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WO1996018133A1 - Plaques d'impression typo a haute resolution et compositions hydrosolubles photopolymerisables comprenant un derive de l'alcool polyvinylique associees - Google Patents

Plaques d'impression typo a haute resolution et compositions hydrosolubles photopolymerisables comprenant un derive de l'alcool polyvinylique associees Download PDF

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Publication number
WO1996018133A1
WO1996018133A1 PCT/US1995/015036 US9515036W WO9618133A1 WO 1996018133 A1 WO1996018133 A1 WO 1996018133A1 US 9515036 W US9515036 W US 9515036W WO 9618133 A1 WO9618133 A1 WO 9618133A1
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WIPO (PCT)
Prior art keywords
range
mol
falls
meth
polymerization
Prior art date
Application number
PCT/US1995/015036
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English (en)
Inventor
David H. Roberts
Mitch G. Male
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Napp Systems, Inc.
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Napp Systems, Inc. filed Critical Napp Systems, Inc.
Publication of WO1996018133A1 publication Critical patent/WO1996018133A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to water- developable photosensitive printing plates and compositions useful for the preparation thereof.
  • Photosensitive resins used for the manufacture of relief printing plates are preferably developable with water rather than organic solvent. This is true for various reasons, such as ease of handling, health of workers who come in contact therewith, safety, and avoidance of environmental pollution. Photosensitive resins used for the manufacture of relief printing plates must also be capable of providing a sharp, preferably durable image, especially when the desired end use is in letterpress applications.
  • photosensitive resins have been employed for the preparation of printing plates.
  • the photosensitive resin compositions employed for conventional photosensitive resin plates are based on liquid unsaturated polyesters, polyvinyl alcohols, chemically modified polyvinyl alcohols, water soluble polyamides, cellulose acetate succinates, alcohol soluble polyamides, etc. All these materials, however, suffer from disadvantages. For instance, liquid unsaturated polyesters are inconvenient to handle and necessitate the use of an alkaline solution or a special air knife for developing. Cellulose acetate succinates require the use of an alkaline solution for development, and alcohol soluble polyamides typically require the use of an inflammable alcohol.
  • Figure 1 illustrates the juncture between the face (top surface) and the shoulder of a character formed by photopolymerized polymeric compositions.
  • Figure 1A illustrates the structure desired for a "sharp" image
  • Figure IB illustrates a structure which gives rise to a poorly defined image.
  • invention compositions which upon exposure to electromagnetic radiation form water insoluble polymer(s) .
  • invention compositions comprise: in the range of about 30 up to 75 wt % of a polymer system comprising a polyvinyl alcohol (PVA) derivative having the structure:
  • X is hydrogen or -C0 2 H
  • X' is -OR, wherein each R is independently selected from -H, -CH 2 CH 3 OH or -C(0)CH 3( when X is hydrogen; or X' is
  • each R 1 is independently selected from H or lower alkyl; each R" is independently selected from
  • a falls in the range of about 65 up to 99 mol%, based on the total moles of monomeric units contained in said PVA derivative (i.e., a+2b) ; and b falls in the range of about 1 up to
  • n falls in the range of about 0 up to
  • wt % in all instances is based on the total weight of the composition.
  • Polymer systems contemplated for use in the practice of the present invention comprise a PVA derivative as defined above, optionally blended with substituted or unsubstituted polyvinyl alcohol (PVA) .
  • PVA polyvinyl alcohol
  • the polymer system will typically contain little, if any, PVA "diluent"; while a substantial portion of the polymer system may comprise PVA as diluent where there is a relatively high concentration of ethylenically unsaturated groups per ethylidene repeat unit of the PVA derivative contemplated for use in the practice of the present invention.
  • the mol % ethylenically unsaturated functionality present in the polymer system of the present invention will fall in the range of about 2 up to 25 mol %, based on the total moles of monomeric units contained in said PVA derivative (or in the PVA-based polymer system) ; with in the range of about 3 up to 15 mol % ethylenically unsaturated functionality in the polymer system preferred. It is presently especially preferred that the mol % of ethylenically unsaturated functionality in the polymer system employed in the practice of the present invention fall in the range of about 4 up to 9.
