EP0000082B1 - Verfahren zur bildmässigen Modifizierung der Oberfläche eines ätzbaren Trägers und Material hierfur enthaltend eine kolloidale Schicht und darin Oxime-estergruppen aufweisende Polymere - Google Patents

Verfahren zur bildmässigen Modifizierung der Oberfläche eines ätzbaren Trägers und Material hierfur enthaltend eine kolloidale Schicht und darin Oxime-estergruppen aufweisende Polymere Download PDF

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Publication number
EP0000082B1
EP0000082B1 EP78200022A EP78200022A EP0000082B1 EP 0000082 B1 EP0000082 B1 EP 0000082B1 EP 78200022 A EP78200022 A EP 78200022A EP 78200022 A EP78200022 A EP 78200022A EP 0000082 B1 EP0000082 B1 EP 0000082B1
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layer
radiation
polymer
alkyl
including substituted
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French (fr)
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EP0000082A1 (de
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Hugo Vital Van Goetham
Marcel August Stroobants
Walter Frans De Winter
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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 a method and materials for producing image-wise modified etchable supports.
  • This method and materials can be used e.g. in the production of printed circuits, in photochemical tooling, in the production of printing plates etc.
  • the surface of an etchable support or an etchable layer on a support is modified image-wise.
  • the image-wise modification in conformity with an image-wise exposure occurs by means of an etchant, whose action is image-wise controlled by means of an etch-resist.
  • etch-resists are known.
  • the etch-resist controls image-wise the action of the etchant so that the surface of the underlying printing member is modified image-wise so as to obtain an image-wise embossed surface.
  • the depressed areas or cavities will receive the printing ink, which ink is transferred from these cavities or ink cells to the printing stock.
  • the transfer of ink to the printing stock is e.g. due to the suction of the printing stock, the adhesion power and/or viscosity of the ink.
  • the etch-resist controlling the action of the etchant on the underlying printing member may consist e.g. of a hardened relief pattern.
  • the thinner said pattern the more intense the etching, in other words the deeper the etchant attacks the support to be etched.
  • Homogeneous mixtures of photopolymerizable monomers and of a photoinitiator in a binder are extremely sensitive to polymerization inhibition caused by oxygen.
  • Non-polymeric as well as polymeric compounds containing oxime-ester groups are known from US Patent Specification 3,558,309 of Urbain Leopold Laridon and whatsoever Albert Delzenne issued January 26, 1971 for use as photoinitiator in the photopolymerization of ethylenically unsaturated monomers and to make etch-resists with the washing-away step according to the method of the above US Patent 2,760,863.
  • These photoinitiators can of course also be used in the procedure of the above US Patent Specification 3,718,473 without washing away step.
  • etch-resist can be made by image-wise photodegradation of polymers containing oxime-ester groups and washing away the decomposed polymer in the exposed areas by means of solvents in which the non-decomposed polymer in the unexposed areas is insoluble.
  • a hydrophilic colloid layer containing a dispersed phase of a polymer with recurring units containing oxime-ester groups in the side-chain can be used to form an etch-resist in the absence of an ethylenically unsaturated monomer.
  • image-wise exposure the permeability of the colloid layer to an etchant is reduced in the exposed areas, so that there is no need for a washing away step before the application of the etchant.
  • the present invention thus provides a process for image-wise modifying the surface of an etchable support or an etchable layer on a support by making an etchant diffuse image-wise through an etch-resist layer applied to said etchable support or layer, the said etch-resist having been formed by image-wise exposure to actinic radiation of a radiation-sensitive hydrophilic colloid layer, whereby the permeability of the said hydrophilic colloid layer to an etchant is reduced in conformity with the image-wise exposure, characterized in that said hydrophilic colloid layer contains, in the absence of any ethylenically unsaturated photopolymerisable monomeric material, a dispersed phase of at least one radiation-sensitive polymer, the said radiation-sensitive polymer being a homopolymer or copolymer derived from a monomer corresponding to the formula wherein one of M l and M 2 is or comprises an ethylenically unsaturated group, and the other is an aliphatic, aromatic or heterocycl
  • the hydrophilic colloid binder wherein a polymer, whose polymer chain comprises units with oxime-ester groups in the side chain, is heterogeneously dispersed, constitutes the medium, through which an etchant e.g. an Fe(III) chloride solution can diffuse in consequence of the porous behaviour of said medium.
