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USRE28789E - Photopolymerizable compositions containing cyclic cis-α-dicarbonyl compounds and selected sensitizers - Google Patents

Photopolymerizable compositions containing cyclic cis-α-dicarbonyl compounds and selected sensitizers Download PDF

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USRE28789E
USRE28789E US05/608,673 US60867375A USRE28789E US RE28789 E USRE28789 E US RE28789E US 60867375 A US60867375 A US 60867375A US RE28789 E USRE28789 E US RE28789E
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compound
composition according
bis
cis
dicarbonyl
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Catherine Teh-Lin Chang
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • This invention relates to novel photopolymerizable compositions having high photospeed. Still more particularly, it relates to compositions having novel combinations of chemical compounds as initiators for photopolymerization.
  • the invention relates to photopolymerizable compositions comprising:
  • At least one non-gaseous ethylenically unsaturated compound having a boiling point above 100° C. at normal atmospheric pressure and being capable of forming a high polymer by photoinitiated, addition polymerization;
  • An actinic radiation absorbing compound capable of sensitizing the polymerization initiating action of said cyclic cis- ⁇ -dicarbonyl compound, said actinic radiation absorbing compound being a nitrogen-containing aromatic or heterocyclic compound, having maximum absorption below 520 nm., selected from the class consisting of bis (p-aminophenyl- ⁇ , ⁇ -unsaturated)ketones; bis(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4-lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines;
  • Constituents (b), (c) and (d) are employed in the respective amounts of 0.001-10, 0.001-10, and 0-10 parts by weight per 100 parts by weight of constituents (a) and (e). Constituents (a) and (e) are present in relative amounts from 3-100 and 0-97 parts by weight, respectively.
  • compositions of the invention have improved photo-initiation and photographic speed when used in imaging elements.
  • Such elements may be self-supporting or comprise a support coated with the above-described composition.
  • imaging elements using the compositions of the invention displayed photographic speeds of at least about 2.5 times the speed of an element containing a cis- ⁇ -dicarbonyl compound without a radiation absorbing sensitizer.
  • the photopolymerizable compositions of this invention preferably comprise the five constituents set forth above. Constituents (a) and (e) are preferably present in relative amounts from 3-95 and 5-97 parts by weight, respectively.
  • the preferred photopolymerizable compositions may contain, in addition to constituents (a), (b), (c), (d), and (e), an additional constituent, i.e., (f) a thermal addition polymerization inhibitor.
  • Suitable free-radical initiated, chain-propagating, addition polymerizable, ethylenically unsaturated compounds include preferably an alkylene or a polyalkylene glycol diacrylate prepared from an alkylene glycol of 2 to 15 carbons or a polyalkylene ether glycol of 1 to 10 ether linkages, and those disclosed in Martin and Barney U.S. Pat. No. 2,927,022, issued Mar.
  • unsaturated esters of alcohols preferably polyols and particularly such of the alphamethylene carboxylic acids, e.g., ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol dimethyacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,4-benzenediol dimethacrylate, pentaerythritol tetramethacrylate, 1,3-propanediol diacrylate, 1,3-pentanediol dimethacrylate, the bis-acrylates and methacrylates of polyethylene glycols of molecular weight 200-500, and the like; unsaturated amides, particularly those of the alphamethylene carboxylic acids, and
  • the preferred monomeric compounds are polyfunctional, but monofunctional monomers can also be used.
  • the polymerizable, ethylenically unsaturated polymers of Burg U.S. Pat. No. 3,043,805, Martin U.S. Pat. No. 2,929,710 and similar materials may be used alone or mixed with other materials.
  • Acrylic and methacrylic esters of polyhydroxy compounds such as pentaerythritol and trimethylolpropane, and acrylic and methacrylic esters of adducts of ethylene oxide and polyhydroxy compounds such as those described in Cohen and Schoenthaler, U.S. Pat. 3,380,831 are also useful.
  • the photocrosslinkable polymers disclosed in Schoenthaler, U.S. Pat. No. 3,418,295, and Celeste, U.S. Pat. No. 3,448,089, may also be used.
  • the amount of monomer added varies with the particular polymer used.
  • the cyclic cis- ⁇ -dicarbonyl compounds useful as component (b) of this invention are those organic compounds having vicinal carbonyl groups in which the oxygen atoms of said carbonyl groups are constrained to lie on one side of the molecule; the remaining portion of the cyclic molecule may contain one or more hetero atoms, in addition to carbon atoms.
  • the atoms adjacent to the two vicinal carbonyl groups are both carbon atoms, they must be saturated.
  • the excited state of the cyclic dicarbonyl compound produced by absorption of radiation or by energy transfer from a sensitizing molecule must not be able to react by intramolecular hydrogen abstraction to form cyclic products.
  • the actinic radiation absorbing compounds useful as component (c) of the composition of this invention which are capable of being raised to an excited state by absorption of actinic radiation and which have been found to sensitize the cyclic cis- ⁇ -dicarbonyl compound when so excited are nitrogen-containing aromatic or heterocyclic compounds having maximum absorption below 520 nm., selected from the class consisting of bis(p-aminophenyl- ⁇ , ⁇ -unsaturated) ketones; bis-(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4-lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines, all as defined below.
  • the above-listed radiation absorbing compounds are defined as follows:
  • the bis(p-aminophenyl- ⁇ , ⁇ -unsaturated) ketones are those of claim 1 of application Ser. No. 53,686 of Baum and Henry, allowed Sept. 7, 1971, .Iadd.now U.S. Pat. No. 3,652,275 .Iaddend.and which are also described on page 3, line 25 to page 4, line 7 and page 6, line 11 to page 8, line 19 of that application.
  • the bis(alkylamino) acridine dyes are those defined by the formula on Column 9, lines 31-42, of U.S. Pat. No. 3,563,751 to Cohen, issued Feb.
  • the cyanine dyes are the simple cyanines having two heterocyclic nuclei joined by a single methine group defined by the formula below: ##EQU1## Some examples of such cyanine dyes are given on Column 3, lines 17-33, of U.S. Pat. No. 3,099,558 to Levinos, issued July 30, 1963.
  • the styryl dye bases have a heterocyclic nucleus and a benzene nucleus joined by a vinyl group and are defined by the following formula: ##EQU2## where R 2 is C 1 -C 4 alkyl. Some compounds of this type are contained in the list on Column 6, line 61 to Column 7, line 9 of the Levinos patent.
  • a preferred styryl dye base is 2-(p-dimethylaminostyryl) benzothiazole.
  • the 7-diloweralkylamino - 4 - lower alkyl coumarins are coumarins, with C 1 -C 4 alkyl substituents in the 4 and 7 positions.
  • Several examples of such coumarins are given on Column 3, line 71 to Column 4, line 4, of U.S. Pat. No. 3,583,797, to James et al., issued Oct. 15, 1970.
  • the p-aminophenyl ketones are those defined by the formula on Column 15, line 71 to Column 16, line 4, of U.S. Pat. No. 3,552,973, to Fishman, issued Jan. 5, 1971. Further description of these ketones is provided on Column 3, line 40 to Column 4, line 10, of that patent.
  • p,p' -Bis(dimethylamino) benzophenone, known as Michler's ketone, is included in this class.
  • the p-dialkylaminophenyl unsaturated compounds are defined by the formula: ##EQU3## where R and R 1 are alkyl groups of 1-4 carbons, and R 2 may be --CN, --CHO, ##SPC1##
  • R 3 may be hydrogen, ##EQU4## halogen, or phenyl.
  • the 6 -dialkylaminoquinaldines are defined by the formula ##SPC2##
  • R and R 1 are alkyl groups of 1-4 carbon atoms.
  • the free-radical producing hydrogen donor compounds useful as component (d) are alkyl and alkoxy alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, amines, and amides, i.e., compounds containing an abstractable hydrogen atom.
  • Suitable active methylene compounds include 5,5-dimethyl-1,3-cyclohexanedione, 1,3-indanedione, 2-phenyl 1,3-indanedione, 1,3-diphenyl-1,3-propanedione, and 4,4,4-trifluoro-2,4-hexanedione.