  • the desired concentration of ethylenically unsaturated functionality can be provided by a blend of the above-described PVA derivative with PVA, or by a PVA derivative as described above which directly provides the desired level of ethylenically unsaturated functionality. Since PVA derivatives as described above can readily be prepared having a wide range of ethylenic unsaturation content, blends containing various ratios of the above- described PVA derivatives and PVA can be prepared for use in the practice of the present invention.
  • polyvinyl alcohol refers to hydrolyzed polyvinyl acetate, having a degree of hydrolysis in the range of about 65 up to 98% (i.e., having about 65-
  • polyvinyl alcohols having in the range of about 80-95% free hydroxyls will be employed.
  • Polyvinyl alcohols having a wide range of molecular weights can be employed in the practice of the present invention.
  • Polymeric species having a MW in the range of about 2,000 up to 100,000 are suitable, while presently preferred polymeric species will have a molecular weight in the range of about 5,000 to 50,000, with molecular weights in the range of about 10,000 up to 30,000 being especially preferred.
  • PVAs employed in the practice of the present invention can be modified, for example, by ethoxylation (see, for example, U.S.
  • PVA derivatives contemplated for use in the practice of the present invention are polymers having the structure :
  • X is hydrogen or -C0 2 H
  • X' is -OR, wherein each R is independently selected from -H, -CH 2 CH 2 OH or -C(0)CH 3 , when X is hydrogen; or X' is -CH 2 C0 2 H when X is -C0 2 H, with the proviso that at least 55 mol% of the X' groups are -OH; each Y is independently selected from -CH j - or -0-CH 2 CH 2 -; each Z is independently selected from
  • PVA derivatives contemplated for use in the practice of the present invention include those wherein X is hydrogen, X' is predominantly -OH (i.e., R is predominantly hydrogen), Y is -CH 2 -, Z is -0-, R" is hydrogen, a falls in the range of about 85 up to 97, b falls in the range of about 3 up to 15, and n falls in the range of about 0 up to 2.
  • X is hydrogen
  • X' is predominantly -OH (i.e., R is predominantly hydrogen)
  • Y is -CH 2 -
  • Z is -0-
  • R" is hydrogen
  • a falls in the range of about 85 up to 97
  • b falls in the range of about 3 up to 15
  • n falls in the range of about 0 up to 2.
  • Especially preferred PVA derivatives contemplated for use in the practice of the present invention are those wherein:
  • X is hydrogen, in the range of 70 up to 85 mol% of the X* groups are -OH, and in the range of 5 up to 25 mol% of the X' groups are -OAc, n is 0 (therefore Y is not present) , Z is -NH-, R" is methyl, a falls in the range of 88 up to 98 mol%, and b falls in the range of 2 up to 12 mol%; or
  • X is hydrogen, in the range of 70 up to 85 mol% of the X' groups are -OH, and in the range of 5 up to 25 mol% of the X' groups are -OAc, Y is -CH 2 - and n is 2, Z is -NH-, R" is methyl, a falls in the range of 88 up to 98 moll, and b falls in the range of 2 up to 12 mol%; or
  • X is hydrogen, in the range of 70 up to 85 mol% of the X' groups are -OH, and in the range of 5 up to 25 mol% of the X' groups are -OAc, n is 0, therefore Y is not present, Z is -O-, R" is methyl, a falls in the range of 88 up to 98 mol%, and b falls in the range of 2 up to 12 mol%.
  • polyvinyl alcohol can be contacted with at least one reactive species having the structure:
  • condensation conditions typically comprise acidic media (e.g., pH ⁇ 3) and mild heating (i.e., temperatures in the range of about 60 up to 90°C) .
  • PVA can be condensed with a suitable reactive species (e.g., methacrylamido- butyraldehyde dimethyl acetal (MABDA) , 2,2-dimethoxyethyl methacrylamide (DEMA) , and the like) in the presence of a suitable acid (e.g., H 3 P0 4 , acidic ion exchange resin, and the like) .
  • a suitable acid e.g., H 3 P0 4 , acidic ion exchange resin, and the like
  • the resulting modified PVA can be mixed directly with the other components appropriate to produce the photopolymerizable composition of the invention.