  • an etchant e.g. an Fe(III) chloride solution
  • the oxime-ester units in said polymer form radicals which crosslink with the hydrophilic binder so that the porosity of the layer is reduced and thus the permeability of the layer for a hydrophilic etchant is reduced.
  • Particularly suitable polymeric compounds having side-substituents comprising an oxime-ester group are polymers obtained by (1) the reaction or a monooxime of an ⁇ , ⁇ -diketone or of a 2-oxo- aldehyde e.g. 1-phenyl-1,2-propanedione-2-oxime, 1-(p-hydroxyphenyl)-1,2-propanedione-2-oxime, p-hydroxyphenyl glyoxaldoxime and 2,3-butanedione monooxime with an ethylenically-unsaturated acid chloride e.g.
  • acryloyl or methacryloyl chloride and polymerization or copolymerization of the thus formed monomer carrying an oxime ester group, or (2) the reaction of an ethylenically unsaturated compound comprising an ⁇ , ⁇ -diketo or a 2-oxo-aidehyde monooxime, with a carboxylic acid chloride which includes an aliphatic, aromatic or heterocyclic acid chloride e.g.
  • acetylchloride propionylchloride, benzoylchloride, p-nitrobenzoyl chjoride, o-methoxybenzoyl chloride, o-chlorobenzoyl chloride, 2-methyl-3-indolizine carbonyl chloride, etc., and polymerization or copolymerization of the thus formed monomer carrying an oxime ester group.
  • Particularly suitable polymers are those comprising recurring units corresponding to one of the following general formulae I and II: wherein:
  • the polymers used according to the present invention can be homopolymers or copolymers. They are preferably copolymers comprising besides the units with oxime ester group in the side chain units derived from a variety of monomers, whereof preferably at least one is hydrophobic. Examples of comonomers are (meth)acrylamide, N-alkyl(meth)acrylamide, alkyl(meth)acrylate, styrene, acrylonitrile, N-vinylpyrrolidone, vinyl acetate and other vinyl esters. Preferred copolymers comprise from 5 to 50 mol % recurring units with oxime-ester groups in the side chain.
  • the solution was cooled to 25°C and 92.4 g of sodium hydrogen carbonate (1.1 mole) were added.
  • the mixture was cooled to ambient temperature (20°C). Dry hydrogen chloride was introduced for 15 min and simultaneously a solution of 200 ml of n-amyl nitrite in 200 ml of trichloromethane were added dropwise. The temperature was kept between 20 and 26°C. Subsequently, hydrogen chloride was introduced for another 15 min with stirring. The resulting mixture was allowed to stand overnight. The residue formed was sucked off and dried under vacuum. A light-yellow powder was obtained.
  • This product may be purified by dissolving in a 10% aqueous solution of sodium hydroxide and again forming a residue with HCI or by recrystallization from a mixture of ethanol and water (2:1)
  • the product was stable for some weeks at 0°C.
  • Monomer 2 was prepared as monomer 1 (starting from compound d of preparation 1. using 2.81 g of benzoyl chloride in lieu of 2-methyl-indolizine-3-carbonyl chloride).
  • the above monomers can be homopolymerized or copolymerized to form polymers with recurring units containing an oxime ester group in the side chain as is illustrated in Research Disclosure June 1973, Havant, England, Disclosure No. 11048 and by the following preparations.
  • the molar ratio of methylmethacrylate units to monomer units 2 was 81:19.
  • the resist-forming layer used according to the present invention comprises dispersed in a hydrophilic colloid binder in the absence of any ethylenically unsaturated monomeric material, at least one radiation sensitive polymer which is a homopolymer or a copolymer derived from a monomer corresponding to the general formula given hereinbefore.
