CA1099439A - Photocross-linkable polymers - Google Patents
Photocross-linkable polymersInfo
- Publication number
- CA1099439A CA1099439A CA278,262A CA278262A CA1099439A CA 1099439 A CA1099439 A CA 1099439A CA 278262 A CA278262 A CA 278262A CA 1099439 A CA1099439 A CA 1099439A
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- Prior art keywords
- groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Abstract of the Disclosure It has been found that certain polymers containing pendant diazo ester groups are photosensitive and have utility in the preparation of both lithographic and relief printing plates, as well as for etching resists for printed circuits.
Description
i~q ~ 4~9 Xramer Case ~-3 This invention relates to novel polymers and their use in preparing printing plates. More particularly, this invention relates to photocross-linkable polymers having pendant diazo ester groups and printing plates prepared therefrom.
Photocross-linkablé polymers are kn~wn in the art. U.S.
Patent No. 3,467,523, for example, shows polymers containing azido-sulfonyl groups attached to a polymer chain, which can be used as light-sensitive substances in printing plates, etc. Unfortunately, the polymers containing azidosulfonyl groups are limited in that they require the use of a sensiti~ing agent to render them cross-linkable at a practical rate with visible or normal ultraviolet light (without a sensitizer, they require the use of short wave-length ultraviolet light).
It has now been found that certain polymers containing pendant diazo ester groups are capable of being photocross-linked without the use of sensiti~ing agen~s and are excellently suited for use in the preparation of both lithographic and relief print-ing plates, as well as for etching resists for printed circuits.
In contrast to many photo~ross-linkable polymer systems, they are not insensiti~ea by the presence of air. Specifically, the poly-mers containing pendant diazo ester groups in accordance with this invention are the polymers that are photocross-linkable under active radiation and that have the following units _ _~ p C=O
C=N2 X
` where P is derived from a soluble hydroxy containing polymer which has been esterified to ~ive the above pendant groups and X
hyo~^og4n or isja radical selected from the group consisting of O O
.. ..
-C-OR, -C-CH3, -CN and -Ar, where Ar is selected from phenyl and phenyl substituted with 1 to 3 -N02, Cl, F, Br, Cl_8 alkyl or Cl_s alkyloxy groups and R is selected from C1_18 alkyl, C5_7
Photocross-linkablé polymers are kn~wn in the art. U.S.
Patent No. 3,467,523, for example, shows polymers containing azido-sulfonyl groups attached to a polymer chain, which can be used as light-sensitive substances in printing plates, etc. Unfortunately, the polymers containing azidosulfonyl groups are limited in that they require the use of a sensiti~ing agent to render them cross-linkable at a practical rate with visible or normal ultraviolet light (without a sensitizer, they require the use of short wave-length ultraviolet light).
It has now been found that certain polymers containing pendant diazo ester groups are capable of being photocross-linked without the use of sensiti~ing agen~s and are excellently suited for use in the preparation of both lithographic and relief print-ing plates, as well as for etching resists for printed circuits.
In contrast to many photo~ross-linkable polymer systems, they are not insensiti~ea by the presence of air. Specifically, the poly-mers containing pendant diazo ester groups in accordance with this invention are the polymers that are photocross-linkable under active radiation and that have the following units _ _~ p C=O
C=N2 X
` where P is derived from a soluble hydroxy containing polymer which has been esterified to ~ive the above pendant groups and X
hyo~^og4n or isja radical selected from the group consisting of O O
.. ..
-C-OR, -C-CH3, -CN and -Ar, where Ar is selected from phenyl and phenyl substituted with 1 to 3 -N02, Cl, F, Br, Cl_8 alkyl or Cl_s alkyloxy groups and R is selected from C1_18 alkyl, C5_7
- 2 ~
q~
~,¢~
cycloal~yl, Cl ~ alkyl substituted C5_7 cycloalkyl and Ar, where Ar ls as defined above.
Any soluble hydroxy containing polymer which can be es-terified to give the desirable pendant groups can be used as the backbone polymer, providing it contains no functional groups which react with or decompose diazo groups thermally (e.g., fumarate esters or sulfonic acids). Typical h~droxyl containing polymers that can be used in this lnvention are the partly or completely hydrolyzed vinyl acetate polymers, such as poly(vinyl acetate), ethylene--vinyl acetate copolymer and vinyl chloride--vinyl acetate copolymer; vinyl alcohol polymers, such as p~ly(vinyl alcohol); allyl alcohol copolymers such as styréne--allyl alcohol copolymer; cellulose and cellulose ethers and esters, such as cellulose, hydroxyethyl cellulose, ethyl cellulose, hydroxvpropyl cellulose, ethyl hydroxyethyl cellulosa and hydroxypropyl methyl cellulose; thermoplastic phenoxy resins, such as the condensa-tion product of bisphenol A and epichlorohydrin without epoxy end groups; and polymers and copolymers o hydroxyalkyl acrylates and methacrylates, such as styrene--hydroxy ethyl acrylate and poly(hydroxyethyl methacrylate~. Polvmer~ ~hich are ~ater sol-uble, or soluble in aqueous solutions, such as water-alcohol mixtures or salt solutions are particularly desirable.
The pol~mers containing pendant diazo ester groups of this invention can be prepared by several methods which will be obvious to those skilled in the art. One method, for example, O .
particularly applicable when X is -C-OR or nitrophenyl is to partially esterify the hydroxyl containing polymer as follows o ~P ~ ~ + Cl--C-CH2--X~ ~ P ~^~ + HCl OH O
C=O
X
and then to dia~otize the resulting ester as f~llows P~~~_ + ~ (C2H5)3~ , ~ 3 C=O C=O
C, H2 C=N2 X X
Typical of the acid chlorides that may be used to esterify the hydroxyl containing polymer are ethyl malonyl chloride, phenyl malonyl chloride, methyl malonyl chloride, 4-nitrophenylacetyl chloride and 2,4-dinitrophenylacetyl chloride.
Another method of synthesis utilizes the reaction of the p-toluenesulfonylhydrazone of a carboxylic acid chloride con-taining an ~-carbonyl group with a hydroxyl containing polymer in the presence of a strong base.
10X--CCOH + ¢~ 502NHNH=CCOH3 ¢~j2NHN=CCCl X (C H5) N
S02NHN=CCCl + ~---- P ~ 2 3 ~ ~,~,_ p __ ¢~ O OH o C=O
CH3 .
C,=N2 X
Typical of carboxylic acids containing an a-carbonyl group which may be used are glyoxylic acid, benzoylformic acid, 4-methoxy-benzoylformic acid, 4-methylbenzoylformic acid, and 4-chlorobenzoylformic acid.
