CA1144804A - Photosensitive composition containing a diazo resin, a polyethylenically unsaturated compound and a photoinitiator - Google Patents
Photosensitive composition containing a diazo resin, a polyethylenically unsaturated compound and a photoinitiatorInfo
- Publication number
- CA1144804A CA1144804A CA000346444A CA346444A CA1144804A CA 1144804 A CA1144804 A CA 1144804A CA 000346444 A CA000346444 A CA 000346444A CA 346444 A CA346444 A CA 346444A CA 1144804 A CA1144804 A CA 1144804A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- resin
- water
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
- G03F7/0955—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Materials For Photolithography (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
FN 915,446 PHOTOSENSITIVE COMPOSITIONS AND ARTICLES
Abstract of the Disclosure Photoreactive lithographic printing plate compositions ordinarily require organic solvents and/or aqueous alkaline solutions to develop the image after exposure to light.
The use of such solvents or solutions for development requires an additional expense in the use of lithographic plates above the cost of the plates and requires the user to store development solutions and solvents.
The present invention provides a truly water developable photoreactive printing plate composition. The plates constructed according to the present invention may be readily developed by pure water.
Abstract of the Disclosure Photoreactive lithographic printing plate compositions ordinarily require organic solvents and/or aqueous alkaline solutions to develop the image after exposure to light.
The use of such solvents or solutions for development requires an additional expense in the use of lithographic plates above the cost of the plates and requires the user to store development solutions and solvents.
The present invention provides a truly water developable photoreactive printing plate composition. The plates constructed according to the present invention may be readily developed by pure water.
Description
EN 915~446 il~l4BC3~
P~OTOSENSITIVE COMPOSITIONS AND ARTICLES
Field of the Invention The present invention relates to polymerizable compositions and in particular to photoreactive composi-tions. These compositions are useful as imageable layers for photoimageable printing systems and as imageable layers in printing plates These compositions are also water developable and can be processed without the use of organic solvents.
~ =
10 Most negative acting printiny plate compositions work in the following manner. A photoreactive composition is applied to a substrate. The coated substrate is imaged by radiation (e.g., visible light, infrared radiation, ultraviolet radiation/ etc.), heat or electron beams.
Where the radiation or other imaying action has struck the photosensitive coating composition, the photoreactive composition polymerizes. This polymerization in imaged areas renders those areas of the composition less soluble in solvents. When a developer solution is applied to the exposed surface of the coated substrate, the unexposed composition is removed more easily and more rapidly than the exposed composition. Removal of the unexposed composition leaves an ink receptive image in the*exposed areas. When used as a printing plate, these coat~d .~ .
.
;
4~
substrates therefore act as negative acting plates.
These imageable systems operate on a change in solubility, and the unexposed area should dissolve or release easily from the substrate while the exposed area should not be disturbed by the solvent. The more easily the unpolymerized composition is removable by developer solutions and the more resistant the polymerized composition becomes, the better the system is.
Most polymerizable systems require organic solvent developer systems rather than aqueous developer systems as it is easier to formulate printing compositions for organic solvents which are soluble before polymerizatlon and insoluble after polymerization.
Organic solvent systems are less desirable than aqueous systems because of the potential for pollution and the higher cost of the organic solvents. However, it has been very difficult to produce aqueous developable systems which have adequate imaging speeds, are easily removed when unexposed, are insoluble when exposed, and are long lasting as a printing plate. Water soluble compositions are disclosed, for example, in U.S. Patent Nos. 3,837,858;
3,899,332; 3,933,499; 4,092,170; and 4,042,386 and British Patent No. 1,447,142.
Those systems which are re~erred to in the prior art as water developable are not readily water developable and often require the use of additional additives such as surfactants. Some of these prior art systems, such as ';
that of U.S. Patent No. 4,104,072, rely on diazo resins as the photopolymerizable material within the composition and tend to be short-lived on the press. Other prior art systems, such as that of U.S. Patent No. 3,036,915 use various polyethylenically unsaturated materials as the photopolymerizable component within the composition.
These systems tend to be very sensitive to humidity and are not storage stable. The active composition lifts from the surface of the plate, easily abrades from the plate, and suffers from reduced resolution with storage under humid conditions Summary of the Invention The present invention relates to polymerizable compositions which are useful as printing plate composi-tions. The present invention further relates to printingplates having these compositions thereon wherein the compositions are solvent or water developable.
The compositions suitable for use in a printing plate system comprise a homogeneous mixture of an organic solvent soluble photoreactive oligomeric resin, an organic solvent soluble film forming resin with oleophilic properties as a binder, a free radical photoinitiator system, a polyfunctional unsaturated monomer or oligomer, and a water softenable polymer.
The plates of the present invention are presensitized and comprise an oleophobic substrate, a ....
.
:.
- . . ' . . ~ :~: . .
.
8~34 water soluble photore~ctive resin on at least one surface of the substrate, and a coating of one of the compositions oE the present invention over said resin.
The broadest ranges of components used in the practice of the pre-sent invention are as :Eollow:
A. 1-75% by weight of organic solvent soluble film forming resin B. 10-65% by weight of free radical polymerizab:Le polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free radical photoinitiator system, D. 5-40% by weight of a water softenable organic solvent soluble poly-mer, and E. 1-20% by weight of organic solvent soluble diazo resin.
Preferably the sum of the water softenable and organic film forming resins would be equal to at least 10% by weight of the composition.
Detailed Description of the Invention The photoreactive solvent soluble oligomeric resin component used in the present invention is a diazo resin. These resins must be organic solvent soluble, but may also be somewhat water soluble and are known in the art as represented by United States Patent Nos. 4,104,072; 3,933,499; 3~837,858;
and 3,899,3~2. Examples of diazos useful in forming such resins, which resins are generally known in the art, are:
4-diazo-diphenylamine, l-diazo-4-N,N-dimethylamino-benzene, l-diazo-4-N,N-diethylamino-benzene, l-diazo-4-N-ethyl-N-hydroxyethylamino-benzene, l-diazo-4-N-methyl-N-hydroxyethylamino-benzelle, l-diazo-2,5-diethoxy-4-benzoylamino-benzene, l-diazo-4-N-benzylamino-benzene, l-diazo-4-N,N-dimethylamino-benzene . - 4 -, ., : .~ . .' '~
, ' ~ ' ~ , '" .:
l-diazo-4-morpholino-benzene~
l-diazo-2,5-climethoxy-4-p-tolylmercaptobenzene, l-diazo-2-ethoxy-4-N,N-dimethylaminobenzene, p-diazo-dimethyl aniline, l-diazo-2,5-dibutoxy-4-morpholino-benzene, l-diazo-2,5-diethoxy-4-morpholino-benzene, - 4a -' , :
.
;
~4~
l-diazo~2,5-dimethoxy-4-morpholino-benzene, l-diazo~2,5-diethoxy-4-morpholino-benzene, l~diazo-2/5-diethoxy-4-p-tolylrnercapto-benzene, l-diazo-3-ethoxy-4-N-methyl-N-benzylamino-benzene, 1-diazo-3-chloro-4-N,N-diethylamlno-benzenef l-diazo-3-methyl-4-pyrrolidino-benzene, l-diazo-2-chloro-4-~,N-dimethylamino-5-methoxy-benzene, and l-diazo-3-methoxy-4-pyrrolidino benzene.
These diazos are organic solvent soluble when an appropriate anion is selectad, for example from amongst those known in the art, such as tetrafluoroborate, trilsopropylonapthalene sulfonate, p-toluene sulfonate, lauryl sulfate, hexafluorophosphate, 2-naphthalene sulfonate, etc. These resins, as noted in the list above, are organic solvent soluble, light-sensitive, negative working aromatic diazo resinsO The diazo resins are generally useful as 1-20% by weight of active ingredients in the printing composition. Preferably they are present as 3-8~ by weight of the composition. The preparation of these resins is generally described in U.S. Patent No.
P~OTOSENSITIVE COMPOSITIONS AND ARTICLES
Field of the Invention The present invention relates to polymerizable compositions and in particular to photoreactive composi-tions. These compositions are useful as imageable layers for photoimageable printing systems and as imageable layers in printing plates These compositions are also water developable and can be processed without the use of organic solvents.
~ =
10 Most negative acting printiny plate compositions work in the following manner. A photoreactive composition is applied to a substrate. The coated substrate is imaged by radiation (e.g., visible light, infrared radiation, ultraviolet radiation/ etc.), heat or electron beams.
Where the radiation or other imaying action has struck the photosensitive coating composition, the photoreactive composition polymerizes. This polymerization in imaged areas renders those areas of the composition less soluble in solvents. When a developer solution is applied to the exposed surface of the coated substrate, the unexposed composition is removed more easily and more rapidly than the exposed composition. Removal of the unexposed composition leaves an ink receptive image in the*exposed areas. When used as a printing plate, these coat~d .~ .
.
;
4~
substrates therefore act as negative acting plates.
These imageable systems operate on a change in solubility, and the unexposed area should dissolve or release easily from the substrate while the exposed area should not be disturbed by the solvent. The more easily the unpolymerized composition is removable by developer solutions and the more resistant the polymerized composition becomes, the better the system is.
Most polymerizable systems require organic solvent developer systems rather than aqueous developer systems as it is easier to formulate printing compositions for organic solvents which are soluble before polymerizatlon and insoluble after polymerization.
Organic solvent systems are less desirable than aqueous systems because of the potential for pollution and the higher cost of the organic solvents. However, it has been very difficult to produce aqueous developable systems which have adequate imaging speeds, are easily removed when unexposed, are insoluble when exposed, and are long lasting as a printing plate. Water soluble compositions are disclosed, for example, in U.S. Patent Nos. 3,837,858;
3,899,332; 3,933,499; 4,092,170; and 4,042,386 and British Patent No. 1,447,142.
Those systems which are re~erred to in the prior art as water developable are not readily water developable and often require the use of additional additives such as surfactants. Some of these prior art systems, such as ';
that of U.S. Patent No. 4,104,072, rely on diazo resins as the photopolymerizable material within the composition and tend to be short-lived on the press. Other prior art systems, such as that of U.S. Patent No. 3,036,915 use various polyethylenically unsaturated materials as the photopolymerizable component within the composition.
These systems tend to be very sensitive to humidity and are not storage stable. The active composition lifts from the surface of the plate, easily abrades from the plate, and suffers from reduced resolution with storage under humid conditions Summary of the Invention The present invention relates to polymerizable compositions which are useful as printing plate composi-tions. The present invention further relates to printingplates having these compositions thereon wherein the compositions are solvent or water developable.
