CA1254787A - Light-sensitive mixture, light-sensitive copying material prepared therefrom, and a process for the preparation of a printing form from the copying material - Google Patents
Light-sensitive mixture, light-sensitive copying material prepared therefrom, and a process for the preparation of a printing form from the copying materialInfo
- Publication number
- CA1254787A CA1254787A CA000442945A CA442945A CA1254787A CA 1254787 A CA1254787 A CA 1254787A CA 000442945 A CA000442945 A CA 000442945A CA 442945 A CA442945 A CA 442945A CA 1254787 A CA1254787 A CA 1254787A
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- CA
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- Prior art keywords
- light
- sensitive
- mixture
- weight
- percent
- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
Abstract
ABSTRACT OF THE DISCLOSURE
Described is a light-sensitive mixture, the solubility of which in an aqueous-alkaline solution changes upon exposure to actinic radiation, containing at least one light-sensitive compound and a binder material comprising a halogenated polyvinyl phenol which is insoluble in water, but soluble in aqueous-alkaline solutions. The mixture is preferably used for the Preparation of lithographic printing plates and leaves virtually no oleophilic remainders on the image-free areas of the support surface when the developed lithographic printing form is heated to temperatures above 200°C.
Described is a light-sensitive mixture, the solubility of which in an aqueous-alkaline solution changes upon exposure to actinic radiation, containing at least one light-sensitive compound and a binder material comprising a halogenated polyvinyl phenol which is insoluble in water, but soluble in aqueous-alkaline solutions. The mixture is preferably used for the Preparation of lithographic printing plates and leaves virtually no oleophilic remainders on the image-free areas of the support surface when the developed lithographic printing form is heated to temperatures above 200°C.
Description
7~7 A LIGHrr'~SENSITIVE MIXl'URE, LIt~HT-SEN,SIl'I~TE COl?YING
MATERIATJ PREPARED THEREFROM, AND A PROCES~S FOR THE
PREP~RA'rION OF A PRI~TI~ FORM FROM THE
COPYI~G l`lA:~E~IAL
~ACRGROUND OF THE INVEMTION
The invention relates to a light-sensitive mixture containing a water-insoluble bin~er, which is solu~le in a~ueous-alkaline solutions, an~ a liqht-sensitive comPound, to a liq'nt-sensitive coPving material co~ose~ of a laYer support an~ a lig~t-., ' ~
?
~5~78~
sensiti~e laver consti~ute~ bv the mixture, and to a orocess ~r the ~re~aration o a ~rintin~ Eorm ',~v exPOSinq, ~evelonin~, an~ heatinq the co~Yinq material.
Processes ~or ~he ~re~aration o~ nrin-ting forms hv heatin~ or baking of the image laver o-E
exPosed an~ developed copYinq materials have heen disclosed, for example, bv Britis'n Patent Specifications ~o. 1,1~ and No. 1,1~4,744. In these processes, a light-sensitive copvin~ material which is either positive-~orkinq (anA ~re~era~lY con-tains an o-quinone-~iazi(1e), or is ne~ative-workinq (and pre~erably contains a ~-quinone-diazide), is ex~osed in an imagewise fashion, developed, and then ~neated to a temPeratUre above 1~0C for such a ~eriod and to such a temperature level t~at the imaqe backqroun~, previouslY develoPed cleanlY, is stainetl ~y thermal Aecom~ositioll ~roducts o~ t~ image laver.
~uhsequentlY, the ima~e background is cleane~ again by once more treatin~ it with develo~er solution.
~ormall~, tem~eratures o~ ~20 - ~4noc are used for heatinq, and the duratlon o~ heatinq is a~out ; - 60 minutes. This post-treatment achieves a hardeninq of the printin~ laver and, hence, a consi~erable exten-sion o~ the print run. When the baking tem~eraturesare at the u~per limit of the indicated range, the required hakint~ times are, o~ course, relativelY
short. It has heen ound that the use o~ relatively hiqh temperatures in this Drocess is disatl~7anta~eous.
30 on t~e one hand, these temperatures cause the ~2~ 787 formatiQll of a relatively firmlv adherinq preciPitate in the background areas, and this can ~e cleanlv removed only ~v means of quite stronq solu~ions, and there is also a risk o~ an attack on the printing stencil. Moreover r at the relatively hiqh bakinq tem~eratures or with khe relativelY long ~aking times, there is a risk o the conventionallY used supPorts o~
aluminum beinq deforme~ an~, thus, of the printing form obtained being damaged or rendere~ useless.
As described in German Offenlequngsschrift ~,h2~,473l the irst-~entione~ ~isadvantaqe can be avoi~ed bv coatin~ the hackqround sur'ace he~ore bakinq with a laver of a water-solu~le orqanic substance or an inorganic salt, which layer can ~e readily washed oE~ ater bakinq. To prevent a ~1e'ormation of the sup~ort, it would be desira~le, however, to he able to 'oake at lower temperatures.
~urthermore, it would also be desira~le to be able to avoid the additional ~rocess ste~ o' che in~ermediate treatment with an aqueous solution.
German O~fenlegungsschrift ~o. 3,107,109 discloses a light-sensitive mixture ~or the prepara-tion of lit-nographic printin~ plates, wherein a halo-genated novolak is contained as hinder. The material has an im~roved resistance to a~ueous-alkaline develo~er solutions, to hv~rocarhon solvents~ and to alcohol-containin~ ountain solutions. ~e ~ehavior ~uring baking o~ the develo~e~ Printinq stencils prePare~l in accordance with this pu~lication is not chanqe~ hY the a~dition o~ these novolaks.
_ 4 ~ ~2~7~7 In German OF~enlequnqsschri~t l~o. ~,3~2,2~0, liqht-sensitive litho~raphic Printing ~lates are described which contain polvvin~l ~henols as ~inders, instead o~ novolaks~ The prin-tinq Eor~s prepared therewith are said to be ~istinquishe~ 'oy oarticularlv high print runs. Nothinq is stated concerning the behavior o~ t~ese printing forms after ba'~in~.
SUM~A~Y ~F ~rHE IN~ NlrIoN
It is therefore an ob~ect Oe the present invention to ~rovide an im~roved light-sensitive mix-ture and a copying material ~reoared there~rom. It is also an obiect o~ -the invention to provide such a co~ying material which is sllitable ~or the oroduction o~ lithoqraphic printin~ forms an~ which, a~ter expo-sure and fleve~o~ment, can he bake~ under conditionssuch that no difficult-to-remove bakin~ remainders are le~t on the non-i~age areas oE t~e layer support.
Anot'ner ob;ect of the invention resides in Providinq a copYing material with whic'n an intermeaiate treatment ste~ compeising the apPlication oE a water-soluhle protective laver can he omitted. Still another obiect of the invention is to provi~e a process ~or preparing a printinq ~orm.
In accomplishinq the foreqoinq ohjects, there has been provide~, in accordance with one aspect o~ the ~resent invention/ a liqht-sensiti~e ~ixture which comPrises ~1) a li~ht-sensitive composition comPrisinq at least one liqht-sensitive compoun~ or a li~ht-sensitive ~ombination o~ com~ounds and (2) ~inder material comorising a halogenated polvvinyl ~2~
phenol comPoun~ which is insoluhle in water ~ut solu~le in aqueous-alkaline solutions, the solubilitY
oF sai~ mixture in an aqueous-alkaline solution l~eing caPable of cban~inq upon exPoSure to actinic radiation.
In Eurther accom~lishinq the ~oreqoing o~jects, there has also heen ~rovit~e~ a liqht-sensitive conYinq material comprise~ of a laver sup2ort an~ a li~ht-sensitive layer which is constitu,.e-~ ~y the above-define-1 mixture.
In accor~ance with t~e invention, there is further ~rovi~e~ a process ~nr the ~renaration o~ a printing form com~rising t'ne stePS o~ (a) ~re~aring a liq'~t-sensitive copvinq material comPrisin~ a la~er suP~ort an~ a light-sensitive laver, the soluhilitv o~
which in an aaueous-alkaline solution is caPable of changinq u~on irra-~iation, said liqht-sensitive layer com~rising (i) a lig~t-sensitive composition which comprises at least ~ne light-sensitive com~oun~ or a li~ht-sensitive comhination oE co~ounds and (ii) binder material comprising a halogenate~ Polvvin~l phenol ~om~ound which is insoluble in water but soluble in aqueous-alkaline solutions; (b) imagewise exposin~
said light-sensitive laYer to actinic radiation; (c) thereafter washing away the non-i~age areas of said light-sensitive layer with an aqueous-alkaline developer solution; an~ ~d) then heating said material suEEicientlv to harden the remaining image areas of said light-sensitive layer.
3n Other objects, features, and advantages of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and ~5~178~
s~eciic examples, ~hile indicatinq pre~errea embodi-~ents of the invention, are qiven hy waY of illustra-tion onl~,7~ since various changes and modifications within ~he spirit and scope of the invention will become aPParent to t'nose skille~ in the art ~rom this detaile~ descrip-tion.
i ~ETAILEn DE~CRIPTION OF PR~FERRED EM~ODIMENT~
._ _ __ _ __ __ _ __ _ _ _~_ _ _ _ _ __ _ __ _ The process of t'~le invention is charac-terized in that the ~olvvinyl phenol emploved as a 'ninder material is halo~enated.
The halo~enated vinvl phenol polYmers emPloved are pre~erahlY chlorinated or bro-minated, in particular brominated, polYmers. Apart from haloqenate~ homo~olYmerst co~olvmers o~ 'nalogenate~
~invl o'~enols and other vinvl compounds, such as, for example, styrene or arvlic acid esters, can also be used. In general, the polYmers o~ p-vinYl phenol are preferred. The halogen content of the halogenated polYvin~l phenols usually varies between 20 an~ nn~ bv 1 20 weight, ~re~erably between ~0 and ~8~ by weiqht.
The brominated pol~-p-vinvl phenol is prepared in a known manner by hrominatinq the corresponaing p-vinvl phenol polYmer~ ~he polYvinvl phenols themselves can be pre~ared bv a mass polymerization, emulsion ~olymerization, or solution polymerization of the corresponding monomers in the ^
~ ~ 7 ~ 20731-844 ~25~7~7 presence of a cationic catalyst. They can, however, also be obtained by means of a free-radical polymerization in the presence of suitable catalysts, such as azodiisobutyric acid nitrile.
Polymerization processes of this kind are described in "Journal of Polymer Science," part A-l, volume 7 (196g), pages 2,175 to 2,184 and 2,405 to 2,410, and in "Journal of Organic Chemistry," volume 24 (1959), pages 1,345 to 1,347.
The concentration of the halogenated polyvinyl phenols in the light-sensitive mixture can vary widely, depending on the nature of the light-sensitive system. In general, their proportion is between 10 and 95% by weight, preferably between 40 and 80~ by weight, relative to the weight of the non-volatile constituents of the light-sensitive mixture.
; Futhermore, the light-sensitive mixtures according to the invention contain a light-sensitive compound or a light-sensitive combination of compounds. Above all, positive-working compounds, that is to say, compounds which are rendered soluble by exposure, are suitable for this purpose. These include o-quinone-diazides andcombinations of photolyticacid donors and compounds which can be split by acid, such as orthocarboxylic acid compounds and acetal compounds. p-Quinone-diazides and diazonium salt polycondensation products are also suitable as light-sensitive compounds.
- R - ~ ~ 5 ~787 The mixture an~ Process accordin~ to the invention have particular advantages le thev are used in combination with liqht-sensitive materials basefl on o-quinone-~iazides, since, employin~ these, the num~er oE Prints ohtained can be particularly considerablY
increasea b~ hakinq. ~uitahle materials o~ this ty~e are '~nown an~ describe~, ~or example in German Patent ~o. 4~8,233, and in German ~Ffenlegun~sschriften No.
~,~31,377, No. ?,~47,90~, and No. ~,8~8,037. The pre~erred o-quinone-~ia~i~es are na~hthoquinone-(1,~)-dia~iae(~)-4- or -~-sulfonic acid esters or amides.
Amongst these, the esters, es~eciallv those o~ the 5-sul~onic acid, are ~articularlv Preferred. In general, the quantitv of o-quinone-~ia2ide com~oun~s is ~ to ~0~ by weight, pre~erahly 7 to 3~% bv weight, relati~Te to the non-volatile constituents o~ t'ne mixture.
Materials based on compounds w~ich can be sPlit hv acid can also he baked with qood e~fect and used in the process accordin~ to the invention.
Co~ying materials of this tYpe are known and are ~escribed, ~or example, in U.S. Patent No.
; ~,779,778 and No. 4,101,32~, in German Patent No.
MATERIATJ PREPARED THEREFROM, AND A PROCES~S FOR THE
PREP~RA'rION OF A PRI~TI~ FORM FROM THE
COPYI~G l`lA:~E~IAL
~ACRGROUND OF THE INVEMTION
The invention relates to a light-sensitive mixture containing a water-insoluble bin~er, which is solu~le in a~ueous-alkaline solutions, an~ a liqht-sensitive comPound, to a liq'nt-sensitive coPving material co~ose~ of a laYer support an~ a lig~t-., ' ~
?
~5~78~
sensiti~e laver consti~ute~ bv the mixture, and to a orocess ~r the ~re~aration o a ~rintin~ Eorm ',~v exPOSinq, ~evelonin~, an~ heatinq the co~Yinq material.
Processes ~or ~he ~re~aration o~ nrin-ting forms hv heatin~ or baking of the image laver o-E
exPosed an~ developed copYinq materials have heen disclosed, for example, bv Britis'n Patent Specifications ~o. 1,1~ and No. 1,1~4,744. In these processes, a light-sensitive copvin~ material which is either positive-~orkinq (anA ~re~era~lY con-tains an o-quinone-~iazi(1e), or is ne~ative-workinq (and pre~erably contains a ~-quinone-diazide), is ex~osed in an imagewise fashion, developed, and then ~neated to a temPeratUre above 1~0C for such a ~eriod and to such a temperature level t~at the imaqe backqroun~, previouslY develoPed cleanlY, is stainetl ~y thermal Aecom~ositioll ~roducts o~ t~ image laver.
~uhsequentlY, the ima~e background is cleane~ again by once more treatin~ it with develo~er solution.
~ormall~, tem~eratures o~ ~20 - ~4noc are used for heatinq, and the duratlon o~ heatinq is a~out ; - 60 minutes. This post-treatment achieves a hardeninq of the printin~ laver and, hence, a consi~erable exten-sion o~ the print run. When the baking tem~eraturesare at the u~per limit of the indicated range, the required hakint~ times are, o~ course, relativelY
short. It has heen ound that the use o~ relatively hiqh temperatures in this Drocess is disatl~7anta~eous.
30 on t~e one hand, these temperatures cause the ~2~ 787 formatiQll of a relatively firmlv adherinq preciPitate in the background areas, and this can ~e cleanlv removed only ~v means of quite stronq solu~ions, and there is also a risk o~ an attack on the printing stencil. Moreover r at the relatively hiqh bakinq tem~eratures or with khe relativelY long ~aking times, there is a risk o the conventionallY used supPorts o~
aluminum beinq deforme~ an~, thus, of the printing form obtained being damaged or rendere~ useless.
As described in German Offenlequngsschrift ~,h2~,473l the irst-~entione~ ~isadvantaqe can be avoi~ed bv coatin~ the hackqround sur'ace he~ore bakinq with a laver of a water-solu~le orqanic substance or an inorganic salt, which layer can ~e readily washed oE~ ater bakinq. To prevent a ~1e'ormation of the sup~ort, it would be desira~le, however, to he able to 'oake at lower temperatures.
~urthermore, it would also be desira~le to be able to avoid the additional ~rocess ste~ o' che in~ermediate treatment with an aqueous solution.
German O~fenlegungsschrift ~o. 3,107,109 discloses a light-sensitive mixture ~or the prepara-tion of lit-nographic printin~ plates, wherein a halo-genated novolak is contained as hinder. The material has an im~roved resistance to a~ueous-alkaline develo~er solutions, to hv~rocarhon solvents~ and to alcohol-containin~ ountain solutions. ~e ~ehavior ~uring baking o~ the develo~e~ Printinq stencils prePare~l in accordance with this pu~lication is not chanqe~ hY the a~dition o~ these novolaks.
_ 4 ~ ~2~7~7 In German OF~enlequnqsschri~t l~o. ~,3~2,2~0, liqht-sensitive litho~raphic Printing ~lates are described which contain polvvin~l ~henols as ~inders, instead o~ novolaks~ The prin-tinq Eor~s prepared therewith are said to be ~istinquishe~ 'oy oarticularlv high print runs. Nothinq is stated concerning the behavior o~ t~ese printing forms after ba'~in~.
SUM~A~Y ~F ~rHE IN~ NlrIoN
It is therefore an ob~ect Oe the present invention to ~rovide an im~roved light-sensitive mix-ture and a copying material ~reoared there~rom. It is also an obiect o~ -the invention to provide such a co~ying material which is sllitable ~or the oroduction o~ lithoqraphic printin~ forms an~ which, a~ter expo-sure and fleve~o~ment, can he bake~ under conditionssuch that no difficult-to-remove bakin~ remainders are le~t on the non-i~age areas oE t~e layer support.
Anot'ner ob;ect of the invention resides in Providinq a copYing material with whic'n an intermeaiate treatment ste~ compeising the apPlication oE a water-soluhle protective laver can he omitted. Still another obiect of the invention is to provi~e a process ~or preparing a printinq ~orm.
In accomplishinq the foreqoinq ohjects, there has been provide~, in accordance with one aspect o~ the ~resent invention/ a liqht-sensiti~e ~ixture which comPrises ~1) a li~ht-sensitive composition comPrisinq at least one liqht-sensitive compoun~ or a li~ht-sensitive ~ombination o~ com~ounds and (2) ~inder material comorising a halogenated polvvinyl ~2~
phenol comPoun~ which is insoluhle in water ~ut solu~le in aqueous-alkaline solutions, the solubilitY
oF sai~ mixture in an aqueous-alkaline solution l~eing caPable of cban~inq upon exPoSure to actinic radiation.
In Eurther accom~lishinq the ~oreqoing o~jects, there has also heen ~rovit~e~ a liqht-sensitive conYinq material comprise~ of a laver sup2ort an~ a li~ht-sensitive layer which is constitu,.e-~ ~y the above-define-1 mixture.
In accor~ance with t~e invention, there is further ~rovi~e~ a process ~nr the ~renaration o~ a printing form com~rising t'ne stePS o~ (a) ~re~aring a liq'~t-sensitive copvinq material comPrisin~ a la~er suP~ort an~ a light-sensitive laver, the soluhilitv o~
which in an aaueous-alkaline solution is caPable of changinq u~on irra-~iation, said liqht-sensitive layer com~rising (i) a lig~t-sensitive composition which comprises at least ~ne light-sensitive com~oun~ or a li~ht-sensitive comhination oE co~ounds and (ii) binder material comprising a halogenate~ Polvvin~l phenol ~om~ound which is insoluble in water but soluble in aqueous-alkaline solutions; (b) imagewise exposin~
said light-sensitive laYer to actinic radiation; (c) thereafter washing away the non-i~age areas of said light-sensitive layer with an aqueous-alkaline developer solution; an~ ~d) then heating said material suEEicientlv to harden the remaining image areas of said light-sensitive layer.
3n Other objects, features, and advantages of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and ~5~178~
s~eciic examples, ~hile indicatinq pre~errea embodi-~ents of the invention, are qiven hy waY of illustra-tion onl~,7~ since various changes and modifications within ~he spirit and scope of the invention will become aPParent to t'nose skille~ in the art ~rom this detaile~ descrip-tion.
i ~ETAILEn DE~CRIPTION OF PR~FERRED EM~ODIMENT~
._ _ __ _ __ __ _ __ _ _ _~_ _ _ _ _ __ _ __ _ The process of t'~le invention is charac-terized in that the ~olvvinyl phenol emploved as a 'ninder material is halo~enated.
The halo~enated vinvl phenol polYmers emPloved are pre~erahlY chlorinated or bro-minated, in particular brominated, polYmers. Apart from haloqenate~ homo~olYmerst co~olvmers o~ 'nalogenate~
~invl o'~enols and other vinvl compounds, such as, for example, styrene or arvlic acid esters, can also be used. In general, the polYmers o~ p-vinYl phenol are preferred. The halogen content of the halogenated polYvin~l phenols usually varies between 20 an~ nn~ bv 1 20 weight, ~re~erably between ~0 and ~8~ by weiqht.
The brominated pol~-p-vinvl phenol is prepared in a known manner by hrominatinq the corresponaing p-vinvl phenol polYmer~ ~he polYvinvl phenols themselves can be pre~ared bv a mass polymerization, emulsion ~olymerization, or solution polymerization of the corresponding monomers in the ^
~ ~ 7 ~ 20731-844 ~25~7~7 presence of a cationic catalyst. They can, however, also be obtained by means of a free-radical polymerization in the presence of suitable catalysts, such as azodiisobutyric acid nitrile.
Polymerization processes of this kind are described in "Journal of Polymer Science," part A-l, volume 7 (196g), pages 2,175 to 2,184 and 2,405 to 2,410, and in "Journal of Organic Chemistry," volume 24 (1959), pages 1,345 to 1,347.
The concentration of the halogenated polyvinyl phenols in the light-sensitive mixture can vary widely, depending on the nature of the light-sensitive system. In general, their proportion is between 10 and 95% by weight, preferably between 40 and 80~ by weight, relative to the weight of the non-volatile constituents of the light-sensitive mixture.
; Futhermore, the light-sensitive mixtures according to the invention contain a light-sensitive compound or a light-sensitive combination of compounds. Above all, positive-working compounds, that is to say, compounds which are rendered soluble by exposure, are suitable for this purpose. These include o-quinone-diazides andcombinations of photolyticacid donors and compounds which can be split by acid, such as orthocarboxylic acid compounds and acetal compounds. p-Quinone-diazides and diazonium salt polycondensation products are also suitable as light-sensitive compounds.
- R - ~ ~ 5 ~787 The mixture an~ Process accordin~ to the invention have particular advantages le thev are used in combination with liqht-sensitive materials basefl on o-quinone-~iazides, since, employin~ these, the num~er oE Prints ohtained can be particularly considerablY
increasea b~ hakinq. ~uitahle materials o~ this ty~e are '~nown an~ describe~, ~or example in German Patent ~o. 4~8,233, and in German ~Ffenlegun~sschriften No.
~,~31,377, No. ?,~47,90~, and No. ~,8~8,037. The pre~erred o-quinone-~ia~i~es are na~hthoquinone-(1,~)-dia~iae(~)-4- or -~-sulfonic acid esters or amides.
Amongst these, the esters, es~eciallv those o~ the 5-sul~onic acid, are ~articularlv Preferred. In general, the quantitv of o-quinone-~ia2ide com~oun~s is ~ to ~0~ by weight, pre~erahly 7 to 3~% bv weight, relati~Te to the non-volatile constituents o~ t'ne mixture.
Materials based on compounds w~ich can be sPlit hv acid can also he baked with qood e~fect and used in the process accordin~ to the invention.
Co~ying materials of this tYpe are known and are ~escribed, ~or example, in U.S. Patent No.
; ~,779,778 and No. 4,101,32~, in German Patent No.
2,718,~4, and in German Of~enlequng~sschri~ten No.
~,8~,S12 and No. ~ 9,~11. As the compounds which can he s~lit hy acid, the a~orementioned cooyin~
materials contain ort'nocar~oxylic acid ~erivatives, monomeric or pol~meric acetals, enol ethers, or acvli-minocar~onates. As the compounds which are sensitive to radiation an~ eliminate acid, the copvin~ materials predominantlv contain orqanic halo~en compounds, in particular s-triazines or ~-trichloromethvl~ ,4-oxadiazoles which are su~stituted by haloqenomethvl grou~s. ~
. .
~lZ5~7~7 ~mong the orthocar~oxvlic aci~ derivatives aescribe~ in IJ.S. Patent Mo. ~,lnl,323, the ~is-1,3-dioxan-2-yl ethers oE aliphatic ~iols are Particularly use~l.
Among tlle polYacetals ~escribed in German Patent No. 2,718,~54, those with alipnatic al~ehvde units and liol units are preEerre~.
Further, verv suita~le mixtures are described in ~,erman Of~enlequngsschrift No. 2,928,63~.
In the latter, Poly~eric ortho-esters with recurrent ortho-ester qrou~s in the main chain are described as com~ounds which can be split by acid.
These qrou~s are 2-alk~l ethers o~
1,3-dioxa-cYcloalkanes havin~ ~ or ~ rin~ members.
Polymers with recurrent l,~-dioxa-cYclohex-~-vl alkyl ether unitsl in which the alkYl ether group can ~e interruPted bY ether oxY~en atoms and is prefera~lY
honded to the 5-position of t~e adiacent rinq, are articularlY preferred.
The quantitative Pro~ortion o~ the compounds wnich can ~e sPlit bv acid in tne liq~t-sensitive ~ixture is in general between ~ and 65~ bv weiqht, Preferahly between 14 and 44~ hv weight, r~lative to the non-volatile constituents of the mixture. The quantitv of the compound which eliminates acid is ~etween n.l and 10~ hv weiqht, preferably hetween 0.2 and ~% hv weight.
Along with the haloqenated polyvinvl ~henols, numerous otner resins can he empl~ved in the light-sensitive mixtures o~ the invention, vinvl polY-mers, such as polYvinyl acetates, Polyacrvlates~
~s~
polYvinvl ethers, ~01~l~7inYl acetals, PolYvinvl pYrroli~ones an~ coPolYmers o~ the monomers on which these are based ~einq pre~erred. Further suitable binders ~hich are soluble or swella~le in alkaline solutions are natural resins, such as shellac an~
colo~honY an~ sYnthetic resins, such as copolYmers o~
stvrene and maleic acid anhyaride,- anA, in partlcular, novolaks. ~he most advantageolls ~roportion of these resins ~epends on the technological requirements and on the in~luence on the ~evelopment con~itions an~, in general, this is not more than ~0% bv weight of the haloqenated Polvvinvl Phenol. To meet special re~uire~ents, such as flexibilitv, a~hesion, qloss, coloration, color change, and the like, the liqht-sensitive svstem can aflditionallv also contain substances, such as ~olyglvcols, cellulose deriva-ti~7es, such as ethyl cellulose, sur~actants, dyes, adhesion ~romotors and inelv divided pigments, and also IrV-absorhers, i~ required.
; 20 For coa~ing a suitable support, the mixtures are in general dissolved in a solvent. The selection of the solvents must be matcned to the envisaged coatin~ Process~ the laver thickness anA the ~rYing conAitions. Suitable solvents for the mix-ture accordinq to the invention are ketones, such as methYl ethYl ketone, chlorinated hy~rocarbons, such as trichloroethvlene and l,l,l-trichloroethane, alcohols, such as n-Pro~anolr ethers such as tetrahv~rofuran, alcohol-ethers, such as ethylene glycol monoethvl ether, and ester~s, such as hutvl acetate. ~t is also 2~L78~
~ossi'ole to use mixtures which, for sPecial pur~oses, can contain additional solvents, such a~s acetonitrile, ~i~xane, or ~imethvlformamide. In ~rinciPle, all those solvents can he used which ~o not irreversihly react with the laver comPonents.
~ he supports used for laver thicknesses o~
less than about 1~ ~m are in most cases metals. The following mav be used for offset prinkinq Plates:
brignt-rolled, mechanicallv or electrochemicallY
roughene~ aluminum whic~ esired, i~s anodicallY
oxidize~ and which additionally can also have been chemicallY pretreated, for e~ample, with Polyvi-nylphospnonic aci~, silicates, 'nexafluoro~irconates, hydrolysed tetraethYl orthosilicate, or phos~hates.
Coatinq of t'ne support material is carried out in a known manner ~v spin-coating, sQraving, flipping, on rollers, by means of slot ~ies or blade-sPreadin~, or bv means Oc coater a~plication.
T.iqht sources customarv in in~ustrv are use for exposure. Irradiation witn electrons or a laser is another Possibility for Pro~ucinq an imaqe.
The aqueous-alkaline solutions whic~ are used or ~evelopinq have qraduate~ alkalinitv, that is, theY have a P'tl whic~ preferably is between ln and 14, an~ thev also can contain minor amounts o~ organic solvents or surfactants, remove t'nose areas o~ the coPyinq laver which have been struck ~v li~ht, an~
thus produce a positive imaqe of the oriqinal.
Ne~ative lavers can he ~evelo~ed bv means o~ similar developerS.
- 12 - ~25~
The preferred use oE the light-sensitive mixtures accordin~ to the invention is in the prePara-tin o~ Printing ~orms, in Particular, o~set ~rintin~
~orms, usinq aluminum as the suoport.
~fter development, the ~rintinq orm is heated in a manner known ~er se. The hakinq tem-Peratures selected can be in the ran~e ~rom about 180 to 240-', prefera'olv ~rom ~OQ to ?40C, and heating periods o 1 - 20, ~re~erably ~ to 10, minutes being normally re~uired. If the supPort material is stable at higher temperatures it is o~ course also possi'~le ~o bake at hi~her ~emperatures above ~4noc and to select corres~onainql~7 shorter heatinq ~eriods.
~he mi~ture o~ this invention and the liqht-sensitive co~yinq material pre~ared t~erqfrom are distinq~lished by the fact that a~ter haking prac-tically no remainders due to baking are le~t on the image-free areas o~ the support. It is therefore no longer necessarv to apply an additional water-soluhle protective laver before hakin~, or to remove the remainders subsequently bv treatment with ~eveloper.
Neit~er ~y means of the known haloqenated novolaks nor by means o~ the known non-haloqenated novolaks is this advantaqe achieved. As compared with non-halogenated polyvinvl Phenol binders, another advantage ~resented by the use o~ haloqenated ~olYvinyl phenols as binders resides in the ~arkedlv improved re~istance of the non-baked ~rinting stencil to auxiliaries used in ~rintinq, such as, ~or exa~ple, certain hyflrocarbon solvents or alcohol-containing ~25~7~
fountain solutions, which are commonlv emploved durinq co~vinq or in the ~rinting press.
The invention is explained in greater detail bv reference to the examples which follow, wherein parts by weiqht (~.b.w.l and parts by ~olume (P.b.v.) have the same relationship as the g to the cm3.
Jnless otherwise stated, -oercentages are precent bv weiqht.
ExamPle 1 An electrochemicallY roughened and anodicallY oxidized aluminum ~late was coated with a solution of 1.~ p.b.w. of the esteri~ication product obtained from 1 mole of 2,3,4-trihydroxv-kenzo-phenone and ~ moles of napht~oquinone-(1,2~-diazide-(2)-~-sulfonic aci~
chloride, h p.b.w. of brominated ~olY-p-vinvl phenol 'naving a melting range of 190 - 220C, a bromine content o~ about ~n~, and an average molecular weiqht oE ~,ono, 0.1~ p,b.w. o~ ~-(4-ethoxv-naphth-1-yl~ 4,fi-bis-trichloro,nethyl-~-triaæine, and - 14 - ~2~7~
n.n7 ~.h.~. o~ crvstal violet, in .
~.b.w. o~ etnvlene ~1YCO1 monometh~l ether and ~0 p.~.w. of tetrahYdrofuran.
~efore application o~ the light-sensitive co~ving layer, the anodicallv oxidized support ~ad been treated with an aqueous solution o~ 0.1~ by weight strenqth Polyvinylphosphonic acid.
The presensitiæed material thus prepared, which had a laver weight o~ %. n q/m~, was exPosed in an imagewise fashion under a crans~arent positive ori-ginal and subsequently develo~ed with an 0.~% strengt~
aqueous solution o~ sodium meta~silicate x 9 H~O.
The areas of the copYinq laYer which had been struck bv liqht were removed bY the development, lS an~ the unexposed image areas remained on the support, ~roducin~ a ~rintin~ stencil corresponding to the original beinq o~tained.
~ n an offset Printin~ ~ress, it was possible to ohtain 100 ,no~ perfect print~ Fro,n tne Printing form thus prepared.
In order to extend the print run and to harden the printing stencil, the Printin~ form was subJected to a heat treatmenc. ~or this purpose, the dried ~rinting ~orm, after develo~ment, r~7a~s heated in a baking oven or 5 minutes to 2~nt`.
As a result oF heating the Drintinq ~orm in the oven, the ~rinting stencil was hardened and the L25;~7~7 laYer became resistant to chemicals, such as, -for examPle~ deletion ~luids, and thus insoluhle in orqanic solvents, SllCh as acetone, alcohols, toluene or xvlene.
After the heatinq steP~ the printing sten~il can be immeaiatelY inXed ~ith ~reasv ink, in the Pre-sence o~ water, without an ad~itional post-treat~ent o~ the Drintinq ~orm bein~ re~uired. ~0 ,n~o perfect prints could be run in an ofset ~rinting press.
The aavantage which the haloqenated Polvvinvl phenol binders of the invention possess in liqht-sensi-tive mix-tures over non-halo~enated polv-vinvl Phenol hinders~ hecomes apparent when the brominated ~olY-p-vinvl ~henol in Exam21e 1 is replaced by the corresponding non-brominated Poly-p-vinyl ~henol. Whereas the printinq stencil ~rePared in accordance with Example 1 is alreadv resistant to deletion fluids and insoluble in organic solvents, such as acetone, after a bakina time of only ; minutes at ~30C, tne Printing stencil of a corresP~nding Drinting form containing the non-hrominated polY-p-vinyl phenol as the binder is dissolved bv the deletion fluid, and the laver remains soluble in acetone, even after a bakin~ time of 10 minutes, under otherwise identical test con~itions.
Even hefore bakin~, the Printing stencil according to Example 1 exhibits an excellent resistance to auxiliaries used in Printinq, such as ~ounta ;n solutions, roller cleansinq aqents, or ~late wash-out solutions. ~hereas the ~rintinq stencil - lh _ ~Z5~7~
preparPd in accordance with Example l is nat visibly attacke~ a~ter ~ minutes' action of a ~0~ strenqt~
isoproPanol solution rendered acidic with phosphoric acid, t~e corres~onding printinq stencil containinq pol~-p-vinyl Phenol as the binder is alreadv detached from the support after 15 seconds.
When the hrominated polv-p-vinyl ~henol in Example 1 is re~laced by t~e same amount o~ a cresol-~ormal~ehyde novolak or of a brominated cresol-formalde-hyde novolak havinq a bromine content Oe 3~%, asdescrihed in D~-A 3,107,1~, and the developed printinq form is ~aked under otherwise identical conditions at ~30C, then, in contrast to the corresPonding printin~ form containinq Poly-p-vinvl hromo~henol as the hin~er, strony ~o?ging ~henomena apPear in the imaqe-free areas uPon inkin~ with greasY
ink, which cannot be removed.
In the ~xamPles below, further coatinq solutions are ~escribea, with whicll similar results were obtained. ~nless other~ise statefl, the Prepara-tion and Processing o~ t'ne ~rintinq plates o~tained usinq tnese solutions correspond to the conditions aescribed in ~xam~le 1.
ExamPle _ __ An electrochemically roughened and anodicallY oxidized aluminum Plate~ the surface o~
which na~ been treated with an a~ueous solution o~
. .
- 17 - ~2~7~7 ~olyvinvlphosPhonic aci~, ~as coated with a solution o~
p.h.w~ of the esteri:~ication product ohtained from 1 mole o~ ,4-trihydroxv-benzo-Phenone and ~ moles oE naphtho~uinone-(l,~)-diaziAe-(~ -sulfonic acid chloride, 4 p.b.w. of the brominated poly-p-vinYl phenol o~
ExamPle 1, 0 ~ o~ . o~ a cresol-~ormaldehyde novolak havinq a soteninq Point o~ ln~ to 120C, 0.16 p.b.w. of ~ (acenaphth-~-Yl)-4,5-bis-trichloromethy~-s-triazine, and n.n7 p.b.w. of crvstal violet, in ~o p.b.w~ of ethvlene glycol monomethvl ether an~
~.b.w. o~ tetra~v~ro~uran.
~ he printing form was exPosed throuqh a trans~arent ~ositive original and developea with a 1 strenqth aqueous solution of sodium metasilicate.
- 18 - ~2 Exam~le ~
An electrochemicallv roughened and anodically oxidized aluminum plate was coated with a solution of 2.4 p.b.w. of a ~0% strenqth solution, in toluene, o~ a polYortho-ester pre~ared from - 7,7-bis-hydroxymethyl-~-oxa-nonan-(1)-ol and trimethvl ortho~ormate n.2 ~.~.w. of ~-(4-ethoxv-naphth-1-yl)-4,~-his-trichloromethYl-s-triazine~
p.~.w. of the brominated poly-~-vinyl phenol of ~xample 1, and .n35 p.h.w. of crystal violet hase, in ~0 p.b.w. o ethvlene ql~col monomethvl ether and p.~.w. o~ tetrahydrofuran.
The printing plate thus prepared was exPosed in an imagewise fashion ~or ~0 seconds, at a distance o~ 110 cm, under a 5 kW metal hali~e lamp and sub-: sequently developed with the developer solution of Example 1.
. .
- 19 - ~2~ 7 ~xam~le d An electrochemicallY roughened an~
anodicall~ oxidized aluminum plate was coated with a solution of n.~5 ~.b.w. of a oolYacetal prenared from triethY-lene glycol and 2-ethyl butYraldehyde 0.1 ~.b.w. of 2-(4-ethoxy-naphth-1-yl1-4,6-bis-trichloromethyl-s-triazine, ~ .w. of the hrominated ~oly-P-vinyl pnenol of ExamPle 1, and 0.~ p.~.w. of a cresol-formaldehyde novolak having ; a softening point of 105 to 1~0C, and O.nlh p.h.w. of crvstal violet base, in 20 p.h.w. of ethylene g1YCO1 monomet'nyl ether and 15 20 p.b.W. of tetrah~drofuran.
The printing plate thus prepared was exPosed in an imagewise fashion for 10 seconds, at a distance o~ lln cm, under a ~ kW metal halide lamp and subsequentl~ developed with a 1~ strength aqueous solution of sodium metasilicate.
~,8~,S12 and No. ~ 9,~11. As the compounds which can he s~lit hy acid, the a~orementioned cooyin~
materials contain ort'nocar~oxylic acid ~erivatives, monomeric or pol~meric acetals, enol ethers, or acvli-minocar~onates. As the compounds which are sensitive to radiation an~ eliminate acid, the copvin~ materials predominantlv contain orqanic halo~en compounds, in particular s-triazines or ~-trichloromethvl~ ,4-oxadiazoles which are su~stituted by haloqenomethvl grou~s. ~
. .
~lZ5~7~7 ~mong the orthocar~oxvlic aci~ derivatives aescribe~ in IJ.S. Patent Mo. ~,lnl,323, the ~is-1,3-dioxan-2-yl ethers oE aliphatic ~iols are Particularly use~l.
Among tlle polYacetals ~escribed in German Patent No. 2,718,~54, those with alipnatic al~ehvde units and liol units are preEerre~.
Further, verv suita~le mixtures are described in ~,erman Of~enlequngsschrift No. 2,928,63~.
In the latter, Poly~eric ortho-esters with recurrent ortho-ester qrou~s in the main chain are described as com~ounds which can be split by acid.
These qrou~s are 2-alk~l ethers o~
1,3-dioxa-cYcloalkanes havin~ ~ or ~ rin~ members.
Polymers with recurrent l,~-dioxa-cYclohex-~-vl alkyl ether unitsl in which the alkYl ether group can ~e interruPted bY ether oxY~en atoms and is prefera~lY
honded to the 5-position of t~e adiacent rinq, are articularlY preferred.
The quantitative Pro~ortion o~ the compounds wnich can ~e sPlit bv acid in tne liq~t-sensitive ~ixture is in general between ~ and 65~ bv weiqht, Preferahly between 14 and 44~ hv weight, r~lative to the non-volatile constituents of the mixture. The quantitv of the compound which eliminates acid is ~etween n.l and 10~ hv weiqht, preferably hetween 0.2 and ~% hv weight.
Along with the haloqenated polyvinvl ~henols, numerous otner resins can he empl~ved in the light-sensitive mixtures o~ the invention, vinvl polY-mers, such as polYvinyl acetates, Polyacrvlates~
~s~
polYvinvl ethers, ~01~l~7inYl acetals, PolYvinvl pYrroli~ones an~ coPolYmers o~ the monomers on which these are based ~einq pre~erred. Further suitable binders ~hich are soluble or swella~le in alkaline solutions are natural resins, such as shellac an~
colo~honY an~ sYnthetic resins, such as copolYmers o~
stvrene and maleic acid anhyaride,- anA, in partlcular, novolaks. ~he most advantageolls ~roportion of these resins ~epends on the technological requirements and on the in~luence on the ~evelopment con~itions an~, in general, this is not more than ~0% bv weight of the haloqenated Polvvinvl Phenol. To meet special re~uire~ents, such as flexibilitv, a~hesion, qloss, coloration, color change, and the like, the liqht-sensitive svstem can aflditionallv also contain substances, such as ~olyglvcols, cellulose deriva-ti~7es, such as ethyl cellulose, sur~actants, dyes, adhesion ~romotors and inelv divided pigments, and also IrV-absorhers, i~ required.
; 20 For coa~ing a suitable support, the mixtures are in general dissolved in a solvent. The selection of the solvents must be matcned to the envisaged coatin~ Process~ the laver thickness anA the ~rYing conAitions. Suitable solvents for the mix-ture accordinq to the invention are ketones, such as methYl ethYl ketone, chlorinated hy~rocarbons, such as trichloroethvlene and l,l,l-trichloroethane, alcohols, such as n-Pro~anolr ethers such as tetrahv~rofuran, alcohol-ethers, such as ethylene glycol monoethvl ether, and ester~s, such as hutvl acetate. ~t is also 2~L78~
~ossi'ole to use mixtures which, for sPecial pur~oses, can contain additional solvents, such a~s acetonitrile, ~i~xane, or ~imethvlformamide. In ~rinciPle, all those solvents can he used which ~o not irreversihly react with the laver comPonents.
~ he supports used for laver thicknesses o~
less than about 1~ ~m are in most cases metals. The following mav be used for offset prinkinq Plates:
brignt-rolled, mechanicallv or electrochemicallY
roughene~ aluminum whic~ esired, i~s anodicallY
oxidize~ and which additionally can also have been chemicallY pretreated, for e~ample, with Polyvi-nylphospnonic aci~, silicates, 'nexafluoro~irconates, hydrolysed tetraethYl orthosilicate, or phos~hates.
Coatinq of t'ne support material is carried out in a known manner ~v spin-coating, sQraving, flipping, on rollers, by means of slot ~ies or blade-sPreadin~, or bv means Oc coater a~plication.
T.iqht sources customarv in in~ustrv are use for exposure. Irradiation witn electrons or a laser is another Possibility for Pro~ucinq an imaqe.
The aqueous-alkaline solutions whic~ are used or ~evelopinq have qraduate~ alkalinitv, that is, theY have a P'tl whic~ preferably is between ln and 14, an~ thev also can contain minor amounts o~ organic solvents or surfactants, remove t'nose areas o~ the coPyinq laver which have been struck ~v li~ht, an~
thus produce a positive imaqe of the oriqinal.
Ne~ative lavers can he ~evelo~ed bv means o~ similar developerS.
- 12 - ~25~
The preferred use oE the light-sensitive mixtures accordin~ to the invention is in the prePara-tin o~ Printing ~orms, in Particular, o~set ~rintin~
~orms, usinq aluminum as the suoport.
~fter development, the ~rintinq orm is heated in a manner known ~er se. The hakinq tem-Peratures selected can be in the ran~e ~rom about 180 to 240-', prefera'olv ~rom ~OQ to ?40C, and heating periods o 1 - 20, ~re~erably ~ to 10, minutes being normally re~uired. If the supPort material is stable at higher temperatures it is o~ course also possi'~le ~o bake at hi~her ~emperatures above ~4noc and to select corres~onainql~7 shorter heatinq ~eriods.
~he mi~ture o~ this invention and the liqht-sensitive co~yinq material pre~ared t~erqfrom are distinq~lished by the fact that a~ter haking prac-tically no remainders due to baking are le~t on the image-free areas o~ the support. It is therefore no longer necessarv to apply an additional water-soluhle protective laver before hakin~, or to remove the remainders subsequently bv treatment with ~eveloper.
Neit~er ~y means of the known haloqenated novolaks nor by means o~ the known non-haloqenated novolaks is this advantaqe achieved. As compared with non-halogenated polyvinvl Phenol binders, another advantage ~resented by the use o~ haloqenated ~olYvinyl phenols as binders resides in the ~arkedlv improved re~istance of the non-baked ~rinting stencil to auxiliaries used in ~rintinq, such as, ~or exa~ple, certain hyflrocarbon solvents or alcohol-containing ~25~7~
fountain solutions, which are commonlv emploved durinq co~vinq or in the ~rinting press.
The invention is explained in greater detail bv reference to the examples which follow, wherein parts by weiqht (~.b.w.l and parts by ~olume (P.b.v.) have the same relationship as the g to the cm3.
Jnless otherwise stated, -oercentages are precent bv weiqht.
ExamPle 1 An electrochemicallY roughened and anodicallY oxidized aluminum ~late was coated with a solution of 1.~ p.b.w. of the esteri~ication product obtained from 1 mole of 2,3,4-trihydroxv-kenzo-phenone and ~ moles of napht~oquinone-(1,2~-diazide-(2)-~-sulfonic aci~
chloride, h p.b.w. of brominated ~olY-p-vinvl phenol 'naving a melting range of 190 - 220C, a bromine content o~ about ~n~, and an average molecular weiqht oE ~,ono, 0.1~ p,b.w. o~ ~-(4-ethoxv-naphth-1-yl~ 4,fi-bis-trichloro,nethyl-~-triaæine, and - 14 - ~2~7~
n.n7 ~.h.~. o~ crvstal violet, in .
~.b.w. o~ etnvlene ~1YCO1 monometh~l ether and ~0 p.~.w. of tetrahYdrofuran.
~efore application o~ the light-sensitive co~ving layer, the anodicallv oxidized support ~ad been treated with an aqueous solution o~ 0.1~ by weight strenqth Polyvinylphosphonic acid.
