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GB2127167A - Water developable light sensitive compositions and printing plates - Google Patents

Water developable light sensitive compositions and printing plates Download PDF

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Publication number
GB2127167A
GB2127167A GB08325083A GB8325083A GB2127167A GB 2127167 A GB2127167 A GB 2127167A GB 08325083 A GB08325083 A GB 08325083A GB 8325083 A GB8325083 A GB 8325083A GB 2127167 A GB2127167 A GB 2127167A
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GB
United Kingdom
Prior art keywords
water
composition according
insoluble polymer
nonionic
light sensitive
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.)
Granted
Application number
GB08325083A
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GB2127167B (en
GB8325083D0 (en
Inventor
Nils Eklund
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polychrome Corp
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Polychrome Corp
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Filing date
Publication date
Application filed by Polychrome Corp filed Critical Polychrome Corp
Publication of GB8325083D0 publication Critical patent/GB8325083D0/en
Publication of GB2127167A publication Critical patent/GB2127167A/en
Application granted granted Critical
Publication of GB2127167B publication Critical patent/GB2127167B/en
Expired legal-status Critical Current

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/016Diazonium salts or compounds
    • G03F7/021Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • G03F7/0212Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

A water developable printing plate is provided with a photopolymerisable coating formed from a latex comprising a water-soluble diazopolymer reaction product of a diazoaryl amine and an aldehyde and an aqueous cationic or nonionic dispersion of a water- insoluble polymer. The inclusion of a water miscible organic solvent improves the shelf-life of the photopolymerisable system and the printing plate especially under high humidity conditions.