The compositions suitable for use in a printing plate system comprise a homogeneous mixture of an organic solvent soluble photoreactive oligomeric resin, an organic solvent soluble film forming resin with oleophilic properties as a binder, a free radical photoinitiator system, a polyfunctional unsaturated monomer or oligomer, and a water softenable polymer.
The plates of the present invention are presensitized and comprise an oleophobic substrate, a ....
.
:.
- . . ' . . ~ :~: . .
.
8~34 water soluble photore~ctive resin on at least one surface of the substrate, and a coating of one of the compositions oE the present invention over said resin.
The broadest ranges of components used in the practice of the pre-sent invention are as :Eollow:
A. 1-75% by weight of organic solvent soluble film forming resin B. 10-65% by weight of free radical polymerizab:Le polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free radical photoinitiator system, D. 5-40% by weight of a water softenable organic solvent soluble poly-mer, and E. 1-20% by weight of organic solvent soluble diazo resin.
Preferably the sum of the water softenable and organic film forming resins would be equal to at least 10% by weight of the composition.
Detailed Description of the Invention The photoreactive solvent soluble oligomeric resin component used in the present invention is a diazo resin. These resins must be organic solvent soluble, but may also be somewhat water soluble and are known in the art as represented by United States Patent Nos. 4,104,072; 3,933,499; 3~837,858;
and 3,899,3~2. Examples of diazos useful in forming such resins, which resins are generally known in the art, are:
4-diazo-diphenylamine, l-diazo-4-N,N-dimethylamino-benzene, l-diazo-4-N,N-diethylamino-benzene, l-diazo-4-N-ethyl-N-hydroxyethylamino-benzene, l-diazo-4-N-methyl-N-hydroxyethylamino-benzelle, l-diazo-2,5-diethoxy-4-benzoylamino-benzene, l-diazo-4-N-benzylamino-benzene, l-diazo-4-N,N-dimethylamino-benzene . - 4 -, ., : .~ . .' '~
, ' ~ ' ~ , '" .:
l-diazo-4-morpholino-benzene~
l-diazo-2,5-climethoxy-4-p-tolylmercaptobenzene, l-diazo-2-ethoxy-4-N,N-dimethylaminobenzene, p-diazo-dimethyl aniline, l-diazo-2,5-dibutoxy-4-morpholino-benzene, l-diazo-2,5-diethoxy-4-morpholino-benzene, - 4a -' , :
.
;
~4~
l-diazo~2,5-dimethoxy-4-morpholino-benzene, l-diazo~2,5-diethoxy-4-morpholino-benzene, l~diazo-2/5-diethoxy-4-p-tolylrnercapto-benzene, l-diazo-3-ethoxy-4-N-methyl-N-benzylamino-benzene, 1-diazo-3-chloro-4-N,N-diethylamlno-benzenef l-diazo-3-methyl-4-pyrrolidino-benzene, l-diazo-2-chloro-4-~,N-dimethylamino-5-methoxy-benzene, and l-diazo-3-methoxy-4-pyrrolidino benzene.
These diazos are organic solvent soluble when an appropriate anion is selectad, for example from amongst those known in the art, such as tetrafluoroborate, trilsopropylonapthalene sulfonate, p-toluene sulfonate, lauryl sulfate, hexafluorophosphate, 2-naphthalene sulfonate, etc. These resins, as noted in the list above, are organic solvent soluble, light-sensitive, negative working aromatic diazo resinsO The diazo resins are generally useful as 1-20% by weight of active ingredients in the printing composition. Preferably they are present as 3-8~ by weight of the composition. The preparation of these resins is generally described in U.S. Patent No.
2,714,066. It must be noted that the diazo resins used in the practice of the present invention is not synonymous with or inclusive of diazonium salts as known in the art.
Diazo resins have more than one diazonium group in the molecule. Diazo resins comprise a number of salts, at least two, covalently bonded together. For example, a , . . . ..
useful diazo resin can be represented by the formula ~ n ~ \CH
wherein n is about 4 or 5. _ It is interesting to note that polymerization does not necessarily occur through generation of a Lewis acid.
The anion shown above does not form or ~enerate a Lewis acid when the diazo resin is photoinitiated. Lewis acids may be generated in othe~ diazo resins, but non-Lewis acid generating resins are useul in the present invention.
The binder resin component, which is an organic solvent soluble film forming resin, is generally known in the art. It is preferably selected from epoxy resins, polyesters, polyallyl orthophthalate prepolymers, pollyallyl isophthalate prepolymers, polyvinyl formals, polyurethanes, polyvinyl butyrals, polyoxyethylene oxides, polyvinyl hydrogen phthalates, polyacrylates, polymethacrylates, cellulose acetate esters, and polyvinyl chlorides. Some of these resins are disclosed as useful in plate compositions in U.S. Patent Nos. 4,104,072;
Diazo resins have more than one diazonium group in the molecule. Diazo resins comprise a number of salts, at least two, covalently bonded together. For example, a , . . . ..
useful diazo resin can be represented by the formula ~ n ~ \CH
wherein n is about 4 or 5. _ It is interesting to note that polymerization does not necessarily occur through generation of a Lewis acid.
The anion shown above does not form or ~enerate a Lewis acid when the diazo resin is photoinitiated. Lewis acids may be generated in othe~ diazo resins, but non-Lewis acid generating resins are useul in the present invention.
The binder resin component, which is an organic solvent soluble film forming resin, is generally known in the art. It is preferably selected from epoxy resins, polyesters, polyallyl orthophthalate prepolymers, pollyallyl isophthalate prepolymers, polyvinyl formals, polyurethanes, polyvinyl butyrals, polyoxyethylene oxides, polyvinyl hydrogen phthalates, polyacrylates, polymethacrylates, cellulose acetate esters, and polyvinyl chlorides. Some of these resins are disclosed as useful in plate compositions in U.S. Patent Nos. 4,104,072;
3,899,332; 3,837,858; and 3,933,499. These binder resins may or may not enter into the polymerization which occurs upon exposure to radiation. Prepolymers or fully .
~14~
-. -7-polymerized materials may be useul as long as they are capable of forming a Eilm with sufficient structural integrity to be self-supporting. These resins are generally useful as 15-75% by weight of the printing composition, excluding solvents and other non-functional additives. Preferably 30-50~ by weight solid ingrsdients are binder resin. A minimum molecular wei~ht of at least 1,000, preferably 2000, and most preerably 3500 is desired. There is no required upper limit for the molecular weight. Molecular weights of 2,000,000 or 3,000,000 are known in the art and are useful. The use of binders having a molecular weight less than 200,000 and preferably less than 100,000 appears to make the compositions more readily developable. It is preferred that these resins be more oleophilic than hydrophilic.
When the binder resin is selected so that it is a prepolymer capable of independently crosslinking or polymerizing upon heating (which can be readily determined outside of the compositions of the present invention), the plate on which the composition is coated can be post-heated (i.e., after development) to control the dot size of the image on the plate and also to strengthen the integrity of the image. This would improve press life.
Because the dots are given more structural integrity by post-heating, underexposure during imaging may be used to produce dots with fine resolution. These dots would ordinarily be removed in development or on the press, but .~
9L8~
post-heating with these particular types of binder resins would make the dots secure to the printing plate. This is believed to be unique in negative acting water developable plates. It is preferred that such crosslinking or polymerizable can be initiated at a temperature of at least 100C. Yigher polymerization temperatures are also advantageous. ~xamples of this class of binder are polyallyl isophthalate and polyallylorthophthalate prepolymers such as _ I
~C-O-CH2-CH-CH2.\
C-O-CH~-CH-CH2 \ ~ C-O-CH2-CH-CH
The polyfunctional unsaturated monomer or oligomer component useful in the present invention is a free radical polymerizable polyethylenically unsaturated compound, These compounds may be true monomers or dimers, trimers, oligomers, or polymers having at least 2, preferably 2 to 12, and most preferably 2 to 5 ethylenically unsaturated groups such as acrylate, methacrylate, vinyl, acrylamide and allyl. Preferred are compounds having multiple acrylate and methacrylate groups such as acrylic and methacrylic esters o polyols.
Examples of these materials are trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentacrythritol triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, pentaerythritol tetra-methacrylate, diallyl phthalate, diallyl adipate, diallyl succinate, etc. Suitable ethyleneically unsaturated, free-radical initiated, chain-propagating addition polymerizable compounds include alkylene or polyalkylene glycol diacrylates, e.g., diethylene glycol diacrylate, glycerol diacrylatel glycerol triacrylate, 1,3-propane-diaol dimethacrylate, 1,3-propanediaol dimethacrylate, 1,2,4butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, sorbitol hexaacrylate; bis[l-(3-acryloxy-~-hydroxy)]p-ethoxy-phenyl~dimethylmethane, tris-hydroxethyl-isocyanurate trimethacrylate~ the bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500 and the like unsaturated amides, e.g., methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexametbylene bisacrylamide, diethylene triamine trisacrylamide, B-methacrylaminoethyl methacrylate; vinyl esters such as divinyl succinate, divinyl adipate, and divinyl phthalate. Mixtures of these esters may also be used as well as mixtures of these compounds with alkyl esters of acrylic acid and methacrylic acid including such esters as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyacrylate, styrene~ diallyl phthalate and the llke. These compounds are generally known in the ' .' '.
~ , .
8~)~
art, as, for example, in British Patant No. t,482,953 and UDS. Patent Nos. 3,954,475 and 3,905,815. The poly-functional unsaturated materials are generally useful as~
10-60% by weight of actlve ingredients in the printing composition. Preferably they are present as 20-40~ by weight of the composition~
The free~radical photoinitiator systems of the present invention are generally known. They are compounds which absorb radiation, generally actinic radiation, and are activated to become agents which abstract hydrogens from hydrogen donorsO There may also be or may need to be sensitizers present to enable the compounds to be photoactivated. Examples of these materials are the benzoins, acetophenones, naphthoquinones and benzophenones (as disclosed in British Patent No. 1,482,953), vinyl substituted halomethyl-s-triazine compounds (as disclosed in U.S. Patent No. 3,954,47$~, and aromatic onium compounds (as disclosed in U,S. Patents Nos. 4,058,400;
~14~
-. -7-polymerized materials may be useul as long as they are capable of forming a Eilm with sufficient structural integrity to be self-supporting. These resins are generally useful as 15-75% by weight of the printing composition, excluding solvents and other non-functional additives. Preferably 30-50~ by weight solid ingrsdients are binder resin. A minimum molecular wei~ht of at least 1,000, preferably 2000, and most preerably 3500 is desired. There is no required upper limit for the molecular weight. Molecular weights of 2,000,000 or 3,000,000 are known in the art and are useful. The use of binders having a molecular weight less than 200,000 and preferably less than 100,000 appears to make the compositions more readily developable. It is preferred that these resins be more oleophilic than hydrophilic.
