can contain small quantities of sub-stances such as polyglycols, cellulose derivatives, such as ethylcellulose, wetting agents, dyestuffs, adhesion promoters and finely divided pigments, and, if required, UV absorbers.
The mixtures are generally dissolved in a solvent in order to coat a suitable layer support. The choice of solvents must be such as to suit the coating process envisaged, the layer thickness and the drying conditions, Suitable solvents for the mixture according to the invention are ketones, such as methyl ethyl ketone, chlorinated hydrocarbons, such as trichloroethylene and 1 ,1,1 trichloroethane, alcohols, such as n-propanol, ethers, such as tetrahydrofuran, alcohol-ethers, such as ethyleneglycol monoethyl ether and esters, such as butyl acetate. It is also possible to use mixtures which additionally can contain, for special purposes, solvents such as acetonitrile, dloxane or o Hoe 81/K 034 dimethylformamide. In principle, it is possible to use any solvent which does not react irreversibly with the components in the layer. Partial ethers of glycols, in particular ethylene glycol monomethyl ether, are particularly preferred, In most cases, metals are used as layer supports for layer thiclcnesses below approximately 10 p~m. The following can be employed for offset printing plates: bright-rolled, mechanically or electrochemically roughened and, if appropriate, anodized alumi-num which can, additionally, be pretreated chemically, for exam-ple with polyvinyl phosphonic acid, silicates, phosphates, hexa-fluorozirconates or hydrolyzed tetraethyl orthosilicate, and also multi-metal plates composed, for example, of Al/Cu/Cr or of brass/chromium. For the production of relief printing plates, the mixture s according to the invention can be applied to zinc or magnesium plates and to commercially available microcrystalline alloys thereof for single-stage etching processes, and also to etchable plastics, such as polyoxymethylene. The mixtures according to the invention are suitable for gravure printing forms or screen printing forms because of their good adhesion and resis-tance to etching on copper and nickel surfaces. The mixtures according to the invention also can be used as photoresists in the production of printed circuit boards and in chemical milling.
Other supports, such as wood, paper, ceramics, textiles and other metals are also suitable for further applications.
Supports which are preferred for layers which are ovèr 10 ~m thick are plastic films, which are then used as temporary supports for ~ansfer layers. Polyester films, for example films 12~3~0 Hoe 81/K 034 composed of polyethylene terephthalate, are preferred for this purpose and for color test films. Polyolefin films, such as polypropylene, are also suitable, however.
The support material is coated in a known manner by spin-coating, spraying, dipping or application by means of rollers, slot dies or doctor blades or by slot-die coating. Finally, the coating of, for example, printed circuit boards, glass or ceramics and silicon disks also can be effected by transferring a layer from a temporary support. Exposure is carried out using the light sources which are customary in the art. IrradiatLon with electrons or lasers also constitutes a possible means of forming an image.
The aqueous alkaline solutions of graded alkalinity which are used for developing, which preferably have a pH within the range from 10 to 14 and which also can contain minor quantities of organic solvents or wetting agents, remove the areas of the copying layer which have been affected by llght, and thus pro-duce a positive image of the orlginal.
The light-sensitive mixtures according to the invention are preferably used in the production of printing forms, i.e., in par-ticular, offset forms and auto-type relief printing and screen printing forms, and in photoresist compositions and dry resists.
The printing plates which are produced using the new com-pounds possess a high practical sensitlvity to light and also an improved resLstance to alkaline developers. The preferred com-pounds themselves are distinguished by very good solubllity in the customary solvents, by a strongly oleophilic character and resis-tance to alcohol and by good compatibility with the remaining constituents of the copying layer.
lZ~3~ 0 Hoe 81/K 034 The invention is illustrated in greater detail by means of the examples which follow, in which parts by weight and parts by volume are in the same relationship as g to ml. Unless otherwise specified, percentages are percentages by weight.
Example 1 An electrolytically roughened and anodized aluminum plate having an oxide layer weighing 3.0 g/m was coated with a solu-tion of:
1 .1 0 parts by weight of the esterification product form~d from 1 mole of 1 ,10-bis-(4-hydroxyphenyl)-decane and 2 moles of 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride, 6.10 parts by weight of a cresol/formaldehyde novolak 'slav-lng a softening point of 10S - 120 C as specified in DIN 53 ,181, 0.12 part by wei~ht of 4-(p-tolylmercapto)-2,5-diethoxy-benzenediazonium hexafluorophosphate and 0. 06 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether and 2 0 5 0 parts by weight of tetrahydrofuran .