The presensitiæed material thus prepared, which had a laver weight o~ %. n q/m~, was exPosed in an imagewise fashion under a crans~arent positive ori-ginal and subsequently develo~ed with an 0.~% strengt~
aqueous solution o~ sodium meta~silicate x 9 H~O.
The areas of the copYinq laYer which had been struck bv liqht were removed bY the development, lS an~ the unexposed image areas remained on the support, ~roducin~ a ~rintin~ stencil corresponding to the original beinq o~tained.
~ n an offset Printin~ ~ress, it was possible to ohtain 100 ,no~ perfect print~ Fro,n tne Printing form thus prepared.
In order to extend the print run and to harden the printing stencil, the Printin~ form was subJected to a heat treatmenc. ~or this purpose, the dried ~rinting ~orm, after develo~ment, r~7a~s heated in a baking oven or 5 minutes to 2~nt`.
As a result oF heating the Drintinq ~orm in the oven, the ~rinting stencil was hardened and the L25;~7~7 laYer became resistant to chemicals, such as, -for examPle~ deletion ~luids, and thus insoluhle in orqanic solvents, SllCh as acetone, alcohols, toluene or xvlene.
After the heatinq steP~ the printing sten~il can be immeaiatelY inXed ~ith ~reasv ink, in the Pre-sence o~ water, without an ad~itional post-treat~ent o~ the Drintinq ~orm bein~ re~uired. ~0 ,n~o perfect prints could be run in an ofset ~rinting press.
The aavantage which the haloqenated Polvvinvl phenol binders of the invention possess in liqht-sensi-tive mix-tures over non-halo~enated polv-vinvl Phenol hinders~ hecomes apparent when the brominated ~olY-p-vinvl ~henol in Exam21e 1 is replaced by the corresponding non-brominated Poly-p-vinyl ~henol. Whereas the printinq stencil ~rePared in accordance with Example 1 is alreadv resistant to deletion fluids and insoluble in organic solvents, such as acetone, after a bakina time of only ; minutes at ~30C, tne Printing stencil of a corresP~nding Drinting form containing the non-hrominated polY-p-vinyl phenol as the binder is dissolved bv the deletion fluid, and the laver remains soluble in acetone, even after a bakin~ time of 10 minutes, under otherwise identical test con~itions.
Even hefore bakin~, the Printing stencil according to Example 1 exhibits an excellent resistance to auxiliaries used in Printinq, such as ~ounta ;n solutions, roller cleansinq aqents, or ~late wash-out solutions. ~hereas the ~rintinq stencil - lh _ ~Z5~7~
preparPd in accordance with Example l is nat visibly attacke~ a~ter ~ minutes' action of a ~0~ strenqt~
isoproPanol solution rendered acidic with phosphoric acid, t~e corres~onding printinq stencil containinq pol~-p-vinyl Phenol as the binder is alreadv detached from the support after 15 seconds.
When the hrominated polv-p-vinyl ~henol in Example 1 is re~laced by t~e same amount o~ a cresol-~ormal~ehyde novolak or of a brominated cresol-formalde-hyde novolak havinq a bromine content Oe 3~%, asdescrihed in D~-A 3,107,1~, and the developed printinq form is ~aked under otherwise identical conditions at ~30C, then, in contrast to the corresPonding printin~ form containinq Poly-p-vinvl hromo~henol as the hin~er, strony ~o?ging ~henomena apPear in the imaqe-free areas uPon inkin~ with greasY
ink, which cannot be removed.
In the ~xamPles below, further coatinq solutions are ~escribea, with whicll similar results were obtained. ~nless other~ise statefl, the Prepara-tion and Processing o~ t'ne ~rintinq plates o~tained usinq tnese solutions correspond to the conditions aescribed in ~xam~le 1.
ExamPle _ __ An electrochemically roughened and anodicallY oxidized aluminum Plate~ the surface o~
which na~ been treated with an a~ueous solution o~
. .
- 17 - ~2~7~7 ~olyvinvlphosPhonic aci~, ~as coated with a solution o~
p.h.w~ of the esteri:~ication product ohtained from 1 mole o~ ,4-trihydroxv-benzo-Phenone and ~ moles oE naphtho~uinone-(l,~)-diaziAe-(~ -sulfonic acid chloride, 4 p.b.w. of the brominated poly-p-vinYl phenol o~
ExamPle 1, 0 ~ o~ . o~ a cresol-~ormaldehyde novolak havinq a soteninq Point o~ ln~ to 120C, 0.16 p.b.w. of ~ (acenaphth-~-Yl)-4,5-bis-trichloromethy~-s-triazine, and n.n7 p.b.w. of crvstal violet, in ~o p.b.w~ of ethvlene glycol monomethvl ether an~
~.b.w. o~ tetra~v~ro~uran.
~ he printing form was exPosed throuqh a trans~arent ~ositive original and developea with a 1 strenqth aqueous solution of sodium metasilicate.
- 18 - ~2 Exam~le ~
An electrochemicallv roughened and anodically oxidized aluminum plate was coated with a solution of 2.4 p.b.w. of a ~0% strenqth solution, in toluene, o~ a polYortho-ester pre~ared from - 7,7-bis-hydroxymethyl-~-oxa-nonan-(1)-ol and trimethvl ortho~ormate n.2 ~.~.w. of ~-(4-ethoxv-naphth-1-yl)-4,~-his-trichloromethYl-s-triazine~
p.~.w. of the brominated poly-~-vinyl phenol of ~xample 1, and .n35 p.h.w. of crystal violet hase, in ~0 p.b.w. o ethvlene ql~col monomethvl ether and p.~.w. o~ tetrahydrofuran.
The printing plate thus prepared was exPosed in an imagewise fashion ~or ~0 seconds, at a distance o~ 110 cm, under a 5 kW metal hali~e lamp and sub-: sequently developed with the developer solution of Example 1.
. .
- 19 - ~2~ 7 ~xam~le d An electrochemicallY roughened an~
anodicall~ oxidized aluminum plate was coated with a solution of n.~5 ~.b.w. of a oolYacetal prenared from triethY-lene glycol and 2-ethyl butYraldehyde 0.1 ~.b.w. of 2-(4-ethoxy-naphth-1-yl1-4,6-bis-trichloromethyl-s-triazine, ~ .w. of the hrominated ~oly-P-vinyl pnenol of ExamPle 1, and 0.~ p.~.w. of a cresol-formaldehyde novolak having ; a softening point of 105 to 1~0C, and O.nlh p.h.w. of crvstal violet base, in 20 p.h.w. of ethylene g1YCO1 monomet'nyl ether and 15 20 p.b.W. of tetrah~drofuran.
The printing plate thus prepared was exPosed in an imagewise fashion for 10 seconds, at a distance o~ lln cm, under a ~ kW metal halide lamp and subsequentl~ developed with a 1~ strength aqueous solution of sodium metasilicate.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A positive-working light-sensitive mixture which comprises:
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combin-ation of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions, said mixture having a solubility in an aqueous-alkaline solution which is capable of changing upon exposure to actinic radiation.
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combin-ation of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions, said mixture having a solubility in an aqueous-alkaline solution which is capable of changing upon exposure to actinic radiation.
2. A light-sensitive mixture as in claim 1, wherein said halogenated polyvinyl phenol is brominated.
3. A light-sensitive mixture as in claim 1, wherein said polyvinyl phenol is a polymer of p-vinyl phenol.
4. A light-sensitive mixture as in claim 1, wherein said light-sensitive compound is an o-quinone diazide.
5. A light-sensitive mixture as in claim 4, wherein said o-quinone diazide is selected from the group consisting of a naphthoquinone-(1,2)-diazide(2)-4-sulfonic acid ester, a naphthoquinone-(1,2)-diazide(2)-5-sulfonic acid ester, and the corresponding sulfonic acid amides.
6. A light-sensitive mixture as in claim 1, wherein said light-sensitive composition comprises a mixture of:
(a) a compound which yields an acid on exposure to actinic radiation and (b) a compound which possesses at least one C-O-C
bond which is acid-cleavable.
(a) a compound which yields an acid on exposure to actinic radiation and (b) a compound which possesses at least one C-O-C
bond which is acid-cleavable.
7. A light-sensitive mixture as in claim 6, wherein said compound (b) is selected from the group consisting of an orthocarboxylic acid derivative, and a polyacetal compound.
8. A light-sensitive copying material composed of a layer support and a light-sensitive layer, the solubility of which in an aqueous-alkaline solution is capable of changing upon irradiation, said light-sensitive layer comprising:
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combination of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions.
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combination of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions.
9. A process for the preparation of a printing form comprising the steps of:
(a) preparing a light-sensitive copying material comprising a layer support and a light-sensitive layer, the solubility of which in an aqueous-alkaline solution is capable of changing upon exposure to actinic radiation, said light-sensitive layer comprising:
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combination of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions, (b) imagewise exposing said light-sensitive layer to actinic radiation;
(c) thereafter washing away the non-image areas of said light-sensitive layer with an aqueous-alkaline developer solution; and (d) then heating said material sufficiently to harden the remaining image areas of said light-sensitive layer.
(a) preparing a light-sensitive copying material comprising a layer support and a light-sensitive layer, the solubility of which in an aqueous-alkaline solution is capable of changing upon exposure to actinic radiation, said light-sensitive layer comprising:
(1) a light-sensitive composition comprising at least one light-sensitive compound or a light-sensitive combination of compounds, said composition being present in an amount between about 3 and 50 percent by weight, relative to the non-volatile constituents of said mixture, and (2) binder material comprising a halogenated polyvinyl phenol which has a halogen content between about 20 and 60 percent by weight and which is present in an amount between about 10 and 95 percent by weight, relative to the non-volatile constituents of said mixture, said binder material being insoluble in water but soluble in aqueous-alkaline solutions, (b) imagewise exposing said light-sensitive layer to actinic radiation;
(c) thereafter washing away the non-image areas of said light-sensitive layer with an aqueous-alkaline developer solution; and (d) then heating said material sufficiently to harden the remaining image areas of said light-sensitive layer.
10. A process as in claim 9, wherein said step (d) comprises heating said image areas to a temperature in the range of from about 200°C to about 240°C for a period of about 5 to about 10 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823246106 DE3246106A1 (en) | 1982-12-13 | 1982-12-13 | LIGHT SENSITIVE MIXTURE, LIGHT SENSITIVE COPY MATERIAL MADE THEREOF, AND METHOD FOR PRODUCING A PRINT FORM FROM THE COPY MATERIAL |
| DEP3246106.2 | 1982-12-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1254787A true CA1254787A (en) | 1989-05-30 |
Family
ID=6180546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000442945A Expired CA1254787A (en) | 1982-12-13 | 1983-12-09 | Light-sensitive mixture, light-sensitive copying material prepared therefrom, and a process for the preparation of a printing form from the copying material |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0111274B1 (en) |
| JP (1) | JPS59114535A (en) |
| AU (1) | AU571190B2 (en) |
| BR (1) | BR8306803A (en) |
| CA (1) | CA1254787A (en) |
| DE (2) | DE3246106A1 (en) |
| ES (1) | ES8503863A1 (en) |
| FI (1) | FI834528A (en) |
| ZA (1) | ZA839215B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8500320A (en) * | 1985-02-06 | 1986-09-01 | Philips Nv | METHOD FOR MANUFACTURING AN APPARATUS AND APPARATUS MADE WITH THE METHOD |
| DE3821585A1 (en) * | 1987-09-13 | 1989-03-23 | Hoechst Ag | POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE AND PRODUCTION OF RADIATION-SENSITIVE RECORDING MATERIAL FOR HIGH-ENERGY RADIATION |
| US4812522A (en) * | 1987-12-04 | 1989-03-14 | Shell Oil Company | Molecularly miscible blends of polyketone with polyvinyl phenol |
| US5100768A (en) * | 1989-05-09 | 1992-03-31 | Kabushiki Kaisha Toshiba | Photosensitive composition |
| DE4106356A1 (en) * | 1991-02-28 | 1992-09-03 | Hoechst Ag | RADIATION-SENSITIVE POLYMERS WITH NAPHTHOQUINONE-2-DIAZIDE-4-SULFONYL GROUPS AND THEIR USE IN A POSITIVE WORKING RECORDING MATERIAL |
| AU2001288865A1 (en) * | 2000-09-08 | 2002-03-22 | Shipley Company, L.L.C. | Polymers and photoresist compositions comprising electronegative groups |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6053301B2 (en) * | 1979-08-31 | 1985-11-25 | 冨士薬品工業株式会社 | Positive photosensitive composition |
| JPS5730829A (en) * | 1980-08-01 | 1982-02-19 | Hitachi Ltd | Micropattern formation method |
| DE3100077A1 (en) * | 1981-01-03 | 1982-08-05 | Hoechst Ag, 6000 Frankfurt | LIGHT SENSITIVE MIXTURE CONTAINING A NAPHTHOCHINONDIAZIDESULPHONIC ACID ESTER, AND METHOD FOR PRODUCING THE NAPHTHOCHINONDIAZIDESULPHONIC ACID ESTER |
| DE3127754A1 (en) * | 1981-07-14 | 1983-02-03 | Hoechst Ag, 6000 Frankfurt | LIGHT SENSITIVE MIXTURE BASED ON O-NAPHTHOCHINONDIAZIDES AND LIGHT SENSITIVE COPY MATERIAL MADE THEREOF |
| DD206518A3 (en) * | 1981-08-10 | 1984-01-25 | Akad Wissenschaften Ddr | METHOD FOR PRODUCING MICROSTRUCTURES |
| DE3246037A1 (en) * | 1982-12-09 | 1984-06-14 | Hoechst Ag, 6230 Frankfurt | LIGHT SENSITIVE MIXTURE, LIGHT SENSITIVE COPY MATERIAL MADE THEREOF, AND METHOD FOR PRODUCING A PRINT FORM FROM THE COPY MATERIAL |
-
1982
- 1982-12-13 DE DE19823246106 patent/DE3246106A1/en not_active Withdrawn
-
1983
- 1983-12-01 JP JP58225518A patent/JPS59114535A/en active Pending
- 1983-12-02 EP EP83112142A patent/EP0111274B1/en not_active Expired
- 1983-12-02 DE DE8383112142T patent/DE3379079D1/en not_active Expired
- 1983-12-07 AU AU22169/83A patent/AU571190B2/en not_active Ceased
- 1983-12-09 CA CA000442945A patent/CA1254787A/en not_active Expired
- 1983-12-09 FI FI834528A patent/FI834528A/en not_active Application Discontinuation
- 1983-12-12 BR BR8306803A patent/BR8306803A/en not_active IP Right Cessation
- 1983-12-12 ZA ZA839215A patent/ZA839215B/en unknown
- 1983-12-12 ES ES527970A patent/ES8503863A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59114535A (en) | 1984-07-02 |
| AU571190B2 (en) | 1988-04-14 |
| FI834528A0 (en) | 1983-12-09 |
| BR8306803A (en) | 1984-07-17 |
| ES527970A0 (en) | 1985-03-16 |
| EP0111274B1 (en) | 1989-01-25 |
| ZA839215B (en) | 1984-08-29 |
| EP0111274A3 (en) | 1986-01-15 |
| ES8503863A1 (en) | 1985-03-16 |
| DE3379079D1 (en) | 1989-03-02 |
| EP0111274A2 (en) | 1984-06-20 |
| FI834528A (en) | 1984-06-14 |
| AU2216983A (en) | 1984-06-21 |
| DE3246106A1 (en) | 1984-06-14 |
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| MKEX | Expiry |