When the binder resin is selected so that it is a prepolymer capable of independently crosslinking or polymerizing upon heating (which can be readily determined outside of the compositions of the present invention), the plate on which the composition is coated can be post-heated (i.e., after development) to control the dot size of the image on the plate and also to strengthen the integrity of the image. This would improve press life.
Because the dots are given more structural integrity by post-heating, underexposure during imaging may be used to produce dots with fine resolution. These dots would ordinarily be removed in development or on the press, but .~
9L8~
post-heating with these particular types of binder resins would make the dots secure to the printing plate. This is believed to be unique in negative acting water developable plates. It is preferred that such crosslinking or polymerizable can be initiated at a temperature of at least 100C. Yigher polymerization temperatures are also advantageous. ~xamples of this class of binder are polyallyl isophthalate and polyallylorthophthalate prepolymers such as _ I
~C-O-CH2-CH-CH2.\
C-O-CH~-CH-CH2 \ ~ C-O-CH2-CH-CH
The polyfunctional unsaturated monomer or oligomer component useful in the present invention is a free radical polymerizable polyethylenically unsaturated compound, These compounds may be true monomers or dimers, trimers, oligomers, or polymers having at least 2, preferably 2 to 12, and most preferably 2 to 5 ethylenically unsaturated groups such as acrylate, methacrylate, vinyl, acrylamide and allyl. Preferred are compounds having multiple acrylate and methacrylate groups such as acrylic and methacrylic esters o polyols.
Examples of these materials are trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentacrythritol triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, pentaerythritol tetra-methacrylate, diallyl phthalate, diallyl adipate, diallyl succinate, etc. Suitable ethyleneically unsaturated, free-radical initiated, chain-propagating addition polymerizable compounds include alkylene or polyalkylene glycol diacrylates, e.g., diethylene glycol diacrylate, glycerol diacrylatel glycerol triacrylate, 1,3-propane-diaol dimethacrylate, 1,3-propanediaol dimethacrylate, 1,2,4butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, sorbitol hexaacrylate; bis[l-(3-acryloxy-~-hydroxy)]p-ethoxy-phenyl~dimethylmethane, tris-hydroxethyl-isocyanurate trimethacrylate~ the bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500 and the like unsaturated amides, e.g., methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexametbylene bisacrylamide, diethylene triamine trisacrylamide, B-methacrylaminoethyl methacrylate; vinyl esters such as divinyl succinate, divinyl adipate, and divinyl phthalate. Mixtures of these esters may also be used as well as mixtures of these compounds with alkyl esters of acrylic acid and methacrylic acid including such esters as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyacrylate, styrene~ diallyl phthalate and the llke. These compounds are generally known in the ' .' '.
~ , .
8~)~
art, as, for example, in British Patant No. t,482,953 and UDS. Patent Nos. 3,954,475 and 3,905,815. The poly-functional unsaturated materials are generally useful as~
10-60% by weight of actlve ingredients in the printing composition. Preferably they are present as 20-40~ by weight of the composition~
The free~radical photoinitiator systems of the present invention are generally known. They are compounds which absorb radiation, generally actinic radiation, and are activated to become agents which abstract hydrogens from hydrogen donorsO There may also be or may need to be sensitizers present to enable the compounds to be photoactivated. Examples of these materials are the benzoins, acetophenones, naphthoquinones and benzophenones (as disclosed in British Patent No. 1,482,953), vinyl substituted halomethyl-s-triazine compounds (as disclosed in U.S. Patent No. 3,954,47$~, and aromatic onium compounds (as disclosed in U,S. Patents Nos. 4,058,400;
4,058r401). Other desirable photoinitiator systems are generally known in the prior art such as in U.S~ Patent Nos. 3,775,113; 3,887,450; 3,8~5,949; and 4,043,819. The photoinitiator systems are generally useful as 0~5-15% by weight of active ingredients in the printing compositionO
Preferably they are present as 1-6~ by weight of the composition. When needed, spectral sensitizers are usually included at a level of about 10 to 70% by weight of the photoinitiator.
The water-softenable polymer of this invention is a water soluble or at least water softenable polymer which is also soluble in organic solvent systems. By water softenable it is meant that the Young's modulus of the polymer decreases in the presence of water. This modulus can be measured on commercially available equipment such as the "Rhe "* m~del D-DV~ C
manufactured by Ibyo Baldwin Cb., Ltd. A polymer which formed a m~lecular suspension in water would be one example of a non-soluble (in~water) polymer that was water softenable. Another example of a water softenable polymer is a polymer in which a portion of the bonds within or without (e.g., hydro-gen bondings) the polymers are broken in the presence of waterO Specific ex-amples of these polymers include polyvinyl pyrrolidone, partially hydrolyzed polyvinyl acetate, hydroxyalkyl cellulose resins (e.g., hydroxypropyl cellu-lose), and organic solvent soluble polyvinyl alcohol derivatives or copolymers.
These materials are generally well known in the art. British Patent No.
1,482,953 discloses the use of photopolymeric co~positions sui-table for the preparation of relief plates developable with wa-ter which contain amino-substituted hydroxyalkyl cellulose resins which would also be useful and are a species of hydroxyaIkyl cellulose resins. m e term water-softenable as used in the practice of the present inven-tion includes water soluble resins unless otherwise stated. The water-* Trade Mark : .
f,~ L~
softenable resins are generally useful as 10-40% by weight of solid ingredients in the printing composition.
Preferably they are present as 12-25~ by weight of the composition.
The substrates of the present invention may be any substrate, including metal, polymer and paper surfaces. Only when the coated article is to be used as a printing plate must the substrates be oleophobic on their surfaces. They are usually hydrophilic at the same time, but this is not essential. The substrate for a printing plate may be any material which is coated on at least one surface thereof to provide t~is oleophobic property. The 1 ~
substrates normally used for lithographic plates, such as those of U.S, Patent NosO 556,380; ~,100,063; ~,251,181;
3,181,461; 2,373,357; and 4,116,695 are useful in the practice of the present invention. Preferred are poly-meric or metal substrates. Particularly desirable are aluminum and zinc substrates. Most preferred are aluminum substrates which have a permanent hydrophilic ccating reacted onto the surface thereof by reaction of an aqueous solution of a soluble silicate as in U.S. Patent No.
2,714,066. This form of aluminum or zinc substrate is referred to as smooth, grained, or grained and anodi~ed.
A variety of alloys may be used with the aluminum, as is known in the prior art such as U.S. Patent No. ~,116,695.
When the term aluminum substrate or aluminum plate is used in the art, it is understood that the material is predominantly but not necessarily exclusively aluminumO
Over this substrate is usually applied another coating which comprises a water-soluble light-sensitive diazo resin which may be the same as some of those described above as part of the photoreactive compositionO
These resins are well known in the art and are also disclosed in U.S. Patent Nos~ 2,714,066 and 3,905,815.
In a preferred practice of the present invention, a sixth component may be added~ This component is an oleophilic polymer which is added to the composition to improve its ink receptivity. As the printing plates operate to provide an image by having areas of ink receptivity (oleophilic areas) and non-ink receptivity (oleophobic areas) in a subtractive development process, enhanced ink reception in the imaged areas where the composition is retained on the plate is desirable. Some of the binder resins listed above are also oleophilic, and resins in that list which are oleophilic may be added to the composition so that more than one organic solvent soluble resin is present. The oleophilic resin need not be a film forming resin, as structural integrity is provided by other components, but it is preferred that the oleophilic resin is a film forming polymer. Any compatible film forming oleophilic resin is useful, and cellulose acetate esters such as cellulose acetate butyrate and cellulose acetate propionate have been found to be particularly desirable. 1'nis ingredient shows ~4~
useful effects in weight percentages of from 0.5 to 75% of the composition (the maximum is where it also constitutes the binder resin).
There are numerous other additives which may be desirably added to these compositions. It is generally desirable to have a solvent system in the compositions when they are applied to the substrate. These solvents oE
course tend to evaporate out o the composition after it has been coated out. These solvent systems may comprise one or more solvents to keep all of the ingredients compatable, The solvents are usually organic polar solvents but some minor amount (e.g., up to about 25~ by weight) of non-polar solvents may be included.
Particularly desirable solvents include methylethyl ketone (and other ketones such as cyclohexanone and acetone), amides (such as dimethyl- formamide), chlorinated hydrocarbons (such as ethylene dichloride), 2-nitro-propane, diacetone alcohol, and short chain (e.g., 1 to 5 carbons) aliphatic alcohols. Many of these materials are disclosed in British Patent No~ 1,447,142. These are the types of organic solvents from amongst which all materials previously referred to as organic solvent soluble can find a solvent system of one or more solvents.
Dyes or pigments may also be used in the printing compositions, Acutance dyes would also be useful in compositions of the present invention. Many of these materials are disclosed in British Patent No. 1,447,142 ~ ~ ~4~30'~
for printing compositions.
For the p~lrpose of inhibiting premature polymerization and reducing any polymerization in non-imaged areas from scattered light, the incorporation of stabilizers such as phenolic stabilizers may be useful.
These materials are well known in the art and are exemplified by di-t-butyl-p-cresol, hydroquinone, quinone, hydroquinone monomethyl ether, amyl quinone, n-butyl phenol etc. These stabilizers are usually present in amounts from 0.0002 to 1 percent by weight of the solids in the composition.
The compositions may also contain inert particulate filler which is transmissive or transparent to actinic light. The particles mdy also be 50 small as to not interrupt light transmission~ Organophilic silicas, bentonites and powdered glass are exaMples of these materials. All should be smaller than 10 microns, preferably smaller than 1 micron, and rnost preferably smaller than 0.1 microns.
Flow control agents, viscosity modifiers, and surEactants may also be useful in the present compositions.
As noted above, many additional materials may be added to the compositions of the present invention. Some, of coursel are more or less desirable than others. Epoxy polymerizable materials are amongst those ingredients whlch are less prefered or undesirable, unless present in . . , amounts less than 10% by weight of solids in the compositions. Preferably there is no epoxy polymerizable materials present. The presence of the epoxy resins in amounts of 9% by weight or more, has been found to contribute only limited capability to water developability. Reduced amounts of epoxy polymer-izable materials has been surprisingly found to provide improved properties, even where koth ethylenically unsa-turated materials and epoxy polymerizable materials were present in that system. In view of the requirement for that minimum amount of epoxy polymerizable components in tha-t system, this was a surprising discovery. An epoxy polymerizable material is defined as any mater-ial (monomer, oligomer, prepolymer or polymer) which has polymerizable eFoxy groups thereon, particularly those materials with an epoxy eq~ivalent weight between 90 and 10,000.