Before the application of the light-sensitive copying layer, the anodized aluminum support was treated with an aqueous solution of polyvinylphosphonic acid, as described in German Patent No.
1 , 621 , 478 O
The presensitized material thus prepared, which had a light-sen sitive layer weighing 2, 00 g/m2, was exposed imagewise under a transparent positive original and was then developed with -` 12~3~C.0 Hoe 81/K 03D~
the following solution:
5 . 3 parts by weight of sodium metasilicate x 9 H2O,
3.4 parts by weight of trisodium phosphate x 12 H2O, and 0 . 3 part by weight of anhydrous sodium dihydrogen phos-phate in 91.0 parts by weight of water, As a result of being developed, the portions of the copy-ing layer which had been affected by light were removed, leaving the unexposed areas of the image on the layer support. About 200, 000 satisfactory prints were produced in an offset machine from the printing form thus prepared. The printing stencll was distinguished by an excellent oleophilic character, resistance to alcohol and adhesion to the support.
Additional coating solutions by means of which similar results were obtained are indicated in the Examples which follow.
Unless otherwise noted, the preparation and processing of the printing plates contained in these Examples corresponds to the conditions described in Example 1, Example 2 2 0 An electrolytically roughened and anodized aluminum plate, which had been subjected to after-treatment with an aqueous solu-tion of polyvinylphosphonic acid, was coated with a solution of:
1.00 part by weight of the esterification product formed from 1 mole of 1,10-bis-(2,4-dihydroxyphenyl)-decane and 4 moles of 1 ,2-naphthoquinone-2-diazide-5-sulfonyl chloride, lZ~3~ 0 Hoe 81/K 034 5 . 70 parts by weight of the novolak indicated in Example 1, 0.12 part by weight of 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether,
Additional coating solutions by means of which similar results were obtained are indicated in the Examples which follow.
Unless otherwise noted, the preparation and processing of the printing plates contained in these Examples corresponds to the conditions described in Example 1, Example 2 2 0 An electrolytically roughened and anodized aluminum plate, which had been subjected to after-treatment with an aqueous solu-tion of polyvinylphosphonic acid, was coated with a solution of:
1.00 part by weight of the esterification product formed from 1 mole of 1,10-bis-(2,4-dihydroxyphenyl)-decane and 4 moles of 1 ,2-naphthoquinone-2-diazide-5-sulfonyl chloride, lZ~3~ 0 Hoe 81/K 034 5 . 70 parts by weight of the novolak indicated in Example 1, 0.12 part by weight of 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether,
4 0 parts by weight of tetrahydrofuran, and parts by -weight of butyl acetate.
ExamPle 3 An electrolytically roughened and anodized aluminum plate was coated with a solution of:
1.20 parts by weight of the esterification product formed from 1 mole of 1 ,1-bis-(4-hydroxy-2 methylphenyl)-dodecane and 2 moles of 1 ,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 6 . 20 parts of the novolak indicated in Example 1, 0.13 part by weight of 4-(p-tolylmercapto)-2 ,5-diethoxy-benzen0diazonium hexafluorophosphate, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether, and parts by weight s)f tetrahydrofuran, ExamPlè 4 An electrolytically roughened and anodized aluminum plate which had been subjected to after-treatment with an aqueous solution of polyvinyl phosphonic acid, was coated with a solu-tion of:
lZ13~GO Hoe 81/K 034 1.10 parts by weight of the esterification product formed ~om 1 mole of 1 ,1 2-bis-(4-hydroxy-2-methylphenyl)-dodecane and 2 moles of 1 ,2-naphthoquinone-2-dia-zide-5-sulfonyl chloride, 6.10 parts by weight of the novolak indicated in Example 1, 0 . 08 part by weight of 2, 3, 4-trihydroxybenzophenone, 0 . 20 part by weight of a polyvinylbutyral containing 69 to 71 percent of vinylbutyral units, 24 to 2 7 percent of vinyl alcohol units and 1 percent of vinyl acetate units, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether, parts by weight of tetrahydrofuran, and parts by weight of butyl acetate.