  • Suitable amines include the monoalkyl, dialkyl and trialkylamines, where alkyl has 1-6 carbon atoms, e.g., triethylamine, dibutylamine and trihexylamine; alkylenediamines of 1-4 carbon atoms, e.g. ethylenediamine and 1,3-propylenediamine; alkanolamines, e.g., ethanolamine, diethanolamine, and triethanolamine; and the polyamines disclosed in Chambers U.S. Pat. No. 3,026,203, issued Mar. 20, 1962. Other suitable amines are disclosed in Chambers U.S. Pat. No. 3,479,185, issued Nov. 18, 1969. Mixtures of two or more of constituents (d) are useful.
  • Triphenylphosphine and electron donor, is also useful as component (d).
  • Macromolecular film forming organic polymers suitable for component (e) are:
  • Polyesters e.g. poly- ⁇ -caprolacetone
  • copolyesters e.g., those prepared from the reaction product of a polymethylene glycol of the formula HO(CH 2 ) n OH, wherein n is a whole number 2 to 10 inclusive, and (1) hexahydroterephthalic, sebacic and terephthalic acids, (2) terephthalic, isophthalic and sebacic acids, (3) terephthalic and sebacic acids, (4) terephthalic and isophthalic acids, and (5) mixtures of copolyesters prepared from said glycols and (i) terephthalic, isophthalic and sebacic acids and (ii) terephthalic, isophthalic, sebacic and adipic acids.
  • Vinylidene chloride copolymers e.g., vinylidene chloride/acrylonitrile; vinylidene chloride/methacrylate and vinylidene chloride/vinylacetate copolymers;
  • Cellulose esters e.g., cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate;
  • Polyvinyl esters e.g., poly(vinyl acetate/acrylate), poly(vinyl acetate/methacrylate) and poly(vinyl acetate);
  • non-thermoplastic or other polymeric compounds to improve certain desirable characteristics, e.g., adhesion to the base support, adhesion to the image-receptive support on transfer, wear properties, chemical inertness, etc.
  • Suitable polymeric compounds for addition include polyvinyl alcohol, cellulose, anhydrous gelatin, phenolic resins and melamineformaldehyde resins, etc.
  • the photopolymerizable layers can also contain immiscible polymeric or nonpolymeric organic or inorganic fillers or reinforcing agnets which are essentially transparent at the wavelengths used for the exposure of the photopolymeric material, e.g., the organophilic silicas, bentonites, silica, powdered glass, colloidal carbon, as well as various types of dyes and pigments. Such materials are used in amounts varying with the desired properties of the photopolymerizable layer.
  • the fillers are useful in improving the strength of the compositions, reducing tack and in addition, as coloring agents.
  • the photopolymerizable compositions of the invention may also be dispersed in a hydrophilic colloid such as gelatin as shown in Example LX.
  • the photopolymerizable compositions may also contain thermal polymerization inhibitors, e.g., p-methoxyphenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyrogallol, copper resinate, naphthylamines, beta-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. They are present in 0.001% to 4% by weight of the compositions.
  • thermal polymerization inhibitors e.g., p-methoxyphenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyrogallol, copper resinate, naphthylamines,
  • the radiation source should usually furnish an effective amount of this radiation.
  • Such sources include carbon arcs, mercury vapor arcs, fluorescent lamps with ultraviolet radiation emitting phosphors, argon glow lamps, electronic flash units and photographic flood lamps.
  • the mercury-vapor arcs are customarily used at a distance of one and one-half to 20 inches from the photopolymerizable layer. It is noted, however, that in certain circumstances it may be advantageous to expose to visible light. In such cases, the radiation source should furnish an effective amount of fisible radiation. Many of the radiation sources listed above furnish the required amount of visible light.
  • the photopolymerizable compositions and elements of this invention may be coated on metal surfaces to make presensitized lithographic printing plates, or to serve as photoresists in making etched or plated circuits or in chemical milling applications. They are also useful for preparing colored images suitable for color proofing from color separation negatives. The images formed with these elements may also be used for making copies by thermal transfer to a substrate. Specific uses will be evident to those skilled in the art; many uses are disclosed in U.S. Pat. Nos. 2,760,863; 3,060,023; and 3,060,026.
  • Suitable support including metal and flexible polymer film supports for the photopolymerizable layers as well as processes for coating the supports, are described in the patents listed in the preceding paragraph.
  • Quantities of cis- ⁇ -dicarbonyl compounds and coinitiators were added to the solution to provide the concentration of initiators and coinitiators in the coated sample shown in Table I.
  • the solutions were coated on 0.001-inch-thick polyethylene terephthalate supports to a wet thickness of 0.002 inch, dried to form a photopolymerizable layer and laminated at room temperature with 0.001-inch-thick polyethylene terephthalate cover sheets.
  • the log exposure which gave an optical density of 0.1 above the optical density of base plus fog was chosen as characteristic of the sensitivity of the layer.
  • the relative speeds of several compositions are given in Table I, expressed as equivalent exposure time, the actual exposure time in seconds required to form an image of optical density 0.1 above base plus fog multiplied by the percent transmission of the step wedge at that point. Note that a lower number means a photographically faster system.
  • the molar concentrations of the ingredients in the coated and dried compositions are given in parentheses after each ingredient.
  • the wavelength of maximum absorption, ⁇ max is given in nanometers. Two or three values for ⁇ max , indicates an absorption doublet or triplet, the highest value being required to be less than 520 nm.
  • Hrms molecular ion, meas. m/e 252.0849; calcd. m/e for C 10 H 12 O 4 , 252.0859.
  • Quantities of cis- ⁇ -dicarbonyl compound and coinitiators were added to the solutions to provide the concentrations of initiators and co-initiators in the coated sample shown in Table II.
  • the solutions were coated on a 0.001-inch-thick polyethylene terephthalate web to a wet thickness of 0.003 inch using a doctor knife, allowed to dry at room temperature and laminated onto the copper surface of a copperclad 0.003-inch-thick polyethylene terephthalate web at 120° C. and 40 lb. per square inch pressure.
  • the elements so prepared were exposed through a ⁇ 2 silver step tablet using a 3750 watt pulsed xenon arc at a distance of 18 inches (nuArc Platemaker FT-26-N), for 30 seconds. After exposure, the cover sheet was removed; the image was developed by spraying with 1,1,1-trichloroethane from a distance of 5 inches at a pressure of 5 lb. per square inch for 45 seconds to remove the unpolymerized portions of the layer, followed by water washing. The samples were then etched in 42° Baume ferric chloride solution which removed the copper where it was not protected by the photopolymerized portions of the layer. The minimum exposure required to produce a film that resisted etching was taken as the speed point. The relative photospeed of each sample is recorded in Table II.
  • a coating solution was prepared as follows:
  • the solution was coated at a wet thickness of 0.002 inch on a 0.0075-inch-thick polyethylene terephthalate web support and allowed to dry.
  • a second coating solution was prepared as follows:
  • the solution was coated at a wet thickness of 0.002 inch with a doctor knife on a 0.004-inch-thick polyethylene terephthalate photographic film base subbed with the resin sub of Alles, U.S. Pat. No. 2,779,684, Example IV support and allowed to dry.
  • the clear layer and black layer were placed together and laminated by passing through heated rolls at 100° C. and suitable pressure.
  • the element so prepared was exposed from the clear side through a ⁇ 2 step tablet with a 1000 w. quartz-iodine lamp at a distance of 5 ft. for 30 sec.
  • the exposed sample was delaminated at 100° C. to give a positive black image on the 0.004-inch-thick support and a negative black image on the 0.0075-inch-thick support.
  • a coating solution was prepared according to the following formula:
  • the solution was coated with a doctor knife on a 0.001-inch-thick unsubbed polyethylene terephthalate web to a wet thickness of 0.002 inch.
  • the coated element was dried and laminated at room temperature with a 0.001-inch-thick unsubbed polyethylene terephthalate cover sheet.
  • a sample of the element so prepared was exposed through a ⁇ 2 step wedge with a rotary diazo printer (Blue Ray, average intensity 3.2 mf./cm. 2 ) for 20 seconds.
  • the cover sheet was removed and the coating was dusted with Quindo Magenta, C.I. Pigment Red 122.
  • the steps up to step 16 inclusive had polymerized and did not accept pigment.
  • This solution was dispersed in a solution of 10 g. of gelatin in 40 g. of water by mixing in a high speed blender for 2 minutes.
  • the dispersion was coated with a doctor knife on a 0.004-inch-thick polyethylene terephthalate web support to a wet thickness of 0.003 inch and dried.
  • a sample of the element so prepared was exposed through a process transparency using a 3750 watt pulsed xenon arc at a distance of 18 inches for five seconds.
  • the exposed element was immersed in a 2% aqueous solution of Rhodamine B Extra dye for 2 minutes, washed with cold water for 15 minutes, and dried. A positive, magenta colored image was obtained.
  • a method for forming a gravure printing plate comprises, in either order, (a) exposing to actinic radiation such a layer coated on a support, e.g., transparent film support, first through a gravure screen and then to a continuous tone image transparency which gives an image in the resist modulated by photopolymerization, and (b) adhering the surface of said layer to the surface to be imaged which has been moistened with water and peeling off the transparent film support, then (c) etching the surface to produce an intaglio printing surface with conventional etching solution, e.g., ferric chloride, (d) washing the etched surface, e.g., with hot water to remove the residual etching solution and the photopolymer resist.
  • the process may also be carried out by exposing the layer to the gravure screen through the transparent support and to the continuous tone image from the opposite side.
  • the dispersion may be coated directly on the surface to be etched

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Abstract

Photopolymerizable compositions comprising an ethylenically unsaturated monomer and an initiating combination of a cyclic cis-α-dicarbonyl compound and certain radiation-absorbing sensitizers are disclosed. Compositions of the invention have improved photospeed and may be chosen to provide a wide range of spectral sensitivity.

Description

BACKGROUND OF THE INVENTION
This invention relates to novel photopolymerizable compositions having high photospeed. Still more particularly, it relates to compositions having novel combinations of chemical compounds as initiators for photopolymerization.
It is known to add certain light absorbing compounds to photopolymerizable compositions containing ethylenically unsaturated monomers for the purpose of increasing the photographic sensitivity of the compositions. The use of α-dicarbonyl compounds and combinations of α-dicarbonyl compounds with ultraviolet radiation-absorbing ketones for photoinsolubilization of photocrosslinkable polymers has been disclosed, e.g., in Laridon, et al., U.S. Pat. No. 3,427,161. However, cyclic cis-α-dicarbonyl compounds are not generally known as photoinitiators in the prior art and have been shown to initiate photopolymerization very poorly (viz., Notley, U.S. Pat. No. 2,951,758, Col. 5, line 39). Surprisingly, it has been found that certain radiation absorbing compounds can transfer energy to the cis-α-dicarbonyl compounds and act as sensitizers therefor. Photopolymerizable compositions containing the novel cis-α-dicarbonyl-sensitizer combinations of this invention have been demonstrated to have greatly improved photospeed and may be chosen to provide a wide range of spectral sensitivity.
SUMMARY OF THE INVENTION
The invention relates to photopolymerizable compositions comprising:
(a) At least one non-gaseous ethylenically unsaturated compound having a boiling point above 100° C. at normal atmospheric pressure and being capable of forming a high polymer by photoinitiated, addition polymerization;
(b) A cyclic cis-α-dicarbonyl compound, the excited state of which cannot react intramolecularly .Iadd., the atoms adjacent to the two vicinal carbonyl groups being saturated when they are carbon atoms.Iaddend.;
(c) An actinic radiation absorbing compound capable of sensitizing the polymerization initiating action of said cyclic cis-α-dicarbonyl compound, said actinic radiation absorbing compound being a nitrogen-containing aromatic or heterocyclic compound, having maximum absorption below 520 nm., selected from the class consisting of bis (p-aminophenyl-α,β-unsaturated)ketones; bis(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4-lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines;
(d) Optionally, a free-radical producing hydrogen or electron donor compound; and
(e) Optionally, a macromolecular organic polymer binder.
Constituents (b), (c) and (d) are employed in the respective amounts of 0.001-10, 0.001-10, and 0-10 parts by weight per 100 parts by weight of constituents (a) and (e). Constituents (a) and (e) are present in relative amounts from 3-100 and 0-97 parts by weight, respectively.
Compositions of the invention have improved photo-initiation and photographic speed when used in imaging elements. Such elements may be self-supporting or comprise a support coated with the above-described composition. As shown in the examples, imaging elements using the compositions of the invention displayed photographic speeds of at least about 2.5 times the speed of an element containing a cis-α-dicarbonyl compound without a radiation absorbing sensitizer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The photopolymerizable compositions of this invention preferably comprise the five constituents set forth above. Constituents (a) and (e) are preferably present in relative amounts from 3-95 and 5-97 parts by weight, respectively.
The preferred photopolymerizable compositions may contain, in addition to constituents (a), (b), (c), (d), and (e), an additional constituent, i.e., (f) a thermal addition polymerization inhibitor.
Suitable free-radical initiated, chain-propagating, addition polymerizable, ethylenically unsaturated compounds include preferably an alkylene or a polyalkylene glycol diacrylate prepared from an alkylene glycol of 2 to 15 carbons or a polyalkylene ether glycol of 1 to 10 ether linkages, and those disclosed in Martin and Barney U.S. Pat. No. 2,927,022, issued Mar. 1, 1960, e.g., those having a plurality of addition polymerizable ethylenic linkages, particularly when present as terminal linkages, and especially those wherein at least one and preferably most of such linkages are conjugated with a doubly bonded carbon, including carbon doubly bonded to carbon and to such heteroatoms as nitrogen, oxygen and sulfur. Outstanding are such materials wherein the ethylenically unsaturated groups, especially the vinylidene groups, are conjugated with ester or amide structures. The following specific compounds are further illustrative of this class; unsaturated esters of alcohols, preferably polyols and particularly such of the alphamethylene carboxylic acids, e.g., ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol dimethyacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,4-benzenediol dimethacrylate, pentaerythritol tetramethacrylate, 1,3-propanediol diacrylate, 1,3-pentanediol dimethacrylate, the bis-acrylates and methacrylates of polyethylene glycols of molecular weight 200-500, and the like; unsaturated amides, particularly those of the alphamethylene carboxylic acids, and especially those of alpha-omega-diamines and oxygen-interrupted omega-diamines, such as methylene bis-acrylamide, methylene bis-methacrylamide ethylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, diethylene triamine tris-methacrylamide, bis(gamma-methacrylamidopropoxy) ethane beta-methacrylamidoethyl methacrylate, N-(beta-hydroxyethyl)-beta-(methacrylamido) ethyl acrylate and N,N-bis (beta-methacryloxyethyl) acrylamide; vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate, and divinyl butane-1,4-disulfonate; styrene and derivatives thereof and unsaturated aldehydes, such as sorbaldehyde (hexadienal). An outstanding class of these preferred addition polymerizable components are the esters and amides of alpha-methylene carboxylic acids and substituted carboxylic acids with polyols and polyamines wherein the molecular chain between the hydroxyls and amino groups is solely carbon or oxygen-interrupted carbon. The preferred monomeric compounds are polyfunctional, but monofunctional monomers can also be used. In addition, the polymerizable, ethylenically unsaturated polymers of Burg U.S. Pat. No. 3,043,805, Martin U.S. Pat. No. 2,929,710 and similar materials may be used alone or mixed with other materials. Acrylic and methacrylic esters of polyhydroxy compounds such as pentaerythritol and trimethylolpropane, and acrylic and methacrylic esters of adducts of ethylene oxide and polyhydroxy compounds such as those described in Cohen and Schoenthaler, U.S. Pat. 3,380,831 are also useful. The photocrosslinkable polymers disclosed in Schoenthaler, U.S. Pat. No. 3,418,295, and Celeste, U.S. Pat. No. 3,448,089, may also be used. The amount of monomer added varies with the particular polymer used.
The cyclic cis-α-dicarbonyl compounds useful as component (b) of this invention are those organic compounds having vicinal carbonyl groups in which the oxygen atoms of said carbonyl groups are constrained to lie on one side of the molecule; the remaining portion of the cyclic molecule may contain one or more hetero atoms, in addition to carbon atoms. When the atoms adjacent to the two vicinal carbonyl groups are both carbon atoms, they must be saturated. The excited state of the cyclic dicarbonyl compound produced by absorption of radiation or by energy transfer from a sensitizing molecule must not be able to react by intramolecular hydrogen abstraction to form cyclic products. This property is found in those cyclic cis-α-dicarbonyl compounds in which the carbonyl groups are held rigidly in a conformation which prevents such cyclization reactions. The required rigid molecular conformation is conveniently obtained by using cyclic cis-α-dicarbonyl compounds in which the carbonyl groups are incorporated in a multiple-ring structure. A preferred such compound is 2,3-bornanedione (also known as camphor-quinone). Others operable are the following:
2,2,5,5-tetramethyl-tetrahydro-3,4-furandione;
Parabanic acid (imidazoletrione);
indole-2,3-dione (Isatin);
1,1,4,4-tetramethyl-tetralin-2,3-dione;
3-methyl-1,2-cyclopentanedione;
2,3-dioxo-5,6-diethoxy-5,6-dicyanopyrazine;
1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazine dicarboxamide.
The actinic radiation absorbing compounds useful as component (c) of the composition of this invention which are capable of being raised to an excited state by absorption of actinic radiation and which have been found to sensitize the cyclic cis-α-dicarbonyl compound when so excited are nitrogen-containing aromatic or heterocyclic compounds having maximum absorption below 520 nm., selected from the class consisting of bis(p-aminophenyl-α,β-unsaturated) ketones; bis-(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4-lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines, all as defined below.
For the purposes of this invention, the above-listed radiation absorbing compounds are defined as follows: The bis(p-aminophenyl-α,β-unsaturated) ketones are those of claim 1 of application Ser. No. 53,686 of Baum and Henry, allowed Sept. 7, 1971, .Iadd.now U.S. Pat. No. 3,652,275 .Iaddend.and which are also described on page 3, line 25 to page 4, line 7 and page 6, line 11 to page 8, line 19 of that application. The bis(alkylamino) acridine dyes are those defined by the formula on Column 9, lines 31-42, of U.S. Pat. No. 3,563,751 to Cohen, issued Feb. 16, 1971, and which are further described on Column 3, lines 21-43 and lines 50-71 of that patent. The cyanine dyes are the simple cyanines having two heterocyclic nuclei joined by a single methine group defined by the formula below: ##EQU1## Some examples of such cyanine dyes are given on Column 3, lines 17-33, of U.S. Pat. No. 3,099,558 to Levinos, issued July 30, 1963. The styryl dye bases have a heterocyclic nucleus and a benzene nucleus joined by a vinyl group and are defined by the following formula: ##EQU2## where R2 is C1 -C4 alkyl. Some compounds of this type are contained in the list on Column 6, line 61 to Column 7, line 9 of the Levinos patent. A preferred styryl dye base is 2-(p-dimethylaminostyryl) benzothiazole.
The 7-diloweralkylamino - 4 - lower alkyl coumarins are coumarins, with C1 -C4 alkyl substituents in the 4 and 7 positions. Several examples of such coumarins are given on Column 3, line 71 to Column 4, line 4, of U.S. Pat. No. 3,583,797, to James et al., issued Oct. 15, 1970. The p-aminophenyl ketones are those defined by the formula on Column 15, line 71 to Column 16, line 4, of U.S. Pat. No. 3,552,973, to Fishman, issued Jan. 5, 1971. Further description of these ketones is provided on Column 3, line 40 to Column 4, line 10, of that patent. p,p' -Bis(dimethylamino) benzophenone, known as Michler's ketone, is included in this class.
The p-dialkylaminophenyl unsaturated compounds are defined by the formula: ##EQU3## where R and R1 are alkyl groups of 1-4 carbons, and R2 may be --CN, --CHO, ##SPC1##
wherein R3 may be hydrogen, ##EQU4## halogen, or phenyl.
The 6 -dialkylaminoquinaldines are defined by the formula ##SPC2##
where R and R1 are alkyl groups of 1-4 carbon atoms.
Of the above actinic radiation absorbing compounds the most preferred are Michler's ketone and its homologues, vinylogs, and analogs, cyanine dyes and styryl dye bases, and their mixtures.
The free-radical producing hydrogen donor compounds useful as component (d) are alkyl and alkoxy alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, amines, and amides, i.e., compounds containing an abstractable hydrogen atom. Suitable active methylene compounds include 5,5-dimethyl-1,3-cyclohexanedione, 1,3-indanedione, 2-phenyl 1,3-indanedione, 1,3-diphenyl-1,3-propanedione, and 4,4,4-trifluoro-2,4-hexanedione. Suitable amines include the monoalkyl, dialkyl and trialkylamines, where alkyl has 1-6 carbon atoms, e.g., triethylamine, dibutylamine and trihexylamine; alkylenediamines of 1-4 carbon atoms, e.g. ethylenediamine and 1,3-propylenediamine; alkanolamines, e.g., ethanolamine, diethanolamine, and triethanolamine; and the polyamines disclosed in Chambers U.S. Pat. No. 3,026,203, issued Mar. 20, 1962. Other suitable amines are disclosed in Chambers U.S. Pat. No. 3,479,185, issued Nov. 18, 1969. Mixtures of two or more of constituents (d) are useful.
Triphenylphosphine, and electron donor, is also useful as component (d).
Macromolecular film forming organic polymers suitable for component (e) are:
(A) Polyesters, e.g. poly-ε -caprolacetone, and copolyesters, e.g., those prepared from the reaction product of a polymethylene glycol of the formula HO(CH2)n OH, wherein n is a whole number 2 to 10 inclusive, and (1) hexahydroterephthalic, sebacic and terephthalic acids, (2) terephthalic, isophthalic and sebacic acids, (3) terephthalic and sebacic acids, (4) terephthalic and isophthalic acids, and (5) mixtures of copolyesters prepared from said glycols and (i) terephthalic, isophthalic and sebacic acids and (ii) terephthalic, isophthalic, sebacic and adipic acids.
(B) Nylons or polyamides, e.g., N-methoxymethyl polyhexamethylene adipamide;
(C) Vinylidene chloride copolymers, e.g., vinylidene chloride/acrylonitrile; vinylidene chloride/methacrylate and vinylidene chloride/vinylacetate copolymers;
(D) Ethylene/vinyl acetate copolymers;
(E) Cellulosic ethers, e.g., methyl cellulose, ethyl cellulose and benzyl cellulose;
(F) Polyethylene;
(G) Synthetic rubbers, e.g., butadiene/acrylonitrile copolymers, and 2-chloro-1,3-butadiene polymers;
(H) Cellulose esters, e.g., cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate;
(I) Polyvinyl esters, e.g., poly(vinyl acetate/acrylate), poly(vinyl acetate/methacrylate) and poly(vinyl acetate);
(J) Polyacrylate and alpha-alkyl polyacrylate esters, e.g., poly(methyl methacrylate) and poly(ethyl methacrylate);
(K) Polyethers, i.e., the polyethylene oxides of polyglycols;
(L) Poly(vinyl chloride) and copolymers, e.g., poly(vinyl chloride/acetate);
(M) Poly(vinyl acetal), e.g., polyvinyl butyral), poly(vinyl formal);
(N) Polyformaldehydes;
(O) Polyurethanes;
(P) Polycarbonates;
(Q) Polystyrenes.
To the polymer constituent of the photo-polymerizable composition there can be added non-thermoplastic or other polymeric compounds to improve certain desirable characteristics, e.g., adhesion to the base support, adhesion to the image-receptive support on transfer, wear properties, chemical inertness, etc. Suitable polymeric compounds for addition include polyvinyl alcohol, cellulose, anhydrous gelatin, phenolic resins and melamineformaldehyde resins, etc. If desired, the photopolymerizable layers can also contain immiscible polymeric or nonpolymeric organic or inorganic fillers or reinforcing agnets which are essentially transparent at the wavelengths used for the exposure of the photopolymeric material, e.g., the organophilic silicas, bentonites, silica, powdered glass, colloidal carbon, as well as various types of dyes and pigments. Such materials are used in amounts varying with the desired properties of the photopolymerizable layer. The fillers are useful in improving the strength of the compositions, reducing tack and in addition, as coloring agents. The photopolymerizable compositions of the invention may also be dispersed in a hydrophilic colloid such as gelatin as shown in Example LX.
The photopolymerizable compositions may also contain thermal polymerization inhibitors, e.g., p-methoxyphenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyrogallol, copper resinate, naphthylamines, beta-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. They are present in 0.001% to 4% by weight of the compositions.
Since free-radical generating addition-polymerization initiators activatable by actinic radiation generally exhibit their maximum sensitivity in the ultraviolet range, the radiation source should usually furnish an effective amount of this radiation. Such sources include carbon arcs, mercury vapor arcs, fluorescent lamps with ultraviolet radiation emitting phosphors, argon glow lamps, electronic flash units and photographic flood lamps. Of these, the mercury-vapor arcs are customarily used at a distance of one and one-half to 20 inches from the photopolymerizable layer. It is noted, however, that in certain circumstances it may be advantageous to expose to visible light. In such cases, the radiation source should furnish an effective amount of fisible radiation. Many of the radiation sources listed above furnish the required amount of visible light.
The photopolymerizable compositions and elements of this invention may be coated on metal surfaces to make presensitized lithographic printing plates, or to serve as photoresists in making etched or plated circuits or in chemical milling applications. They are also useful for preparing colored images suitable for color proofing from color separation negatives. The images formed with these elements may also be used for making copies by thermal transfer to a substrate. Specific uses will be evident to those skilled in the art; many uses are disclosed in U.S. Pat. Nos. 2,760,863; 3,060,023; and 3,060,026.
Suitable support, including metal and flexible polymer film supports for the photopolymerizable layers as well as processes for coating the supports, are described in the patents listed in the preceding paragraph.
The practice of the invention will be illustrated by the examples which follow.
EXAMPLES I-XLVIII
Several portions of coating solutions were prepared as follows:
                            G.                                            
Cellulose acetate (acetyl 40.0%, ASTM visc.                               
25)                         2.7                                           
Cellulose acetate butyrate (butyrate 17%, ASTM                            
visc. 15)                   4.2                                           
Trimethylolpropane triacrylate                                            
                            13.5                                          
Acetone                     116.0
Quantities of cis-α-dicarbonyl compounds and coinitiators were added to the solution to provide the concentration of initiators and coinitiators in the coated sample shown in Table I. The solutions were coated on 0.001-inch-thick polyethylene terephthalate supports to a wet thickness of 0.002 inch, dried to form a photopolymerizable layer and laminated at room temperature with 0.001-inch-thick polyethylene terephthalate cover sheets.
Samples were exposed through an Eastman Kodak M-type step tablet No. 5 composed of carbon particles dispersed in gelatin and sealed in cellulose acetate, having a density gradation of 3√2 optical density units per step. Exposures were made with a 1000 watt tungsten-filament bulb (General Electric DXW) operated at 120 volts to give a color temperature of 3200° K., at a distance of 44 inches from the sample. After exposure, the cover sheet was removed, and the photopolymerizable layer was dusted with Jungle Black (Pigment Black I, C.I. 50440) to give a positive image. The optical densities of the steps of the image were measured and plotted against log exposure. The log exposure which gave an optical density of 0.1 above the optical density of base plus fog was chosen as characteristic of the sensitivity of the layer. The relative speeds of several compositions are given in Table I, expressed as equivalent exposure time, the actual exposure time in seconds required to form an image of optical density 0.1 above base plus fog multiplied by the percent transmission of the step wedge at that point. Note that a lower number means a photographically faster system. The molar concentrations of the ingredients in the coated and dried compositions are given in parentheses after each ingredient. The wavelength of maximum absorption, λmax, is given in nanometers. Two or three values for λmax, indicates an absorption doublet or triplet, the highest value being required to be less than 520 nm.
                                  TABLE I                                 
__________________________________________________________________________
Example    Cis-α-dicarbonyl compound Sensitizers                    
__________________________________________________________________________
I     2,3-bornanedione       0.047 Michler's ketone        0.047          
II    do                     0.047 4,4'-bis(diethylamino)-benzophenone    
                                                           0.047          
III   do                     0.047 4-dimethylaminobenzophenone            
                                                           0.047          
IV    do                     0.047 4-dimethylaminoacetophenone            
                                                           0.047          
V     do                     0.047 4-dimethylaminobenzoin  0.047          
VI    do                     0.047 4-dimethylaminobenzaldehyde            
                                                           0.047          
VII   do                     0.047 4-dimethylaminobenzonitrile            
                                                           0.047          
VIII  do                     0.047 7-diethylamine-1-methylconmarin        
                                                           0.047          
IX    do                     0.094 3,3'-diethylthiacyanine-p-toleunesulfon
                                   ate                     0.023          
X     do                     0.094 do                      0.023          
                                   Michler's ketone        0.047          
XI    do                     0.094 3,3'-diethylthiacyaninic               
                                   p-toluenesulfonate      0.023          
                                   7-diethylamino-4-methylcoumarin        
                                                           0.047          
XII   do                     0.047 2-p-dimethylaminostyryl)-benzothiazole 
                                                           0.047          
                                   2-(p-dimethylaminostyryl)benzothiazole 
                                                           0.047          
XIII  do                     0.047 Michler's ketone        0.047          
                                   [3-ethyl-naphthoxazole]13'-ethyl-naphth
                                   othia-                  0.024          
XIV   do                     0.047 zole]monomethinecyanine                
                                   p-toluenesulfonate.                    
                                   Michler's ketone        0.047          
XV    do                     0.094 3,3'-diethylthiacyanine-p-toluenesulfon
                                   ate                     0.023          
                                   Triethanolamineg        0.2            
XVI   do                     0.091 3,3'-diethylthiacyanine                
                                   p-toluenesulfonate      0.023          
                                   5,5-dipethyl-1,3-cyclohexanedione      
                                                           0.094          
XVII  do                     0.094 3,3'diethylthiacyanine                 
                                   p-toluenesulfonate      0.023          
                                   N-phenylglycine         0.094          
XVIII do                     0.094 3,3'diethylthiacyanine                 
                                   p-toluenesulfonate      0.023          
                                   4-dimethylaminobenzophenone            
                                                           0.047          
XIX   do                     0.094 2,5-bis(p-diethylaminobenzilidene)     
                                                           0.047          
                                   cyclopentanone.                        
XX    2,2,5,5-tetramethyltetrahydro-3,4-                                  
                             0.094 do                      0.023          
      furandione.                                                         
XXI   do                     0.094 Micher's ketone         0.047          
                                   Micher's ketone         0.047          
XXII  do                     0.094 2,5-bis(p-diethylaminobenzilidene)     
                                                           0.023          
                                   cyclpentanone                          
XXIII do                     0.094 3,3'-diethylthiacyanine-p-toluenesulfon
                                   ate                     0.023          
XXIV  do                     0.094 3,3'-diethylthiacyanine-p-toluenesulfon
                                   ate                     0.023          
                                   Michler's ketone        0.047          
XXV   Parabanic acid (imidazoletrione)                                    
                             0.094 Michler's ketone        0.047          
                                   Michler's ketone        0.047          
XXVI  2,3-bornanedione       0.047 Triphenylphosphine      0.047          
                                   3,3'-diethylthiacyanine-p-toluenesulfon
                                   ate                     0.023          
XXVII do                     0.094 Michler's ketone        0.047          
                                   Triphenylphosphine      0.947          
XXVIII                                                                    
      1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazine-                          
                             0.047 Michler's ketone        0.047          
      dicarboximide.                                                      
XXIX  2,3-dioxo-5,6-diethoxy-5,6-dicyanopyrazine-                         
                             0.047 do                      0.047          
XXX   1,1,4,4-tetramethyltetralin-2,3-dione                               
                             0.007 do                      0.047          
XXXI  Indole-2,3-dione       0.047 do                      0.047          
XXXII 3-methyl-1,2-cyclopentanedione                                      
                             0.094 do                      0.047          
XXXIII                                                                    
      2,3-bornanedione       0.188 1,3-bis(p-dimethylaminobenzylidene)acet
                                   one                     0.023          
XXXIV do                     0.094 Auramine-O-[bis(p-dimethylaminophenyl)-
                                                           0.024          
                                   methyleneamine].                       
XXXV  do                     0.047 N-(p-dimethylaminobenzylidene)-p-anisid
                                   ene                     0.047          
XXXVI do                     0.094 Acridine orange         0.023          
XXXVII                                                                    
      do                     0.094 6-dimethylaminoquinaldine              
                                                           0.047          
XXXVIII                                                                   
      do                     0.094                                        
XXXIX do                      0.24                                        
XL    2,2,5,5-tetramethyltetrahydro-3,4-                                  
                              0.24                                        
      furandione.                                                         
XLI   do                     0.188 1,3-bis(p-dimethylaminobenzylidene)acet
                                   one                     0.023          
XLII  do                     0.094 2,5-bis(p-dimethylaminocinnamylidene)  
                                                           0.047          
                                   cyclopentanone.                        
XLIII 2,3-bornanedione       0.094 ω-p-dimethylaminobenzylidene-4-me
                                   thylace-                0.047          
                                   tophenone.                             
XLIV  2,2,5,5-tetramethyltetrahydro-3,4-                                  
                             0.094 do                      0.047          
      furandione.                                                         
XLV   2,3-bornanedione       0.094 Diethyl orange          0.023          
                                   Diethyl orange          0.023          
XLVI  do                     0.094 N-phenylglycine         0.094          
                                   Diethyl orange          0.023          
XLVII                        N-phenylglycine                              
                                   0.094                                  
XLVIII                                                                    
      2,2,5,5-tetramethyltetrahydro-3,4-                                  
                             0.094 Diethyl orange          0.023          
      furandione.                                                         
__________________________________________________________________________
              Equivalent                                                  
              exposure                                                    
Example                                                                   
      λmax.                                                        
              time                                                        
__________________________________________________________________________
I     358     2.9                                                         
II    370     1.9                                                         
III   350     18.0                                                        
IV    325     24.0                                                        
V     343     11.6                                                        
VI    3.23    14.4                                                        
VII   312     36.0                                                        
VIII  370     7.2                                                         
IX    410,430 36.0                                                        
X     410,430 1.8                                                         
      358                                                                 
XI    410,430 3.2                                                         
      370                                                                 
XII   412,428 18.0                                                        
      412,428 1                                                           
XIII  358                                                                 
      398,425 1.6                                                         
XIV   358                                                                 
XV    410,430 9.5                                                         
XVI   410,430 9.5                                                         
XVII  410,430 2.3                                                         
XVIII 410,430 2.9                                                         
XIX   475     90.0                                                        
XX    475     12.0                                                        
XXI   358     5.8                                                         
      358     4.7                                                         
XXII  475                                                                 
XXIII 410,430 140.0                                                       
XXIV  410,430 4.0                                                         
XXV   358     16.0                                                        
XXVI  358     1.5                                                         
      410,430 0.7                                                         
XXVII 358                                                                 
XXVIII                                                                    
      358     68                                                          
XXIX  358     44                                                          
XXX   358     11                                                          
XXXI  358     5.7                                                         
XXXII 358     15                                                          
XXXIII                                                                    
      435     5.7                                                         
XXXIV 375,396,440                                                         
              12                                                          
XXXV  314     36                                                          
XXXVI 490     150                                                         
XXXVII                                                                    
      380     90                                                          
XXXVIII       ˜400                                                  
XXXIX         220                                                         
XL            >400                                                        
XLI   435     3.8                                                         
XLII  505     115                                                         
XLIII 410     9.5                                                         
XLIV  410     15                                                          
XLV   470,502 45                                                          
XLVI  470,502 1.8                                                         
XLVII 470,502 5.7                                                         
XLVIII                                                                    
      470,502 36                                                          
__________________________________________________________________________
All of the components used in the preceding table have been previously described in the literature, except the cis-α-dicarbonyl compounds of Examples XXVIII and XXIX; they are prepared as follows:
(A) 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarboximide
A solution of 2,3-dioxo-5,6-dicyano-1,2,3,4-tetrahydropyrazine (14.57 g., 0.09 mole, prepared as described by H. Bredereck and G. Schmotzer, Ann., 600, 95-108 (1956)) in concentrated sulfuric acid (150 ml.) was stirred at room temperature for one week, then poured onto ice (650 g.). The precipitate was washed twice with water (500 ml.) and then with acetone (500 ml.). The product obtained (12.9 g., 79% yield, M.P. 408° C., dec.) was analytically pure and yielded the following analysis:
Ir: 3175 cm.- 1 (NH); 1780, 1730 cm.- 1 (imide C=O); 1700, 1680 cm.- 1 (C=O); 1600 cm.- 1 (C=C); 1525 cm.- 1 (NH).
Uv: λmax.H.sbsp.2O 222 mμ (ε 11,370); 301 mμ (ε 9,650); 375 mμ (ε 960).
Analysis.-- Calcd. for C6 H3 O4 N3 (percent): C, 39.79; H, 1.67; N, 23.20. Found (percent): C, 39.61, 39.75; H, 1.89, 1.76; N, 22.99, 23.12.
This reaction may be summarized by the following equation: ##SPC3##
The 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarboximide prepared by this procedure was then used in Example XXVIII.
(b) 2,3-dioxo-5,6-diethoxy-5,6-dicyanopyrazine
A solution of diiminosuccinonitrile (DISN) (20 g., 0.188 mole, prepared as described by Webster, U.S. Pat. No. 3,564,039, issued Feb. 16, 1971) in acetonitrile (250 ml.) was slowly added (1.75 hr.) at room temperature to oxalyl chloride (60 g., 0.475 mole) in diethyl ether (150 ml.). After further stirring at room temperature (3 hours), the solvents and excess oxalyl chloride were removed (oil pump), followed by dissolution in acetonitrile (100 ml.) and absolute ethanol (100 ml.). This mixture was stirred overnight at room temperature and then filtered. The filtrate was pre-absorbed in SilicAR CC7 and chromatographed. Elution with diethyl ether gave crude product as a viscous oil which solidified on standing. Recrystallization from acetonitrile: carbon tetrachloride (1:1) gave pure product (2.04 g., 4.3% yield, M.P. 205-208° C.) as analyzed below for use in Example XXIX.
Ir: 3340 to 2860 cm.- 1 (broad, N-- H); 2245 cm.- 1 (C=N); 1725 cm.- 1 (C=O); 1103 cm.- 1 (C-- O-- C).
Hrms: molecular ion, meas. m/e 252.0849; calcd. m/e for C10 H12 O4, 252.0859.
Analysis.-- Calcd. for C10 H12 O4 N4 (percent): C, 47.62; H, 4.80; N, 22.22. Found (percent): C, 47.91, 47.82; H, 4.88, 4.82; N, 22.32, 22.31.
The reactions may be summarized by the following equation: ##SPC4##
EXAMPLES XLIX-LVII
Several portions of coating solution were prepared having the following composition.
______________________________________                                    
                         G.                                               
Poly(methyl methacrylate)                                                 
                         57.9                                             
Triethyleneglycol dimethacrylate                                          
                         33.1                                             
Victoria Pure Blue B.O. (C.I. 42595)                                      
                         0.03                                             
Trichloroethylene        364.0                                            
______________________________________
Quantities of cis-α -dicarbonyl compound and coinitiators were added to the solutions to provide the concentrations of initiators and co-initiators in the coated sample shown in Table II. The solutions were coated on a 0.001-inch-thick polyethylene terephthalate web to a wet thickness of 0.003 inch using a doctor knife, allowed to dry at room temperature and laminated onto the copper surface of a copperclad 0.003-inch-thick polyethylene terephthalate web at 120° C. and 40 lb. per square inch pressure. The elements so prepared were exposed through a √2 silver step tablet using a 3750 watt pulsed xenon arc at a distance of 18 inches (nuArc Platemaker FT-26-N), for 30 seconds. After exposure, the cover sheet was removed; the image was developed by spraying with 1,1,1-trichloroethane from a distance of 5 inches at a pressure of 5 lb. per square inch for 45 seconds to remove the unpolymerized portions of the layer, followed by water washing. The samples were then etched in 42° Baume ferric chloride solution which removed the copper where it was not protected by the photopolymerized portions of the layer. The minimum exposure required to produce a film that resisted etching was taken as the speed point. The relative photospeed of each sample is recorded in Table II.
                                  TABLE II                                
__________________________________________________________________________
Example    Cis-α-dicarbonyl compound                                
                                          Sensitizers                     
__________________________________________________________________________
XLIX 2,3-bornanedione        0.045                                        
                                  Michler's ketone         0.022          
L    Parabanic acid          0.045                                        
                                  do                       0.022          
LI   2,3-bornanedione        0.045                                        
                                  3,3'-diethylthiacyanine                 
                                  p-toluene-sulfonate      0.024          
                                  Michler's ketone         0.022          
LII  2,3-bornanedione        0.045                                        
                                  7-diethylamino-4-methylcoumarin         
                                                           0.022          
LIII 2,3-bornanedione        0.045                                        
                                  3,3'-diethylthiacyanine                 
                                  p-toluene-sulfonate      0.024          
LIV  2,3-bornanedione        0.045                                        
                                  3,3'-diethylthiacyanine-p-toluene-sulfon
                                  ate                      0.024          
                                  Triethanolamine          0.078          
LV   2,3-bornanedione        0.045                                        
                                  3,3'-diethylthiacyanine                 
                                  p-toluene-sulfonate      0.024          
                                  5,5-dimethyl-1,3-cyclohexanedione       
                                                           0.055          
LVI  2,3-bornanedione        0.045                                        
LVII 2,2,5,5-tetramethyltetrahydro-3,4-furandione                         
                             0.090                                        
                                  2,5-bis(p-diethylaminobenzilidene)cyclop
                                  entanone                 0.023          
Control                                                                   
     None                         Michler's ketone         0.45           
            Relative                                                      
Example                                                                   
     λ max:                                                        
            photospeed                                                    
XLIX 358    2.8                                                           
L    358    1.4                                                           
LI   410,430                                                              
            11.0                                                          
     358                                                                  
LII  370    1.2                                                           
LIII 410,430                                                              
            0.6                                                           
LIV  410,430                                                              
            2.8                                                           
LV   410,430                                                              
            2.0                                                           
LVI                                                                       
LVII 475    0.36                                                          
Control     1.0                                                           
__________________________________________________________________________
EXAMPLE LVIII
A coating solution was prepared as follows:
                          G.                                              
Poly(methyl methacrylate) (M.W. 60,000)                                   
                          2.53                                            
Triethyleneglycol dimethacrylate                                          
                          2.17                                            
3,3'-diethylthiacyanine p-toluenesulfonate                                
                          0.08                                            
Michler's ketone          0.08                                            
2,3-boronanedione         0.10                                            
Trichloroethylene         20.0
The solution was coated at a wet thickness of 0.002 inch on a 0.0075-inch-thick polyethylene terephthalate web support and allowed to dry.
A second coating solution was prepared as follows:
                           G.                                             
Poly(methyl methacrylate) (M.W. 60,000)                                   
                           1.27                                           
Triethyleneglycol dimethacrylate                                          
                           1.42                                           
25% dispersion of carbon black in isopropanol                             
                           6.2                                            
3,3'-diethylthiacyanine p-toluenesulfonate                                
                           0.05                                           
Michler's ketone           0.05                                           
2,3-boronanedione          0.08                                           
Trichloroethylene          39.4
The solution was coated at a wet thickness of 0.002 inch with a doctor knife on a 0.004-inch-thick polyethylene terephthalate photographic film base subbed with the resin sub of Alles, U.S. Pat. No. 2,779,684, Example IV support and allowed to dry.
The clear layer and black layer were placed together and laminated by passing through heated rolls at 100° C. and suitable pressure. The element so prepared was exposed from the clear side through a √2 step tablet with a 1000 w. quartz-iodine lamp at a distance of 5 ft. for 30 sec. The exposed sample was delaminated at 100° C. to give a positive black image on the 0.004-inch-thick support and a negative black image on the 0.0075-inch-thick support.
EXAMPLE LIX
A coating solution was prepared according to the following formula:
                          G.                                              
Cellulose acetate (acetyl 40%, ASTM visc. 25)                             
                          0.16                                            
Cellulose acetate butyrate (butyrate 17%, ASTM                            
 visc. 15)                0.25                                            
Trimethylolpropane triacrylate                                            
                          0.80                                            
Acetone                   6.9                                             
Michler's ketone          0.0128                                          
2,3-bornanedione          0.0080
The solution was coated with a doctor knife on a 0.001-inch-thick unsubbed polyethylene terephthalate web to a wet thickness of 0.002 inch. The coated element was dried and laminated at room temperature with a 0.001-inch-thick unsubbed polyethylene terephthalate cover sheet.
A sample of the element so prepared was exposed through a √2 step wedge with a rotary diazo printer (Blue Ray, average intensity 3.2 mf./cm.2) for 20 seconds. The cover sheet was removed and the coating was dusted with Quindo Magenta, C.I. Pigment Red 122. The steps up to step 16 inclusive had polymerized and did not accept pigment.
A control element made as above but without the 2,3-bornanedione polymerized only to step 6 inclusive when exposed as above.
EXAMPLE LX
The following solution was prepared.
______________________________________                                    
                            G.                                            
Methyl methacrylate/methacrylic acid copolymer                            
 (90/10 mole ratio)         2                                             
Diethylene glycol diacrylate                                              
                            5                                             
4,4'-bis(diethylamino)benzophenone                                        
                            0.05                                          
2,3-bornanedione            0.10                                          
Ethyleneglycol monoethyl ether                                            
                            8                                             
______________________________________
This solution was dispersed in a solution of 10 g. of gelatin in 40 g. of water by mixing in a high speed blender for 2 minutes. The dispersion was coated with a doctor knife on a 0.004-inch-thick polyethylene terephthalate web support to a wet thickness of 0.003 inch and dried. A sample of the element so prepared was exposed through a process transparency using a 3750 watt pulsed xenon arc at a distance of 18 inches for five seconds. The exposed element was immersed in a 2% aqueous solution of Rhodamine B Extra dye for 2 minutes, washed with cold water for 15 minutes, and dried. A positive, magenta colored image was obtained.
The above element may also be used for preparing gravure printing plates. A method for forming a gravure printing plate, for example, comprises, in either order, (a) exposing to actinic radiation such a layer coated on a support, e.g., transparent film support, first through a gravure screen and then to a continuous tone image transparency which gives an image in the resist modulated by photopolymerization, and (b) adhering the surface of said layer to the surface to be imaged which has been moistened with water and peeling off the transparent film support, then (c) etching the surface to produce an intaglio printing surface with conventional etching solution, e.g., ferric chloride, (d) washing the etched surface, e.g., with hot water to remove the residual etching solution and the photopolymer resist. The process may also be carried out by exposing the layer to the gravure screen through the transparent support and to the continuous tone image from the opposite side. In addition, the dispersion may be coated directly on the surface to be etched.

Claims (12)

I claim:
1. A photopolymerizable composition comprising
(a) at least one non-gaseous ethylenically unsaturated compound having a boiling point above 100° C. at normal atomspheric pressure and being capable of forming a high polymer by photoinitiated, addition polymerization;
(b) a cyclic cis-α-dicarbonyl compound, the excited state of which cannot react intramolecularly .Iadd., the atoms adjacent to the two vicinyl carbonyl groups being saturated when they are carbon atoms.Iaddend.; and
(c) an actinic radiation absorbing compound capable of sensitizing the polymerization initiating action of said cyclic cis-α-dicarbonyl compound, said actinic radiation absorbing compound being a nitrogen-containing aromatic or heterocyclic compound, having maximum absorption below 520 nm., selected from the class consisting of bis(p-aminophenyl-α,β-unsaturated) ketones; bis(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4 lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines.
2. A composition according to claim 1 wherein said cyclic cis-α-dicarbonyl compound is selected from the group consisting of 2,3-bornanedione; 2,2,5,5-tetramethyltetrahydro-3,4-furandione; imidazoletrione; indole-2,3-dione; 1,1,4,4-tetramethyl-tetralin-2,3-dione; 3-methyl-1,2-cyclopentanedione; 2,3-dioxo-5,6-diethoxy-5,6-dicyanopyrazine; and 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazine dicarboximide.
3. A composition according to claim 1 additionally containing a macromolecular organic polymer binder, said ethylenically unsaturated compound and said binder being present in relative amounts of from 3-95 and 5-97 parts by weight, respectively.
4. A composition according to claim 1 wherein said cyclic cis-α-dicarbonyl compound and said actinic radiation absorbing compound are each present in amounts of 0.001 to 10 parts by weight per 100 parts of the combined weight of said ethylenically unsaturated compound and any binder.
5. A composition according to claim 4 additionally containing up to 10 parts by weight of a free-radical producing hydrogen or electron donor compound per 100 parts of the combined weight of said ethylenically unsaturated compound and any binder.
6. A composition according to claim 1 wherein said cis-α-dicarbonyl compound is 2,3-bornanedione.
7. A composition according to claim 6 wherein said actinic radiation absorbing compound is selected from the group consisting of Michler's ketone; 4,4'-bis(diethylamino)benzophenone; 3,3'-diethylthiacyanine p-toluenesulfonate; 2-(p-dimethylaminostyryl)benzothiazole; [3-ethyl-naphthoxazole] [3'-ethyl-naphthiazole] monomethinecyanine p-toluenesulfonate; Diethyl Orange; 7-diethylamino-4-methyl-coumarin; and 2,5-bis(p-diethylaminobenzilidene) cyclopentanone.
8. A composition according to claim 1 additionally containing a thermal addition polymerization inhibitor.
9. A composition according to claim 1 dispersed in a hydrophilic colloid.
10. A photographic element comprising a support coated with a composition of claim 1.
11. A photographic element according to claim 10 wherein said support is a polymeric film or metallic surface.
12. A photographic element according to claim 11 wherein the photpolymerizable composition is dispersed in a hydrophilic colloid.
US05/608,673 1972-01-25 1975-08-28 Photopolymerizable compositions containing cyclic cis-α-dicarbonyl compounds and selected sensitizers Expired - Lifetime USRE28789E (en)

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US4175971A (en) 1976-09-14 1979-11-27 Fuji Photo Film Co., Ltd. Light-sensitive photopolymerizable composition
US4289844A (en) 1979-06-18 1981-09-15 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
US4366228A (en) 1980-09-05 1982-12-28 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
US4367280A (en) 1977-01-20 1983-01-04 Fuji Photo Film Co., Ltd. Photopolymerizable composition
US4517266A (en) 1982-01-18 1985-05-14 Fujitsu Limited Holographic recording material and process for producing holograms
US4535052A (en) 1983-05-02 1985-08-13 E. I. Du Pont De Nemours And Company Constrained n-alkylamino aryl ketones as sensitizers for photopolymer compositions
US4603726A (en) 1982-11-05 1986-08-05 Espe Fabrik Pharmazeutischer Praparate Gmbh Method of making individual castings
US4721703A (en) 1982-06-07 1988-01-26 Sony Corporation Sublimation transfer system color hard copy printing paper
US4894314A (en) 1986-11-12 1990-01-16 Morton Thiokol, Inc. Photoinitiator composition containing bis ketocoumarin dialkylamino benzoate, camphorquinone and/or a triphenylimidazolyl dimer
US5238782A (en) * 1986-12-26 1993-08-24 Fuji Photo Film Co., Ltd. Photopolymerizable composition
US5514521A (en) * 1990-08-22 1996-05-07 Brother Kogyo Kabushiki Kaisha Photocurable composition
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5672760A (en) * 1995-06-07 1997-09-30 International Business Machines Corporation Ablatively photodecomposable compositions
US5686503A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and applications therefor
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5786132A (en) * 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5849411A (en) * 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5858586A (en) * 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6025112A (en) 1996-02-09 2000-02-15 Brother Kogyo Kabushiki Kaisha Photocurable composition and photosensitive capsules
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6063551A (en) 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6171759B1 (en) 1992-05-14 2001-01-09 Brother Kogyo Kabushiki Kaisha Photocurable composition
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242149B1 (en) 1997-12-22 2001-06-05 Brother Kogyo Kabushiki Kaisha Fast-curing photosensitive composition and recording sheet
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
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US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
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US20040198859A1 (en) * 2003-04-03 2004-10-07 Nguyen Chau K. Photopolymerization systems and their use
US20060293404A1 (en) * 2003-04-24 2006-12-28 Santobianco John G New class of amine coinitiators in photoinitiated polymerizations
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US4175971A (en) 1976-09-14 1979-11-27 Fuji Photo Film Co., Ltd. Light-sensitive photopolymerizable composition
US4298679A (en) 1976-09-14 1981-11-03 Fuji Photo Film Co., Ltd. Light-sensitive composition
US4386153A (en) 1976-09-14 1983-05-31 Fuji Photo Film Co., Ltd. Light-sensitive photopolymerizable composition
US4367280A (en) 1977-01-20 1983-01-04 Fuji Photo Film Co., Ltd. Photopolymerizable composition
US4289844A (en) 1979-06-18 1981-09-15 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
US4366228A (en) 1980-09-05 1982-12-28 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
US4517266A (en) 1982-01-18 1985-05-14 Fujitsu Limited Holographic recording material and process for producing holograms
US4721703A (en) 1982-06-07 1988-01-26 Sony Corporation Sublimation transfer system color hard copy printing paper
US4603726A (en) 1982-11-05 1986-08-05 Espe Fabrik Pharmazeutischer Praparate Gmbh Method of making individual castings
US4535052A (en) 1983-05-02 1985-08-13 E. I. Du Pont De Nemours And Company Constrained n-alkylamino aryl ketones as sensitizers for photopolymer compositions
US4894314A (en) 1986-11-12 1990-01-16 Morton Thiokol, Inc. Photoinitiator composition containing bis ketocoumarin dialkylamino benzoate, camphorquinone and/or a triphenylimidazolyl dimer
US5238782A (en) * 1986-12-26 1993-08-24 Fuji Photo Film Co., Ltd. Photopolymerizable composition
US5514521A (en) * 1990-08-22 1996-05-07 Brother Kogyo Kabushiki Kaisha Photocurable composition
US6171759B1 (en) 1992-05-14 2001-01-09 Brother Kogyo Kabushiki Kaisha Photocurable composition
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US6127073A (en) 1993-08-05 2000-10-03 Kimberly-Clark Worldwide, Inc. Method for concealing information and document for securely communicating concealed information
US6054256A (en) 1993-08-05 2000-04-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for indicating ultraviolet light exposure
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6120949A (en) 1993-08-05 2000-09-19 Kimberly-Clark Worldwide, Inc. Photoerasable paint and method for using photoerasable paint
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US6060200A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US6060223A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Plastic article for colored printing and method for printing on a colored plastic article
US5858586A (en) * 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
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US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6090236A (en) 1994-06-30 2000-07-18 Kimberly-Clark Worldwide, Inc. Photocuring, articles made by photocuring, and compositions for use in photocuring
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6235095B1 (en) 1994-12-20 2001-05-22 Ronald Sinclair Nohr Ink for inkjet printers
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US6063551A (en) 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5849411A (en) * 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5786132A (en) * 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5919868A (en) 1995-06-07 1999-07-06 International Business Machines Corporation Ablatively photodecomposable compositions
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US5705570A (en) * 1995-06-07 1998-01-06 International Business Machines Corporation Ablatively photodecomposable compositions
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US6025112A (en) 1996-02-09 2000-02-15 Brother Kogyo Kabushiki Kaisha Photocurable composition and photosensitive capsules
US6242149B1 (en) 1997-12-22 2001-06-05 Brother Kogyo Kabushiki Kaisha Fast-curing photosensitive composition and recording sheet
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US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
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US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US20080103222A1 (en) * 2002-04-26 2008-05-01 Albemarle Corporation New Class of Amine Coinitiators in Photoinitiated Polymerizations
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