The following exc~mples will show additional aspects of the present invention. All percentages are by weight unless otherwise stated. A11 plates were treated with co~mercially available diazo desensitizing ccmpositions after development.
~.
A photoreactive composition of the present invention was for~ulated by sequentially mixing ingredient~ as follows:
diallyl orthophthalate prepolymer (having the structure shown above) as a 25%
solution in methylethyl ketone 363 g polyvinylpyrrolidone as a 7% solution in ethyleneglycol monomethyl ether 590 g pentaerythritol tetraacrylate 68075 g cellulose acetate butyrate );.75 9 polyurethane resins as a 10~ solution in dimethylformamide ~.79 9 2(p-methoxystryl)4/6-bis~trichloromethyl) -s-triazine 5,5 g fluoroborate salt of the condensation product of paraformaldehyde and p-dia~.o diphenyla~lne 16.5 g yellow oil soluble dye 2.4 g dispersion of 18% Microlith Blue 4GK dye in methylethyl ketone (a copper phthalocyanine pigmant) 168 9 After homogeneous mixing of these compositions, the final solution was reduced to 8% solids by the addition of 250 g methylethyl ketone, 500 g dimethylformamide and 1293 g of ethyleneglycol monomethyl ether. The polyurethane resin used in this and other examples was a thermoplastic polyurethane having repeating units of the formula:
O O
-NC ~ CH2 ~ C-N-whlch has a Shore hardness of 78A, tensile strength of ., .
: - ~ ' ~, .. .
8900 (p.s.i.), and 300% Modulus at 1490 (psi).
The pigment dispersion in this and other examples was 60~ pigment in 40% vinyl copolymer comprising 86% units derived from vinylchloride and 14% units derived from vinyl acetate.
A lithographic ~upport plate structure for use in the examples was prepared according to the example in U.S. Patent No. 2,714,066. A smooth surfaced aluminum sheet was washed with trisodium phosphate, then treated with a nitric acid solution and rinsed in water. The sheet was then treated with an aqueous silicate solution and washed clean of any remaining water-soluble material.
An intially water-soluble/ light sensitive resin, p-diazodiphenylamine-formaldehyde resin as a 2.5~ aqueous solution, was then coated over the silicate treated surface. A dry coating weight of 120-140 mg/ft2 of the above described photoreactive composition was then applied and air dried at 71-88C.
A portion of this printing plate was exposed to a carbon arc source of ultraviolet radiation for 100 seconds at a distance of 1~37 meters. Development was with tap water and a few seconds of gentle rubbing with a soft cloth. After the coating in the unexposed areas was removed, the entire surface of the plate was treated with an aque~ous desensitizing and gumming solution. The plate was bu~fed dry, mounted on a lithographic printing plate, and in an overpacked condition was run for over ~,000 ',,,;
' ' ':
. . ~, 8~
i~pressions without loss of detail. Under normal packing conditions 50,000 impressions would be expected when used with fine quality halftone negatives. These plates can faithfully reproduce 176 line screens containing 3 highlight dots and 97~ shadows.
The water developed plate required only 3 to 5 paper copies being passed through the press before all light exposed areas would accept ink, being fully converted from a generally hydrophilic surface to a hydrophobic olephilic surface. This compares favorably with organic solvent deYeloped plates.
Example 2 A conventional grained and anodized substrate generally prepared according to the teachings of U.S.
15 Patents Nos. 3,181,461 and 3,865,700 was first coated with an initially water-soluble light sensitive p-diazodiphenyl-amine-formaldehyde resin as a 0.5~ aqueous solution and then coated with the following composition at a dry coating weight o~ 170-200mg/ft2:
Weight %
diallyl orthophthalate prepolymer (having the structure shown above) as a 25%
solution in methylethyl ketone 30 g polyvinylpyrrolidone as a 7% solution in ethylenglycol monomethyl ether 16 g pentaerythritol tetraacrylate 24.0 g , - . .
: -.
- ~, .
. .
. , .
cellulose acetate butyrate 2.0 g polyurethane resin as a 10% solution in dimethylformamide 5.5 g 2(p-methoxystyryl)4,6-bis(trichloromethyl) -s-triazine 2.0 g fluoroborate salt of the condensation product of paraformaldehyde and p-diazo diphenylamine 8.0 g yellow oil soluble dye 0.5 9 dispersion of 18% Microlith ~lue 46K dye in methylethyl ketone12.0 g After exposure and development as in Example 1, press testing under accelerated conditions indicated an expected durability of about one hundred thousand impressions under normal conditions. Roll-up of the plate required only 5 copies and image quality was believed to be sufficien~ to develop and hold 176 line screen with 3~97% dots.
Example 3 This example shows the utility of the plates of 0 the present invention for underexposure and post-heating.
A plate as prepared in Example 1 was exposed through a halftone negative in a step and repeat fashion so that different sections of the plate had 1/4, 1/2, 3/4, and full exposure as in Example 1. This plate was then developed as in Example 1 with tap water and treated with gum-desensitizer. The plate was then placed in an oven at about 230C for six minutes which helped to crosslink the underexposed portions of the plate and to preserve the sharp dot structure of the image.
4~
When mounted on a press along with a commercially available solvent developed plate which had a normal full exposure, the ur.derexposed portions of the water developed plates printed with a sharper dot structure and yet the section receiving only one-quarter o its normal exposure time ran equally as long as did the control solvent developed plate~
Example 4 The coating composition of Exa~ple 1, without the pentaerythritol tetraacrylate, was coated, exposed, developed and desensitized as in Example 1. The plate showed good dot quality and resolution. The plate, however, showed very poor resistance to contact with solvents, such as might be present in press rooms and in certain conventional inks. This result confirms the necessity of the polyethylenic~lly unsaturated component in the composition and plates of the present invention.
_ample 5 When the composition of Example 1, wlthout the organic solvent soluble diazo resinl was coated out on grained and anodized aluminum, no visible image appeared after exposure~ although development was good. There was poor adhesion of the coating, however, as the grey scale could be rubbed off almost completely with only water.
This shows the independent criticality of the diazo resin , ~ . . .
. .
to the composition~ It is believed that one of the significant aspects of the present invention is the combination of the ethylenically unsaturated component and organic solvent soluble diazo resin into one composition.
The combination of these two diverse imaging materials provides a composition of unique quality and performance as a water developable composition.
Examples 6-11 A ~aster batch of photoreactive composition without the organic solvent soluble film forming resin was constituted as follows:
diallyl phthalate prepolymer of Example 1 38 polyvinylpyrrolidone 20 %
pentecrythritol triacrylate 20 %
cellulose acetate butyrate 5 2-(p-methoxystyryl)-4,6-bis(trichloromethyl) -2-trizaine 3 %
fluoroborate salt of Example 1 6 %
Yellow oil soluble dye 0.5 ~
To portions of this composition each one of the following resins was added to a 7.S% level to form six different compositions which were coated on grained and anodized aluminum at the weight indicated in parentheses:
6. no additional film for~ing resin 7. polyvinylformal (167 mg/ft2) 8. diglycidyl ether of Bisphenol A (M.W~ of 1750-2050) (173 mg/ft2) ....
.
, 1~4~0'~
9. terpolymer of vinyl chloride (86%), vinylacetate (13%), and maleic acid (1~), (183 mg/ft2) 10. the polymer of Example 8, methacrylated by mixing 500g of the polymer with 806 g methacrylic acid, 0.49 triphenyl antimony and 0.065g triphenyl ~hosphorous and heating at 100C for 24 hours (183 mg/ft~) 11. (~oly) ~ ~methacryloxypropyltrimethoxy silane (198 gm~ft ) ~
These solutions were coated at 8% solids using a #10 wire wound Meyer bar on both smooth and grained aluminum hase both of which had been precoated with a 1% solution of the water soluble diazo resin used as a coating in Example 1 After exposure, development and press mounting, all samples ran for a longer press life than the same composi-lS tion without polymeric additive. The polyvinylformal and terpolymer appeared to be the most durable compositions of these resins.
Examples 12 and 13 The composition of Example 1 was replicated, once without any cellulose acetate butyrate and once with an equal weight amount of cellulose acetate propionate replacing the butyrate. The cellulose acetate propionate containing film performed in substantially the same fashion as the composition of claims 1 when exposed, developed and placed on press. Both compositions having the cellulose acetate esters retained portions of the ink charge applied to the developed plates by the inking roll more efficiently than the plates without them. This .. :
:
Qf~
property enables faster roll up and faster start-ups in the use of presses.
Examples 14-18 . _ A composition having no photoinitiator system therein was prepared having the following ingredients:
diallylorthophthalate prepolymer of Example 1 as a 10% solution in methylethyl ketone 13.1 %
polyvinylpyrrolidone tas a 7% solution in ethylene glycol monomethyl ether 24.7 %
triacrylate of tris(2-hydroxyethyl) isocyanurate (as a S0~ solution in methylethyl ketone) 30.3 %
cellulose acetate butyrate (10~ in dimethylformamide) 1.2 polyurethane of Example 1 (10% in dimethyl formamide) 6.1 %
fluoroborate salt of Example 1 7.2 %
yellow oil soluble dye 0.4 %
pigment dispersion o Example 1 t32.5 g) 17.0 ~
To this was added 152 g of ethleneglycol monomethyl ether 485 g of methylethyl ketone and 768g of dimethylformamide.
Five portions of 105 g each of this composition were taken and one of the following four photoinitiators were added thereto:
1. 2-(p-methoxystyryl)-4,6-bis-(trichloromethyl)-s-triazine 0.4 g 2. 2-chloro-thioxanthone 0.4 g 3. diphenyliodonium hexafluorophosphate (0.4g) and 4l4-bistdimethylamino)-benzophenone 004 9 ;: ,, 4~
4. isopropyl benzoin ether (0.~9) and 4,4'-bis(dimethylamino)benzophenone 0.2 g The fifth portlon contained no photoinitiator system. The first portion showed good organic solvent resistance, indicating good crosslinking. The second and third portions showed fair solvent resistance, some of which would be improved by higher intensity exposure. The fourth and fifth samples showed no solvent resistance. In the case of the ether, the glass window of the exposure frame may have acted as a special filter for the peak sensitivity range for that particular well known free radical photoinitiator.
Examples 19~20 To portions of a composition having all of the ingredients of Example 1, except for the polyvinyl-pyrrolidone, and having the following composition:
prepolymer 31~, tetraacrylate 31%, triazine photoinitiator 3%, diazo resin 3%, cellulose acetate butyrate 3%, yellow oil dye 1%, pigment dispersion 9% and dimethylformamide in an amount equal to about 31 times the combined weight of the initiator, diazo resin, butyrate and yellow oil dye were added the following polymers in an amount equal to 19% of the total composition solids (as 10~ solutions in dimethylformamide):
1. Low molecular weight hydroxypropyl cellulose.
2. copolymer (50/50) of polyvinyl acetate and polyvinyl alcohol.
':
. ~Lf.~f,a~
Both compositions were coa-ted at a 20% solids level on ~mooth aluminutn base having a coating of water soluble diazo resin thereon. ~1 all cases the pre-dispersed pigtttent tended -to fall out of solution. After ~posure through a halftone transparency and tap water development it was noted tha-t the copolym~r ccm~osition deve~oped easier and the resulting image was tougher than that of the composition with the cellulose. The first composition still developed easily and the image portions accepted ink readily. The use of a higher molecular weight hydroxypropyl cellulose resins caused the composition to develop with more difficulty, but it did develop with tap water and the images accepted the ink af-ter desensitization with conventional lithographic process gum.
Examples 21 and 22 .
Fbur portions of composition of Example 1 were duplicated except that the prepolymer was replaced by equal weight portions of two diglycid~l ethers of Bisphenol A having high (MW 875-1025) and low tMW 450-550) molecular weight, polymethacrylated digylcidyl ether of Bisphenol A, and a polyacrylated polycaprolactone-2,4-toluene diisocyanate-hexane diol oligomer ~aught in Example 2 of U.S. Patent No. 4,249,011. The compositions with~ut the acrylate groups either had little solvent and abrasion resistance or developed with difficulty. Both compositions containing the .~
., .
4i~30~
ethylenically unsaturated materials performed well in comparison to the com-position of Example 1.
The diglycidyl ether prepolymers had the following structure CH IH C 2 ~ ~ I ~ OC~I2CH-C~I2 1 0 ~ C ~r ~ o-C}I2-C~ ~ Cll2 Cl13 n CH3 0 wherein n in the low molecular weight prepolymer is about 2.5 and n in the high molecular weight prepolymer is about 6.
Examples 23 - 25 The following examples investigate the extreme limits of the ranges for certain ingredients. All compositions were formed from the same components:
l) monomer: trishydroxyethylisocyanurate triacrylate 2) water softenable binder: polyvinylpyrrolidone (as a 7% solution in ethyleneglycol monomethyl ether) 3) film forming binders: a) the polyallylorthophthalate prepolymer the structural formula of which is shown earlier, b) a copolymer of vinyl acetate and vinyl chloride (14/86), and c) cellulose acetate butyrate 4) solvent soluble diazo resin: the tetrafluoroborate salt of the con-densation product of paraformaldehyde and p-diazo diphenylamine
Preferably they are present as 1-6~ by weight of the composition. When needed, spectral sensitizers are usually included at a level of about 10 to 70% by weight of the photoinitiator.
The water-softenable polymer of this invention is a water soluble or at least water softenable polymer which is also soluble in organic solvent systems. By water softenable it is meant that the Young's modulus of the polymer decreases in the presence of water. This modulus can be measured on commercially available equipment such as the "Rhe "* m~del D-DV~ C
manufactured by Ibyo Baldwin Cb., Ltd. A polymer which formed a m~lecular suspension in water would be one example of a non-soluble (in~water) polymer that was water softenable. Another example of a water softenable polymer is a polymer in which a portion of the bonds within or without (e.g., hydro-gen bondings) the polymers are broken in the presence of waterO Specific ex-amples of these polymers include polyvinyl pyrrolidone, partially hydrolyzed polyvinyl acetate, hydroxyalkyl cellulose resins (e.g., hydroxypropyl cellu-lose), and organic solvent soluble polyvinyl alcohol derivatives or copolymers.
These materials are generally well known in the art. British Patent No.
1,482,953 discloses the use of photopolymeric co~positions sui-table for the preparation of relief plates developable with wa-ter which contain amino-substituted hydroxyalkyl cellulose resins which would also be useful and are a species of hydroxyaIkyl cellulose resins. m e term water-softenable as used in the practice of the present inven-tion includes water soluble resins unless otherwise stated. The water-* Trade Mark : .
f,~ L~
softenable resins are generally useful as 10-40% by weight of solid ingredients in the printing composition.
Preferably they are present as 12-25~ by weight of the composition.
The substrates of the present invention may be any substrate, including metal, polymer and paper surfaces. Only when the coated article is to be used as a printing plate must the substrates be oleophobic on their surfaces. They are usually hydrophilic at the same time, but this is not essential. The substrate for a printing plate may be any material which is coated on at least one surface thereof to provide t~is oleophobic property. The 1 ~
substrates normally used for lithographic plates, such as those of U.S, Patent NosO 556,380; ~,100,063; ~,251,181;
3,181,461; 2,373,357; and 4,116,695 are useful in the practice of the present invention. Preferred are poly-meric or metal substrates. Particularly desirable are aluminum and zinc substrates. Most preferred are aluminum substrates which have a permanent hydrophilic ccating reacted onto the surface thereof by reaction of an aqueous solution of a soluble silicate as in U.S. Patent No.
2,714,066. This form of aluminum or zinc substrate is referred to as smooth, grained, or grained and anodi~ed.
A variety of alloys may be used with the aluminum, as is known in the prior art such as U.S. Patent No. ~,116,695.
When the term aluminum substrate or aluminum plate is used in the art, it is understood that the material is predominantly but not necessarily exclusively aluminumO
Over this substrate is usually applied another coating which comprises a water-soluble light-sensitive diazo resin which may be the same as some of those described above as part of the photoreactive compositionO
These resins are well known in the art and are also disclosed in U.S. Patent Nos~ 2,714,066 and 3,905,815.
In a preferred practice of the present invention, a sixth component may be added~ This component is an oleophilic polymer which is added to the composition to improve its ink receptivity. As the printing plates operate to provide an image by having areas of ink receptivity (oleophilic areas) and non-ink receptivity (oleophobic areas) in a subtractive development process, enhanced ink reception in the imaged areas where the composition is retained on the plate is desirable. Some of the binder resins listed above are also oleophilic, and resins in that list which are oleophilic may be added to the composition so that more than one organic solvent soluble resin is present. The oleophilic resin need not be a film forming resin, as structural integrity is provided by other components, but it is preferred that the oleophilic resin is a film forming polymer. Any compatible film forming oleophilic resin is useful, and cellulose acetate esters such as cellulose acetate butyrate and cellulose acetate propionate have been found to be particularly desirable. 1'nis ingredient shows ~4~
useful effects in weight percentages of from 0.5 to 75% of the composition (the maximum is where it also constitutes the binder resin).
There are numerous other additives which may be desirably added to these compositions. It is generally desirable to have a solvent system in the compositions when they are applied to the substrate. These solvents oE
course tend to evaporate out o the composition after it has been coated out. These solvent systems may comprise one or more solvents to keep all of the ingredients compatable, The solvents are usually organic polar solvents but some minor amount (e.g., up to about 25~ by weight) of non-polar solvents may be included.
Particularly desirable solvents include methylethyl ketone (and other ketones such as cyclohexanone and acetone), amides (such as dimethyl- formamide), chlorinated hydrocarbons (such as ethylene dichloride), 2-nitro-propane, diacetone alcohol, and short chain (e.g., 1 to 5 carbons) aliphatic alcohols. Many of these materials are disclosed in British Patent No~ 1,447,142. These are the types of organic solvents from amongst which all materials previously referred to as organic solvent soluble can find a solvent system of one or more solvents.
Dyes or pigments may also be used in the printing compositions, Acutance dyes would also be useful in compositions of the present invention. Many of these materials are disclosed in British Patent No. 1,447,142 ~ ~ ~4~30'~
for printing compositions.
For the p~lrpose of inhibiting premature polymerization and reducing any polymerization in non-imaged areas from scattered light, the incorporation of stabilizers such as phenolic stabilizers may be useful.
These materials are well known in the art and are exemplified by di-t-butyl-p-cresol, hydroquinone, quinone, hydroquinone monomethyl ether, amyl quinone, n-butyl phenol etc. These stabilizers are usually present in amounts from 0.0002 to 1 percent by weight of the solids in the composition.
The compositions may also contain inert particulate filler which is transmissive or transparent to actinic light. The particles mdy also be 50 small as to not interrupt light transmission~ Organophilic silicas, bentonites and powdered glass are exaMples of these materials. All should be smaller than 10 microns, preferably smaller than 1 micron, and rnost preferably smaller than 0.1 microns.
Flow control agents, viscosity modifiers, and surEactants may also be useful in the present compositions.
As noted above, many additional materials may be added to the compositions of the present invention. Some, of coursel are more or less desirable than others. Epoxy polymerizable materials are amongst those ingredients whlch are less prefered or undesirable, unless present in . . , amounts less than 10% by weight of solids in the compositions. Preferably there is no epoxy polymerizable materials present. The presence of the epoxy resins in amounts of 9% by weight or more, has been found to contribute only limited capability to water developability. Reduced amounts of epoxy polymer-izable materials has been surprisingly found to provide improved properties, even where koth ethylenically unsa-turated materials and epoxy polymerizable materials were present in that system. In view of the requirement for that minimum amount of epoxy polymerizable components in tha-t system, this was a surprising discovery. An epoxy polymerizable material is defined as any mater-ial (monomer, oligomer, prepolymer or polymer) which has polymerizable eFoxy groups thereon, particularly those materials with an epoxy eq~ivalent weight between 90 and 10,000.
The following exc~mples will show additional aspects of the present invention. All percentages are by weight unless otherwise stated. A11 plates were treated with co~mercially available diazo desensitizing ccmpositions after development.
~.
A photoreactive composition of the present invention was for~ulated by sequentially mixing ingredient~ as follows:
diallyl orthophthalate prepolymer (having the structure shown above) as a 25%
solution in methylethyl ketone 363 g polyvinylpyrrolidone as a 7% solution in ethyleneglycol monomethyl ether 590 g pentaerythritol tetraacrylate 68075 g cellulose acetate butyrate );.75 9 polyurethane resins as a 10~ solution in dimethylformamide ~.79 9 2(p-methoxystryl)4/6-bis~trichloromethyl) -s-triazine 5,5 g fluoroborate salt of the condensation product of paraformaldehyde and p-dia~.o diphenyla~lne 16.5 g yellow oil soluble dye 2.4 g dispersion of 18% Microlith Blue 4GK dye in methylethyl ketone (a copper phthalocyanine pigmant) 168 9 After homogeneous mixing of these compositions, the final solution was reduced to 8% solids by the addition of 250 g methylethyl ketone, 500 g dimethylformamide and 1293 g of ethyleneglycol monomethyl ether. The polyurethane resin used in this and other examples was a thermoplastic polyurethane having repeating units of the formula:
O O
-NC ~ CH2 ~ C-N-whlch has a Shore hardness of 78A, tensile strength of ., .
: - ~ ' ~, .. .
8900 (p.s.i.), and 300% Modulus at 1490 (psi).
The pigment dispersion in this and other examples was 60~ pigment in 40% vinyl copolymer comprising 86% units derived from vinylchloride and 14% units derived from vinyl acetate.
A lithographic ~upport plate structure for use in the examples was prepared according to the example in U.S. Patent No. 2,714,066. A smooth surfaced aluminum sheet was washed with trisodium phosphate, then treated with a nitric acid solution and rinsed in water. The sheet was then treated with an aqueous silicate solution and washed clean of any remaining water-soluble material.
An intially water-soluble/ light sensitive resin, p-diazodiphenylamine-formaldehyde resin as a 2.5~ aqueous solution, was then coated over the silicate treated surface. A dry coating weight of 120-140 mg/ft2 of the above described photoreactive composition was then applied and air dried at 71-88C.
A portion of this printing plate was exposed to a carbon arc source of ultraviolet radiation for 100 seconds at a distance of 1~37 meters. Development was with tap water and a few seconds of gentle rubbing with a soft cloth. After the coating in the unexposed areas was removed, the entire surface of the plate was treated with an aque~ous desensitizing and gumming solution. The plate was bu~fed dry, mounted on a lithographic printing plate, and in an overpacked condition was run for over ~,000 ',,,;
' ' ':
. . ~, 8~
i~pressions without loss of detail. Under normal packing conditions 50,000 impressions would be expected when used with fine quality halftone negatives. These plates can faithfully reproduce 176 line screens containing 3 highlight dots and 97~ shadows.
The water developed plate required only 3 to 5 paper copies being passed through the press before all light exposed areas would accept ink, being fully converted from a generally hydrophilic surface to a hydrophobic olephilic surface. This compares favorably with organic solvent deYeloped plates.
Example 2 A conventional grained and anodized substrate generally prepared according to the teachings of U.S.
15 Patents Nos. 3,181,461 and 3,865,700 was first coated with an initially water-soluble light sensitive p-diazodiphenyl-amine-formaldehyde resin as a 0.5~ aqueous solution and then coated with the following composition at a dry coating weight o~ 170-200mg/ft2:
Weight %
diallyl orthophthalate prepolymer (having the structure shown above) as a 25%
solution in methylethyl ketone 30 g polyvinylpyrrolidone as a 7% solution in ethylenglycol monomethyl ether 16 g pentaerythritol tetraacrylate 24.0 g , - . .
: -.
- ~, .
. .
. , .
cellulose acetate butyrate 2.0 g polyurethane resin as a 10% solution in dimethylformamide 5.5 g 2(p-methoxystyryl)4,6-bis(trichloromethyl) -s-triazine 2.0 g fluoroborate salt of the condensation product of paraformaldehyde and p-diazo diphenylamine 8.0 g yellow oil soluble dye 0.5 9 dispersion of 18% Microlith ~lue 46K dye in methylethyl ketone12.0 g After exposure and development as in Example 1, press testing under accelerated conditions indicated an expected durability of about one hundred thousand impressions under normal conditions. Roll-up of the plate required only 5 copies and image quality was believed to be sufficien~ to develop and hold 176 line screen with 3~97% dots.
Example 3 This example shows the utility of the plates of 0 the present invention for underexposure and post-heating.
A plate as prepared in Example 1 was exposed through a halftone negative in a step and repeat fashion so that different sections of the plate had 1/4, 1/2, 3/4, and full exposure as in Example 1. This plate was then developed as in Example 1 with tap water and treated with gum-desensitizer. The plate was then placed in an oven at about 230C for six minutes which helped to crosslink the underexposed portions of the plate and to preserve the sharp dot structure of the image.
4~
When mounted on a press along with a commercially available solvent developed plate which had a normal full exposure, the ur.derexposed portions of the water developed plates printed with a sharper dot structure and yet the section receiving only one-quarter o its normal exposure time ran equally as long as did the control solvent developed plate~
Example 4 The coating composition of Exa~ple 1, without the pentaerythritol tetraacrylate, was coated, exposed, developed and desensitized as in Example 1. The plate showed good dot quality and resolution. The plate, however, showed very poor resistance to contact with solvents, such as might be present in press rooms and in certain conventional inks. This result confirms the necessity of the polyethylenic~lly unsaturated component in the composition and plates of the present invention.
_ample 5 When the composition of Example 1, wlthout the organic solvent soluble diazo resinl was coated out on grained and anodized aluminum, no visible image appeared after exposure~ although development was good. There was poor adhesion of the coating, however, as the grey scale could be rubbed off almost completely with only water.
This shows the independent criticality of the diazo resin , ~ . . .
. .
to the composition~ It is believed that one of the significant aspects of the present invention is the combination of the ethylenically unsaturated component and organic solvent soluble diazo resin into one composition.
The combination of these two diverse imaging materials provides a composition of unique quality and performance as a water developable composition.
Examples 6-11 A ~aster batch of photoreactive composition without the organic solvent soluble film forming resin was constituted as follows:
diallyl phthalate prepolymer of Example 1 38 polyvinylpyrrolidone 20 %
pentecrythritol triacrylate 20 %
cellulose acetate butyrate 5 2-(p-methoxystyryl)-4,6-bis(trichloromethyl) -2-trizaine 3 %
fluoroborate salt of Example 1 6 %
Yellow oil soluble dye 0.5 ~
To portions of this composition each one of the following resins was added to a 7.S% level to form six different compositions which were coated on grained and anodized aluminum at the weight indicated in parentheses:
6. no additional film for~ing resin 7. polyvinylformal (167 mg/ft2) 8. diglycidyl ether of Bisphenol A (M.W~ of 1750-2050) (173 mg/ft2) ....
.
, 1~4~0'~
9. terpolymer of vinyl chloride (86%), vinylacetate (13%), and maleic acid (1~), (183 mg/ft2) 10. the polymer of Example 8, methacrylated by mixing 500g of the polymer with 806 g methacrylic acid, 0.49 triphenyl antimony and 0.065g triphenyl ~hosphorous and heating at 100C for 24 hours (183 mg/ft~) 11. (~oly) ~ ~methacryloxypropyltrimethoxy silane (198 gm~ft ) ~
These solutions were coated at 8% solids using a #10 wire wound Meyer bar on both smooth and grained aluminum hase both of which had been precoated with a 1% solution of the water soluble diazo resin used as a coating in Example 1 After exposure, development and press mounting, all samples ran for a longer press life than the same composi-lS tion without polymeric additive. The polyvinylformal and terpolymer appeared to be the most durable compositions of these resins.
Examples 12 and 13 The composition of Example 1 was replicated, once without any cellulose acetate butyrate and once with an equal weight amount of cellulose acetate propionate replacing the butyrate. The cellulose acetate propionate containing film performed in substantially the same fashion as the composition of claims 1 when exposed, developed and placed on press. Both compositions having the cellulose acetate esters retained portions of the ink charge applied to the developed plates by the inking roll more efficiently than the plates without them. This .. :
:
Qf~
property enables faster roll up and faster start-ups in the use of presses.
Examples 14-18 . _ A composition having no photoinitiator system therein was prepared having the following ingredients:
diallylorthophthalate prepolymer of Example 1 as a 10% solution in methylethyl ketone 13.1 %
polyvinylpyrrolidone tas a 7% solution in ethylene glycol monomethyl ether 24.7 %
triacrylate of tris(2-hydroxyethyl) isocyanurate (as a S0~ solution in methylethyl ketone) 30.3 %
cellulose acetate butyrate (10~ in dimethylformamide) 1.2 polyurethane of Example 1 (10% in dimethyl formamide) 6.1 %
fluoroborate salt of Example 1 7.2 %
yellow oil soluble dye 0.4 %
pigment dispersion o Example 1 t32.5 g) 17.0 ~
To this was added 152 g of ethleneglycol monomethyl ether 485 g of methylethyl ketone and 768g of dimethylformamide.
Five portions of 105 g each of this composition were taken and one of the following four photoinitiators were added thereto:
1. 2-(p-methoxystyryl)-4,6-bis-(trichloromethyl)-s-triazine 0.4 g 2. 2-chloro-thioxanthone 0.4 g 3. diphenyliodonium hexafluorophosphate (0.4g) and 4l4-bistdimethylamino)-benzophenone 004 9 ;: ,, 4~
4. isopropyl benzoin ether (0.~9) and 4,4'-bis(dimethylamino)benzophenone 0.2 g The fifth portlon contained no photoinitiator system. The first portion showed good organic solvent resistance, indicating good crosslinking. The second and third portions showed fair solvent resistance, some of which would be improved by higher intensity exposure. The fourth and fifth samples showed no solvent resistance. In the case of the ether, the glass window of the exposure frame may have acted as a special filter for the peak sensitivity range for that particular well known free radical photoinitiator.
Examples 19~20 To portions of a composition having all of the ingredients of Example 1, except for the polyvinyl-pyrrolidone, and having the following composition:
prepolymer 31~, tetraacrylate 31%, triazine photoinitiator 3%, diazo resin 3%, cellulose acetate butyrate 3%, yellow oil dye 1%, pigment dispersion 9% and dimethylformamide in an amount equal to about 31 times the combined weight of the initiator, diazo resin, butyrate and yellow oil dye were added the following polymers in an amount equal to 19% of the total composition solids (as 10~ solutions in dimethylformamide):
1. Low molecular weight hydroxypropyl cellulose.
2. copolymer (50/50) of polyvinyl acetate and polyvinyl alcohol.
':
. ~Lf.~f,a~
Both compositions were coa-ted at a 20% solids level on ~mooth aluminutn base having a coating of water soluble diazo resin thereon. ~1 all cases the pre-dispersed pigtttent tended -to fall out of solution. After ~posure through a halftone transparency and tap water development it was noted tha-t the copolym~r ccm~osition deve~oped easier and the resulting image was tougher than that of the composition with the cellulose. The first composition still developed easily and the image portions accepted ink readily. The use of a higher molecular weight hydroxypropyl cellulose resins caused the composition to develop with more difficulty, but it did develop with tap water and the images accepted the ink af-ter desensitization with conventional lithographic process gum.
Examples 21 and 22 .