  • aqueous medium contemplates water alone, as well as mixtures of water and organic media such as C, - C alcohols (in a ratio anywhere from 1 part water per 10 parts alcohol up to 10 parts water per 1 part alcohol) .
  • Aqueous medium is typically employed in the range of about 1 up to 15 wt %; with media levels in the range of about 2-10 wt % being preferred; with 3-6 wt % aqueous media being presently preferred.
  • the range of about 10 up to 60 wt % of at least one monomer is employed as part of the photopolymerizable composition.
  • the range of about 20 up to 50 wt % monomer is employed, with in the range of about 35 up to 40 wt % being presently preferred.
  • reference to "at least one monomer” embraces monounsaturated, monofunctional monomeric species, as well as unsaturated, polyfunctional monomeric species.
  • the term "monounsaturated, monofunctional monomeric species” refers to compounds having only one ⁇ ,?-ethylenic site of unsaturation, and embraces a variety of acrylate and ethacrylate compounds such as glycerol mono(meth)acrylate (i.e., glycerol monoacrylate or glycerol monomethacrylate) , yff-hydroxyethyl (meth) acrylate, ff-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, carboxyethyl acrylate ( / ff-CEA) , carboxyethyl methacrylate, dimethylaminopropyl (meth)acrylamide, and the like.
  • the term "unsaturated, polyfunctional monomeric species” refers to compounds having more than one ⁇ ,yS-ethylenic site of unsaturation, and embraces such compounds as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, epoxy (meth)acrylates of glycols, aliphatic or aromatic urethane acrylates, and the like.
  • photopolymerization initiators can be used in the practice of the present invention.
  • photoinitiator embraces ordinary photoreaction initiators such as ⁇ -diketone compounds or monoketal derivatives thereof (e.g., diacetyl, benzil, benzil ketals, and the like), acyloins (e.g., benzoin, pivaloin, and the like), acyloin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin vinyl ether, benzoin allyl ether, and the like) , polynuclear quinones (anthraquinone, 1,4-naphthoquinone) , benzophenone, hydroxy acetophenones, acyl phosphine oxides, and the like.
  • photoreaction initiators such as ⁇ -diketone compounds or monoketal derivatives thereof (e.g.
  • Such compounds are typically employed at levels in the range of about 0.1 up to 3.0 wt %.
  • the presently preferred initiator for use in the practice of the present invention is benzil dimethyl ketal.
  • compositions of the invention include polymerization inhibitors (e.g., hydroxyaromatic compounds (e.g., hydroquinone, hydroquinone methyl ether (MEHQ; also known as p-methoxyphenol) , p-t-butylcatechol, 2,6-di-t-butyl- p-cresol, pyrogallol, butylated hydroxytoluene (BHT) , butylated hydroxyaniline (BHA) , and the like) ; quinones (e.g., hydroxyaromatic compounds (e.g., hydroquinone, hydroquinone methyl ether (MEHQ; also known as p-methoxyphenol) , p-t-butylcatechol, 2,6-di-t-butyl- p-cresol, pyrogallol, butylated hydroxytoluene (BHT) , butylated hydroxyaniline (BHA) , and the like)
  • invention compositions may also contain a plasticizer, which acts to reduce the glass transition temperature of the polymer, thereby improving the flexibility of the resulting composition.
  • plasticizers useful in the practice of the present invention include glycerin, ethoxylated phenols, ethoxylated glycerin, ethylene glycol, propylene glycol, and the like.
  • One of the desirable characteristics of invention compositions is their developability with water of substantially neutral pH. Thus, there is no need to use pH modified (i.e., acidic or basic) media when developing invention compositions.
  • Another desirable characteristic of invention compositions is the high photosensitivity thereof, thus such resins require only a relatively short time for light exposure to accomplish the crosslinking thereof.
  • invention compositions can be developed with water in 1 to 10 minutes or longer, depending on the water temperature, specific resin composition, resin thickness, and the like. Typically, invention compositions are developed for in the range of about l up to 5 minutes. After the resin is developed, it is dried in suitable fashion, optionally subjected to a post-cure exposure to strengthen the resin. Photocured and developed compositions can be used for printing immediately after drying and optional post-cure (which involves additional exposure of the dried plate to appropriate wavelength radiation for about 0.1 up to 20 minutes or longer).
  • solid water- developable photosensitive resin plates comprising a support having deposited thereon a layer of the above- described photopolymerizable composition.
  • invention resin plates are characterized by: producing a sharp image, as determined by the method described in Example 2A, after photo ⁇ polymerization and development thereof, producing an image capable of holding 2% dots at 120 lines per inch, as determined by the highlight dot holding test described in Example 2B, after photo-polymerization and development thereof, being relatively insensitive to variations in processing conditions employed for washout of the photopolymerizable composition, and producing a durable printing surface after photo ⁇ polymerization and development thereof.
  • Resin compositions of the present invention produce resin plates having the above-described excellent physical performance properties, while avoiding the need for high cost starting materials. Instead, invention compositions can be prepared from relatively low-cost, off- the-shelf starting materials (e.g., standard grade polyvinyl alcohol) , and readily prepared ethylenically unsaturated derivatives thereof.
  • starting materials e.g., standard grade polyvinyl alcohol
  • a “sharp image” (determined by the method described in Example 2A) , after photo-polymerization and development thereof refers to the profile of isolated dots and letters (referred to hereinafter as characters) on a developed plate.
  • the juncture between the face (top surface) and the shoulder of the character is evaluated.
  • the point where the character face meets the shoulder should be well defined, the face of the character dropping- off crisply to the shoulder (as illustrated in Figure 1A) .
  • Unacceptable image sharpness is demonstrated by characters which are "rounded", i.e., the point where the character face meets the shoulder is not angular and well defined, but forms an arc (as illustrated in Figure IB) .
  • a particularly stringent test of image sharpness is the highlight dot holding test, wherein a high density grid of dot images is produced on a test plate, then observed to see how well the dot shape is retained after development of the plate. The finer the size of dots that can be retained, the greater the resolution which can be achieved. See Example 2B for a detailed description of how the highlight dot holding test is carried out. It is consistently observed that plates made with invention resin display improved dot holding properties, relative to plates made with prior art resins (see, for example, the Table presented following Example l) .
  • invention resins are the relative insensitivity of such resins to variations in processing conditions employed for washout of the photopolymerizable composition.
  • invention compositions can be cured over a wide range of conditions (e.g., water temperature and wash times when developing the photopolymerized resins) , without substantially affecting the properties of the resulting product.
  • invention resins are the production of a durable printing surface after photo ⁇ polymerization and development thereof.
  • invention compositions can be used in a variety of applications which entail long-term printing runs, high stress applications, and the like.
  • Supports contemplated for use in the practice of the present invention can be prepared of a variety of materials, e.g., metal, plastic, paper, wood, glass, and the like.
  • Exemplary support materials include steel, aluminum and plastic (e.g., polyethylene terephthalate, Mylar, and the like) .
  • "Depositing" of the above-described compositions onto support can be carried out in a variety of ways, e.g., by extrusion, roll coating, heat processing, solvent casting, and the like. These techniques can be readily carried out by those of skill in the art.
  • the thickness of the layer of photopolymerizable composition applied in the preparation of invention photosensitive resin plates can vary widely. Typically, a resin thickness of at least 7 mils (i.e., 0.007 inches) will be applied, with resin thickness of up to about 250 mils contemplated. Preferably, resin thicknesses in the range of about 5 up to 100 mils will be employed, with current commercial plates typically having a resin thickness in the range of about 10 up to 70 mils.
  • an adhesive layer is applied to the support before the layer of photopolymerizable composition is deposited in the support.
  • Suitable materials for use in preparing and applying such adhesive layers are well known in the art. See, for example, United States Patent No. 3,360,746 (incorporated by reference herein), and the Examples which follow.
  • a matte coat is applied on top of the layer of photopolymerizable composition once said composition has been deposited on the support.
  • Suitable materials for use in preparing and applying such matte coatings are well known in the art. See, for example, United States Patent No. 4,126,460, incorporated by reference herein, as well as the Examples which follow.
  • relief printing plates comprising support having deposited thereon a photopolymerized layer of photopolymerizable composition of the invention at a thickness of at least 7 mils.
  • Invention printing plates are characterized as described above in terms of producing a sharp image, producing an image capable of holding 2% dots at 120 lines per inch, being relatively insensitive to variations in processing conditions employed for washout of the photopolymerizable composition, and producing a durable printing surface after photo-polymerization and development thereof.
  • a method for preparing water-developable photosensitive relief printing plates comprising depositing onto a suitable support a substantially homogeneous photopolymerizable composition as described above at a thickness of at least 7 mils.
  • the resulting plates are characterized as described above in terms of producing a sharp image, producing an image capable of holding 2% dots at 120 lines per inch, being relatively insensitive to variations in processing conditions employed for washout of the photopolymerizable composition, and producing a durable printing surface after photo-polymerization and development thereof.
  • a method for preparing a relief printing plate comprising: exposing a photosensitive resin plate as described above through a negative film having an image thereon to electromagnetic radiation of sufficient energy to promote the polymerization of said resin, and washing said plate with a sufficient quantity of water to remove the photosensitive resin composition from the non-exposed portions of said plate.
  • said plate is characterized, after photopolymerization and development thereof, as described above in terms of producing a sharp image, producing an image capable of holding 2% dots at 120 lines per inch, being relatively insensitive to variations in processing conditions employed for washout of the photopolymerizable composition, and producing a durable printing surface.
  • a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of about 300 and a number average hydrolysis value of about 80 mol% were dissolved in 400 parts by weight of deionized water.
  • Six (6) parts by weight of methacrylamidobutyraldehyde dimethyl acetal (MABDA) and 8.2 parts by weight of H 3 P0 4 were added to the PVA solution.
  • MABDA methacrylamidobutyraldehyde dimethyl acetal
  • H 3 P0 4 H 3 P0 4
  • the coated steel support comprises a steel support having deposited thereon (for example, by roll coating) -65 micron wet thickness of an adhesion layer of a composition containing pigment (for anti-reflectance) , PVA, thickeners and latex adhesive.
  • the dried resin film on the coated steel support was then exposed to ultraviolet light provided by a fluorescent cold lamp through a negative mask.
  • the negative was removed and the non- polymerized areas of the resin were washed out with plain water (i.e., water containing no additives).
  • plain water i.e., water containing no additives.
  • the resulting relief plates were dried (at -110°C for about 5 minutes) , and then post-cured for about 5 minutes.
  • Invention Composition 1 The procedure employed for the preparation of Invention Composition 1 was repeated, except that 100 parts of a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of 300 and number average degree of hydrolysis of about 80 mol% were substituted in place of the PVA derivative employed in the preparation of Invention Composition 1. The film was imaged and developed as described above for the evaluation of Invention Composition 1.
  • 106 parts by weight of the PVA derivative solution prepared as described in the preceding paragraph were added to a resin kettle containing 0.006% of a dye (e.g., eosin) .
  • 70 parts by weight of a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of about 300 and a number average hydrolysis value of about 80 mol% were added to the resin kettle. The components were then heated to 85°C, and then mixed for about 40 minutes.
  • the coated steel support comprises a steel support having deposited thereon (for example, by roll coating) -65 micron wet thickness of an adhesion layer of a composition containing pigment (for anti-reflectance) , PVA, thickeners and latex adhesive.
  • the dried resin film on the coated steel support was then exposed to ultraviolet light provided by a fluorescent cold lamp through a negative mask.
  • the negative was removed and the non- polymerized areas of the resin were washed out with plain water (i.e., water containing no additives).
  • plain water i.e., water containing no additives.
  • the resulting relief plates were dried (at ⁇ 110°C for about 5 minutes) , and then post-cured for about 5 minutes.
  • Invention Composition 2 The procedure employed for the preparation of Invention Composition 2 was repeated, except that 100 parts of a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of 300 and number average degree of hydrolysis of about 80 mol% were substituted in place of the PVA derivative employed in the preparation of Invention Composition 2. In addition, 6 parts by weight of MABDA were added to the monomer solution. The film was imaged and developed as described above for the evaluation of Invention Compositions 1 and 2. Evaluation of the relief image showed that the shoulder angles were rounded (see Figure IB) and 0% of the 2 mil highlight dots at 120 lpi were held.