It will be understood that the above preparatory meth-ods are only illustrative and that other approaches and varia-tions will be obvious to those skilled in the art. It is desir-able in most cases to only partially esterify the hydroxyl groups of the hydroxyl-containing polymers and thus obtain a polymer with fewer diazo ester groups. In general, only enough diazo ester groups to effect cross-linking of the polymer are required.
Most desirably, there will be approximately one diazo ester group per 1 to 10~ hydroxyl-containing monomer units in the polymer chain in the case of vinyl and condensation polyrners and approx-imately one diazo ester group per 0.4 to 25 anhydroglucose units in the case of cellulose and cellulose derivatives.
Typical of the photocross-linkable polymers containing pendant diazo ester groups of this invention are the diazoacetyl ester of the condensation product of bisphenol A and epichloro-hydrin containing no epoxy end groups, the ethyldiazomalonyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the phenyl-diazomalonyl ester of hydrolyzed ethylene--vinyl acetate co-polymer, the diazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the p-nitrophenyldiazoacetyl ester of hydro-lyzed ethylene--vinyl acetate copolymer, the phenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the diazoacetyl ester of styrene--allyl alcohol copolymer, the ethyl ; 20 diazomalonyl ester of poly(vinyl alcohol), the 2,4-dinitrophenyl-diazoacetyl ester of hydroxypropyl cellulose, the methyl diazo-malonyl ester of ethyl cellulose, the diazoacetyl ester of methyl acrylate--hydroxyethyl acrylate copolymer, the p-chloro-phenyldiazoacetyl ester of hydroxypropyl cellulose, the p-methoxyphenyldiazoacetyl ester of ethyl cellulose, the cyanodi-azoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the acetodiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the acetodiazoacetyl ester of poly(vinyl alcohol~, the o-, m-, and p-tolyldiazoacetyl esters of hydroxypropyl cellulose, the ethyldiazomalonyl ester of styrene--hydroxypropyl acrylate copolyrner, the acetodiazoacetyl ester of poly~vinyl alcohol), the methyldiazomalonyl ester of the condensation product of bis-phenol A and epichlorohydrin containing no epoxy ond groups, the acetodiazoacetyl ester of hy~roxyethyl cellulose, the p-nitrophenyldiazoacetyl ester of poly(vinyl alcohol), the ethyl diazomalonyl ester of hydroxypropyl cellulose, the ethyldiazo-malonyl ester of methyl hydroxypropyl cellulose, the methyldiazo-malonyl ester of the condensation product of hisphenol A and epi-chlorohydrin containing no epoxy end groups, the acetodiazoacetyl ester of methyl methacrylate--hydroxyethyl methacrylate copoly-mer, the chlorophenyldiazoacetyl ester of poly~vinyl alcohol), the m-fluorophenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the octyldiazomalonyl ester of poly~vinyl alcohol), the stearyldiazomalonyl e~ter of poly~vinyl alcohol~, the p-bromophenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the 4-tert.-butylcyclohexyldiazomalonyl ester of poly(vinvl alcohol), the 4-methylcycloheptyldiazomalonyl ester of poly(vinyl alcohol), the cyclopentyldiazomalonyl ester of hydroxyethyl cellulose, the cyclohexyldiazomalonyl ester of hydroxyethyl cellulose, the cycloheptyldiazomalonyl ester of hydroxyethyl cellulose, the p-nitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4-dinitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4,6-trinitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4,6-trichlorophenyldiazo-malonyl ester of hydroxyathy~ cellulose, the p-tolyldiazomalo~yl ester of partially hydrolyzed poly~vinyl acetate~, the m-ethyl- :
phenyldiazomalonyl ester of partially hydrolyzed polyCvinyl acetate), the p-hexy~phenyldiazomalonyl ester of partially hydrolyzed poly~vinyl acetatel, the p-octylphenyldiazomalonyl ester of partially hydrolyzed poly(vinyl acetate~, the p-methoxy-phenyldiazomalonyl ester o~ partially hydrolyzed poly~vinyl acetate), the m-butyloxyphenyldiazomalonyl ester of partially hydrolyzed poly(vinyl acetate), the p-amyloxyphenyldiazomalonyl ester of partially hydrolyzed poly~vinyl acetate) t the p-amyloxy-phenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate Qn~
copolymer,~the p-octylphenyldia~oacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, ~x~
The polymers containing pendant diazo ester groups may be utilized alone or in admixture with other materials~ It may be desirable in certain cases to extend the dia~o ester containing polymer with inorganic or organic fillers, including other poly-mers, with solubility characteristics similar to those of the photocross-linkable polymer employed. It may also be desirable to add other compounding ingredients such as plastici~ers, anti-oxidants, etc., just as long as they do not interfere with the absorption of light by the polymer and do not cause decomposition of khe diazo groups. Obviously, there are many cases in which plasticizers and fillers are not required or desired, and ex-cellent printing plates can be prepared with the dia~o ester containing polymer alone.
In practice, the photocross-linkable polymer will gen-erally be coated on a suitable support. Typical supports that can be used are grained or ungrained plastic sheets such as poly-amides, polyesters, polycarbonates and polyolefins; paper and paper foils; and grained or ungrained metal sheets such as alum-inum, zinc, copper, iron, steel, silver and gold. Obviously, the more expensive metals will not normally be used as supports in printing plates but can be used as a laminate over plastic in preparing etching resists for printed circuits. By the term "grainea", used above, is meant a lithographic graining generally described as a microscopic surface roughness essentially devoid of scratches. In a~dition to or in place of graining, it will be understood that the support may be first treated with some mate-rial, such as described in U.S. Patent 3,440,959 or 3,470,~13, or Defensive Publication T-868,002, to vary the affinity of the surface to water or ink. The photocross-linkahle polymer can be coated on the support by several methods, such as hy compression molding or solvent casting. By the latter method the photocross-linkable polymer will be dissolved in a suitable solvent such as water, alcohol, a halogenated hydrocarbon, ketone~ aromat c, c~e.
and by trailing blade coating, spraying, curtain coating~ dipping, ctc.~ applied to the support and the solvent allowed to evaporate~
q~
~,¢~
cycloal~yl, Cl ~ alkyl substituted C5_7 cycloalkyl and Ar, where Ar ls as defined above.
Any soluble hydroxy containing polymer which can be es-terified to give the desirable pendant groups can be used as the backbone polymer, providing it contains no functional groups which react with or decompose diazo groups thermally (e.g., fumarate esters or sulfonic acids). Typical h~droxyl containing polymers that can be used in this lnvention are the partly or completely hydrolyzed vinyl acetate polymers, such as poly(vinyl acetate), ethylene--vinyl acetate copolymer and vinyl chloride--vinyl acetate copolymer; vinyl alcohol polymers, such as p~ly(vinyl alcohol); allyl alcohol copolymers such as styréne--allyl alcohol copolymer; cellulose and cellulose ethers and esters, such as cellulose, hydroxyethyl cellulose, ethyl cellulose, hydroxvpropyl cellulose, ethyl hydroxyethyl cellulosa and hydroxypropyl methyl cellulose; thermoplastic phenoxy resins, such as the condensa-tion product of bisphenol A and epichlorohydrin without epoxy end groups; and polymers and copolymers o hydroxyalkyl acrylates and methacrylates, such as styrene--hydroxy ethyl acrylate and poly(hydroxyethyl methacrylate~. Polvmer~ ~hich are ~ater sol-uble, or soluble in aqueous solutions, such as water-alcohol mixtures or salt solutions are particularly desirable.
The pol~mers containing pendant diazo ester groups of this invention can be prepared by several methods which will be obvious to those skilled in the art. One method, for example, O .
particularly applicable when X is -C-OR or nitrophenyl is to partially esterify the hydroxyl containing polymer as follows o ~P ~ ~ + Cl--C-CH2--X~ ~ P ~^~ + HCl OH O
C=O
X
and then to dia~otize the resulting ester as f~llows P~~~_ + ~ (C2H5)3~ , ~ 3 C=O C=O
C, H2 C=N2 X X
Typical of the acid chlorides that may be used to esterify the hydroxyl containing polymer are ethyl malonyl chloride, phenyl malonyl chloride, methyl malonyl chloride, 4-nitrophenylacetyl chloride and 2,4-dinitrophenylacetyl chloride.
Another method of synthesis utilizes the reaction of the p-toluenesulfonylhydrazone of a carboxylic acid chloride con-taining an ~-carbonyl group with a hydroxyl containing polymer in the presence of a strong base.
10X--CCOH + ¢~ 502NHNH=CCOH3 ¢~j2NHN=CCCl X (C H5) N
S02NHN=CCCl + ~---- P ~ 2 3 ~ ~,~,_ p __ ¢~ O OH o C=O
CH3 .
C,=N2 X
Typical of carboxylic acids containing an a-carbonyl group which may be used are glyoxylic acid, benzoylformic acid, 4-methoxy-benzoylformic acid, 4-methylbenzoylformic acid, and 4-chlorobenzoylformic acid.
It will be understood that the above preparatory meth-ods are only illustrative and that other approaches and varia-tions will be obvious to those skilled in the art. It is desir-able in most cases to only partially esterify the hydroxyl groups of the hydroxyl-containing polymers and thus obtain a polymer with fewer diazo ester groups. In general, only enough diazo ester groups to effect cross-linking of the polymer are required.
Most desirably, there will be approximately one diazo ester group per 1 to 10~ hydroxyl-containing monomer units in the polymer chain in the case of vinyl and condensation polyrners and approx-imately one diazo ester group per 0.4 to 25 anhydroglucose units in the case of cellulose and cellulose derivatives.
Typical of the photocross-linkable polymers containing pendant diazo ester groups of this invention are the diazoacetyl ester of the condensation product of bisphenol A and epichloro-hydrin containing no epoxy end groups, the ethyldiazomalonyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the phenyl-diazomalonyl ester of hydrolyzed ethylene--vinyl acetate co-polymer, the diazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the p-nitrophenyldiazoacetyl ester of hydro-lyzed ethylene--vinyl acetate copolymer, the phenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the diazoacetyl ester of styrene--allyl alcohol copolymer, the ethyl ; 20 diazomalonyl ester of poly(vinyl alcohol), the 2,4-dinitrophenyl-diazoacetyl ester of hydroxypropyl cellulose, the methyl diazo-malonyl ester of ethyl cellulose, the diazoacetyl ester of methyl acrylate--hydroxyethyl acrylate copolymer, the p-chloro-phenyldiazoacetyl ester of hydroxypropyl cellulose, the p-methoxyphenyldiazoacetyl ester of ethyl cellulose, the cyanodi-azoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the acetodiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the acetodiazoacetyl ester of poly(vinyl alcohol~, the o-, m-, and p-tolyldiazoacetyl esters of hydroxypropyl cellulose, the ethyldiazomalonyl ester of styrene--hydroxypropyl acrylate copolyrner, the acetodiazoacetyl ester of poly~vinyl alcohol), the methyldiazomalonyl ester of the condensation product of bis-phenol A and epichlorohydrin containing no epoxy ond groups, the acetodiazoacetyl ester of hy~roxyethyl cellulose, the p-nitrophenyldiazoacetyl ester of poly(vinyl alcohol), the ethyl diazomalonyl ester of hydroxypropyl cellulose, the ethyldiazo-malonyl ester of methyl hydroxypropyl cellulose, the methyldiazo-malonyl ester of the condensation product of hisphenol A and epi-chlorohydrin containing no epoxy end groups, the acetodiazoacetyl ester of methyl methacrylate--hydroxyethyl methacrylate copoly-mer, the chlorophenyldiazoacetyl ester of poly~vinyl alcohol), the m-fluorophenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the octyldiazomalonyl ester of poly~vinyl alcohol), the stearyldiazomalonyl e~ter of poly~vinyl alcohol~, the p-bromophenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, the 4-tert.-butylcyclohexyldiazomalonyl ester of poly(vinvl alcohol), the 4-methylcycloheptyldiazomalonyl ester of poly(vinyl alcohol), the cyclopentyldiazomalonyl ester of hydroxyethyl cellulose, the cyclohexyldiazomalonyl ester of hydroxyethyl cellulose, the cycloheptyldiazomalonyl ester of hydroxyethyl cellulose, the p-nitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4-dinitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4,6-trinitrophenyldiazomalonyl ester of hydroxyethyl cellulose, the 2,4,6-trichlorophenyldiazo-malonyl ester of hydroxyathy~ cellulose, the p-tolyldiazomalo~yl ester of partially hydrolyzed poly~vinyl acetate~, the m-ethyl- :
phenyldiazomalonyl ester of partially hydrolyzed polyCvinyl acetate), the p-hexy~phenyldiazomalonyl ester of partially hydrolyzed poly~vinyl acetatel, the p-octylphenyldiazomalonyl ester of partially hydrolyzed poly(vinyl acetate~, the p-methoxy-phenyldiazomalonyl ester o~ partially hydrolyzed poly~vinyl acetate), the m-butyloxyphenyldiazomalonyl ester of partially hydrolyzed poly(vinyl acetate), the p-amyloxyphenyldiazomalonyl ester of partially hydrolyzed poly~vinyl acetate) t the p-amyloxy-phenyldiazoacetyl ester of hydrolyzed ethylene--vinyl acetate Qn~
copolymer,~the p-octylphenyldia~oacetyl ester of hydrolyzed ethylene--vinyl acetate copolymer, ~x~
The polymers containing pendant diazo ester groups may be utilized alone or in admixture with other materials~ It may be desirable in certain cases to extend the dia~o ester containing polymer with inorganic or organic fillers, including other poly-mers, with solubility characteristics similar to those of the photocross-linkable polymer employed. It may also be desirable to add other compounding ingredients such as plastici~ers, anti-oxidants, etc., just as long as they do not interfere with the absorption of light by the polymer and do not cause decomposition of khe diazo groups. Obviously, there are many cases in which plasticizers and fillers are not required or desired, and ex-cellent printing plates can be prepared with the dia~o ester containing polymer alone.