Fbur portions of composition of Example 1 were duplicated except that the prepolymer was replaced by equal weight portions of two diglycid~l ethers of Bisphenol A having high (MW 875-1025) and low tMW 450-550) molecular weight, polymethacrylated digylcidyl ether of Bisphenol A, and a polyacrylated polycaprolactone-2,4-toluene diisocyanate-hexane diol oligomer ~aught in Example 2 of U.S. Patent No. 4,249,011. The compositions with~ut the acrylate groups either had little solvent and abrasion resistance or developed with difficulty. Both compositions containing the .~
., .
4i~30~
ethylenically unsaturated materials performed well in comparison to the com-position of Example 1.
The diglycidyl ether prepolymers had the following structure CH IH C 2 ~ ~ I ~ OC~I2CH-C~I2 1 0 ~ C ~r ~ o-C}I2-C~ ~ Cll2 Cl13 n CH3 0 wherein n in the low molecular weight prepolymer is about 2.5 and n in the high molecular weight prepolymer is about 6.
Examples 23 - 25 The following examples investigate the extreme limits of the ranges for certain ingredients. All compositions were formed from the same components:
l) monomer: trishydroxyethylisocyanurate triacrylate 2) water softenable binder: polyvinylpyrrolidone (as a 7% solution in ethyleneglycol monomethyl ether) 3) film forming binders: a) the polyallylorthophthalate prepolymer the structural formula of which is shown earlier, b) a copolymer of vinyl acetate and vinyl chloride (14/86), and c) cellulose acetate butyrate 4) solvent soluble diazo resin: the tetrafluoroborate salt of the con-densation product of paraformaldehyde and p-diazo diphenylamine
5~ photoinitiator system: 2-~p-methoxystyryl)-4,4-bis-(trichloromethyl)-s-triazine
6) pigment: Microlith Blue 4GK in methyl ethyl ketone (18% dispersion) The compositions evaluated are shown in percentages by weight in the following table.
Example 23 24 25 Monomer 50 65 65 Water Softenable Binder 30 10 5 Film Forming Binder 5.0a, 3.2b 8a, 3.2b, 2c 9a, 3.2b , Diazo S
Photoinitiators 2 2 2 Pigment 4.8 4.8 4.8 Each of ~he compositions were homogeneously mixed and coated at 120-140 mg/ft2 onto separate lithographic support plate struckures as recited in Example 1. The plates were then exposed and developed in tap water according to -the procedures of Example 1. All plates were developable with water and held ink well. The plate of Example 25 was more difficult to develop (required more with water), but did provide a usable plate. The higher amounts of monomer made the plates more tacky, but all performed reasonably well.
The water softenable binder does, in fact, provide some coherent film forming properties to the composition and printing plate in a manner similar to the organic solvent solwble film forming binder. The main reqwire-ment for the presence of at least 1% by weight of the la~ter is to assist in providing ink receptivity.
: '
Example 23 24 25 Monomer 50 65 65 Water Softenable Binder 30 10 5 Film Forming Binder 5.0a, 3.2b 8a, 3.2b, 2c 9a, 3.2b , Diazo S
Photoinitiators 2 2 2 Pigment 4.8 4.8 4.8 Each of ~he compositions were homogeneously mixed and coated at 120-140 mg/ft2 onto separate lithographic support plate struckures as recited in Example 1. The plates were then exposed and developed in tap water according to -the procedures of Example 1. All plates were developable with water and held ink well. The plate of Example 25 was more difficult to develop (required more with water), but did provide a usable plate. The higher amounts of monomer made the plates more tacky, but all performed reasonably well.
The water softenable binder does, in fact, provide some coherent film forming properties to the composition and printing plate in a manner similar to the organic solvent solwble film forming binder. The main reqwire-ment for the presence of at least 1% by weight of the la~ter is to assist in providing ink receptivity.
: '
Claims (23)
1. A photoreactive composition comprising a homogeneous mixture of:
A. 15-75% by weight of an organic solvent soluble film forming resin, B. 10-60% by weight of free radical polymerizable polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free-radical photoinitiator system, D. 10-40% by weight of a water-softenable organic solvent soluble polymer, and E. 1-20% by weight of organic solvent soluble diazo resin.
A. 15-75% by weight of an organic solvent soluble film forming resin, B. 10-60% by weight of free radical polymerizable polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free-radical photoinitiator system, D. 10-40% by weight of a water-softenable organic solvent soluble polymer, and E. 1-20% by weight of organic solvent soluble diazo resin.
2. An imageable system comprising a substrate having coated on at least one surface thereof the photoreactive composition of claim 1.
3. The imageable system of claim 2 wherein the substrate comprises aluminum the surface of which is coated with the photoreactive composition is oleophilic.
4, The imageable system of claim 3 wherein there is a coating of a water soluble diazo resin on the aluminum surface under the coating of the photoreactive composition.
5. The composition of claim 1 wherein at least two of the ethylenically unsaturated groups on said ethylenically unsaturated compounds are selected from the class consisting of acrylate and methacrylic groups.
6. The composition of claim 5 wherein said ethylenically unsaturated compounds have from 2 to 5 groups selected from the group consisting of acrylate and methacrylate groups.
7. The composition of claims 1 or 5 wherein said watersoftenable polymer is selected from the group consisting of polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetate, hydroxyalkyl cellulose resins, and organic solvent soluble polyvinyl alcohol derivatives.
8. The composition of claim 5 wherein said water-softenable resin comprises polyvinylpyrrolidone.
9. The composition of claim 6 wherein said water-softenable resin comprises polyvinylpyrrolidone.
10. The composition of claims 1 or 5 wherein at least 0.5% by weight of a second film forming resin which is oleophilic is present.
11. The composition of claim 8 wherein at least 0.5% by weight of oleophilic film forming resin is present.
12. The composition of claim 11 wherein said oleophilic film forming resin is selected from the group consisting of cellulose acetate butyrate and cellulose acetate propionate.
13. The composition of claim 5 wherein said the group consisting of epoxy resins, polyesters, polyallyl orthophthalate prepolymers, polyallyl isophthalate prepolymers, polyvinyl formal, polyurethanes/ polyvinyl-butyral, polyoxyethylene oxides, polyvinylhydrogen phthalates, polyacrylates, polymethacrylates, cellulose acetate esters, and polyvinylchloride having a molecular weight of at least 1,000.
14. The composition of claim 5 wherein said the group consisting of epoxy resins, polyesters, polyallyl orthophthalate prepolymers, polyallyl isophthalate prepolymers, polyvinyl formal, polyurethanes, polyvinyl-butyral, polyoxyethylene oxides, polyvinylhydrogen phthalates, polyacrylates, polymethacrylates, cellulose acetate esters, and polyvinylchloride having a molecular weight of at least 1,000.
15. The composition of claim 5 wherein said the group consisting of epoxy resins, polyesters, polyallyl orthophthalate prepolymers, polyallyl isophthalate prepolymers, polyvinyl formal, polyurethanes, polyvinyl-butyral, polyoxyethylene oxides, polyvinylhydrogen phthalates, polyacrylates, polymethacrylates, cellulose acetate esters, and polyvinylchloride having a molecular weight of at least 1, 000.
16. The composition of claim 5 wherein the said group consisting of epoxy resins, polyesters, polyallyl orthophthalate prepolymers, polyallyl isophthalate prepolymers, polyvinyl formal, polyurethanes, polyvinyl-butyral, polyoxyethylene oxides, polyvinylhydrogen phthalates, polyacxylates, poly-methacrylates, cellulose acetate esters, and polyvinylchloride having a molecular weight of at least 1,000.
17. An imageable system comprising a grained and anodized aluminum substrate, a water soluble diazo resin on one surface thereof, and the photoreactive ccmposition of claim 5, 6 or 8 coated over said water soluble diazo resin.
18. A photoreactive composition comprising in homogeneous mixture a diazo resin, a free radical polymerizable polyethylenically unsaturated compound, and a free radical photoinitiator system.
19. The ccmposition of claim 6 wherein said solvent soluble film form-ing resin comprises a resin which is capable of crosslinking or polymerizing by itself when heated to a temperature of at least 100°C.
20. An imageable system comprising a grained and anodized aluminum substrate, a water soluble diazo resin on one surface thereof, and the photo-reactive composition of claim 7 coated over said water soluble diazo resin.
21. An imageable system comprising a grained and anodized aluminum substrate, a water soluble diazo resin on one surface thereof, and the photo-reactive composition of claims 10 coated over said water soluble diazo resin.
22. A photoreactive composition comprising a homogeneous mixture of:
A. 1-75% by weight of organic solvent soluble film forming resin, B. 10-65% by weight of free radical polymerizable polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free radical photoinitiator system, D. 5-40% by weight of a water softenable organic solvent soluble polymer, and E. 1-20% by weight of organic solvent soluble diazo resin.
A. 1-75% by weight of organic solvent soluble film forming resin, B. 10-65% by weight of free radical polymerizable polyethylenically unsaturated compounds having at least two ethylenically unsaturated groups, C. 0.5 to 15% by weight of a free radical photoinitiator system, D. 5-40% by weight of a water softenable organic solvent soluble polymer, and E. 1-20% by weight of organic solvent soluble diazo resin.
23. A photoreactive composition comprising a homogeneous mixture according to claim 22 wherein the sum of the water softenable and organic film forming resins would be equal to at least 10% by weight of the com-position.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1558479A | 1979-02-27 | 1979-02-27 | |
| US15,584 | 1979-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144804A true CA1144804A (en) | 1983-04-19 |
Family
ID=21772291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000346444A Expired CA1144804A (en) | 1979-02-27 | 1980-02-26 | Photosensitive composition containing a diazo resin, a polyethylenically unsaturated compound and a photoinitiator |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS55120028A (en) |
| BE (1) | BE881956A (en) |
| BR (1) | BR8001128A (en) |
| CA (1) | CA1144804A (en) |
| DE (1) | DE3007212A1 (en) |
| ES (1) | ES8103397A1 (en) |
| FR (1) | FR2450473A1 (en) |
| GB (1) | GB2044788B (en) |
| NL (1) | NL8001085A (en) |
| ZA (1) | ZA801085B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4652604A (en) * | 1985-08-02 | 1987-03-24 | American Hoechst Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
| US4707437A (en) * | 1985-08-02 | 1987-11-17 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
| US4772538A (en) * | 1985-08-02 | 1988-09-20 | American Hoechst Corporation | Water developable lithographic composition |
| US4780392A (en) * | 1985-08-02 | 1988-10-25 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymerizable acrylic monomer |
| US4822720A (en) * | 1985-08-02 | 1989-04-18 | Hoechst Celanese Corporation | Water developable screen printing composition |
| US5120772A (en) * | 1985-08-02 | 1992-06-09 | Walls John E | Radiation-polymerizable composition and element containing a photopolymerizable mixture |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57141640A (en) * | 1981-02-03 | 1982-09-02 | Konishiroku Photo Ind Co Ltd | Photosensitive image forming material |
| JPS57197537A (en) * | 1981-05-29 | 1982-12-03 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
| JPS582847A (en) * | 1981-06-30 | 1983-01-08 | Konishiroku Photo Ind Co Ltd | Lithographic plate |
| JPS58199341A (en) * | 1982-05-17 | 1983-11-19 | Tokyo Ohka Kogyo Co Ltd | Heat resistant photosensitive resin composition |
| JPS5953836A (en) * | 1982-09-21 | 1984-03-28 | Fuji Photo Film Co Ltd | Photosensitive lithographic plate |
| JPS59101644A (en) * | 1982-12-01 | 1984-06-12 | Fuji Photo Film Co Ltd | Photosensitive composition |
| US4600679A (en) * | 1984-05-25 | 1986-07-15 | W. R. Grace & Co. | Water-developable, negative-working, diazo lithographic printing plate with oleophilic ester overlayer |
| DE3425328A1 (en) * | 1984-07-10 | 1986-01-16 | Hoechst Ag, 6230 Frankfurt | LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
| EP0184725B1 (en) * | 1984-12-06 | 1989-01-04 | Hoechst Celanese Corporation | Light-sensitive composition |
| DE3504658A1 (en) * | 1985-02-12 | 1986-08-14 | Hoechst Ag, 6230 Frankfurt | LIGHT-SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREFOR |
| DE3605717A1 (en) * | 1985-02-28 | 1986-08-28 | Hoechst Celanese Corp., Somerville, N.J. | POLYMERIZABLE MIXTURE BY RADIATION |
| US4851319A (en) * | 1985-02-28 | 1989-07-25 | Hoechst Celanese Corporation | Radiation polymerizable composition, photographic element, and method of making element with diazonium salt, and monofunctional and polyfunctional acrylic monomers |
| US5080999A (en) * | 1985-06-10 | 1992-01-14 | Fuji Photo Film Co., Ltd. | Light-sensitive diazo resin composition containing a higher fatty acid or higher fatty acid amide |
| DE3528309A1 (en) * | 1985-08-07 | 1987-02-12 | Hoechst Ag | LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
| JPS6278544A (en) * | 1985-10-01 | 1987-04-10 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JPS62238553A (en) * | 1986-04-10 | 1987-10-19 | Nippon Foil Mfg Co Ltd | Photosensitive resin composition |
| US4877711A (en) * | 1986-05-19 | 1989-10-31 | Fuji Photo Film Co., Ltd. | Light-sensitive diazo photopolymerizable composition with polyurethane having carbon-carbon unsaturated and a carboxyl group |
| DE3644160A1 (en) * | 1986-12-23 | 1988-07-14 | Hoechst Ag | LIGHT-SENSITIVE RECORDING MATERIAL WITH A LIGHT-SENSITIVE INTERLAYER |
| US4886731A (en) * | 1987-01-05 | 1989-12-12 | Cookson Graphics Inc. | Multilayer photopolymeric printing plates with photoreactive diazo compounds and photopolymerizable compositions |
| JPH0727208B2 (en) * | 1987-04-20 | 1995-03-29 | 富士写真フイルム株式会社 | Photosensitive composition |
| DE3738863A1 (en) * | 1987-11-16 | 1989-05-24 | Hoechst Ag | LIGHT-SENSITIVE PRINTING PLATE FOR WATERLESS OFFSET PRINTING |
| US5340681A (en) * | 1988-01-29 | 1994-08-23 | International Paper Company | Method for preparing photographic elements having single photosensitive layer containing photopolymerizable compound, photoinitiator, diazonium compound and barrier material encapsulated pigment particles; and negative image formation process |
| US5286594A (en) * | 1988-01-29 | 1994-02-15 | International Paper Company | Photographic elements utilizing a single photosensitive layer containing a photopolymerizable compound, photoinitiator, diazonium compound and barrier material encapsulated pigment particles |
| CA2000712A1 (en) * | 1988-10-21 | 1990-04-21 | Thomas Dunder | Negative-working, photopolymerizable color proofing film without triplet oxygen quenching |
| DE3903001A1 (en) * | 1989-02-02 | 1990-08-16 | Hoechst Ag | LIGHT-SENSITIVE MIXTURE AND LIGHT-SENSITIVE RECORDING MATERIAL MADE THEREOF |
| JP6962216B2 (en) * | 2018-01-24 | 2021-11-05 | 日本製鉄株式会社 | Anti-rust treatment liquid for welded steel pipes, chemical conversion treatment methods for welded steel pipes, molded products of welded steel pipes and welded steel pipes |
| CN113105570B (en) * | 2021-04-12 | 2022-05-03 | 之江实验室 | Liquid two-photon initiator and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1141544A (en) * | 1966-07-13 | 1969-01-29 | Gordon Owen Shipton | Polymer compositions |
| US3905815A (en) * | 1971-12-17 | 1975-09-16 | Minnesota Mining & Mfg | Photopolymerizable sheet material with diazo resin layer |
| IT1000315B (en) * | 1972-12-14 | 1976-03-30 | Polychrome Corp | IMPROVEMENT IN POTOSENSITIVE UNSATURATED DIAZOIC MONOMERE COMPOSITIONS |
| FI207474A (en) * | 1973-08-16 | 1975-02-17 | Hercules Inc | |
| JPS50108003A (en) * | 1974-02-01 | 1975-08-26 | ||
| JPS50114122A (en) * | 1974-02-16 | 1975-09-06 | ||
| GB1523762A (en) * | 1975-02-25 | 1978-09-06 | Oce Van Der Grinten Nv | Photocopying materials |
| US4042386A (en) * | 1976-06-07 | 1977-08-16 | Napp Systems | Photosensitive compositions |
| JPS549619A (en) * | 1977-06-23 | 1979-01-24 | Oji Paper Co | Photosensitive composition |
| AU526602B2 (en) * | 1977-10-06 | 1983-01-20 | Polychrome Corp. | Lithographic printing plate |
-
1980
- 1980-02-22 NL NL8001085A patent/NL8001085A/en not_active Application Discontinuation
- 1980-02-25 ES ES488890A patent/ES8103397A1/en not_active Expired
- 1980-02-26 DE DE19803007212 patent/DE3007212A1/en not_active Ceased
- 1980-02-26 GB GB8006481A patent/GB2044788B/en not_active Expired
- 1980-02-26 ZA ZA00801085A patent/ZA801085B/en unknown
- 1980-02-26 CA CA000346444A patent/CA1144804A/en not_active Expired
- 1980-02-26 FR FR8004164A patent/FR2450473A1/en not_active Withdrawn
- 1980-02-26 BR BR8001128A patent/BR8001128A/en unknown
- 1980-02-27 BE BE0/199576A patent/BE881956A/en not_active IP Right Cessation
- 1980-02-27 JP JP2394780A patent/JPS55120028A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4652604A (en) * | 1985-08-02 | 1987-03-24 | American Hoechst Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
| US4707437A (en) * | 1985-08-02 | 1987-11-17 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
| US4772538A (en) * | 1985-08-02 | 1988-09-20 | American Hoechst Corporation | Water developable lithographic composition |
| US4780392A (en) * | 1985-08-02 | 1988-10-25 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymerizable acrylic monomer |
| US4822720A (en) * | 1985-08-02 | 1989-04-18 | Hoechst Celanese Corporation | Water developable screen printing composition |
| US5120772A (en) * | 1985-08-02 | 1992-06-09 | Walls John E | Radiation-polymerizable composition and element containing a photopolymerizable mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA801085B (en) | 1981-07-29 |
| ES488890A0 (en) | 1981-02-16 |
| BE881956A (en) | 1980-08-27 |
| NL8001085A (en) | 1980-08-29 |
| GB2044788B (en) | 1983-05-25 |
| DE3007212A1 (en) | 1980-08-28 |
| ES8103397A1 (en) | 1981-02-16 |
| JPS55120028A (en) | 1980-09-16 |
| BR8001128A (en) | 1980-11-04 |
| GB2044788A (en) | 1980-10-22 |
| FR2450473A1 (en) | 1980-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1144804A (en) | Photosensitive composition containing a diazo resin, a polyethylenically unsaturated compound and a photoinitiator | |
| US3620726A (en) | Process using colored particles to develop photohardenable imaging layers | |
| US6420089B1 (en) | On press developable printing plate precursor | |
| US4340657A (en) | Novel radiation-sensitive articles | |
| DE4418645C1 (en) | Photosensitive mixture and recording material which can be produced therefrom | |
| EP1000387B1 (en) | Overcoat for light-sensitive materials comprising a (1-vinylimidazole) polymer or copolymer | |
| US3905815A (en) | Photopolymerizable sheet material with diazo resin layer | |
| US3458311A (en) | Photopolymerizable elements with solvent removable protective layers | |
| US3549367A (en) | Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones | |
| US3926643A (en) | Photopolymerizable compositions comprising initiator combinations comprising thioxanthenones | |
| JPH02135351A (en) | Photopolymerizing mixture, recording material produced therefrom and manufacture of copy | |
| US4054635A (en) | Copolymer of glycidyl methacrylate and allyl glycidyl ether | |
| US4264708A (en) | Radiation sensitive element having a thin photopolymerizable layer | |
| US4845011A (en) | Visible light photoinitiation compositions | |
| US4245031A (en) | Photopolymerizable compositions based on salt-forming polymers and polyhydroxy polyethers | |
| US3445229A (en) | Photopolymerizable compositions,elements,and processes | |
| CA1153236A (en) | Long-running water developable printing plates and compositions | |
| US4239609A (en) | Photopolymerizable coating and recording materials containing a photoinitiator and an organic halogen compound | |
| DE2651864B2 (en) | Photopolymerizable recording material and methods for reproducing images | |
| US4247624A (en) | Photopolymerizable elastomeric compositions with carbamated poly(vinyl alcohol) binder | |
| EP0585164B1 (en) | Use of alkali soluble photopolymer in color proofing constructions | |
| US4251618A (en) | Positive and negative working imaging systems from photoactive plastisols | |
| GB1571191A (en) | Photosensitive composition for printing screens | |
| AU610960B2 (en) | Photopolymerizable mixture, and a recording material produced therefrom | |
| US4340686A (en) | Carbamated poly(vinyl alcohol) useful as a binder in elastomeric photopolymer compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |