CA1298510C - Light-sensitive material and a process for producing negative copies utilizing the material - Google Patents
Light-sensitive material and a process for producing negative copies utilizing the materialInfo
- Publication number
- CA1298510C CA1298510C CA000492839A CA492839A CA1298510C CA 1298510 C CA1298510 C CA 1298510C CA 000492839 A CA000492839 A CA 000492839A CA 492839 A CA492839 A CA 492839A CA 1298510 C CA1298510 C CA 1298510C
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- Prior art keywords
- light
- sensitive material
- diazide
- sensitive
- quinone
- 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.)
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Paper (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a light-sensitive material and a process for producing negative relief copies utilizing the light-sensitive material. The light-sensitive material comprises, as the light-sensitive compound, a 1,2-quinone diazide and a quarternary phosphonium com-pound. The light-sensitive material is imagewise exposed and heated. After cooling, the material is sub-jected again to an overall exposure, and then developed.
By means of this light sensitive material and process, it is possible to produce negative copies from a material yielding positive copies when processed in the customary manner.
Disclosed is a light-sensitive material and a process for producing negative relief copies utilizing the light-sensitive material. The light-sensitive material comprises, as the light-sensitive compound, a 1,2-quinone diazide and a quarternary phosphonium com-pound. The light-sensitive material is imagewise exposed and heated. After cooling, the material is sub-jected again to an overall exposure, and then developed.
By means of this light sensitive material and process, it is possible to produce negative copies from a material yielding positive copies when processed in the customary manner.
Description
~L29~35~L~
A LIGHT-SENSITIVE MATERIAL AND A PROCESS FOR
PRODUCING NEGATIVE COPIES UTI~IZING THE MATERIAL
BACKGROUND OF THE INVENTION
The present invention relates to a light-sensitive material and a reversal process for producing negative copies utilizing the light-sensitive material.
rhe light-sensitive material includes a normally positive-workin~ light-sensitive material comprising 1,2-quinone diazides.
It is known that positive-working reproduction materials comprising 1,2-naphthoquinone diazides can be negatively processed by a particular sequence of treat-ment steps. U.S. Patent No. 3,264,104 describes a reversal process of this ~ype in which the light-sensitive layer, which preferably contains thermoplas-tic polymers, is exposed imagewise. The layer is then treated with an alkaline solution or with water, if appropriate at an elevated temperature, without washing off the exposed areas in the process. Thereafter, the layer is ~xposed again without an original, and then developed in the usual manner, such that the original imagewise exposed areas remain on the support and the other areas are washed off the support.
The above process is disadvantageous in that a comparatively large number of treatment steps are re~
quired. Furthermore~ the first treatment with alkali must invariably be carried out with particular care in order to detach as little of the exposed layer, which ~2~8S~(~
is soluble in aqueous alkali, as possible. Also, it is necessary to add polymers which are sparingly soluble in the alkali and which limit the applicability of the material to other uses.
European Patent Application No. 0,024,916 discloses a similar reversal process for the production of resist layers, in which a material comprising 1,2-quinone diazides is heated after imagewise exposure, then e~posed again without an original and developed ~ith an aqueous alkaline solution to form a negative.
The light-sensitive layer of the material contains par-ticular photochromic compounds which react with the products of the photoreaction of the quinone diazide UpOII heating of the material and are said to effect curing of the layer. In this material, photochromic substances must be present. The photoreaction of the photochromic substances, however, produces a discolora-tion which is inconvenient in some applications.
British Patent Application No. 2,082,339 describes a light-sensitive composition comprising an o-quinone diazide and at least one resol, for use in the manufacture of a lithographic printing plate which is also suitable both for positive and negative proces-sing. The reversal process disclosed by this document covers the same sequence of steps as the afore-mentioned process~ Its action is based on the fact that the photodecomposition products of the o-quinone diazide form an insoluble reaction product with the resol, under the action of heat. The printing plates produced have the disadvanta~e of a relatively poor shelf li~e, due to the self-curing character of resols.
In German Offenlegungsschriften No. 2~855/723 and No. 2,529,054 (corresponding to U.S. Patent No. 4,104,070) resist layers comprising 1,2-quinone diazides are described, which are used for a reversal process and contain N~acyl-N'-methylol-ethylenediamines ~z~ o or hydroxyethylimidazoles to efEect thermal curing of the layer. A similar material which comprises second-ary or tertiary amines i5 described in U.S. Patent No. 4,196,003.
German Offenlegungsschrift No. 3,325,022 has proposed a reversal process involving 1,2-quinonedia-~ides, in which the light-sensitive material contains an ether of hexamethylol melamine for the thermal curing of the layer.
Admixtures of this type, comprising basic groupsr generally negatîvely influence the image con-trast following exposure, especially in those cases where the decrease or change in color intensity is caus~d by certain acid products and/or free radicals formed upon exposure, in combination with a dyestuff that is sensitive to acids and/or free radicals.
Additives of the above type, however, general-ly have an adverse influence on the shelf life of the copying layers and on particular properties relating to copyiny technique, such as, for example, sensitivity to light and image contrast after exposure. Moreover, for many applications, the temperature which is required for obtaining an image reversal is too high or the period of heating at a lower temperature is too long.
SUMMARY OF THE INVENTION
It is, therefore~ an object of the present invention to provide an improved light-sensitive mater-ial for producing negative copies in a reversal process which improves the shelf life and image contrast of the copying layer after exposure.
Another object of the present invention is to provide an improved light-sensitive material for pro-ducing negative copies in a reversal process which re-quires only a short heating time to relatively low temperatures to provide for thermal curing of the exposed layer areas.
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Still another object of the present invention is to provide a reversal process for producing negative copies by means of a normally positive-working light-sensitive material comprising 1,2-quinone diazides, which requires only a short heating time to relativel~
low temperatures to provide for thermal curing o~ the exposed layer areas.
In accomplishing the ~oregoing objects, there has been provided in accordance with one aspect of the present invention, a li~ht-sensitive material ~or pro-ducing negative copies in a reversal process, compris-ing a support and a li~ht-sensitive layer which includes a 1,2-quinone diazide, and a compound which promotes thermal curing comprising at least one quater-nary phosphonium compound of the general formula t(R)3-P-R'~6kal~3 wherein R and ~' are identical or different and are selected ~rom alkyl, alkenyl or aryl, and Hal is a halogen. Preferably, R arld R' are selected from an alkyl or an alkenyl comprising about 1 to ~ carbon atoms or a substituted phenyl, and Hal is selected from chlorine or bromine. Most preEerably~ the phosphonium compound is tetramethylphosphonium chloride, tetrabutyl-- , phosphonium bromide or, especially, tetraphenylphospho-nium bromide.
Preferably, the 1,2-quinone diazide comprises an ester or an amide of a 1,2-quinone-diazide-4-sulfo-nic acid or a 1,2-quinone-diazide-4-carboxylic acid.
In accordance with another aspect of the pre-sent invention, there has been provided a process for producing negative relief copies, comprising the steps of (a) lmagewise exposing to light, through an original, a light-sensitive material comprising a support and a light-sensitive layer which comprises in admixture (i) a compound comprising at least one quaternary phos-phonium compound of the general formula 129~
[(R)3-P-R~ ~ Hal ~7 wherein R and R' can be identical or di~ferent and are an alk~l, a:Lkenyl or aryl and Hal is a halogen, said compound being present in an amount sufficient to ~ro-mote thermal curing, and (ii) at leas-t one 1,2-quinone-diazide present in an amount sufficient to impart light-sensiti~iity to said layer; (b) thereafter he~ting said material such that imagewise exposed portions of said material are rendered insoluble in alkaline developer;
(c) then, after cooling, exposing said material again ~o light without said original; and thereafter (d) developing said material with an aqueous-alkaline deve-loper to re~ove from said substrate portions of said layer not imagewise exposed in step (a). The tempera-ture of said heating step is in the range from about 70 to 150C, and the length of said heating step is in the range from about `10 seconds to 10 minutes.