  • the hydrophilic colloid used as the binder for the dispersed polymer particles is preferably gelatin, but other hydrophilic colloids can also be used, e.g. colloidal albumin, alginic acid and derivatives thereof, a cellulose derivative e.g. carboxymethylcellulose and hydroxyethylcellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, copolymers of acrylic acid and polyacrylamides. If desired, compatible mixtures of two or more of these colloids can be employed for dispersing the polymer particles.
  • hydrophilic colloids e.g. colloidal albumin, alginic acid and derivatives thereof, a cellulose derivative e.g. carboxymethylcellulose and hydroxyethylcellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, copolymers of acrylic acid and polyacrylamides.
  • the weight ratio of hydrophilic colloid to radiation sensitive polymer is preferably comprised between 20:1 and 1:1.
  • the radiation-sensitive polymers can be dispersed in the hydrophilic colloids using any of the dispersion techniques known for incorporating photographic ingredients e.g. colour couplers in silver halide emulsion layers.
  • a particularly suitable technique is to disperse the polymers from solutions in high-boiling water-immiscible solvents or mixtures of high-boiling and low-boiling water-immiscible solvents, in aqueous solutions of the hydrophilic colloid.
  • high-boiling solvents are tricresyl phosphate, dibutyl phthalate and other esters of organic dicarboxylic acids e.g. diethyl- malonate, diethyloxalate and diethyl succinate.
  • aqueous colloid surfactants which include anionic, non-ionic and amphoteric compounds, e.g. sodium alkylnaphthalene sulphonates, sodium lauryl sulphate, sulphonated derivatives of fatty acid amines, sodium dioctylsulphate, sodium isotetradecyl sulphate and sorbitol monolaurate.
  • anionic, non-ionic and amphoteric compounds e.g. sodium alkylnaphthalene sulphonates, sodium lauryl sulphate, sulphonated derivatives of fatty acid amines, sodium dioctylsulphate, sodium isotetradecyl sulphate and sorbitol monolaurate.
  • the polymers are dispersed in the hydrophilic colloid medium in the form of oily droplets.
  • the average diameter of these droplets may be between 0.01 and 20 microns, preferably between 0.05 and 5 microns.
  • the radiation sensitive resist-forming layer used according to the present invention may comprise, in addition to the binder and radiation sensitive polymer, compounds increasing the sensitivity e.g. Michler's ketone and analogous aromatic ketones which increase the spectral response especially in the range of 270 to 380 ⁇ m.
  • the layer may also comprise so-called "filler"-compounds that are non light-sensitive and do not crosslink with the hydrophilic binder.
  • filler compounds are e.g. co(ethylene glycol isophthalate/isopropylene glycol isophthalate 50:50), co(vinyl chloride/vinyl acetate/maleic acid anhydride), co(vinyl acetate/vinyl chloride), co(vinyl chloride/vinyl acetate/maleic acid), polyvinyl-n-butyral, polyisobutyl methacrylate, polystyrene, polymethyl methacrylate, cellulose acetate butyrate, co(styrene/butadiene), and an epoxy resin of bisphenol A and epichlorohydrin, marketed by Ciba-Geigy, Basel, Switzerland under the trademark of ARALDITE GY 250 being preferred.
  • the layer may also contain antioxidizing agents, coating aids and dyes.
  • Rendering visible the exposure makes possible sensitometric evaluation and follow up of the subsequent etching. Moreover, by producing a colour during exposure, the amount of light transmitted through the layer is reduced and this consequently decreases the sensitivity and gradation of the said layer, which is favourable for continuous-tone reproduction.
  • the resist-forming radiation-sensitive layer can be applied to any support known in the art.
  • Metal supports or supports coated with metals such as for example zinc, and especially aluminium are excellently suited as base materials for planographic printing plates.
  • metal supports suitable for etching are used e.g. metal plates or cylinders of zinc, copper, steel or an etchable magnesium alloy.
  • the photoresist composition is applied e.g. to a supported copper layer, which can be easily etched.
  • the present radiation-sensitive layers can likewise be used in the production of microimages.
  • the photoresist coatings are applied to a relatively thin highly opaque black or grey metal coating that can be etched.
  • Suitable metal coatings are made of tellurium or a tellurium alloy having a thickness in the range of 50 nm to 500 nm or bismuth coatings having a thickness in the range of 25 nm to 300 nm.
  • composition of the metal layer to be etched tellurium alloys comprising at least 50 atomic percent of tellurium are used.
  • Typical tellurium compositions which are etchable with an opaque hypochlorite solution are described in US Patent Specifications 3,271,591 and 3,530,441 of Stanford R. Ovshinsky issued respectively September 6, 1966 and September 22, 1970.
  • the metal layer to be etched consists of bismuth.
  • Bismuth possesses the advantage of directly adhering to organic resin supports such as a polyethylene terephthalate support when deposited thereon from bismuth vapour under reduced pressure conditions.
  • Vapour deposition techniques are sufficiently known to those skilled in the art of preparing photoconductive selenium coatings (see e.g. US Patent Specifications 3,874,917 of Charles Wood, John C. Schottmiller and Francis W. Ryan issued April 1, 1975 and 3,884,688 of John C. Schottmiller, Francis W. Ryan and Charles Wood issued May 20, 1975).
  • aqueous acidic iron(III) chloride solution For the etching of the bismuth layer preference is given to aqueous acidic iron(III) chloride solution.
  • concentration of iron(III) chloride is e.g. in the range of 5 to 20% by weight.
  • Said solution contains preferably from 0.25 to 1% by weight of citric acid.
  • a likewise useful etching solution for the removal of bismuth is an aqueous solution containing 3 to 6% by weight of hydrogen peroxide and 5 to 10% by weight of sulphuric acid.
  • the radiation-sensitive layers according to the invention can be applied to the surfaces to be modified by any known coating technique e.g. by spin-coating, whirl coating, spraying, dip-coating, roller coating, air-knife coating and doctor-blade coating.
  • Preferred temporary supports are transparent film supports which permit exposure through the support. Examples of such transparent supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials.
  • Other suitable temporary supports are paper and paper which has been coated with a-olefin polymers, e.g. polyethylene, polypropylene and polyisobutylene-polyethylene mixtures.
  • an antihalation layer between the radiation-sensitive layer and the temporary support e.g. between the stripping layer and the support or between the radiation-sensitive layer and the stripping layer. It is also possible to provide the antihalation layer on the side of the transparent support opposite to that carrying the radiation-sensitive layer.
  • the exposure of the radiation-sensitive resist forming layer preferably occurs by means of UV- radiation sources e.g. carbon arcs and mercury vapour lamps. Exposure may occur through a contacted transparent master pattern or by a projection exposure.
  • UV- radiation sources e.g. carbon arcs and mercury vapour lamps. Exposure may occur through a contacted transparent master pattern or by a projection exposure.
  • aqueous phase containing 60 g of gelatine, 340 g of water, 40 g of a 5% aqueous solution of the sodium salt of diisooctyl sulphosuccinate was prepared as follows: gelatin was allowed to swell for 1 h in water and then heated to 50°C, whereupon the other ingredients of the aqueous phase were added.
  • an organic phase was prepared by dissolving 30 g of tricresyl phosphate, 3 g of Michier's ketone and 20 g of co(ethylene glycol isophthalate/isopropylene glycol isophthalate) (50:50) in 90 g of ethyl acetate and 90 g of m-xylene and then dissolving therein 40 g of the polymer of preparation 4.
  • the organic phase was emulsified in the aqueous phase by means of an homogenizer. Then 760 ml of water and 12.5 g of aqueous formaldehyde (4% by weight) were added to obtain the desired viscosity.
  • the emulsion was dip-coated on a polyethylene terephthalate support and dried.
  • the thickness of the coated layer varied from 5 to 10 ⁇ m.
  • Preparation of the coating composition and coating occurred under darkroom illumination.
  • the image-wise exposure was performed in contact in a vacuum frame in two stages.
  • An exposure was carried out through a gravure screen of 65 lines per cm, in which the ratio of the dark lines to the transparent parts was 1:2.5.
  • the light source used was a mercury vapour lamp.
  • the time ratio between the continuous tone exposure and the screen exposure was 0.66:1.
  • the etch-resist layer showing a brown negative image was transferred by pressure to a wet copper surface.
  • the polyethylene terephthalate support was stripped off and the etch-resist was dried in the air.
  • the parts of the copper surface that were not covered by etch resist were coated with an asphalt derivative.
  • the etching was performed with an iron(lll) chloride solution of 39-43° Baume for about 15 min.
  • the etching was stopped by abundantly rinsing with hot water. The etch-resist was rubbed off easily. The resulting etch depths reached 3 to 45 ,um. No undercutting was observed.
  • Example 1 was repeated with the difference that the aqueous phase contained:
  • the organic phase was dispersed in the aqueous phase and after dilution as in example 1 coated on a polyethylene terephthalate support.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (10)

1. Verfahren zur bildmässigen Abänderung der Oberfläche einer ätzbaren Unterlage bzw. einer ätzbaren Schicht auf einer Unterlage durch bildmässige Diffusion eines Ätzmittels durch eine auf der Unterlage bzw. Schicht angeordnete, durch bildmässige Belichtung einer strahlungsempfindlichen hydrophilen Kolloidschicht mit einer aktinischen Strahlung gebildete Ätzreserveschicht, wobei die Ätzmitteldurchlässigkeit dieser hydrophilen Kolloidschicht bildgemäss entsprechend der bildmässigen Belichtung herabgesetzt wird, dadurch gekennzeichnet, dass die hydrophile Kolloidschicht, bei fehlendem, äthylenisch ungesättigtem, photopolymerisierbarem monomerem Material, eine dispergierte Phase wenigstens eines strahlungsempfindlichen Polymeren in der Form eines von einem Monomeren gemäss der untenstehenden allgemeinen Formel abgeleiteten Homopolymeren oder Copolymeren enthält:
Figure imgb0019
in der
eine der beiden Gruppen M1 und M2 eine äthylenisch ungesättigte Gruppe ist oder eine derartige Gruppe enthält und die zweite dieser beiden Gruppen eine gegebenenfalls substituierte aliphatische, aromatische oder heterocyclische Gruppe ist, und
R ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkyl- oder Arylgruppe ist.
2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das vorgenannte strahlungsempfindliche Polymere sich wiederholende, den untenstehenden allgemeinen Formel I oder 11 entsprechende Einheiten enthält:
Figure imgb0020
in denen bedeuten:
R1 ein Wasserstoffatom oder eine C1-Cs-Alkylgruppe;
R2 ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkyl- oder Arylgruppe,
R3 eine gegebenenfalls substituierte Alkyl- oder Arylgruppe,
X -NH- oder -O-, und
R4 eine aliphatische, aromatische oder heterocyclische Gruppe.
3. Verfahren gemäss irgendeinem der vorhergehenden Ansprüche 1-2, dadurch gekennzeichnet, dass das Polymere ein 5-50 Mol-% sich wiederholender Einheiten mit Oximestergruppen in der Seitenkette enthaltendes Copolymeres ist.
4. Verfahren gemäss irgendeinem der vorhergehenden Ansprüche 1-3, dadurch gekennzeichnet, dass das Polymere ein sich wiederholende Alkyl(meth)acrylat-Einheiten enthaltendes Copolymeres ist.
5. Verfahren gemäss irgendeinem der vorhergehenden Ansprüche 1-4, dadurch gekennzeichnet, dass das Mengenverhältnis zwischen dem hydrophilen Kolloid und dem strahlungsempfindlichen Polymeren 20:1 bis 1:1 beträgt.
6. Verfahren gemäss irgendeinem der vorhergehenden Ansprüche 1-5, dadurch gekennzeichnet, dass die Anordnung der Ätzreserveschicht auf der abzuändernden Oberfläche nach Belichtung dieser auf einer Hilfsunterlage befindlichen Schicht stattfindet, welche nach Übertragung der Ätzreserveschicht auf die abzuändernde Oberfläche abgezogen wird.
7. Strahlungsempfindliches Material, das eine Unterlage und eine hydrophile Kolloidschicht enthält, dadurch gekennzeichnet, dass die hydrophile Kolloidschicht, bei fehlendem äthylenisch ungesättigtem photopolymerisierbarem monomerem Material, eine dispergierte Phase wenigstens eines strahlungsempfindlichen, sich zur Herabsetzung der Ätzmitteldurchlässigkeit der hydrophilen Kolloidschicht durch Belichtung mit aktinischer Strahlung eignenden Polymeren in der Form eines Homopolymeren oder Copolymeren eines Monomeren gemäss der untenstehenden allgemeinen Formel enthält:
Figure imgb0021
in der
eine der beiden Gruppen M1 und M2 eine äthylenisch ungesättigte Gruppe ist oder eine derartige Gruppe enthält und die zweite dieser Gruppen eine gegebenenfalls substituierte aliphatische, aromatische oder heterocyclische Gruppe ist, und
R ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkyl- oder Arylgruppe ist.
. 8. Strahlungsempfindliches Material gemäss Anspruch 7, dadurch gekennzeichnet, dass das Polymere ein 5-50 Mol-% sich wiederholender Einheiten mit Oximestergruppen in der Seitenkette enthaltendes Copolymeres ist.
9. Strahlungsempfindliches Material gemäss Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Polymere ein sich widerholende Alkyl(meth)acrylat-Einheiten enthaltendes Copolymeres ist.
10. Strahlungsempfindliches Material demäss irgendeinem der vorhergehenden Ansprüche 7-9, dadurch gekennzeichnet, dass das Mengenverhältnis zwischen dem hydrophilen Kolloid und dem strahlungsempfindlichen Polymeren 20:1 bis 1:1 beträgt.
EP78200022A 1977-06-01 1978-06-01 Verfahren zur bildmässigen Modifizierung der Oberfläche eines ätzbaren Trägers und Material hierfur enthaltend eine kolloidale Schicht und darin Oxime-estergruppen aufweisende Polymere Expired EP0000082B1 (de)

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GB2320377 1977-06-01
GB2320377 1977-06-01

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EP0000082A1 EP0000082A1 (de) 1978-12-20
EP0000082B1 true EP0000082B1 (de) 1982-07-21

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US (1) US4202697A (de)
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JP (1) JPS53149330A (de)
DE (1) DE2861959D1 (de)
FR (1) FR2393345A1 (de)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5011626A (en) * 1988-06-13 1991-04-30 Rolls-Royce Inc. Barrier materials for laser drilling
SG77689A1 (en) * 1998-06-26 2001-01-16 Ciba Sc Holding Ag New o-acyloxime photoinitiators
AU4102100A (en) 1999-03-03 2000-09-21 Ciba Specialty Chemicals Holding Inc. Oxime derivatives and the use thereof as photoinitiators
SG97168A1 (en) * 1999-12-15 2003-07-18 Ciba Sc Holding Ag Photosensitive resin composition
NL1016815C2 (nl) * 1999-12-15 2002-05-14 Ciba Sc Holding Ag Oximester-fotoinitiatoren.
US6783914B1 (en) 2000-02-25 2004-08-31 Massachusetts Institute Of Technology Encapsulated inorganic resists
US7189489B2 (en) * 2001-06-11 2007-03-13 Ciba Specialty Chemicals Corporation Oxime ester photoiniators having a combined structure
KR101032582B1 (ko) * 2002-12-03 2011-05-06 시바 홀딩 인크 헤테로방향족 그룹을 갖는 옥심 에스테르 광개시제
CN101014569B (zh) * 2004-08-18 2013-01-02 西巴特殊化学品控股有限公司 肟酯光引发剂
DE602005019888D1 (de) * 2004-08-20 2010-04-22 Adeka Corp Oximesterverbindung und photopolymerisationsinitiator, der eine solche verbindung enthält
KR100763744B1 (ko) * 2005-11-07 2007-10-04 주식회사 엘지화학 옥심 에스테르를 포함하는 트리아진계 광활성 화합물
KR100814232B1 (ko) * 2005-12-01 2008-03-17 주식회사 엘지화학 옥심 에스테르를 포함하는 트리아진계 광활성 화합물을포함하는 착색 감광성 조성물
JP5680274B2 (ja) * 2005-12-01 2015-03-04 チバ ホールディング インコーポレーテッドＣｉｂａ Ｈｏｌｄｉｎｇ Ｉｎｃ． オキシムエステル光開始剤
US8586268B2 (en) * 2005-12-20 2013-11-19 Basf Se Oxime ester photoinitiators
CN102702073B (zh) 2007-05-11 2015-06-10 巴斯夫欧洲公司 肟酯光引发剂
WO2008138732A1 (en) 2007-05-11 2008-11-20 Basf Se Oxime ester photoinitiators
US8349548B2 (en) * 2007-05-11 2013-01-08 Basf Se Oxime ester photoinitiators
KR101007440B1 (ko) * 2007-07-18 2011-01-12 주식회사 엘지화학 옥심 에스테르를 포함하는 수지상 광활성 화합물 및 이의제조방법
US8507725B2 (en) 2008-06-06 2013-08-13 Basf Se Oxime ester photoinitiators
GB0823025D0 (en) * 2008-12-18 2009-01-28 Eastman Kodak Co Method of making a planographic printing plate
JP4344400B1 (ja) * 2009-02-16 2009-10-14 株式会社日本化学工業所 オキシムエステル化合物及びこれらを用いた感光性樹脂組成物
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US8816211B2 (en) 2011-02-14 2014-08-26 Eastman Kodak Company Articles with photocurable and photocured compositions
US20120208914A1 (en) 2011-02-14 2012-08-16 Deepak Shukla Photoinitiator compositions and uses
KR20180091232A (ko) 2017-02-06 2018-08-16 동우 화인켐 주식회사 옥심 에스테르계 화합물 및 이를 포함하는 광경화성 조성물
KR20180099105A (ko) 2017-02-28 2018-09-05 동우 화인켐 주식회사 옥심 에스테르계 화합물 및 이를 포함하는 광경화성 조성물
US10976483B2 (en) * 2019-02-26 2021-04-13 Facebook Technologies, Llc Variable-etch-depth gratings

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074869A (en) * 1960-12-23 1963-01-22 Minnesota Mining & Mfg Photo-sensitive compositions and articles therefrom
US3255002A (en) * 1961-03-09 1966-06-07 Polaroid Corp Color photographic process and product
US3306744A (en) * 1962-12-17 1967-02-28 Polaroid Corp Copying process using dithioxamides, heavy metal salts and photopolymerizable monomers and photocross linkable polymers
GB1141925A (en) * 1965-07-02 1969-02-05 Horizons Inc Photography
GB1230771A (de) * 1967-03-31 1971-05-05
GB1180845A (en) * 1967-08-08 1970-02-11 Agfa Gevaert Nv Light-Sensitive Polymers and their use in the preparation of Photographic Printing Plates
GB1180846A (en) * 1967-08-08 1970-02-11 Agfa Gevaert Nv Photopolymerisation of Ethylenically Unsaturated Organic Compounds
US3558831A (en) * 1968-04-18 1971-01-26 Bell Telephone Labor Inc Telephone set base structure with exterior plug cavities in the base bottom secured by a detachable baseplate
GB1264308A (de) * 1968-06-17 1972-02-23
BE754916A (nl) * 1969-11-11 1971-02-17 Agfa Gevaert Nv Fotopolymerisatie van ethylenisch onverzadigde organische verbindingen
US3718473A (en) * 1971-01-27 1973-02-27 Du Pont Photopolymerizable elements containing hydro philic colloids and polymerizable monomers for making gravure printing plate resists

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US4202697A (en) 1980-05-13
EP0000082A1 (de) 1978-12-20
JPS53149330A (en) 1978-12-26
FR2393345A1 (fr) 1978-12-29
DE2861959D1 (en) 1982-09-09
FR2393345B1 (de) 1980-04-25

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