  • Invention Composition 3 100 parts by weight of a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of about 300 and a number average hydrolysis value of about 80 mol% were dissolved in 70 parts by weight of deionized water containing 0.006% of a dye (e.g., eosin) in a resin kettle. 6 parts by weight of methacrylamido- butyraldehyde dimethyl acetal (MABDA) and 1.5 parts by weight of H 3 P0 4 were added to the PVA solution. The mixture was stirred at about 85°C for about 40 minutes.
  • MABDA methacrylamido- butyraldehyde dimethyl acetal
  • the coated steel support comprises a steel support having deposited thereon (for example, by roll coating) ⁇ 65 micron wet thickness of an adhesion layer of a composition containing pigment (for anti-reflectance) ,
  • the dried resin film on the coated steel support was then exposed to ultraviolet light provided by a fluorescent cold lamp through a negative mask.
  • the negative was removed and the non- polymerized areas of the resin were washed out with plain water (i.e., water containing no additives).
  • the resulting relief plates were dried (at ⁇ 110°C for about 5 minutes) , and then post-cured for about 5 minutes.
  • Comparative Composition C The procedure employed for the preparation of
  • Invention Composition 3 was repeated, except that no MABDA, no H 3 P0 4 and no NaOH was added to the reaction mixture. The film was imaged and developed as described above for the evaluation of Invention Composition 1, 2 or 3.
  • a partially hydrolyzed polyvinyl alcohol having an average degree of polymerization of about 300 and a number average hydrolysis value of about 80 mol% were dissolved in 350 parts by weight of deionized water.
  • DEMA 2,2-dimethoxyethyl methacrylamide
  • a solid phase acidic ion exchange resin e.g., Amberlyst 15
  • the mixture was stirred at about 70°C for about 3 hours. After 3 hours of stirring, the product was precipitated in acetone, then washed with acetone.
  • the resulting PVA derivative was dried in a vacuum oven at about 50°C, then ground into a powder in a blender.
  • the coated steel support comprises a steel support having deposited thereon (for example, by roll coating) -65 micron wet thickness of an adhesion layer of a composition containing pigment (for anti-reflectance) , PVA, thickeners and latex adhesive.
  • the dried resin film on the coated steel support was then exposed to ultraviolet light provided by a fluorescent cold lamp through a negative mask.
  • the negative was removed and the non- polymerized areas of the resin were washed out with plain water (i.e., water containing no additives).
  • plain water i.e., water containing no additives.
  • the resulting relief plates were dried (at ⁇ 110°C for about 5 minutes) , and then post-cured for about 5 minutes.
  • Image sharpness assessment is based on the appearance of the profile of letters and isolated dots on a developed plate, the letters and isolated dots being referred to hereinafter as characters.
  • the juncture between the face (top surface) and the shoulder of the character is evaluated.
  • the point where the character face meets the shoulder should be well defined, the face of the character dropping-off crisply to the shoulder (as illustrated in Figure 1A) .
  • Unacceptable image sharpness is demonstrated by characters which are "rounded", i.e., the point where the character face meets the shoulder is not angular and well defined, but forms an arc (as illustrated in Figure IB) .
  • Highlight dot holding is assessed by inspection of the 2% 120 lines per inch (lpi) highlight dots with an optical microscope. The dots are viewed from directly above at 5X or 10X magnification, with the focus set for the top of the dots. The number of missing dots are then manually counted, and the percent held calculated based on the total number of dots in the field of view. Four different regions of 2% highlight dots are viewed to ensure a representative accounting.

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  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention porte sur des compositions photopolymérisables et se développant dans l'eau, servant à produire des planches d'impression durables, d'un très haut niveau de résolution. Une fois photopolymérisées, les planches réalisées à l'aide des susdites compositions présentent d'excellentes propriétés physiques compatibles avec des utilisations très exigeantes telles que l'impression typo ou de journaux, utilisations exigeant que la résine, une fois durcie, produise une image nette et présente une bonne durabilité. La photopolymérisation desdites résines donne un produit présentant d'excellentes caractéristiques physiques, et qui est non seulement compatible avec les normes en matière d'impression typo, mais d'une résistance suffisante pour supporter de forts tirages dans les domaines de la décoration des métaux, de la presse, des emballages en plastique, des formulaires commerciaux et autres.
PCT/US1995/015036 1994-12-06 1995-11-15 Plaques d'impression typo a haute resolution et compositions hydrosolubles photopolymerisables comprenant un derive de l'alcool polyvinylique associees WO1996018133A1 (fr)

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US35069994A 1994-12-06 1994-12-06
US08/350,699 1994-12-06

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WO1996018133A1 true WO1996018133A1 (fr) 1996-06-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19824546A1 (de) * 1998-06-03 1999-12-09 Basf Drucksysteme Gmbh Herstellung vernetzbarer wasserlöslicher oder wasserdispergierbarer Zusammensetzungen und daraus erhältlicher strahlungsempfindlicher Gemische
EP1574528A4 (fr) * 2002-12-10 2007-02-28 Toyo Gosei Co Ltd Resine photosensible a base d'acetate de polyvinyle saponifie, composition de resine photosensible, procede de formation de gel aqueux a partir de cette composition, et compose
WO2007131336A1 (fr) * 2006-05-17 2007-11-22 American Dye Source Inc. Nouveaux matériaux pour revêtements de planches lithographiques, planches lithographiques et revêtements contenant ceux-ci, procédés de préparation et utilisation
WO2019106082A1 (fr) 2017-11-29 2019-06-06 Flint Group Germany Gmbh Procédé de production d'un acétate de polyvinyle partiellement hydrolysé fonctionnalisé

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GB834337A (en) * 1956-08-27 1960-05-04 Du Pont Photopolymerisable compositions and elements containing the same
GB1233883A (fr) * 1968-01-22 1971-06-03
US4042386A (en) * 1976-06-07 1977-08-16 Napp Systems Photosensitive compositions
US4355093A (en) * 1980-04-22 1982-10-19 Basf Aktiengesellschaft Laminate useful for the production of printing plates and relief plates
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Cited By (11)

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Publication number Priority date Publication date Assignee Title
DE19824546A1 (de) * 1998-06-03 1999-12-09 Basf Drucksysteme Gmbh Herstellung vernetzbarer wasserlöslicher oder wasserdispergierbarer Zusammensetzungen und daraus erhältlicher strahlungsempfindlicher Gemische
US6368772B1 (en) 1998-06-03 2002-04-09 Basf Drucksytems Gmbh Preparation of crosslinkable water-soluble or water-dispersible compositions and radiation-sensitive mixtures obtainable therefrom
EP1574528A4 (fr) * 2002-12-10 2007-02-28 Toyo Gosei Co Ltd Resine photosensible a base d'acetate de polyvinyle saponifie, composition de resine photosensible, procede de formation de gel aqueux a partir de cette composition, et compose
US7348128B2 (en) 2002-12-10 2008-03-25 Toyo Gosei Co., Ltd. Photosensitive resin based on saponified polyvinyl acetate photosensitive resin composition, method of forming aqueous gel from the same, and compound
WO2007131336A1 (fr) * 2006-05-17 2007-11-22 American Dye Source Inc. Nouveaux matériaux pour revêtements de planches lithographiques, planches lithographiques et revêtements contenant ceux-ci, procédés de préparation et utilisation
JP2009537458A (ja) * 2006-05-17 2009-10-29 アメリカン・ダイ・ソース・インコーポレーテッド 平版印刷版コーティング用新規材料、それを含有する平版印刷版およびコーティング、調製方法ならびに使用
US7910768B2 (en) 2006-05-17 2011-03-22 American Dye Source, Inc. Materials for lithographic plates coatings, lithographic plates and coatings containing same, methods of preparation and use
US8021827B2 (en) 2006-05-17 2011-09-20 American Dye Source, Inc. Materials for lithographic plates coatings, lithographic plates and coatings containing same, methods of preparation and use
US8323867B2 (en) 2006-05-17 2012-12-04 American Dye Source, Inc. Materials for lithographic plates coatings, lithographic plates and coatings containing same, methods of preparation and use
WO2019106082A1 (fr) 2017-11-29 2019-06-06 Flint Group Germany Gmbh Procédé de production d'un acétate de polyvinyle partiellement hydrolysé fonctionnalisé
US11498988B2 (en) 2017-11-29 2022-11-15 Flint Group Germany Gmbh Method for the production of functionalized partially hydrolyzed polyvinyl acetate

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