Other objects, features and advantages of the present invention will become apparent from a review of the detailed description of preferred embodiments which ~ollows.
DETAILED l)ESCRIPTION OF THE PREFERRED EMBO~IMENTS
The present invention provides an improved light-sensitive material and an improved process for producing negative relief copies. The light-sensitive material comprises a support and a light-sensitive layer which comprises, as the essential constituents, a compound which promotes thermal curing and a 1,2-qui-none diazide. The material is exposed imagewise, thereafte~ heated and, after cooling, completely exposed again, without an original, and then developed by means of an aqueous-alkaline developer.
The present invention is characterized in that the light-sensitive layer comprises, as the compound promoting thermal curing, at least one quaternary phosphonium compound of the general formula 12~8~i~L0 t(R)3-P-R~36~al~3 in which R and R' are identical or different and denote an alkyl, an alkenyl or an aryl, and Hal denotes a halogen. Preferably, R and R' denote an alkyl or an alkenyl having about 1 to 4 carbon atoms, or optionally denote a substituted phenyl, and Hal denotes chlorine or bromine. Particular preference is given to com-pounds such as tetramethylphosphonium chloride, tetra-butylphosphonium bromide or tetraphenylphosphonium bromide.
The phosphonium compounds are obtained by alkylation or arylation of tertiary phosphines. The various methods of preparing these compounds are described in "Methoden der Organischen Chem~s" (Methods of Organic Chemistry) (Houben-Weyl), volume XII/l (1963), pages 79 to 104~
Sensitizers which are suitable for use ac-cording to the present invention comprise any 1,2 qui-nonediazide-sulfonic acid esters, 1,2 quinonediazide-sulfonic acid amides, 1~2 quinonediazide-carboxylic acid esters and 1,2-quinonediaæide-carboxylic acid am-ides, which are rendered soluble in aqueous-alkaline solutions after irradiation with actinic light.
Included are the reaction products of the 4- or 5-sulfonic acid of 1,2-ben20quinone diazide or of 1,2-naphthoquinone diazide or of the acid chlorides thereof with phenol-aldehyde/acetone condensation pro-ducts or with polymers of p-hydroxystyrene, p-aminostyrene or copolymers of these two compounds.
The amides and esters of the 4-sulfonic acids and the 4-carboxylic acids of 1,2-quinone diazide are particularly advantageously used, since, in the pro-cessing according to the present invention, these materials yield a reversal effect, even without an addition of quaternary phosphonium compounds. When these compounds are used, it is, therefore, possible ~2~
either to lower the amount of quaternary phosphonium compounds, or to reduce the time or the temperature of heating.
Esters of the 1,2-quinone diazide derivatives which may be used include the known reaction products of the acids or the halides thereof with phenols, in particular with polyhydric phenols, for example, with 2,3,4-trihydroxy-benzophenone, 2,4-dihydroxy-benzophen-one, 4-decanoyl-resorcinol, 4-(2-phenyl-prop-2-yl)-phenol, gallic acid octyl ester or 4,4-bis-(4-hydroxyphenyl)-valeric acid butyl ester. The amides may be derived from longer-chain aliphatic amines or, preferably, from aromatic amines, in a known manner~
The amount of o-quinonediazide compounds generally ranges from about 3 to 50% by weight, pre-ferably from about 7 to 35~ by weight, based on the weight o~ the non-volatile constituents of the light-sensitive layer.
The concentration of the quaternary phospho-nium compounds in the light-sensitive composition can be varied within relatively wide limits. In general, they are present in amounts from about 1 to 50% by weight, preferably from about 3 to 30% by weight, based on the weight of the non-volatile constituents of the light-sensitive layer.
Preferably~ the light-sensitive layer further comprises a polymeric, water-insoluble resinous binder which is soluble in the solvents used for the com-position according to the invention and is also soluble~ or at least swellable, in aqueous alkalis.
The novolak condensation resins, well-established in many positive copying materials based on naphthoquinone diazides, have also proved to be advan-tageous ~or use as binders in the process according to the present invention. These novolaks can also be modified, in a known manner, by reacting part of their ~2~S~
hydroxy groups, for example, with chloroacetic acid, isocyanates, epoxides or carboxylic acid anhydrides.
Other preferred binders which are soluble or swellable in alkali include polyhydroxyphenyl resins which are prepared by condensing phenols with aldehydes or ke-tones, copolymers of styrene and maleic anhydride, polyvinylphenols, or copolymers of acrylic acid or methacrylic acid, in particular with acrylic or meth-acrylic acid esters. The type and quantity of the alkali-soluble resin may vary depending on the intended use. Preferably, the proportion of alkali-soluble resins in the total solids is between about 90 and 30%
by weight, particularly preferably between about 85 and 55% by weight.
Moreover, numerous other resins can also be used. Preferably these resins include epoxy resins and vinyl polymers, such as polyvinyl acetates, polyacry-lates, polyvinyl acetals, polyvinyl ethers, polyvinyl-pyrrolidones and copolymers of the monomers on which these are based, as well as hydrogenated or partially hydrogenated colophony derivatives. The most advanta-geous proportion of these resins depends on the tech-nological requirements and on the influence on the development conditions and is, in general, not more than about 50% by weight, preferably from about 2 to 35~ by weight, of the allcali-soluble resin. To meet special requirements, such as flexibility, adhesion, gloss and coloration, the light-sensitive layer can additionally comprise substances such as polyglycols, cellulose derivatives, such as ethylcellulose, surfac-tants, dyes, adhesion-promotors and finely-divided pigments, and also ultraviolet absorbers, if required.
For color change after exposure, the light-sensitive composition can also be admixed with small amounts of radiation-sensitive components which pre-ferably form or split off strong acids upon exposure ~298~
and produce a color change in a consequent reaction with a suitable dye. Radiation-sensitive components of this type include, for example, 1,2-naphthoquinone-diazide-4-sulfonic acid chloride, halogenomethyl-s-triazines which have chromophoric substituents ordiazonium compounds in the form of their salts with complex acids, such as hydrofluoroboric acid or hexafluorophosphoric acid.
For coating a suitable support, the constit-uents are, in general, dissolved in a solvent. Theselection of the solvents should be matchad to the envisaged coating process, the layer thickness and the drying conditions. Suitable solvents for the com-position according to the present invention include ketones, such as methyl ethyl ketone, chlorinated hydrocarbonsS such as trichloroethylene and l,l,l-tri-chloroethane, alcohols, such an n-propanol, ethers such as tetrahydrofuran, alcohol-ethers, such as ethylene glycol monethyl ether, and esters, such as butyl ace-tate. It is also possible to use mixtures which, forspecial purposes, can additionally comprise solvents, such as acetonitrile, dioxane or dimethyIformamide. In principle, all those solvents can be used which do not irreversibly react with the layer components.
~5 Particularly preferred solvents comprise the partial ethers of glycols, especiall~ propylene glycol mono-methyl ether and ethylene glycol monomethyl ether.
The supports used for layer thicknesses of less than about 10/um are in most cases metals. The following may be used for offset printing plates: mill-finished~ mechanically or electrochemcially roughened aluminum which, if desired, has been anodically oxi-dized and which additionally can also have been chemi-cally pretreated, for example, with polyvinyl phosphonic acid, silicates, phosphates, hexafluorozir-conat~s, or with hydrolyzed tetraethyl orthosilicate.
~L~9~5~0 Coatiny of the support material is carried out in a known manner by spin-coating, spraying, dipping, roller-coating, by means of slot dies, blade-spreading or by means of a coater application. Light sources customary in industry are used for exposure. Irradi-tion with electrons or a laser is another possibility for producing an image.
The aqueous-alkaline solutions which are used for developing have a graduated alkalinity. In other words, the solutions have a pH which is preferably in the range between about 10 and 14. The solutions can also contain minor amounts of organic solvents or surfactants.
After imagewise irradiation or exposure, re-spectively, the material is heated without any furtherintermediate treatment. Heating ~an be effected by irradiation, convection, contact with heated surfaces, for example, with rollers, or by immersion into a heated bath comprising an inert li~uid, for example, water. The temperature can range between about 70 and 150C, preferab]y, between about 90 and 130C. These temperatures are tolerated by the compositions without any considerable change in the properties of the unex-posed areas. The duration of heating can vary widely, depending on the method chosen for the application of heat. If a heat-transferring medium is used, the heating time generally ranges between about 10 seconds ~nd 10 minutes, preferably between about 30 seconds and 4 minutes.
Following heating and cooling, the light-sensitive layer is subjected to an overall exposure, without an original, by which the layer areas which are still sensîtive to light are completely converted into their photodecomposition products~ For the second exposure, the light source employed in the imagewise exposure is advantageously used again.
85~) The second exposure is followed by developing with conventional developers, by which the layer areas which were not struck by light in the original image-wise exposure are washed off. Suitable developers pre-ferably comprise aqueous solutions of alkalinesubstances, for example, of alkali-metal phosphates, alkali-metal silicates, alkali-metal carbonates or alkali-metal hydroxides, which can additionally contain surfactants or relatively small amounts of organic solvents. In particular cases, suitable developers also comprise organic solvents or mixtures of organic solvents with water. The material can be developed either immediately after heating and cooling or aEter a time interval of, for example, several hours, without any attack occurring in the cured layer areas. This indicates ~hat the exposed layer areas are irreversibly cured by heating.
Compared with conventional reversal processes, the process of the present invention has the advantage that, notwithstanding a good shelf life of the copying layers, curing of the imagewise exposed layer areas at an elevated temperature takes place relatively quickly, and the temperature of baking which is required for the reversal step is relatively low and the dwell time at elevated temperature is relatively short.
Another advantage offered by the present invention resides in the fact that the image contrast after exposure is not adversely affected by the addi-tion of the quaternary phosphonium compounds~
30The process of the present invention can, for example, be applied in the production of printing forms for letterpress printing, gravure printing and plano-graphic printing. The process can also be applied in the production of photoresist stencils for the subtrac-tive and additive preparation of printed circuit boards, in the production of nickel screen-printing ~Z~8~
cylinders prepared by an electroplating process, and in the production of masks in micro-electronics, according to the lift-off technique.
In the examples which follow, preferred embod-iments of the process according to the present inven-tion are described. Percentages and quantitative ratios are to be understood as units of weight, unless otherwise indicated.
ExamPle 1 ~n electrolytically roughened and anodically oxidized aluminu~ sheet was coated with a solution comprising:
2.00 p.b.w. (parts of weight) of the esterification product of 1 mol of 2,3,4-trihydroxyben-zophenone and 3 mol of naphthoquinone-1,2-diazide-(2)-5-sulfonic acid chloride, 7.00 p.b.w. of a cresol-formaldehyde novolak having a softening range from 105 to 120C, as measured according to the capillary method DIN 53,181, 0.15 p.b.w. of 2-~4-ethoxy naphth-1-yl)-4,6-bis-tri-chloromethyl-s-triazine, 1.00 p.b.w. of tetrabutylphosphonium bromide, and 0.06 p~b.w. of crystal violet, in 60.00 p.b~w. of ethylene glycol monomethyl ether, and 60.00 p.b.w. of tetrahydrofuran.
The anodically oxidized aluminum support had been treated with an aqueous solution comprising 0.1%
of polyvinylphosphonic acid, as described in German Patent No. 1,621,478, before the light-sensitive copying layer was applied.
The presensitized material prepared in this manner, in which the light-sensitive layer had a weight of 2.3 g/m2, was exposed imagewise for 65 seconds, 85~q3 through a transparent positive original using a 5 kW
metal hallde lamp and at a distance of 110 cm, and then developed with a 10~ strength aqueous solution of sodium metasilicate. In the developing procedure, the portions of the copying layer which had been struck by light were removed and the unexposed image areas remained on the support to produce a printing stencil corresponding to the original. Inking with a greasy printing ink yielded a positive printing form which was ready for printing.
Another sample of the same presensitized material was processed to provide a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated for 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise positive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
Both the positive printin~ form and the nega-tive printing form are capable of being baked at tem-peratures above 180C, as a result of which the number of printed copies obtained can be increased many times over.
When a printing plate was prepared in accord-ance with this Example, but without the tetrabutyl-phosphonium bromide admixture, a printing form corresponding to the original form employed was obtained after imagewise exposure and development.
Without the addition of tetrabutylphosphonium bromide it was, however, not possible to produce usable nega-tive copies from the presensitized positive-working ma~erial by means of the process of the present inven-tion as described above.
12~51(:~
e 2 An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution comprising 0.1% by weight of polyvi-nylphosphonic acid, was coated with a solutioncomprising:
2.00 p.b.w. of the esterification product obtained from 1 mol 4-(2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-~1,2~-dia-zide-(2)-4-sulfonic acid chloride, 6O00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.20 p~b.w. of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid chloride, 2.00 p.b.w. of tetrabutylphosphonium bromide, and 0.06 p~b~wo of crystal violet, in 50.00 p.b.w. o ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
As described in Example 1, the presensitized material prepared in this manner, which had a layer weight o 2.4 g/m2, was imagewise exposed under a transparent positive original for 50 seconds and then developed with a 10% strength solution of sodium meta-silicate to produce a positive printing stencil corresponding to the original.
Another sample of the same material was pro-cessed to produce a negative printing plate. For this purpose, the sample was exposed under a negative origi-nal for 50 seconds, thereafter heated to 120C for 2 minutes, and exposed again without an original, for the same period of time as used in the imagewise exposure.
On developing in the same developer as used above, a reversed image of the original was obtained.
12~8S~O
Example 3 An electrochemically roughened and anodically oxidized aluminum plate was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of the ethoxy-ethyl ester of 4,4-bis-t4-hydroxyphenyl)-n-valeric acid and 2 mol of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride, 0 7.00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.15 p.b~w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazineT
1.00 p.b.w. of tetrabutylphosphonium bromide, and 0.37 p.b.w. of crystal violet, in50.00 p.b.w. o ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, in which the light-sensitive layer had a layer weight of 2.50 g/m2, was exposed imagewise under a transparent positive original for 50 seconds as described in Example 1, and then developed with a 10%
strength solution of sodium metasilicate to produce a positive printing stencil corresponding to the original.
Another sample of the same material was pro-cessed to produce a negative printing plate. For this purpose, the sample was exposed under a negativ~ origi-nal for 100 seconds, thereafter heated or 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise posi-tive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
~2~S~
xample 4 An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution containing 0.1% by weight of polyvin-ylphosphonic acid, was coated with a solutioncomprising:
1.30 p.b.w. of the esterification product obtained from 1 mol of 4-t2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-(1,2~-diazide-(2)-4-sulfonic acid chloride, 8.60 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.14 p.b.w. of 2,4-bis-(trichloromethyl)-6-p-methoxy-styryl-s-triazine, 0.15 p.b.w. of tetrabutylphosphonium bromide and 0.07 p.b.w. of crystal violet, in 50.00 p.b.w. of ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, which had a layer weight of 2.7 g/m2, was exposed image-wlse, for 40 seconds, ùnder a positive transparent original as described in Example 1 and then developed with a 10%
strength solution of sodium ~etasilicate to produce a positive printing stencil cor~esponding to the original.
Another sample of the same material was pro-cessed to give a negative printing plate. For this purpose, the sample was exposed under a negative origi-nal for 80 seconds, thereafter heated for 2 minutes at 130C, and then exposed again without an oriyinal for another 40 seconds. Upon developing, a reversed image of the original was obtained.
851~3 _xample 5 An electrochemically roughened and anodically oxidized aluminum plate~ which had been treated with an aqueous solution containing 0.1% by weight of poly-vinylphosphonic acid, was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of 2r3,4-trihydroxy-benzo-phenone and 3 mol of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride, 6.00 p.b.w. of a phenol-formaldehyde novolak resin having a melt range of 83 to 88C, 0.15 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 2.00 p.b.w~ of tetraphenylphosphonium ~romide, and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 70.00 p.b.w. of tetrahydrouran.
The presensitized material prepared in this manner, which had a layer weight of 2.30 g/m2, was exposed imagewise under a transparent positive original for 45 seconds, as described in Example 1, and was then developed with a 3% strength solution of sodium ; 25 metasilicate. A printing stencil corresponding to the original was obtained.
For producing a negative printing plate, another sample of the material was exposed under a negative original for 90 seconds, thereafter heated at 130C for 2 minutes, and then exposed again without an original for 45 seconds. Upon developing in the same developer, a reversed image of the original was obtained.
~2~8~
An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution containing 0.1% by weight of polyvin-ylphosphonic acid, was coated with a solution comprising:
2~00 prb~w~ of the esterification product obtained from 1 mol oE 2,3,4-trihydroxy-benzo-phenone and 3 mol of naphthoquinone-(1,2~-diazide-(2)-5-sulfonic acid chloride, 8~00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0~15 p.b.w. of 2-(4-ethoxy-naphth-1-yl)-4,6-bis-tri-chloromethyl-s-triazine, 1O50 p.b.w. of tetrabutylphosphonium bromide and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 70.00 p.b.w. of tetrahydroEuran.
The presensitized material prepared in this manner, which had a layer weight of 2.4 g/m2, was exposed under a transparent positive original for 65 seconds, as described in Example 1, and then developed with a 10~ strength solution of sodium metasilicate.
The printing stencil obtained corresponded to the original.
Another sample of the same presensitized material was processed to produce a negative printing plate. For this purpose, the sample was exposed under a negative original for 65 seconds, thereafter heated at 130C for 2 minutes, and then exposed again without an original for 65 second5. Upon developing in the same developer, a reversed image of the original was obtained.
1298~0 Example 7 ~ n electrochemicall~ roughened and anodically oxidized aluminum plate, which had been treated with an aqueQus solution containing 001% by weight of polyvinyl-phosphonic acid was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtainedfrom 1 mol of 4-(2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-(1,2~-dia~ide-(2)-4-sulfonic acid chloride, 0 5.00 p.b.w. of the phenol-formaldehyde novolak of Example 5, 0015 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 1.00 p.b.w. of tetraphenylphosphonium bromide, and 0.06 p.b~w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, which had a layer weight of 2.30 g/m2, was exposed under a transparent positive original for 45 seconds, as described in Example 1, and was then devel-oped with a 2~ strength solution of sodium metasilicate.
The printing stencil obtained corresponded to the origi-nal.
Another sample of the materials was processed to give a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated at 130C for 2 minutes, and then exposed again for 45 seconds without an original.
Upon developing with the same developer, a reversed image of the original was obtained.
~2!98~
Example 8 An electrochemically roughened and anodically oxidized aluminum plate was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of 2,3,4-trihydroxybenzo-phenone and 3 mol of naphthoquinonP-(1?2)-diazide-(2)-5-sulfonic acid chloride, 0 7.00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.15 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 1.00 p.b.w. of tetramethylphosphonium chloride, and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylcne glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this way, which had a layer weight of 2.3 g/m~/ was exposed for 65 seconds through a positive transparency, using a 5 kW metal halide lamp and at a distance of 110 cm, and was then developed with a 9% strength aqueous solution of sodium metasilicate. In the developing procedure, the portions of the copying layer which had been struck by light were removed and the unexposed image areas remained on the support, such that a printing stencil corresponding to the original was obtained. Inking with a greasy printing ink yielded a positive printing fQrm which was ready for printing.
~Z98~
Another sample of the same presensitized matexial was processed to give a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated for 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise positive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
A LIGHT-SENSITIVE MATERIAL AND A PROCESS FOR
PRODUCING NEGATIVE COPIES UTI~IZING THE MATERIAL
BACKGROUND OF THE INVENTION
The present invention relates to a light-sensitive material and a reversal process for producing negative copies utilizing the light-sensitive material.
rhe light-sensitive material includes a normally positive-workin~ light-sensitive material comprising 1,2-quinone diazides.
It is known that positive-working reproduction materials comprising 1,2-naphthoquinone diazides can be negatively processed by a particular sequence of treat-ment steps. U.S. Patent No. 3,264,104 describes a reversal process of this ~ype in which the light-sensitive layer, which preferably contains thermoplas-tic polymers, is exposed imagewise. The layer is then treated with an alkaline solution or with water, if appropriate at an elevated temperature, without washing off the exposed areas in the process. Thereafter, the layer is ~xposed again without an original, and then developed in the usual manner, such that the original imagewise exposed areas remain on the support and the other areas are washed off the support.
The above process is disadvantageous in that a comparatively large number of treatment steps are re~
quired. Furthermore~ the first treatment with alkali must invariably be carried out with particular care in order to detach as little of the exposed layer, which ~2~8S~(~
is soluble in aqueous alkali, as possible. Also, it is necessary to add polymers which are sparingly soluble in the alkali and which limit the applicability of the material to other uses.
European Patent Application No. 0,024,916 discloses a similar reversal process for the production of resist layers, in which a material comprising 1,2-quinone diazides is heated after imagewise exposure, then e~posed again without an original and developed ~ith an aqueous alkaline solution to form a negative.
The light-sensitive layer of the material contains par-ticular photochromic compounds which react with the products of the photoreaction of the quinone diazide UpOII heating of the material and are said to effect curing of the layer. In this material, photochromic substances must be present. The photoreaction of the photochromic substances, however, produces a discolora-tion which is inconvenient in some applications.
British Patent Application No. 2,082,339 describes a light-sensitive composition comprising an o-quinone diazide and at least one resol, for use in the manufacture of a lithographic printing plate which is also suitable both for positive and negative proces-sing. The reversal process disclosed by this document covers the same sequence of steps as the afore-mentioned process~ Its action is based on the fact that the photodecomposition products of the o-quinone diazide form an insoluble reaction product with the resol, under the action of heat. The printing plates produced have the disadvanta~e of a relatively poor shelf li~e, due to the self-curing character of resols.
In German Offenlegungsschriften No. 2~855/723 and No. 2,529,054 (corresponding to U.S. Patent No. 4,104,070) resist layers comprising 1,2-quinone diazides are described, which are used for a reversal process and contain N~acyl-N'-methylol-ethylenediamines ~z~ o or hydroxyethylimidazoles to efEect thermal curing of the layer. A similar material which comprises second-ary or tertiary amines i5 described in U.S. Patent No. 4,196,003.
German Offenlegungsschrift No. 3,325,022 has proposed a reversal process involving 1,2-quinonedia-~ides, in which the light-sensitive material contains an ether of hexamethylol melamine for the thermal curing of the layer.
Admixtures of this type, comprising basic groupsr generally negatîvely influence the image con-trast following exposure, especially in those cases where the decrease or change in color intensity is caus~d by certain acid products and/or free radicals formed upon exposure, in combination with a dyestuff that is sensitive to acids and/or free radicals.
Additives of the above type, however, general-ly have an adverse influence on the shelf life of the copying layers and on particular properties relating to copyiny technique, such as, for example, sensitivity to light and image contrast after exposure. Moreover, for many applications, the temperature which is required for obtaining an image reversal is too high or the period of heating at a lower temperature is too long.
SUMMARY OF THE INVENTION
It is, therefore~ an object of the present invention to provide an improved light-sensitive mater-ial for producing negative copies in a reversal process which improves the shelf life and image contrast of the copying layer after exposure.
Another object of the present invention is to provide an improved light-sensitive material for pro-ducing negative copies in a reversal process which re-quires only a short heating time to relatively low temperatures to provide for thermal curing of the exposed layer areas.
8SgL~
Still another object of the present invention is to provide a reversal process for producing negative copies by means of a normally positive-working light-sensitive material comprising 1,2-quinone diazides, which requires only a short heating time to relativel~
low temperatures to provide for thermal curing o~ the exposed layer areas.
In accomplishing the ~oregoing objects, there has been provided in accordance with one aspect of the present invention, a li~ht-sensitive material ~or pro-ducing negative copies in a reversal process, compris-ing a support and a li~ht-sensitive layer which includes a 1,2-quinone diazide, and a compound which promotes thermal curing comprising at least one quater-nary phosphonium compound of the general formula t(R)3-P-R'~6kal~3 wherein R and ~' are identical or different and are selected ~rom alkyl, alkenyl or aryl, and Hal is a halogen. Preferably, R arld R' are selected from an alkyl or an alkenyl comprising about 1 to ~ carbon atoms or a substituted phenyl, and Hal is selected from chlorine or bromine. Most preEerably~ the phosphonium compound is tetramethylphosphonium chloride, tetrabutyl-- , phosphonium bromide or, especially, tetraphenylphospho-nium bromide.
Preferably, the 1,2-quinone diazide comprises an ester or an amide of a 1,2-quinone-diazide-4-sulfo-nic acid or a 1,2-quinone-diazide-4-carboxylic acid.
In accordance with another aspect of the pre-sent invention, there has been provided a process for producing negative relief copies, comprising the steps of (a) lmagewise exposing to light, through an original, a light-sensitive material comprising a support and a light-sensitive layer which comprises in admixture (i) a compound comprising at least one quaternary phos-phonium compound of the general formula 129~
[(R)3-P-R~ ~ Hal ~7 wherein R and R' can be identical or di~ferent and are an alk~l, a:Lkenyl or aryl and Hal is a halogen, said compound being present in an amount sufficient to ~ro-mote thermal curing, and (ii) at leas-t one 1,2-quinone-diazide present in an amount sufficient to impart light-sensiti~iity to said layer; (b) thereafter he~ting said material such that imagewise exposed portions of said material are rendered insoluble in alkaline developer;
(c) then, after cooling, exposing said material again ~o light without said original; and thereafter (d) developing said material with an aqueous-alkaline deve-loper to re~ove from said substrate portions of said layer not imagewise exposed in step (a). The tempera-ture of said heating step is in the range from about 70 to 150C, and the length of said heating step is in the range from about `10 seconds to 10 minutes.
Other objects, features and advantages of the present invention will become apparent from a review of the detailed description of preferred embodiments which ~ollows.
DETAILED l)ESCRIPTION OF THE PREFERRED EMBO~IMENTS
The present invention provides an improved light-sensitive material and an improved process for producing negative relief copies. The light-sensitive material comprises a support and a light-sensitive layer which comprises, as the essential constituents, a compound which promotes thermal curing and a 1,2-qui-none diazide. The material is exposed imagewise, thereafte~ heated and, after cooling, completely exposed again, without an original, and then developed by means of an aqueous-alkaline developer.
The present invention is characterized in that the light-sensitive layer comprises, as the compound promoting thermal curing, at least one quaternary phosphonium compound of the general formula 12~8~i~L0 t(R)3-P-R~36~al~3 in which R and R' are identical or different and denote an alkyl, an alkenyl or an aryl, and Hal denotes a halogen. Preferably, R and R' denote an alkyl or an alkenyl having about 1 to 4 carbon atoms, or optionally denote a substituted phenyl, and Hal denotes chlorine or bromine. Particular preference is given to com-pounds such as tetramethylphosphonium chloride, tetra-butylphosphonium bromide or tetraphenylphosphonium bromide.
The phosphonium compounds are obtained by alkylation or arylation of tertiary phosphines. The various methods of preparing these compounds are described in "Methoden der Organischen Chem~s" (Methods of Organic Chemistry) (Houben-Weyl), volume XII/l (1963), pages 79 to 104~
Sensitizers which are suitable for use ac-cording to the present invention comprise any 1,2 qui-nonediazide-sulfonic acid esters, 1,2 quinonediazide-sulfonic acid amides, 1~2 quinonediazide-carboxylic acid esters and 1,2-quinonediaæide-carboxylic acid am-ides, which are rendered soluble in aqueous-alkaline solutions after irradiation with actinic light.
Included are the reaction products of the 4- or 5-sulfonic acid of 1,2-ben20quinone diazide or of 1,2-naphthoquinone diazide or of the acid chlorides thereof with phenol-aldehyde/acetone condensation pro-ducts or with polymers of p-hydroxystyrene, p-aminostyrene or copolymers of these two compounds.
The amides and esters of the 4-sulfonic acids and the 4-carboxylic acids of 1,2-quinone diazide are particularly advantageously used, since, in the pro-cessing according to the present invention, these materials yield a reversal effect, even without an addition of quaternary phosphonium compounds. When these compounds are used, it is, therefore, possible ~2~
either to lower the amount of quaternary phosphonium compounds, or to reduce the time or the temperature of heating.
Esters of the 1,2-quinone diazide derivatives which may be used include the known reaction products of the acids or the halides thereof with phenols, in particular with polyhydric phenols, for example, with 2,3,4-trihydroxy-benzophenone, 2,4-dihydroxy-benzophen-one, 4-decanoyl-resorcinol, 4-(2-phenyl-prop-2-yl)-phenol, gallic acid octyl ester or 4,4-bis-(4-hydroxyphenyl)-valeric acid butyl ester. The amides may be derived from longer-chain aliphatic amines or, preferably, from aromatic amines, in a known manner~
The amount of o-quinonediazide compounds generally ranges from about 3 to 50% by weight, pre-ferably from about 7 to 35~ by weight, based on the weight o~ the non-volatile constituents of the light-sensitive layer.
The concentration of the quaternary phospho-nium compounds in the light-sensitive composition can be varied within relatively wide limits. In general, they are present in amounts from about 1 to 50% by weight, preferably from about 3 to 30% by weight, based on the weight of the non-volatile constituents of the light-sensitive layer.
Preferably~ the light-sensitive layer further comprises a polymeric, water-insoluble resinous binder which is soluble in the solvents used for the com-position according to the invention and is also soluble~ or at least swellable, in aqueous alkalis.
The novolak condensation resins, well-established in many positive copying materials based on naphthoquinone diazides, have also proved to be advan-tageous ~or use as binders in the process according to the present invention. These novolaks can also be modified, in a known manner, by reacting part of their ~2~S~
hydroxy groups, for example, with chloroacetic acid, isocyanates, epoxides or carboxylic acid anhydrides.
Other preferred binders which are soluble or swellable in alkali include polyhydroxyphenyl resins which are prepared by condensing phenols with aldehydes or ke-tones, copolymers of styrene and maleic anhydride, polyvinylphenols, or copolymers of acrylic acid or methacrylic acid, in particular with acrylic or meth-acrylic acid esters. The type and quantity of the alkali-soluble resin may vary depending on the intended use. Preferably, the proportion of alkali-soluble resins in the total solids is between about 90 and 30%
by weight, particularly preferably between about 85 and 55% by weight.
Moreover, numerous other resins can also be used. Preferably these resins include epoxy resins and vinyl polymers, such as polyvinyl acetates, polyacry-lates, polyvinyl acetals, polyvinyl ethers, polyvinyl-pyrrolidones and copolymers of the monomers on which these are based, as well as hydrogenated or partially hydrogenated colophony derivatives. The most advanta-geous proportion of these resins depends on the tech-nological requirements and on the influence on the development conditions and is, in general, not more than about 50% by weight, preferably from about 2 to 35~ by weight, of the allcali-soluble resin. To meet special requirements, such as flexibility, adhesion, gloss and coloration, the light-sensitive layer can additionally comprise substances such as polyglycols, cellulose derivatives, such as ethylcellulose, surfac-tants, dyes, adhesion-promotors and finely-divided pigments, and also ultraviolet absorbers, if required.