Description

SPECIFICATION Water developable, light sensitive, compositions and printing plates This invention relates to photopolymerisable systems which include photopolymerisable compositions that are light sensitive latices which form water developable printing plates when coated on suitable backing members. Selected image areas can be insolubilised and cross linked by exposure to actinic radiation and the composition in the non-radiated non-image areas can be washed away with water to provide the desired planographic image.
Emulsion photopolymerisable systems are taught in US Patents 4 186069,4224398, and 4 288 520. In these systems, the photopolymerisable coating is an emulsion mixture of a polymer component having water insoluble polymer particulates within an aqueous suspension medium, together with a water soluble or water dispersible light-sensitive component including a polymer having at least two moieties per molecule. Such polymers are sensitive to actinic radiation, and by generating a free radical or other cross linking species form a matrix of crosslinked polymer which encapsulate or entrap therein and disperse therethrough the water insoluble polymer. Prior to curing this system is a three phase emulsion including the water insoluble polymer particulates within the aqueous suspension medium with which is also mixed the light-sensitive polymer.When the coating composition is applied to a suitable backing member, the aqueous suspension is substantially removed to realise a two-phase mixture of the polymer particulates and light sensitive polymer.
It has long been known to use water insoluble polymers in producing light sensitive coatings for use on substrates such as planographic printing plates in which the polymers are incorporated as part of a solvent system layer which uses organic materials and which must be driven off from the plate, a requirementwhich is time and energy consuming, wasteful of solvents and possibly hazardous to the operator and the environment.
Use of water soluble systems generally avoids the disadvantages of the organic base systems, but they are not particularly long lasting because the polymers are water soluble and are therefore subject to erosion of the image area when in use and/or through the action of atmospheric moisture. The emulsion systems of the aforementioned patents provide an improved stability with respect to other water based systems, but they are still characterised by a shelf-life which is less than optimum, especially under high humidity conditions. Additionally, the images provided by such emulsion systems often include spots which are commercially unacceptable.
It is our object to provide a photopolymerisable system and a water developable printing plate which exhibits improved properties, particularly with respecs to shelf life under high humidity conditions.
A light sensitive coating composition according to the invention comprises a water soluble diazo polymer reaction product of a diazoarylamine and an aldehyde and an aqueous cationic or nonionic dispersion of a water insoluble polymer.
The invention also includes presensitised printing plates comprising a substrate carrying a coating of this composition, and printing plates comprising a substrate carrying such a coating and which has been cured in preselected areas.
The light sensitive coating composition of the present invention is an emulsion mixture of a cationic or nonionic polar emulsion component having water insoluble polymer particulates within an aqueous suspension medium together with a water soluble or water dispersible component which is a diazo polymer reaction product of a diazoarylamine and an aldehyde. The water insoluble polymer emulsion component and the light sensitive component are generally present in quantities of the same order of magnitude but can vary from a weight percent ratio of about 25:1 to 1:25, preferably about 5:1 to 1:5.
The water soluble diazo polymers used in the present invention are prepared by the well known condensation reaction of a diazoaryl amine such as a p-diazodiphenylamine and an aldehyde such as formaldehyde or paraformaldehyde which results in the formation of an oligomer or low molecular weight polymer. Many such diazo polymers are commercially available and typical examples include Diazo-8000 sold by Polychrome Corporation of Yonkers, New York, which is a zinc chloride salt of the reaction product of para-diazodiphenylamine with paraformaldehyde, and Diazo Resin No 4 of Fairmount Chemicals, which is a reaction product of para-diphenylamine diazonium chloride with formal- dehyde. Salts of the reaction product of pdiazodiphenylamine with paraformaldehyde are especially preferred.Zinc chloride, phosphate, sulfate salts and the like can be utilised, the zinc chloride salts being preferred.
The aqueous dispersion of the water insoluble polymer of the present invention is cationic or nonionic either as a result of the use of an emulsifier or by having the cationic or nonionic group linked to the polymer. The water insoluble polymer is preferably a solid particulate having a size in the range of about 100 Angstroms to 10 microns in diameter. In general, any polymer which carries a cationic or nonionic group orwhich can be formulated into an emulsion using a cationic or nonionic emulsifier can be employed in the present invention.Suitable polymers include the homopolymers and copolymers of styrene, ethyl acrylate, butyl acrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, methylstyrene, vinyl toluene, dimethylaminoethyl acrylate, acrylic acid, methacrylic acid, isoprene, chloroprene, maleic anhydride, ethylene glycol acrylates such as polyethylene glycol acrylate, halogenated vinyl aromatics such as chlorostyrene and bromostyrene, methylvinyl ether, vinyl pyrrolidone, polyurethane and the like.
Among the cationic and nonionic emulsifiers which can be used in the present invention are ammonium salts of substituted amines containing alkyl and/or aryl groups attached to the nitrogen, alkyl or aryl sulfonium salts, alkyl and alkyl-aryl polyethers, cationic or nonionic fluorosurfactants and polyoles.
Various cationic and nonionic emulsions are com merciaily available and can be used in the practice of the present invention. For example, Witcobond W-212, a cationomeric polyurethane emulsion sold by Witco can be used in the present invention.
Reference should be made to US Patents 3 873484 and 4 160 065 which describe such emulsions. A typical nonionic emulsion is Vondic 131 OF sold by Dainippon Inc., which is available as a polyurethane emulsion. Witcobond and Vondic are trade marks.
When it is desired to enhance the sensitivity of the light sensitive diazo polymer, known sensitisers can be included in the composition. For example, the composition can contain Michler's ketone, benzoin, benzoin methyl ether and other well known sensitisers which may be water solubilised as required by the use of amines, amine salts, quaternary amines, or polyalkoxy groups.
The light sensitive composition of the present invention generally contains stabilisers which are derivatives of pyridine-N-oxide or other quaternised ammonium compounds. Typical examples include nicotinamide-N-oxide, pyridine-N-oxide, quinoline N-oxide, 4-nitroquinoline-N-oxide, tetra-methyl ammonium chloride, dimethyldiallyl ammonium chloride. These stabilisers are present at a weight percent ratio range of from about 1:50 to 2:1, preferably 1 :10 to 1:1, relative to the light sensitive diazo polymers.
The compositions of the present invention can also include antihalation agents, dyes, pigments, fillers, plasticisers, extenders, crosslinked particles, and other materials for aiding in maintaining or modifying the viscosity, plasticity and/or stability of the compositions. It will be appreciated that any dues should be water soluble cationic or nonionic dyes although anionic dyes having at most one anionic group can also be used.
It has been found that the inclusion of a water miscible organic solvent in the aqueous dispersion of the water insoluble polymer improves the shelf life of the composition especially under high humidity conditions. Typical organic solvents which can be used include methanol, ethanol, acetone, dimethylformamide, methylcellosolve, acetonitrile, dioxane, propanol, etc. The water miscible organic solvent will generally be about 0.1 -75 weight percent, preferably about 1 to 40 weight percent, based on the weight of the total solvent system.
The photosensitive compositions of the present invention can be applied to any conventional substrate such as aluminium, copper, zinc, magnesium, steel or plastic, in any convenient fashion such as spray, roll or dip methods. After coating, the aqueous phase is evaporated or dried to remove the water or water and miscible organic solvent at low or elevated temperatures with or without imposition of a vacuum to leave the water insoluble emulsion and light sensitive polymer together with a small amount of residual water or water and miscible organic solvent on the substrate. Areas of the composition which are exposed to actinic radiation harden abd become hydrophobic, while the portions which are not so exposed remain water receptive and can be removed by simple water development.
In order to further illustrate the invention, various examples are set forth below. Throughout these examples, as well as throughout this specification and claims, all parts and percentages are by weight and all temperatures in degrees Centigrade unless otherwise specified.
Example 1 A photopolymerisable composition was prepared by mixing 5.37 percent of a cationomeric polyurethane emulsion (Witcobond W-212) and 0.64 percent of a water soluble diazopolymer which was the zinc chloride salt of a reaction product of para-diazodiphenylamine and paraformaldehyde.
The composition additionally contained 0.16 percent zinc chloride, 0.48 percent tris(2chloroethyl)phosphate, 0.16 percent nicotinamide N-oxide, 0.032 percent methyl green, 76.6 percent water and 16.5 percent dimethylformamide. The photosensitive composition was coated on a grained anodised and silicated sheet of aluminium and allowed to dry. The plate was thereafter exposed to ultraviolet radiation, developed with tap water and gummed in the conventional fashion. The resulting lithographic plate was found to produce 30,000 good quality copies. A sample of the resultant plate with a coating weight of 0.75g/m2 was subjected to accelerated shelf-life testing under high humidity conditions by exposure to 90 percent humidity at 380C for 120h. The plate showed quite satisfactory properties in exposure speed, adhesion and development.
Another sample subjected to accelerated shelf-life testing at 600C and low humidity for 120h also performed satisfactorily.
Example 11 The substrate used in the previous example was coated with an emulsion containing 4.09 percent of a nonionic polyurethane emulsion (Vondic 1310F, Dainippin Inc.) and 0.66 percent of the same diazopolymer used in Example 1. The composition additionally contained 0.16 percent zinc chloride, 0.49% tris(2-chloroethyl)-phosphate, 0.16 percent nicotina mide-N-oxide, 0.25% Surfynol SE (Air Products Inc), 0.04 percent Zonyl FSC (du Pont), 77.8 percent water and 16.4% 2-methoxyethanol (methylCellosolve).
The composition was ubjected to the same accelerated shelf life as in Example 1 without any negative effects. Vondic Surfynol, Zonyl and Cellosolve are trade marks.

Claims (10)

1. A light-sensitive latex coating composition comprising a water soluble diazo polymer reaction product of a diazoarylamine and an aldehyde and an aqueous cationic or nonionic dispersion of a water insoluble polymer.
2. A composition according to claim 1 in which the aqueous cationic or nonionic dispersion contains a water miscible organic solvent.
3. A composition according to claim 1 or claim 2, and which contains a quaternary nitrogen containing stabiliser.
4. A composition according to any preceding claim and which contains a compatible dye.
5. A composition according to any preceding claim and which additionally contains a zinc salt.
6. A composition according to any preceding claim wherein the water insoluble polymer is dispersed in a cationic emulsifier.
7. A composition according to any of claims 1 to 5, wherein the water insoluble polymer is dispersed in a nonionic emulsifier.
8. A composition according to claim 1, substantially as herein described with reference to either of the Examples.
9. A presensitised printing plate comprising a substrate carrying a light-sensitive latex coating of a composition according to any preceding claim.
10. A printing plate comprising a substrate carrying a coating of a composition according to any of claims 1 to 8 and which has been cured on preselected areas thereof.
GB08325083A 1982-09-21 1983-09-20 Water developable light sensitive compositions and printing plates Expired GB2127167B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US42075482A 1982-09-21 1982-09-21