In practice, the photocross-linkable polymer will gen-erally be coated on a suitable support. Typical supports that can be used are grained or ungrained plastic sheets such as poly-amides, polyesters, polycarbonates and polyolefins; paper and paper foils; and grained or ungrained metal sheets such as alum-inum, zinc, copper, iron, steel, silver and gold. Obviously, the more expensive metals will not normally be used as supports in printing plates but can be used as a laminate over plastic in preparing etching resists for printed circuits. By the term "grainea", used above, is meant a lithographic graining generally described as a microscopic surface roughness essentially devoid of scratches. In a~dition to or in place of graining, it will be understood that the support may be first treated with some mate-rial, such as described in U.S. Patent 3,440,959 or 3,470,~13, or Defensive Publication T-868,002, to vary the affinity of the surface to water or ink. The photocross-linkahle polymer can be coated on the support by several methods, such as hy compression molding or solvent casting. By the latter method the photocross-linkable polymer will be dissolved in a suitable solvent such as water, alcohol, a halogenated hydrocarbon, ketone~ aromat c, c~e.
and by trailing blade coating, spraying, curtain coating~ dipping, ctc.~ applied to the support and the solvent allowed to evaporate~
3~
Coatings of various thicknesses can be e~ployed, depending upon the ultimate utility. For example, if the coated support is to be used in preparing relief printing pla~es, the thickness of the light-sensitive coating will be from about ~ mils to about 50 mils. On the other hand, lf the coated support is to be used in preparing lithographic printing plates, then a thinner light-sensitive coating of from about 2 microns to about 50 microns will be used. If the coated support is to be used as an etching resist for printed circuits, the thickness of the light-sensitive coating will be from about 0.5 micron to ahout S microns.
The photocross-linkable polymers having pendant diazo ester groups of this invention can be cross-linked by exposure to actinic radiation of from about 2000 A to about S000 A. Most preferably, the light will be from about 3000 A to about ~000 A.
Any of the commercial light sources emitting in this region, such as mercury vapor ~ights, carbon arc, tungstén filament, etc., can be used to expose and cross-link the polymers. Various time periods are required for the exposure, depending upon the specific diazo ester containing polymer and the intensity of the light. In general, exposure of from about 3~ seconds to about 30 minutes will be sufficient to effect cross-linking. After exposure of a photocross-linkable polyme~ coated support, as for example, through a negative, the exposed portions will be cross-linked and insoluble in the usual sol~ent for the polymer, while the unex-posed portions will be uncross-linked and removable by washing (i.e., developing) in a solvent for the polymer. The same sol-vents disclosed above as useful in solvent casting the polymers on a substrate can be used to wash away unexposed (i.e., uncross-linked) polymer. In the case of etching resists for printed cir-cuits, a typical procedure is to expose the photocross-linkable polymer coating through a negative or some other ~asking means, wash a~ay uncross-linked polymer to exposë the metal laminate surface and then etch away the exposed metal.
The following examples are presented for purposes of illustration, parts and percentages being by weight unless other-wise speciied.
Example 1 This example illustrates the preparation of a polymer containing pe~dant dia~oacetyl groups.
A p-toluenesulfonyl hydraæone of glyoxylic acid is prepared from 22.7 parts of glyoxylic acid and 46.~ parts of p-toluenesulfonylhydrazide. After recrystalli~ing from ethyl acetate-carbon tetrachloride, 20 parts of the hydrazone glyoxylic acid and 24 part~ thionyl chloirde are refluxed in approximately 100 parts of benzene ~or two hours, after which the volatiles are removed at aspirator pressure. The residue is triturated with a small amount of warm benzene, collected and recrystalli~ed from a mixture of benzene and petroleum ether to yield the p-toluene-sulfonyl hydrazone of glyoxylic acid chloride, which can he shown ; as follows:
~ CH3 `~ .
S02NHN=CHC--Cl A solution is prepared containing 7 parts of the p-toluenesulfonyl hydra~one of glyoxylic acid chloride and 5.7 parts of a phenoxy resin, having the general formula oCH2--CH-CH2 ~--i~ approximately 100 parts of methylene chloride. To the solu-tion is added drop~ise with stirring in the dark 6.1 parts of tri-ethylami~e. The reaction mixture is allowed to sta~d in the dark for three- hours and the~ ~recipitated hy adding to methanol. The resulting product ~ontains monomer units with the general formula ~ CH2--Ci.H-CH2 ~
C=O
l=N2 H
The modified resin exhibits strong infrared absorption at 4.75 and 5.9~, showing the presence of ~C=N2 and ~C=0 groups, and indicating that about 26% of the hydroxyl groups are substituted.
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a solution of the dia~o-acetyl modified resin in methylene chloride and evaporating the solvent with a stream of nitrogen. The resulting 20 mil coated ; film is covered with a photographic transparency and exposed for 30 minutes to a 450 watt mercury lamp at a distance of approx-imately 2 inches. The exposed coating is then washed with methylene chloride to give a sharp high resolution relief image. Similarly, a 0.5 mil ilm of the diazoacetyl modified resin on a grained aluminum lithographic plate is prepared, exposed and developed as described above to give a high resolution image which accepts ink relative to the aluminum substrate.
Exa~ple 2 This example illustrates the praparation of a polymer containing dendant ethyldiazomalonyl groups.
To a solution of 3.4 parts of the hydroxypropyl cellu-lose shown in U.S. Patent 3,27~,521 and having a molar su~stitu--tion (M.S.) of 3.5 disso~ved in equal parts of tetrahydrofuran and methylene chloride is added 1.6 parts of pyridine and 3.0 parts of ethylmalonyl chloride with stirring. The reaction mixture is allowed to stand for two days and then the solids Cpyrid;ne hydrochloride) removed by filtration. The solvent is stripped from the filtrate at reduced pressure, the product is redissolved in tetrahydrofuran ahd reprecipitated by pouring into water at 3~
60C. ApproxLmately 75% of the hydroxyl groups of the hydroxy-propyl cellulose are esterified.
To a solution of 2.8 parts of the above ethylmalonyl derivative of the hydroxypropyl cellulose in methylene chloride is added 1 part triethylamine and 2 parts of p-toluenesulfonyl azide. The solution is allowed to stand in the dark for two days and the solvent removed under vacuum. The residue is dissolved i~ tetrahydrofuran and reprecipitated by pouring into water at 60C. The resulting product exhibits a strong infrared absorption N
at 4.7~ showing the presence of -C- groups.
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a solution of the ethyl-diazomalonyl modified cellulose in methylene chloride and evap-orating the solvent with a stream of nitrogen. The resulting 5 mil coated fil~ is covered with a photographic transparency and exposed for 20 minutes to a 450 watt medium pressure mercury lamp at a distance of approximately 2 inches. The exposed coat-ing is then washed with methylene chloride to give a sharp relief image.
Exampl-e 3 This example illustrates the preparation of another polymer containing pendant ethyldiazomalonyl groups.
An ethyle~e--vinyl acetate copolymer, containing approx-imately 28 weight percent of groups derived from vinyl acetate, is saponified to yield a copolymer having the general formula ~--(CH2--CH2) ~8--CH-CH2 ~
OH
To a mixture of 2.6 parts of the saponified copolymer and 88 parts of benzene is added 1.5 parts of ethylmalonyl chloride and the mixture heated at reflux for 1.5 hours during which time all the solids go into solution. To the resulting solution is aaded 1.1 parts of 2,6-lutidine and tha mixture heated at reflux. After 2 hours the refluxing mixture is filtered hot and the filtrate poured with stirring into 316 parts of methanol. The precipitate is collected and washed with methanol. The resulting ethyl mal-onate modified copolymer exhibits a strong infrared absorption at 5.75~ and has monomer units with the general formula .,(CH2--CH2) ~,8-CI H--CH2--o C=O
IC=O
o To a solution o 1.8 parts of the ethyl malonate modified copoly-mer in methylene chloride is added 0.5 part of triethylamine and l 0 part of p-toluenesulfonylazide. The mixture is allowed to stand at room temperature in the dark for two days and then the product is precipitated by pouriny it into about 150 parts of methanol. The precipitatea product is collected and washed with methanol. The resulting ethyl dia~omalonate modified copolymer exhibits strong infrared absorption at 4.7~ and 5.75~ and has structural units with the general formula v~ ~(cH2-cH2)~8--CIH CH2 ~~~--~~~~~
O
C=O
C=N2 C=O
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a lO~ solution of the ethyl diazomalonate modified copol~mer in toluene and drying in a stream of nitrogen, The resulting lO mil coated film is covered with a photographic negative and exposea 15 minutes to a 450 watt mercury lamp at a distance of 2 inches. The exposed film is then ~ ~4~'~3~
washed with methylene chloride to give a high resolution image in which the half-tone dots are claarly visible.
~xample 4 This e~ample lllustrates the preparation of a polymer containing pendant acetodia~oacetyl groups.
To a suspensio~ of 2,~ parts of the saponified copolymer described in Example 3 in 44 parts of benzene is added 2.5 parts of diketene dissolved in an equal amount of acetone. The mixture is heated on a steam bath for 5 minutes and poured with stirring into approximately 400 parts of methanol. The precipitate is collected and washed with methanol. The resulting acetoacetate modified copolymer is dia~oti~ed using triethylamine and p-toluenesulfonylazide by the method described in Example 3. The resulting diazoacetoacetate modified copolymer exhibits strong infrared absorption at 4.7~ and 5.8~ and has structural units with the general formula _v~ (cH~-cH2~8--lH CH2--~~'~
I
C=O
l=N2 C=O
C~
A ~ solution of the dia~oacetoacetate modified polymer in methylene chloride is coated on a grained sheet of polyethylene terephthalate, and the solvent evaporated to give a coated thick-ness of 8 mils. The film is covered with a photographic trans-parency and exposed to a 450 watt mercury lamp for 30 minutes.
The exposed coating is washed with methylene chlorid~ to give a well defined relief lmage.
Example 5 This example illustrates the preparation of a polymer containing pendant p-nitropheny~diazoacetate groups.
To a suspension of 2.6 parts of the saponified copolymer described in Example 3 in 44 parts of ben~ene is- added 2 parts 1(J~9~39 of p-nitrophenylacetyl chloride. The mixture is heated at reflux for 3 hours and 0.8 part of pyridine added. After standing at room temperature for an hour, the reaction mixture is poured into 240 parts of methanol. The precipitate is collected and washed with methanol.
To a solution of 2 parts of the p-nitrophenylacetate modified polymer in 98 parts of dry pyridine, cooled in an ice bath, is added 0.4 part of piperidine and 1.0 part of p-toluene-sulfonylazide with stirring. The solution is stored in the dark overnight and then poured into 31~ parts of methanol. The bright yellow preaipitate is collected and washed with methanol. The resulting p-nitrophenyldiazoacetate modified copolymer exhibits strong infrared absorption at 4.8~, 6.6~ and 7.S~ and has structural units with the general formula _~A~ (CH2--CH2)~8-IH CH2 O ~ ':
C=O
=N 2 [~
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate wïth a solution of the p-nitrophenyldiazoacetate modified copolymer in methylene chloride and evaporating the solvent with a stream of nitrogen. The re-sulting 5 mil coated film is covered with a photographic negativeand exposed to a 450 watt meraury lamp a~ a distance of 2 inches.
T~ exposed' coating i5 then washad with toluene to give a good raised image. Exceptionally high resolution of the half-tone dots is noted.
Example 6 To a suspension o 3.0 parts of the saponified copoly-mer described in Example 3 and 50 parts of ben~ene is added ~.4 parts of phenylmalonyl chloride and 1.0 part o pyridine. The ~0~9439 mixture is heated at reflu~ for l.S hours and allowed to cool to room temperature. The reaction mixture is poured into 300 parts of methanol and the precipitated polymer collected and washed with methanol. To a solution of 2.1 parts of the phenyl malonate modified copolymer in methylene chloride is added 0.5 part tri-ethylamine and 1.0 part o p-toluenesulfonylazide. The mixture is allowed to stand at room temperature in the dark for 2 days, and the polymer precipitated by pouring into 200 parts of meth-anol. After washing with methanol, the polymer exhibits strong infrared absorption at 4.7~.
A lithographic plate is prepared by whirl coating a 5%
solution of the phenyldiazomalonate modified copolymer in chloro-form onto a brush grained aluminum plate. After drying at room temperature, the plate is covered with a photographic negative containing line work and half-tone pictures, and exposed to a bank of four meraury arcs rated as 80 watts/linear inch. The exposed film is washed with chloroform to give a good image. The plate was rubbed with gum arabic solutions and gave excellent prints when used on an offset lithographic press.
EXam~le 7 To a solution of 11.0 parts of poly~vinyl alcohol~, having a molecular weight of approximately 96,000, in 20Q parts of N-methyl pyrrolidone is added 18.9 parts of ethylmalonyl chloride and 5.0 parts of acetyl chloride with stirring. The reaction mix~
ture is poured into ~000 parts o water to precipitate the poly-mer. The solids are collected and washed with water.
To a solution o 17.8 parts of the ethyl malonate mod-ified polymer in 310 parts of acetonitrile is added successively 8.1 parts of triethylamine and 15.7 parts of p-toluenesulfonyl-azide. The solution is stored in the dark for two days, and poured into 2500 parts of water. The solids are collected, taken up in 27~ parts of acetonitril~ and reprecipitated. The infrared spec-trum has a band at 4.7~ indlcating the presence o~ dia~o ester groups.
~ 1~9439 A 5% (wt./vol.~ solution of the above ethyl diazomal-onate polymer in chloroorm is whirl coated on a 6-mil grained aluminum plate, dried at room temperature, and exposed for two minutes through a photographic negative and a Stauffer 21 Step Sensitivity Guide (AT 20 x 0.15) to a bank of four medium pres-sure mercury arcs rated at 80 watts/linear inch. The plate is washed with acetone to yield a sharp image and a solid coating at step 5 on the guide. The plate is rubbed successively with gum arabic solution, commércial fountain solution (3 oz./gal.), and commercial lithographic rub up ink. The image areas accept the ink while the substrate aluminum does not.
Example 8 To a solution of 8.8 parts o~ the polytvinyl alcohol), 96,000 mol wt., described in Example 7, in lS0 parts of N-methyl pyrrolidone is added 7.8 parts of acetyl chloride and 20.0 parts of p-nitrophenylacetyl chloride with stirring. The solution is allowed to stand for ~4 hours, and is poured into 4000 parts of water. The precipitate is collected and washed with water.
To a solution of 2.9 parts of the p-nitrophenyl acetate modified polymer in 145 parts of dry pyridine is added 0.9 part of piperidine and 2.0 parts of p-toluenesulfonyl a~ide. The solution is kept in the dark overnight and poured with stirring into 465 parts of methanol. The yellow precipitate i5 collected, chopped, and washed with methanol. The infrarad spectrum of the dried polymer shows strong absorption at 4.8~
A solution of the p-nitrophenyldiazoacetate modified polymer in chloroorm is whirl coated on a 6 mil grained aluminum plate and dried at room temperature in the dark to give a film approximately 5~ thick. The film is exposed through a phbto-graphic negati~e to the light from a 650 watt quart~-halogen tung-sten lamp at a distance of 1~ inches. The plate i`s washed gently with chloroform. An orange image remains in the areas exposed to the light, while the bac~ground dissolves, exposing the aluminum substrate. The pla~e is rubbed with 14 Baume gum arabic ~ Oq9~,9 solution and then with commercial lithographic rub up ink. The image areas accept the ink while the substrate aluminum does not.
Coatings of various thicknesses can be e~ployed, depending upon the ultimate utility. For example, if the coated support is to be used in preparing relief printing pla~es, the thickness of the light-sensitive coating will be from about ~ mils to about 50 mils. On the other hand, lf the coated support is to be used in preparing lithographic printing plates, then a thinner light-sensitive coating of from about 2 microns to about 50 microns will be used. If the coated support is to be used as an etching resist for printed circuits, the thickness of the light-sensitive coating will be from about 0.5 micron to ahout S microns.
The photocross-linkable polymers having pendant diazo ester groups of this invention can be cross-linked by exposure to actinic radiation of from about 2000 A to about S000 A. Most preferably, the light will be from about 3000 A to about ~000 A.
Any of the commercial light sources emitting in this region, such as mercury vapor ~ights, carbon arc, tungstén filament, etc., can be used to expose and cross-link the polymers. Various time periods are required for the exposure, depending upon the specific diazo ester containing polymer and the intensity of the light. In general, exposure of from about 3~ seconds to about 30 minutes will be sufficient to effect cross-linking. After exposure of a photocross-linkable polyme~ coated support, as for example, through a negative, the exposed portions will be cross-linked and insoluble in the usual sol~ent for the polymer, while the unex-posed portions will be uncross-linked and removable by washing (i.e., developing) in a solvent for the polymer. The same sol-vents disclosed above as useful in solvent casting the polymers on a substrate can be used to wash away unexposed (i.e., uncross-linked) polymer. In the case of etching resists for printed cir-cuits, a typical procedure is to expose the photocross-linkable polymer coating through a negative or some other ~asking means, wash a~ay uncross-linked polymer to exposë the metal laminate surface and then etch away the exposed metal.
The following examples are presented for purposes of illustration, parts and percentages being by weight unless other-wise speciied.
Example 1 This example illustrates the preparation of a polymer containing pe~dant dia~oacetyl groups.
A p-toluenesulfonyl hydraæone of glyoxylic acid is prepared from 22.7 parts of glyoxylic acid and 46.~ parts of p-toluenesulfonylhydrazide. After recrystalli~ing from ethyl acetate-carbon tetrachloride, 20 parts of the hydrazone glyoxylic acid and 24 part~ thionyl chloirde are refluxed in approximately 100 parts of benzene ~or two hours, after which the volatiles are removed at aspirator pressure. The residue is triturated with a small amount of warm benzene, collected and recrystalli~ed from a mixture of benzene and petroleum ether to yield the p-toluene-sulfonyl hydrazone of glyoxylic acid chloride, which can he shown ; as follows:
~ CH3 `~ .
S02NHN=CHC--Cl A solution is prepared containing 7 parts of the p-toluenesulfonyl hydra~one of glyoxylic acid chloride and 5.7 parts of a phenoxy resin, having the general formula oCH2--CH-CH2 ~--i~ approximately 100 parts of methylene chloride. To the solu-tion is added drop~ise with stirring in the dark 6.1 parts of tri-ethylami~e. The reaction mixture is allowed to sta~d in the dark for three- hours and the~ ~recipitated hy adding to methanol. The resulting product ~ontains monomer units with the general formula ~ CH2--Ci.H-CH2 ~
C=O
l=N2 H
The modified resin exhibits strong infrared absorption at 4.75 and 5.9~, showing the presence of ~C=N2 and ~C=0 groups, and indicating that about 26% of the hydroxyl groups are substituted.
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a solution of the dia~o-acetyl modified resin in methylene chloride and evaporating the solvent with a stream of nitrogen. The resulting 20 mil coated ; film is covered with a photographic transparency and exposed for 30 minutes to a 450 watt mercury lamp at a distance of approx-imately 2 inches. The exposed coating is then washed with methylene chloride to give a sharp high resolution relief image. Similarly, a 0.5 mil ilm of the diazoacetyl modified resin on a grained aluminum lithographic plate is prepared, exposed and developed as described above to give a high resolution image which accepts ink relative to the aluminum substrate.
Exa~ple 2 This example illustrates the praparation of a polymer containing dendant ethyldiazomalonyl groups.
To a solution of 3.4 parts of the hydroxypropyl cellu-lose shown in U.S. Patent 3,27~,521 and having a molar su~stitu--tion (M.S.) of 3.5 disso~ved in equal parts of tetrahydrofuran and methylene chloride is added 1.6 parts of pyridine and 3.0 parts of ethylmalonyl chloride with stirring. The reaction mixture is allowed to stand for two days and then the solids Cpyrid;ne hydrochloride) removed by filtration. The solvent is stripped from the filtrate at reduced pressure, the product is redissolved in tetrahydrofuran ahd reprecipitated by pouring into water at 3~
60C. ApproxLmately 75% of the hydroxyl groups of the hydroxy-propyl cellulose are esterified.
To a solution of 2.8 parts of the above ethylmalonyl derivative of the hydroxypropyl cellulose in methylene chloride is added 1 part triethylamine and 2 parts of p-toluenesulfonyl azide. The solution is allowed to stand in the dark for two days and the solvent removed under vacuum. The residue is dissolved i~ tetrahydrofuran and reprecipitated by pouring into water at 60C. The resulting product exhibits a strong infrared absorption N
at 4.7~ showing the presence of -C- groups.
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a solution of the ethyl-diazomalonyl modified cellulose in methylene chloride and evap-orating the solvent with a stream of nitrogen. The resulting 5 mil coated fil~ is covered with a photographic transparency and exposed for 20 minutes to a 450 watt medium pressure mercury lamp at a distance of approximately 2 inches. The exposed coat-ing is then washed with methylene chloride to give a sharp relief image.
Exampl-e 3 This example illustrates the preparation of another polymer containing pendant ethyldiazomalonyl groups.
An ethyle~e--vinyl acetate copolymer, containing approx-imately 28 weight percent of groups derived from vinyl acetate, is saponified to yield a copolymer having the general formula ~--(CH2--CH2) ~8--CH-CH2 ~
OH
To a mixture of 2.6 parts of the saponified copolymer and 88 parts of benzene is added 1.5 parts of ethylmalonyl chloride and the mixture heated at reflux for 1.5 hours during which time all the solids go into solution. To the resulting solution is aaded 1.1 parts of 2,6-lutidine and tha mixture heated at reflux. After 2 hours the refluxing mixture is filtered hot and the filtrate poured with stirring into 316 parts of methanol. The precipitate is collected and washed with methanol. The resulting ethyl mal-onate modified copolymer exhibits a strong infrared absorption at 5.75~ and has monomer units with the general formula .,(CH2--CH2) ~,8-CI H--CH2--o C=O
IC=O
o To a solution o 1.8 parts of the ethyl malonate modified copoly-mer in methylene chloride is added 0.5 part of triethylamine and l 0 part of p-toluenesulfonylazide. The mixture is allowed to stand at room temperature in the dark for two days and then the product is precipitated by pouriny it into about 150 parts of methanol. The precipitatea product is collected and washed with methanol. The resulting ethyl dia~omalonate modified copolymer exhibits strong infrared absorption at 4.7~ and 5.75~ and has structural units with the general formula v~ ~(cH2-cH2)~8--CIH CH2 ~~~--~~~~~
O
C=O
C=N2 C=O
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate with a lO~ solution of the ethyl diazomalonate modified copol~mer in toluene and drying in a stream of nitrogen, The resulting lO mil coated film is covered with a photographic negative and exposea 15 minutes to a 450 watt mercury lamp at a distance of 2 inches. The exposed film is then ~ ~4~'~3~
washed with methylene chloride to give a high resolution image in which the half-tone dots are claarly visible.
~xample 4 This e~ample lllustrates the preparation of a polymer containing pendant acetodia~oacetyl groups.
To a suspensio~ of 2,~ parts of the saponified copolymer described in Example 3 in 44 parts of benzene is added 2.5 parts of diketene dissolved in an equal amount of acetone. The mixture is heated on a steam bath for 5 minutes and poured with stirring into approximately 400 parts of methanol. The precipitate is collected and washed with methanol. The resulting acetoacetate modified copolymer is dia~oti~ed using triethylamine and p-toluenesulfonylazide by the method described in Example 3. The resulting diazoacetoacetate modified copolymer exhibits strong infrared absorption at 4.7~ and 5.8~ and has structural units with the general formula _v~ (cH~-cH2~8--lH CH2--~~'~
I
C=O
l=N2 C=O
C~
A ~ solution of the dia~oacetoacetate modified polymer in methylene chloride is coated on a grained sheet of polyethylene terephthalate, and the solvent evaporated to give a coated thick-ness of 8 mils. The film is covered with a photographic trans-parency and exposed to a 450 watt mercury lamp for 30 minutes.
The exposed coating is washed with methylene chlorid~ to give a well defined relief lmage.
Example 5 This example illustrates the preparation of a polymer containing pendant p-nitropheny~diazoacetate groups.
To a suspension of 2.6 parts of the saponified copolymer described in Example 3 in 44 parts of ben~ene is- added 2 parts 1(J~9~39 of p-nitrophenylacetyl chloride. The mixture is heated at reflux for 3 hours and 0.8 part of pyridine added. After standing at room temperature for an hour, the reaction mixture is poured into 240 parts of methanol. The precipitate is collected and washed with methanol.
To a solution of 2 parts of the p-nitrophenylacetate modified polymer in 98 parts of dry pyridine, cooled in an ice bath, is added 0.4 part of piperidine and 1.0 part of p-toluene-sulfonylazide with stirring. The solution is stored in the dark overnight and then poured into 31~ parts of methanol. The bright yellow preaipitate is collected and washed with methanol. The resulting p-nitrophenyldiazoacetate modified copolymer exhibits strong infrared absorption at 4.8~, 6.6~ and 7.S~ and has structural units with the general formula _~A~ (CH2--CH2)~8-IH CH2 O ~ ':
C=O
=N 2 [~
A relief printing plate is prepared by coating a grained sheet of polyethylene terephthalate wïth a solution of the p-nitrophenyldiazoacetate modified copolymer in methylene chloride and evaporating the solvent with a stream of nitrogen. The re-sulting 5 mil coated film is covered with a photographic negativeand exposed to a 450 watt meraury lamp a~ a distance of 2 inches.
T~ exposed' coating i5 then washad with toluene to give a good raised image. Exceptionally high resolution of the half-tone dots is noted.
Example 6 To a suspension o 3.0 parts of the saponified copoly-mer described in Example 3 and 50 parts of ben~ene is added ~.4 parts of phenylmalonyl chloride and 1.0 part o pyridine. The ~0~9439 mixture is heated at reflu~ for l.S hours and allowed to cool to room temperature. The reaction mixture is poured into 300 parts of methanol and the precipitated polymer collected and washed with methanol. To a solution of 2.1 parts of the phenyl malonate modified copolymer in methylene chloride is added 0.5 part tri-ethylamine and 1.0 part o p-toluenesulfonylazide. The mixture is allowed to stand at room temperature in the dark for 2 days, and the polymer precipitated by pouring into 200 parts of meth-anol. After washing with methanol, the polymer exhibits strong infrared absorption at 4.7~.
A lithographic plate is prepared by whirl coating a 5%
solution of the phenyldiazomalonate modified copolymer in chloro-form onto a brush grained aluminum plate. After drying at room temperature, the plate is covered with a photographic negative containing line work and half-tone pictures, and exposed to a bank of four meraury arcs rated as 80 watts/linear inch. The exposed film is washed with chloroform to give a good image. The plate was rubbed with gum arabic solutions and gave excellent prints when used on an offset lithographic press.
EXam~le 7 To a solution of 11.0 parts of poly~vinyl alcohol~, having a molecular weight of approximately 96,000, in 20Q parts of N-methyl pyrrolidone is added 18.9 parts of ethylmalonyl chloride and 5.0 parts of acetyl chloride with stirring. The reaction mix~
ture is poured into ~000 parts o water to precipitate the poly-mer. The solids are collected and washed with water.
To a solution o 17.8 parts of the ethyl malonate mod-ified polymer in 310 parts of acetonitrile is added successively 8.1 parts of triethylamine and 15.7 parts of p-toluenesulfonyl-azide. The solution is stored in the dark for two days, and poured into 2500 parts of water. The solids are collected, taken up in 27~ parts of acetonitril~ and reprecipitated. The infrared spec-trum has a band at 4.7~ indlcating the presence o~ dia~o ester groups.
~ 1~9439 A 5% (wt./vol.~ solution of the above ethyl diazomal-onate polymer in chloroorm is whirl coated on a 6-mil grained aluminum plate, dried at room temperature, and exposed for two minutes through a photographic negative and a Stauffer 21 Step Sensitivity Guide (AT 20 x 0.15) to a bank of four medium pres-sure mercury arcs rated at 80 watts/linear inch. The plate is washed with acetone to yield a sharp image and a solid coating at step 5 on the guide. The plate is rubbed successively with gum arabic solution, commércial fountain solution (3 oz./gal.), and commercial lithographic rub up ink. The image areas accept the ink while the substrate aluminum does not.
Example 8 To a solution of 8.8 parts o~ the polytvinyl alcohol), 96,000 mol wt., described in Example 7, in lS0 parts of N-methyl pyrrolidone is added 7.8 parts of acetyl chloride and 20.0 parts of p-nitrophenylacetyl chloride with stirring. The solution is allowed to stand for ~4 hours, and is poured into 4000 parts of water. The precipitate is collected and washed with water.
To a solution of 2.9 parts of the p-nitrophenyl acetate modified polymer in 145 parts of dry pyridine is added 0.9 part of piperidine and 2.0 parts of p-toluenesulfonyl a~ide. The solution is kept in the dark overnight and poured with stirring into 465 parts of methanol. The yellow precipitate i5 collected, chopped, and washed with methanol. The infrarad spectrum of the dried polymer shows strong absorption at 4.8~
A solution of the p-nitrophenyldiazoacetate modified polymer in chloroorm is whirl coated on a 6 mil grained aluminum plate and dried at room temperature in the dark to give a film approximately 5~ thick. The film is exposed through a phbto-graphic negati~e to the light from a 650 watt quart~-halogen tung-sten lamp at a distance of 1~ inches. The plate i`s washed gently with chloroform. An orange image remains in the areas exposed to the light, while the bac~ground dissolves, exposing the aluminum substrate. The pla~e is rubbed with 14 Baume gum arabic ~ Oq9~,9 solution and then with commercial lithographic rub up ink. The image areas accept the ink while the substrate aluminum does not.
Claims (5)
1. A polymer photocross-linkable to actinic radiation containing the following units where P is derived from a soluble hydroxy containing polymer which has been esterified to give the above pendant groups and X
is hydrogen or a radical selected from the group consisting of , , -CN and -Ar, where Ar is selected from phenyl and phenyl substituted with 1 to 3 -NO2, Cl, F, Br, C1-8 alkyl or C1-5 alkyloxy groups and R is selected from C1-18 alkyl, C5-7 cycloalkyl, C1-4 alkyl substituted C5-7 cycloalkyl and Ar, where Ar is as defined above.
is hydrogen or a radical selected from the group consisting of , , -CN and -Ar, where Ar is selected from phenyl and phenyl substituted with 1 to 3 -NO2, Cl, F, Br, C1-8 alkyl or C1-5 alkyloxy groups and R is selected from C1-18 alkyl, C5-7 cycloalkyl, C1-4 alkyl substituted C5-7 cycloalkyl and Ar, where Ar is as defined above.
2. The photosensitive polymer of claim 1 wherein the pendant diazo ester groups are diazoacetate groups.
3. The photosensitive polymer of claim 1 wherein the pendant diazo ester groups are diazomalonate groups.
4. The photosensitive polymer of claim 1 wherein the pendant diazo ester groups are acetodiazoacetate groups.
5. The photosensitive polymer of claim 1 wherein the pendant diazo ester groups are p-nitrophenyldiazoacetate groups.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/692,166 US4038253A (en) | 1973-11-02 | 1976-06-02 | Photocross-linkable polymers containing pendant diazoester groups |
| US692,166 | 1976-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099439A true CA1099439A (en) | 1981-04-14 |
Family
ID=24779515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA278,262A Expired CA1099439A (en) | 1976-06-02 | 1977-05-12 | Photocross-linkable polymers |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS52147686A (en) |
| BE (1) | BE855321A (en) |
| CA (1) | CA1099439A (en) |
| DE (1) | DE2723448A1 (en) |
| FR (1) | FR2353879A1 (en) |
| IT (1) | IT1076782B (en) |
| NL (1) | NL7705653A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013018851A (en) * | 2011-07-11 | 2013-01-31 | Sumitomo Bakelite Co Ltd | Cellulose fiber, cellulose fiber-containing polymer, resin composition, and molding |
-
1977
- 1977-05-12 CA CA278,262A patent/CA1099439A/en not_active Expired
- 1977-05-23 NL NL7705653A patent/NL7705653A/en not_active Application Discontinuation
- 1977-05-24 DE DE19772723448 patent/DE2723448A1/en not_active Withdrawn
- 1977-05-24 FR FR7715848A patent/FR2353879A1/en not_active Withdrawn
- 1977-06-01 IT IT2425677A patent/IT1076782B/en active
- 1977-06-01 JP JP6341177A patent/JPS52147686A/en active Granted
- 1977-06-02 BE BE178136A patent/BE855321A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7705653A (en) | 1977-12-06 |
| IT1076782B (en) | 1985-04-27 |
| JPS6251963B2 (en) | 1987-11-02 |
| DE2723448A1 (en) | 1977-12-15 |
| FR2353879A1 (en) | 1977-12-30 |
| JPS52147686A (en) | 1977-12-08 |
| BE855321A (en) | 1977-12-02 |
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