For color change after exposure, the light-sensitive composition can also be admixed with small amounts of radiation-sensitive components which pre-ferably form or split off strong acids upon exposure ~298~
and produce a color change in a consequent reaction with a suitable dye. Radiation-sensitive components of this type include, for example, 1,2-naphthoquinone-diazide-4-sulfonic acid chloride, halogenomethyl-s-triazines which have chromophoric substituents ordiazonium compounds in the form of their salts with complex acids, such as hydrofluoroboric acid or hexafluorophosphoric acid.
For coating a suitable support, the constit-uents are, in general, dissolved in a solvent. Theselection of the solvents should be matchad to the envisaged coating process, the layer thickness and the drying conditions. Suitable solvents for the com-position according to the present invention include ketones, such as methyl ethyl ketone, chlorinated hydrocarbonsS such as trichloroethylene and l,l,l-tri-chloroethane, alcohols, such an n-propanol, ethers such as tetrahydrofuran, alcohol-ethers, such as ethylene glycol monethyl ether, and esters, such as butyl ace-tate. It is also possible to use mixtures which, forspecial purposes, can additionally comprise solvents, such as acetonitrile, dioxane or dimethyIformamide. In principle, all those solvents can be used which do not irreversibly react with the layer components.
~5 Particularly preferred solvents comprise the partial ethers of glycols, especiall~ propylene glycol mono-methyl ether and ethylene glycol monomethyl ether.
The supports used for layer thicknesses of less than about 10/um are in most cases metals. The following may be used for offset printing plates: mill-finished~ mechanically or electrochemcially roughened aluminum which, if desired, has been anodically oxi-dized and which additionally can also have been chemi-cally pretreated, for example, with polyvinyl phosphonic acid, silicates, phosphates, hexafluorozir-conat~s, or with hydrolyzed tetraethyl orthosilicate.
~L~9~5~0 Coatiny of the support material is carried out in a known manner by spin-coating, spraying, dipping, roller-coating, by means of slot dies, blade-spreading or by means of a coater application. Light sources customary in industry are used for exposure. Irradi-tion with electrons or a laser is another possibility for producing an image.
The aqueous-alkaline solutions which are used for developing have a graduated alkalinity. In other words, the solutions have a pH which is preferably in the range between about 10 and 14. The solutions can also contain minor amounts of organic solvents or surfactants.
After imagewise irradiation or exposure, re-spectively, the material is heated without any furtherintermediate treatment. Heating ~an be effected by irradiation, convection, contact with heated surfaces, for example, with rollers, or by immersion into a heated bath comprising an inert li~uid, for example, water. The temperature can range between about 70 and 150C, preferab]y, between about 90 and 130C. These temperatures are tolerated by the compositions without any considerable change in the properties of the unex-posed areas. The duration of heating can vary widely, depending on the method chosen for the application of heat. If a heat-transferring medium is used, the heating time generally ranges between about 10 seconds ~nd 10 minutes, preferably between about 30 seconds and 4 minutes.
Following heating and cooling, the light-sensitive layer is subjected to an overall exposure, without an original, by which the layer areas which are still sensîtive to light are completely converted into their photodecomposition products~ For the second exposure, the light source employed in the imagewise exposure is advantageously used again.
85~) The second exposure is followed by developing with conventional developers, by which the layer areas which were not struck by light in the original image-wise exposure are washed off. Suitable developers pre-ferably comprise aqueous solutions of alkalinesubstances, for example, of alkali-metal phosphates, alkali-metal silicates, alkali-metal carbonates or alkali-metal hydroxides, which can additionally contain surfactants or relatively small amounts of organic solvents. In particular cases, suitable developers also comprise organic solvents or mixtures of organic solvents with water. The material can be developed either immediately after heating and cooling or aEter a time interval of, for example, several hours, without any attack occurring in the cured layer areas. This indicates ~hat the exposed layer areas are irreversibly cured by heating.
Compared with conventional reversal processes, the process of the present invention has the advantage that, notwithstanding a good shelf life of the copying layers, curing of the imagewise exposed layer areas at an elevated temperature takes place relatively quickly, and the temperature of baking which is required for the reversal step is relatively low and the dwell time at elevated temperature is relatively short.
Another advantage offered by the present invention resides in the fact that the image contrast after exposure is not adversely affected by the addi-tion of the quaternary phosphonium compounds~
30The process of the present invention can, for example, be applied in the production of printing forms for letterpress printing, gravure printing and plano-graphic printing. The process can also be applied in the production of photoresist stencils for the subtrac-tive and additive preparation of printed circuit boards, in the production of nickel screen-printing ~Z~8~
cylinders prepared by an electroplating process, and in the production of masks in micro-electronics, according to the lift-off technique.
In the examples which follow, preferred embod-iments of the process according to the present inven-tion are described. Percentages and quantitative ratios are to be understood as units of weight, unless otherwise indicated.
ExamPle 1 ~n electrolytically roughened and anodically oxidized aluminu~ sheet was coated with a solution comprising:
2.00 p.b.w. (parts of weight) of the esterification product of 1 mol of 2,3,4-trihydroxyben-zophenone and 3 mol of naphthoquinone-1,2-diazide-(2)-5-sulfonic acid chloride, 7.00 p.b.w. of a cresol-formaldehyde novolak having a softening range from 105 to 120C, as measured according to the capillary method DIN 53,181, 0.15 p.b.w. of 2-~4-ethoxy naphth-1-yl)-4,6-bis-tri-chloromethyl-s-triazine, 1.00 p.b.w. of tetrabutylphosphonium bromide, and 0.06 p~b.w. of crystal violet, in 60.00 p.b~w. of ethylene glycol monomethyl ether, and 60.00 p.b.w. of tetrahydrofuran.
The anodically oxidized aluminum support had been treated with an aqueous solution comprising 0.1%
of polyvinylphosphonic acid, as described in German Patent No. 1,621,478, before the light-sensitive copying layer was applied.
The presensitized material prepared in this manner, in which the light-sensitive layer had a weight of 2.3 g/m2, was exposed imagewise for 65 seconds, 85~q3 through a transparent positive original using a 5 kW
metal hallde lamp and at a distance of 110 cm, and then developed with a 10~ strength aqueous solution of sodium metasilicate. In the developing procedure, the portions of the copying layer which had been struck by light were removed and the unexposed image areas remained on the support to produce a printing stencil corresponding to the original. Inking with a greasy printing ink yielded a positive printing form which was ready for printing.
Another sample of the same presensitized material was processed to provide a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated for 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise positive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
Both the positive printin~ form and the nega-tive printing form are capable of being baked at tem-peratures above 180C, as a result of which the number of printed copies obtained can be increased many times over.
When a printing plate was prepared in accord-ance with this Example, but without the tetrabutyl-phosphonium bromide admixture, a printing form corresponding to the original form employed was obtained after imagewise exposure and development.
Without the addition of tetrabutylphosphonium bromide it was, however, not possible to produce usable nega-tive copies from the presensitized positive-working ma~erial by means of the process of the present inven-tion as described above.
12~51(:~
e 2 An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution comprising 0.1% by weight of polyvi-nylphosphonic acid, was coated with a solutioncomprising:
2.00 p.b.w. of the esterification product obtained from 1 mol 4-(2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-~1,2~-dia-zide-(2)-4-sulfonic acid chloride, 6O00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.20 p~b.w. of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid chloride, 2.00 p.b.w. of tetrabutylphosphonium bromide, and 0.06 p~b~wo of crystal violet, in 50.00 p.b.w. o ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
As described in Example 1, the presensitized material prepared in this manner, which had a layer weight o 2.4 g/m2, was imagewise exposed under a transparent positive original for 50 seconds and then developed with a 10% strength solution of sodium meta-silicate to produce a positive printing stencil corresponding to the original.