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Publication Number Publication Date
GB8325083D0 GB8325083D0 (en) 1983-10-19
GB2127167A true GB2127167A (en) 1984-04-04
GB2127167B GB2127167B (en) 1986-03-05

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GB08325083A Expired GB2127167B (en) 1982-09-21 1983-09-20 Water developable light sensitive compositions and printing plates

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JP (1) JPS59146049A (en)
CA (1) CA1208473A (en)
DE (1) DE3328019A1 (en)
FR (1) FR2533227B1 (en)
GB (1) GB2127167B (en)
NL (1) NL8303171A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4430680A1 (en) 1994-08-29 1996-03-07 Hoechst Ag Photosensitive mixture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1517961A (en) * 1975-05-20 1978-07-19 Nippon Paint Co Ltd Photosensitive composition and process for preparing same
GB2007379A (en) * 1977-10-11 1979-05-16 Eastman Kodak Co Light sensitive diazo resin compositions for producing dye images
GB2013918A (en) * 1978-01-30 1979-08-15 Richardson Co Photopolymerizable latex systems
GB2075702A (en) * 1980-05-09 1981-11-18 Fuji Photo Film Co Ltd Photosensitive printing plate precursor
EP0048160A1 (en) * 1980-09-15 1982-03-24 Napp Systems (Usa) Inc. Photosensitive recording material, and method of half-tone etching
EP0008038B1 (en) * 1978-08-03 1983-05-18 Hoechst Aktiengesellschaft Process for the preparation of a light-sensitive copying material based on condensation products of diazonium salts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1447954C3 (en) * 1960-08-05 1975-11-06 Hoechst Ag, 6000 Frankfurt Presensitized planographic printing plate
US3382069A (en) * 1964-06-18 1968-05-07 Azoplate Corp Planographic printing plate
DD96345A1 (en) * 1972-01-05 1973-03-12
GB1523762A (en) * 1975-02-25 1978-09-06 Oce Van Der Grinten Nv Photocopying materials
CA1091969A (en) * 1975-06-19 1980-12-23 Robert W. Hallman Photosensitive unilayer film structure cast from a polymeric emulsion dispersion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1517961A (en) * 1975-05-20 1978-07-19 Nippon Paint Co Ltd Photosensitive composition and process for preparing same
GB2007379A (en) * 1977-10-11 1979-05-16 Eastman Kodak Co Light sensitive diazo resin compositions for producing dye images
GB2013918A (en) * 1978-01-30 1979-08-15 Richardson Co Photopolymerizable latex systems
EP0008038B1 (en) * 1978-08-03 1983-05-18 Hoechst Aktiengesellschaft Process for the preparation of a light-sensitive copying material based on condensation products of diazonium salts
GB2075702A (en) * 1980-05-09 1981-11-18 Fuji Photo Film Co Ltd Photosensitive printing plate precursor
EP0048160A1 (en) * 1980-09-15 1982-03-24 Napp Systems (Usa) Inc. Photosensitive recording material, and method of half-tone etching

Also Published As

Publication number Publication date
GB2127167B (en) 1986-03-05
DE3328019A1 (en) 1984-03-22
GB8325083D0 (en) 1983-10-19
JPS59146049A (en) 1984-08-21
NL8303171A (en) 1984-04-16
CA1208473A (en) 1986-07-29
FR2533227A1 (en) 1984-03-23
FR2533227B1 (en) 1986-09-26

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