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present inven-tion without departing from the spirit thereof, and the invention includes all such modifications.
ExamPle 3 An electrolytically roughened and anodized aluminum plate was coated with a solution of:
1.20 parts by weight of the esterification product formed from 1 mole of 1 ,1-bis-(4-hydroxy-2 methylphenyl)-dodecane and 2 moles of 1 ,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 6 . 20 parts of the novolak indicated in Example 1, 0.13 part by weight of 4-(p-tolylmercapto)-2 ,5-diethoxy-benzen0diazonium hexafluorophosphate, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether, and parts by weight s)f tetrahydrofuran, ExamPlè 4 An electrolytically roughened and anodized aluminum plate which had been subjected to after-treatment with an aqueous solution of polyvinyl phosphonic acid, was coated with a solu-tion of:
lZ13~GO Hoe 81/K 034 1.10 parts by weight of the esterification product formed ~om 1 mole of 1 ,1 2-bis-(4-hydroxy-2-methylphenyl)-dodecane and 2 moles of 1 ,2-naphthoquinone-2-dia-zide-5-sulfonyl chloride, 6.10 parts by weight of the novolak indicated in Example 1, 0 . 08 part by weight of 2, 3, 4-trihydroxybenzophenone, 0 . 20 part by weight of a polyvinylbutyral containing 69 to 71 percent of vinylbutyral units, 24 to 2 7 percent of vinyl alcohol units and 1 percent of vinyl acetate units, and 0. 07 part by weight of Crystal Violet in parts by weight of ethylene glycol monomethyl ether, parts by weight of tetrahydrofuran, and parts by weight of butyl acetate.
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present inven-tion without departing from the spirit thereof, and the invention includes all such modifications.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A light-sensitive mixture which contains, as the light-sensitive compound, a 1,2-naphthoquinone-2-diazide-4-sulfonic or 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of a bis-hydroxyphenylalkane, wherein the naphthoquinonediazide sulfonic acid ester corresponds to the general formula I
I
in which D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical or the 1,2-naphthoquinone-2-diazide-4-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radicals of the formula DO, and n denotes an integer from 6 to 18, and additionally contains a binder which is insoluble in water, but soluble or at least swellable in aqueous alkaline solutions.
I
in which D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical or the 1,2-naphthoquinone-2-diazide-4-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radicals of the formula DO, and n denotes an integer from 6 to 18, and additionally contains a binder which is insoluble in water, but soluble or at least swellable in aqueous alkaline solutions.
2. A light-sensitive mixture as claimed in claim 1 which contains 3 to 50 percent by weight of a naphthoquinonediazide sulfonic acid ester, based upon its content of non-volatile constituents.
3. A light-sensitive mixture as claimed in claim 1 which contains a compound of the formula I in which at least one of the radicals R and R' is a DO radical.
4. A light-sensitive mixture as claimed in claim 1 which contains a compound of the formula I in which n is an integer from 8 to 14.
5. A light-sensitive copying material composed of a layer support and a light-sensitive layer containing a 1,2-naphthoquinone-2-diazide sulfonic acid ester of a bis-hydroxy-phenylalkane, wherein the naphthoquinonediazide sulfonic acid ester corresponds to the general formula I
in which D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical or the 1,2-naphthoquinone-2-diazide-4-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radicals of the formula DO, and n denotes an integer from 6 to 18.
in which D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical or the 1,2-naphthoquinone-2-diazide-4-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radicals of the formula DO, and n denotes an integer from 6 to 18.
6. A light-sensitive copying material as claimed in claim 5 wherein the layer support is composed of aluminum.
7. A compound having the formula in which D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical or the 1,2-naphthoquinone-2-diazide-4-sulfonyl radical, R and R' are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or radicals of the formula DO, and n denotes an integer from 6 to 18.
8. A compound as claimed in claim 7, wherein D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical, R and R' are radicals of the formula DO, and n is 10.
9. A compound as claimed in claim 7, wherein D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical, R and R' are hydrogen atoms, and n is 12.
10. A compound as claimed in claim 7, wherein D is the 1,2-naphthoquinone-2-diazide-5-sulfonyl radical, R and R' are hydrogen atoms, and n is 10.