Another sample of the same material was pro-cessed to produce a negative printing plate. For this purpose, the sample was exposed under a negative origi-nal for 50 seconds, thereafter heated to 120C for 2 minutes, and exposed again without an original, for the same period of time as used in the imagewise exposure.
On developing in the same developer as used above, a reversed image of the original was obtained.
12~8S~O
Example 3 An electrochemically roughened and anodically oxidized aluminum plate was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of the ethoxy-ethyl ester of 4,4-bis-t4-hydroxyphenyl)-n-valeric acid and 2 mol of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride, 0 7.00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.15 p.b~w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazineT
1.00 p.b.w. of tetrabutylphosphonium bromide, and 0.37 p.b.w. of crystal violet, in50.00 p.b.w. o ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, in which the light-sensitive layer had a layer weight of 2.50 g/m2, was exposed imagewise under a transparent positive original for 50 seconds as described in Example 1, and then developed with a 10%
strength solution of sodium metasilicate to produce a positive printing stencil corresponding to the original.
Another sample of the same material was pro-cessed to produce a negative printing plate. For this purpose, the sample was exposed under a negativ~ origi-nal for 100 seconds, thereafter heated or 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise posi-tive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
~2~S~
xample 4 An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution containing 0.1% by weight of polyvin-ylphosphonic acid, was coated with a solutioncomprising:
1.30 p.b.w. of the esterification product obtained from 1 mol of 4-t2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-(1,2~-diazide-(2)-4-sulfonic acid chloride, 8.60 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.14 p.b.w. of 2,4-bis-(trichloromethyl)-6-p-methoxy-styryl-s-triazine, 0.15 p.b.w. of tetrabutylphosphonium bromide and 0.07 p.b.w. of crystal violet, in 50.00 p.b.w. of ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, which had a layer weight of 2.7 g/m2, was exposed image-wlse, for 40 seconds, ùnder a positive transparent original as described in Example 1 and then developed with a 10%
strength solution of sodium ~etasilicate to produce a positive printing stencil cor~esponding to the original.
Another sample of the same material was pro-cessed to give a negative printing plate. For this purpose, the sample was exposed under a negative origi-nal for 80 seconds, thereafter heated for 2 minutes at 130C, and then exposed again without an oriyinal for another 40 seconds. Upon developing, a reversed image of the original was obtained.
851~3 _xample 5 An electrochemically roughened and anodically oxidized aluminum plate~ which had been treated with an aqueous solution containing 0.1% by weight of poly-vinylphosphonic acid, was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of 2r3,4-trihydroxy-benzo-phenone and 3 mol of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride, 6.00 p.b.w. of a phenol-formaldehyde novolak resin having a melt range of 83 to 88C, 0.15 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 2.00 p.b.w~ of tetraphenylphosphonium ~romide, and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 70.00 p.b.w. of tetrahydrouran.
The presensitized material prepared in this manner, which had a layer weight of 2.30 g/m2, was exposed imagewise under a transparent positive original for 45 seconds, as described in Example 1, and was then developed with a 3% strength solution of sodium ; 25 metasilicate. A printing stencil corresponding to the original was obtained.
For producing a negative printing plate, another sample of the material was exposed under a negative original for 90 seconds, thereafter heated at 130C for 2 minutes, and then exposed again without an original for 45 seconds. Upon developing in the same developer, a reversed image of the original was obtained.
~2~8~
An electrochemically roughened and anodically oxidized aluminum plate, which had been treated with an aqueous solution containing 0.1% by weight of polyvin-ylphosphonic acid, was coated with a solution comprising:
2~00 prb~w~ of the esterification product obtained from 1 mol oE 2,3,4-trihydroxy-benzo-phenone and 3 mol of naphthoquinone-(1,2~-diazide-(2)-5-sulfonic acid chloride, 8~00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0~15 p.b.w. of 2-(4-ethoxy-naphth-1-yl)-4,6-bis-tri-chloromethyl-s-triazine, 1O50 p.b.w. of tetrabutylphosphonium bromide and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 70.00 p.b.w. of tetrahydroEuran.
The presensitized material prepared in this manner, which had a layer weight of 2.4 g/m2, was exposed under a transparent positive original for 65 seconds, as described in Example 1, and then developed with a 10~ strength solution of sodium metasilicate.
The printing stencil obtained corresponded to the original.
Another sample of the same presensitized material was processed to produce a negative printing plate. For this purpose, the sample was exposed under a negative original for 65 seconds, thereafter heated at 130C for 2 minutes, and then exposed again without an original for 65 second5. Upon developing in the same developer, a reversed image of the original was obtained.
1298~0 Example 7 ~ n electrochemicall~ roughened and anodically oxidized aluminum plate, which had been treated with an aqueQus solution containing 001% by weight of polyvinyl-phosphonic acid was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtainedfrom 1 mol of 4-(2-phenyl-prop-2-yl)-phenol and 1 mol of naphthoquinone-(1,2~-dia~ide-(2)-4-sulfonic acid chloride, 0 5.00 p.b.w. of the phenol-formaldehyde novolak of Example 5, 0015 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 1.00 p.b.w. of tetraphenylphosphonium bromide, and 0.06 p.b~w. of crystal violet, in 60.00 p.b.w. of ethylene glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this manner, which had a layer weight of 2.30 g/m2, was exposed under a transparent positive original for 45 seconds, as described in Example 1, and was then devel-oped with a 2~ strength solution of sodium metasilicate.
The printing stencil obtained corresponded to the origi-nal.
Another sample of the materials was processed to give a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated at 130C for 2 minutes, and then exposed again for 45 seconds without an original.
Upon developing with the same developer, a reversed image of the original was obtained.
~2!98~
Example 8 An electrochemically roughened and anodically oxidized aluminum plate was coated with a solution comprising:
2.00 p.b.w. of the esterification product obtained from 1 mol of 2,3,4-trihydroxybenzo-phenone and 3 mol of naphthoquinonP-(1?2)-diazide-(2)-5-sulfonic acid chloride, 0 7.00 p.b.w. of the cresol-formaldehyde novolak of Example 1, 0.15 p.b.w. of 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 1.00 p.b.w. of tetramethylphosphonium chloride, and 0.06 p.b.w. of crystal violet, in 60.00 p.b.w. of ethylcne glycol monomethyl ether and 60.00 p.b.w. of tetrahydrofuran.
The presensitized material prepared in this way, which had a layer weight of 2.3 g/m~/ was exposed for 65 seconds through a positive transparency, using a 5 kW metal halide lamp and at a distance of 110 cm, and was then developed with a 9% strength aqueous solution of sodium metasilicate. In the developing procedure, the portions of the copying layer which had been struck by light were removed and the unexposed image areas remained on the support, such that a printing stencil corresponding to the original was obtained. Inking with a greasy printing ink yielded a positive printing fQrm which was ready for printing.
~Z98~
Another sample of the same presensitized matexial was processed to give a negative printing plate. For this purpose, the sample was exposed under a negative original for 90 seconds, thereafter heated for 2 minutes to 130C, and then exposed again without an original for the same period of time as used in the imagewise positive exposure. Upon developing in the same developer, a reversed image of the original was obtained.
Claims (16)
1. A light-sensitive material for producing negative copies in a reversal process, comprising:
a support; and a light-sensitive layer which includes:
a 1,2-quinone diazide; and a compound which promotes thermal curing comprising at least one quaternary phosphonium compound of the general formula [(R)3-P-R']?Hal?
wherein:
R and R' can be identical or different and are an alkyl, alkenyl or aryl, and Hal is a halogen.
a support; and a light-sensitive layer which includes:
a 1,2-quinone diazide; and a compound which promotes thermal curing comprising at least one quaternary phosphonium compound of the general formula [(R)3-P-R']?Hal?
wherein:
R and R' can be identical or different and are an alkyl, alkenyl or aryl, and Hal is a halogen.
2. A light-sensitive material as claimed in Claim 1, wherein R and R' are an alkyl or alkenyl comprising from about 1 to 4 carbon atoms or a substi-tuted phenyl, and Hal is chlorine or bromine.
3. A light-sensitive material as claimed in Claim 1, wherein said phosphonium compound is tetra-methylphosphonium chloride.
4. A light-sensitive material as claimed in Claim 1, wherein said phosphonium compound is tetrabut-ylphosphonium bromide.
5. A light-sensitive material as claimed in Claim 1, wherein said phosphonium compound is tetraphen-ylphosphonium bromide.
6 A light-sensitive material as claimed in Claim 1, wherein said light-sensitive layer comprises from about 1 to 50 percent by weight of said quaternary phosphonium compound, relative to the non-volatile layer constituents.
7. A light-sensitive material as claimed in Claim 1, further comprising a binder which is insoluble in water and soluble in aqueous-alkaline solutions.
8. A light-sensitive material as claimed in Claim 7, wherein said binder comprises a novolak.
9. A light-sensitive material as claimed in Claim 1, wherein said 1,2-quinone diazide comprises an ester of a 1,2-quinone-diazide-4-sulfonic acid.
10. A light-sensitive material as claimed in Claim 1, wherein said 1,2-quinone diazide comprises an amide of a 1,2-quinone-diazide-4-sulfonic acid.
11. A light-sensitive material as claimed in Claim 1, wherein said 1,2-quinone diazide comprises an ester of a 1,2-quinone-diazide-4-carboxylic acid.
12. A light-sensitive material as claimed in Claim 1, wherein said 1,2-quinone diazide comprises an amide of a 1,2-quinone-diazide-4-carboxylic acid.
13. A light-sensitive material as claimed in Claim 1, wherein said light-sensitive layer comprises from about 3 to 50 percent by weight of said 1,2-quinone diazide compound relative to the non-volatile constituents.
14. A process for producing negative relief copies, comprising the steps of:
(a) imagewise exposing to light, through an original, a light-sensitive material comprising a sup-port and a light-sensitive layer which comprises in ad-mixture (i) a compound comprising at least one quaternary phosphonium compound of the general formula [(R)3-P-R']?Hal?
wherein:
R and R' can be identical or different and are an alkyl, alkenyl or aryl and Hal is a halogen, said compound being present in an amount sufficient to promote thermal curing, and (ii) at least one 1,2-quinone diazide present in an amount sufficient to impart light-sensitivity to said layer;
(b) thereafter heating said material such that imagewise exposed portions of said material are ren-dered insoluble in alkaline developer;
(c) then, after cooling, exposing said material again to light without said original; and there-after (d) developing said material with an aqueous-alkaline developer to remove from said substrate portions of said layer not imagewise exposed in step (a).
(a) imagewise exposing to light, through an original, a light-sensitive material comprising a sup-port and a light-sensitive layer which comprises in ad-mixture (i) a compound comprising at least one quaternary phosphonium compound of the general formula [(R)3-P-R']?Hal?
wherein:
R and R' can be identical or different and are an alkyl, alkenyl or aryl and Hal is a halogen, said compound being present in an amount sufficient to promote thermal curing, and (ii) at least one 1,2-quinone diazide present in an amount sufficient to impart light-sensitivity to said layer;
(b) thereafter heating said material such that imagewise exposed portions of said material are ren-dered insoluble in alkaline developer;
(c) then, after cooling, exposing said material again to light without said original; and there-after (d) developing said material with an aqueous-alkaline developer to remove from said substrate portions of said layer not imagewise exposed in step (a).
15. A process as claimed in Claim 14, wherein the temperature of said heating step is in the range from about 70 to 150°C.
16. A process as claimed in Claim 14, wherein the length of said heating step is in the range from about 10 seconds to 10 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3437687.9 | 1984-10-15 | ||
| DE3437687A DE3437687A1 (en) | 1984-10-15 | 1984-10-15 | METHOD FOR PRODUCING NEGATIVE COPIES BY MEANS OF A MATERIAL BASED ON 1,2-CHINONDIAZIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1298510C true CA1298510C (en) | 1992-04-07 |
Family
ID=6247891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000492839A Expired - Fee Related CA1298510C (en) | 1984-10-15 | 1985-10-11 | Light-sensitive material and a process for producing negative copies utilizing the material |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0178594B1 (en) |
| JP (1) | JPS6197647A (en) |
| AT (1) | ATE64662T1 (en) |
| BR (1) | BR8505087A (en) |
| CA (1) | CA1298510C (en) |
| DE (2) | DE3437687A1 (en) |
| ZA (1) | ZA857887B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE47631T1 (en) * | 1985-03-11 | 1989-11-15 | Hoechst Celanese Corp | PROCESS FOR MAKING PHOTORESIST STRUCTURES. |
| JPS61241745A (en) * | 1985-04-18 | 1986-10-28 | Oki Electric Ind Co Ltd | Negative type photoresist composition and formation of resist pattern |
| ATE42419T1 (en) * | 1985-08-12 | 1989-05-15 | Hoechst Celanese Corp | METHOD OF MAKING NEGATIVE IMAGES FROM POSITIVE-WORKING PHOTORESIST. |
| DE3664824D1 (en) * | 1985-10-25 | 1989-09-07 | Hoechst Celanese Corp | Process for producing a positive photoresist |
| DE3674141D1 (en) * | 1985-10-28 | 1990-10-18 | Hoechst Celanese Corp | RADIATION-SENSITIVE, POSITIVE WORKING MIXTURE AND PHOTORESIST MATERIAL MADE THEREOF. |
| NL8601096A (en) * | 1986-04-29 | 1987-11-16 | Philips Nv | METHOD FOR MANUFACTURING A SEMICONDUCTOR DEVICE INSERTING A NEGATIVE IMAGE ON A SEMICONDUCTOR SUBSTRATE IN A POSITIVE PHOTO LACQUER. |
| US4873176A (en) * | 1987-08-28 | 1989-10-10 | Shipley Company Inc. | Reticulation resistant photoresist coating |
| JPH03142918A (en) * | 1989-10-30 | 1991-06-18 | Matsushita Electron Corp | Formation of resist pattern |
| DE3940911A1 (en) * | 1989-12-12 | 1991-06-13 | Hoechst Ag | PROCESS FOR PRODUCING NEGATIVE COPIES |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1169682B (en) * | 1983-11-08 | 1987-06-03 | I M G Ind Materiali Grafici Sp | COMPOSITION FOR PHOTOS REPRODUCTIONS |
-
1984
- 1984-10-15 DE DE3437687A patent/DE3437687A1/en not_active Withdrawn
-
1985
- 1985-10-11 AT AT85112875T patent/ATE64662T1/en not_active IP Right Cessation
- 1985-10-11 DE DE8585112875T patent/DE3583277D1/en not_active Expired - Fee Related
- 1985-10-11 CA CA000492839A patent/CA1298510C/en not_active Expired - Fee Related
- 1985-10-11 EP EP85112875A patent/EP0178594B1/en not_active Expired - Lifetime
- 1985-10-14 BR BR8505087A patent/BR8505087A/en not_active IP Right Cessation
- 1985-10-15 JP JP60227970A patent/JPS6197647A/en active Pending
- 1985-10-15 ZA ZA857887A patent/ZA857887B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0178594A2 (en) | 1986-04-23 |
| EP0178594A3 (en) | 1988-03-23 |
| ZA857887B (en) | 1986-05-28 |
| JPS6197647A (en) | 1986-05-16 |
| DE3583277D1 (en) | 1991-07-25 |
| EP0178594B1 (en) | 1991-06-19 |
| DE3437687A1 (en) | 1986-04-17 |
| BR8505087A (en) | 1986-07-29 |
| ATE64662T1 (en) | 1991-07-15 |
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| MKLA | Lapsed |