14.
14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813124936 DE3124936A1 (en) | 1981-06-25 | 1981-06-25 | LIGHT SENSITIVE MIXTURE BASED ON O-NAPHTHOCHINONDIAZIDES AND LIGHT SENSITIVE COPY MATERIAL MADE THEREOF |
| DEP3124936.1 | 1981-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213600A true CA1213600A (en) | 1986-11-04 |
Family
ID=6135331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404463A Expired CA1213600A (en) | 1981-06-25 | 1982-06-04 | Light-sensitive mixture based on o- naphthoquinonediazides, and light-sensitive copying material prepared therefrom |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4517275A (en) |
| EP (1) | EP0068346B1 (en) |
| JP (1) | JPS585737A (en) |
| AT (1) | ATE10141T1 (en) |
| AU (1) | AU8509082A (en) |
| BR (1) | BR8203685A (en) |
| CA (1) | CA1213600A (en) |
| DE (2) | DE3124936A1 (en) |
| ES (1) | ES513403A0 (en) |
| FI (1) | FI822257L (en) |
| ZA (1) | ZA824004B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735885A (en) * | 1985-12-06 | 1988-04-05 | Allied Corporation | Deep UV photoresist composition with 1,3-disubstituted-5-diazobarbituric acids |
| JP2552891B2 (en) * | 1988-01-26 | 1996-11-13 | 富士写真フイルム株式会社 | Positive photoresist composition |
| JP2700918B2 (en) * | 1989-04-26 | 1998-01-21 | 富士写真フイルム株式会社 | Positive photoresist composition |
| US5196517A (en) * | 1989-10-30 | 1993-03-23 | Ocg Microelectronic Materials, Inc. | Selected trihydroxybenzophenone compounds and their use as photoactive compounds |
| US5019478A (en) * | 1989-10-30 | 1991-05-28 | Olin Hunt Specialty Products, Inc. | Selected trihydroxybenzophenone compounds and their use in photoactive compounds and radiation sensitive mixtures |
| US5219714A (en) * | 1989-10-30 | 1993-06-15 | Ocg Microelectronic Materials, Inc. | Selected trihydroxybenzophenone compounds and their use in photoactive compounds and radiation sensitive mixtures |
| US5618932A (en) * | 1995-05-24 | 1997-04-08 | Shipley Company, L.L.C. | Photoactive compounds and compositions |
| US6461794B1 (en) * | 1999-08-11 | 2002-10-08 | Kodak Polychrome Graphics Llc | Lithographic printing forms |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE508815A (en) * | 1949-07-23 | |||
| NL77540C (en) * | 1950-12-23 | |||
| NL247588A (en) * | 1959-01-21 | |||
| US3647443A (en) * | 1969-09-12 | 1972-03-07 | Eastman Kodak Co | Light-sensitive quinone diazide polymers and polymer compositions |
| JPS53494B2 (en) * | 1972-09-08 | 1978-01-09 | ||
| DE2742631A1 (en) * | 1977-09-22 | 1979-04-05 | Hoechst Ag | LIGHT SENSITIVE COPY DIMENSIONS |
| DE2828037A1 (en) * | 1978-06-26 | 1980-01-10 | Hoechst Ag | LIGHT SENSITIVE MIXTURE |
| DE3040157A1 (en) * | 1980-10-24 | 1982-06-03 | Hoechst Ag, 6000 Frankfurt | LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE COPY MATERIAL PRODUCED THEREOF |
| DE3043967A1 (en) * | 1980-11-21 | 1982-06-24 | Hoechst Ag, 6000 Frankfurt | LIGHT SENSITIVE MIXTURE BASED ON O-NAPHTHOCHINONDIAZIDES AND LIGHT SENSITIVE COPY MATERIAL MADE THEREOF |
-
1981
- 1981-06-25 DE DE19813124936 patent/DE3124936A1/en not_active Withdrawn
-
1982
- 1982-06-04 CA CA000404463A patent/CA1213600A/en not_active Expired
- 1982-06-08 ZA ZA824004A patent/ZA824004B/en unknown
- 1982-06-18 AT AT82105342T patent/ATE10141T1/en not_active IP Right Cessation
- 1982-06-18 DE DE8282105342T patent/DE3261128D1/en not_active Expired
- 1982-06-18 EP EP82105342A patent/EP0068346B1/en not_active Expired
- 1982-06-22 AU AU85090/82A patent/AU8509082A/en not_active Abandoned
- 1982-06-23 JP JP57106974A patent/JPS585737A/en active Granted
- 1982-06-23 ES ES513403A patent/ES513403A0/en active Granted
- 1982-06-23 FI FI822257A patent/FI822257L/en not_active Application Discontinuation
- 1982-06-23 US US06/391,005 patent/US4517275A/en not_active Expired - Fee Related
- 1982-06-24 BR BR8203685A patent/BR8203685A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0068346B1 (en) | 1984-10-31 |
| BR8203685A (en) | 1983-06-21 |
| JPS585737A (en) | 1983-01-13 |
| ZA824004B (en) | 1983-03-30 |
| AU8509082A (en) | 1983-01-06 |
| FI822257A0 (en) | 1982-06-23 |
| JPH0339301B2 (en) | 1991-06-13 |
| DE3124936A1 (en) | 1983-01-20 |
| FI822257L (en) | 1982-12-26 |
| ATE10141T1 (en) | 1984-11-15 |
| DE3261128D1 (en) | 1984-12-06 |
| ES8404065A1 (en) | 1984-04-01 |
| ES513403A0 (en) | 1984-04-01 |
| US4517275A (en) | 1985-05-14 |
| EP0068346A1 (en) | 1983-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1168657A (en) | Light-sensitive mixture comprising o- naphthoquinonediazides and light-sensitive copying material prepared therefrom | |
| CA1183379A (en) | Light-sensitive mixture and copying material prepared therefrom including a novolak containing brominated phenol units | |
| US3869292A (en) | Light-sensitive compositions and light-sensitive materials such as printing plates | |
| US4642282A (en) | Light-sensitive positive copying material with alkali soluble polycondensation binder | |
| US4308368A (en) | Photosensitive compositions with reaction product of novolak co-condensate with o-quinone diazide | |
| US3890152A (en) | Light-sensitive copying composition containing diazo resin and quinone diazide | |
| US3402044A (en) | Light-sensitive naphthoquinone diazide composition and material containing an alkali insoluble polymer | |
| CA1151933A (en) | Light-sensitive mixture and copying material produced therefrom | |
| CA1214676A (en) | Light-sensitive mixture based on o-naphthoquinone diazides and light-sensitive copying material prepared therefrom | |
| US4536465A (en) | Positive-working photosensitive composition with o-quinone diazide and admixture of resins | |
| EP0021718A1 (en) | Photosensitive condensation product, photosensitive compositions and lithographic printing plates containing said condensation product | |
| JPH02197844A (en) | Manufacture of naphtoquinone diazide ester sulfonate | |
| US5006443A (en) | Radiation sensitive reproduction composition and element with perfluoroalkyl group containing polymer | |
| CA1213600A (en) | Light-sensitive mixture based on o- naphthoquinonediazides, and light-sensitive copying material prepared therefrom | |
| JPS5934293B2 (en) | photosensitive composition | |
| US4639406A (en) | Light-sensitive compound, light-sensitive mixture, and light-sensitive copying material prepared therefrom with 0-naphthoquinone diazide compound | |
| US4628020A (en) | Light-sensitive compound mixture and copying material comprising o-naphthquinonediazide compound | |
| US5017462A (en) | Process of producing negative relief copies utilizing photosensitive copying material with thermal hardening triazine compound | |
| JPS5887554A (en) | Photosensitive mixture and photosensitive copying material produced therefrom | |
| US4618562A (en) | Aqueous developable lithographic printing plates containing an admixture of diazonium salts and polymers and composition therefor | |
| US4681833A (en) | Light-sensitive negative working composition with diazonium condensate, epoxy resin, and combination of polymers with acrylic groups | |
| CA1193275A (en) | Light-sensitive compounds, light-sensitive mixture, and light-sensitive copying material prepared therefrom | |
| JPS6223788B2 (en) | ||
| KR960016307B1 (en) | Photosensitive composition based on 1,2-naphtoquinone diazides, and registration material prepared therefrom | |
| US5143815A (en) | Light-sensitive mixture based on 1,2-naphthoquinone-diazides, and reproduction material produced with this mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |