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US3579343A - Photoresist-forming compositions - Google Patents

Photoresist-forming compositions Download PDF

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Publication number
US3579343A
US3579343A US721621A US3579343DA US3579343A US 3579343 A US3579343 A US 3579343A US 721621 A US721621 A US 721621A US 3579343D A US3579343D A US 3579343DA US 3579343 A US3579343 A US 3579343A
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US
United States
Prior art keywords
hydrogen atom
alkyl group
lower alkyl
polymer
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US721621A
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English (en)
Inventor
Motoo Kogure
Shoichiro Hoshino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
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Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
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Publication of US3579343A publication Critical patent/US3579343A/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/126—Halogen compound containing

Definitions

  • a photoresist-forming composition comprising a photo activator having a polychlorinated or polybrominated methyl group capable of forming a free radical by the action of light and a homopolymer or a co-polymer with other vinyl monomer, of a monomer represented by the general formula wherein A is a hydrogen atom, a carboxylic acid or carboxylic acid amide; X is COOCH CH
  • a photoresist-forming composition comprising a polymer and a photo-activator having a polyhalogeriated methyl group capable of forming a free radical by action of light.
  • a conventional light-sensitive compositions using polymers there have been known those in which gelatine or polyvinyl alcohol and a bichromate are used in combination, and those in which a polymer and a diazo compound are used in combination. Further, light-sensitive compositions which contain polyvinyl cinnamate so as to utilize the photodimerization of the cinnamate group also have been known. These conventional light-sensitive compositions, however, have such drawbacks that even when they are exposed to light through negatives, image portions cannot be discriminated from non-image portions, unless they are treated with a developer to form relief images.
  • the conventional light-sensitive compositions using poly mers have had such drawback that, in order to obtain visible images, they should necessarily be subjected to developing and dyeing treatment steps. Accordingly, when said compositions have been left merely in an exposed state without any further treatment, exposed portions have not been able to be discriminated from unexposed portions to bring about much fear of double exposure.
  • the light-sensitive compositions of the present invention are novel compositions which have overcome all the above-mentioned drawbacks.
  • polymers contained therein are cross-linked imagewise, with dye formation, to give faintly colored images, and when they are subjected to developing treatment, the exposed portions are clearly developed in deep color, with removal of unexposed portions, thereby to form visible relief images.
  • the polymers employed in the present invention are homopolymers, or copolymers with other vinyl monomers, of monomers represented by the general formula wherein A is a hydrogen atom, or a carboxylic acid or carboxylic acid amide group; X is a group capable of connecting the carbon in the main chain with an amino group which has substituted the aromatic ring; R is a hydrogen atom or a lower alkyl group; R is a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group; and R and R are individually a hydrogen atom or a lower alkyl group, provided that in the case of Formula II, R and R may form a heterocyclic ring together with nitrogen and the benzene ring, and R and R may form a naphthalene ring together with the benzene ring.
  • vinyl monomers are any of such monomers as styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, methyl acrylate, .ethyl acrylate, butyl acrylate, methyl methacrylate, methyl achloro-acrylate, ethyl a-chloroacrylate, ethyl methacrylate, ethyl ethacrylate, maleic anhydride, vinylidene chloride, and the like.
  • polymers usable in the present invention are not limited thereto.
  • the ether is vaporized off and the reaction liquid liquid is then subjected to reduce pressure distillation at 135 C. and 4 mm. Hg to obtain N-ethyl-N-phenylaminoethyl methacrylate.
  • 1 g. of the N-ethyl-N-phenylaminoethyl methacrylate is dissolved in cc. of methyl ethyl ketone.
  • the solution is charged wifll 5 mg. of a,ot'- azo-bis-isobutyronitrile and is then heated at 60 C. for 5 hours to obtain a polymer solution.
  • This reaction liquid is poured into ether, whereby a white polymer is precipitated.
  • N-ethyl-N-phenylaminoethyl rnethacrylamide and 0.5 g. of styrene are dissolved in 10 cc. of methyl ethyl ketone.
  • the solution is charged with 5 mg. of 11,01.- azo-bis-isobutyronitrile and is then heated at 70 C. for 12 hours. Subsequently, the solution is charged into a large amount of methanol to obtain a white polymer.
  • the photoactivators employed in the present invention i.e. photoactivators having a polyhalogenated methyl group capable of forming a free radical by action of light, are compounds represented by the general formula R4- S Oz-CXaRa,
  • R is a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a heterocyclic ring;
  • R is a hydrogen or halogen atom;
  • R is a common substituent such as a nitro group, a halogen atom or an alkyl group;
  • R is an alkyl group, an aryl group or a heterocyclic ring;
  • X is a chlorine or bromine atom.
  • halogen-containing compounds represented by the above-mentioned general formulas include, for example,
  • 2,2,2 tribromoethanol p-nitro a,a,a-tribromoacetophenone, w,w,w-tribromoquinalidine, 2-w,w,w-tribromomethyl- S-nitroquinoline, 2-w,w,w-trichloromethyl-6-nitrobenzothiazole, a,w,w-dibromomethyl-4-chloropyridine, hexabromodimethyl sulfoxide, tribromomethyl-phenyl sulfone, 4-nitrotribromomethyl-phenyl sulfone, and 2-tribromomethylsulfonyl benzothiazole.
  • the light-sensitive compositions of the present invention are composed of the above-mentioned specific polymers and photoactivators.
  • the present composition is dissolved in an organic solvent, and the solution is coated onto such a support as aluminum plate, zinc plate, copper plate, plastic film or sheet, or paper, and is then dried.
  • the organic solvent is ethanol, acetone, dioxane or methyl Cellosolve.
  • the coating liquid composition of the present invention is preferably 1-50 parts of polymer and 0.1-50 parts of photoactivator per parts by weight of solvent. However, the proportions of polymer and photoactivator may be greater or smaller than said proportions.
  • the polymer employed in the present invention has, in the aromatic ring, an active hydrogen in the paraposition to the amino group which has substituted the aromatic ring positioned on the side chain of the polymer.
  • the photoactivator which is a compound having a polyhalogenated methyl group, is such that when it is irradiated with light, the polyhalogenated methyl group yields a carbon free radical. Accordingly, when the present composition, in which said polymer and photoactivator are present together, is exposed to light, the polyhalogenated methyl group of the photoactivator is connected through a carbon-carbon to the active hydrogen-bearing carbon in the para-position to the amino group of the aromatic ring in the side chain of the polymer.
  • the polymer and the photoactivator are successively cross-linked with dye formation to give a faintly colored image.
  • the exposed material is treated with a solvent capable of dissolving the polymer, the exposed portion which is now composed of the crosslinked polymer in the form of a high molecular weight dye of the diphenylmethane or triphenylmethane type remains intact while the unexposed portion is removed olf, whereby a visible relief image is obtained.
  • novel photoresist-forming compositions of the present invention can also be color sensitized. That is, when the compounds having polyhalogenated methyl groups are incorporated with acridine dye, merocyanine dye or styryl dye, the compositions can be greatly improved in sensitivity.
  • compositions are free from dark reaction and, when the compositions are exposed to light through negatives, exposed portions which give faintly colored images greatly differ in solvent solubility from unexposed portions. Accordingly, when the compositions after exposure are treated with solvents capable of dissolving the polymers contained therein, visible relief images can be obtained without necessitating a dyeing step.
  • the thus obtained relief images are stable against etching liquids, so that they can be used for metal etch resist, offset printing, relief printing, etc.
  • EXAMPLE 1 0.5 g. of p-nitro-tribromomethyl-phenyl sulfone and 0.7 g. of a 1:1 copolymer of styrene and N-ethyl-N- phenylaminoethyl acrylamide are dissolved in 10 cc. of methyl ethyl ketone, and the solution is coated onto an aluminum plate and is then dried. On the thus treated aluminum plate, a negative is placed, and the composite is subjected to a vacuum printer and is exposed for 10 minutes to a 500 w. tungsten lamp to form a pale blue positive image. When this aluminum plate is rubbed with absorbent cotton impregnated with dioxane, unexposed portion is dissolved and removed to leave a deep blue positive relief image on the aluminum plate. This image is useful as a name plate or the like.
  • EXAMPLE 2 g. of poly (N-phenyl-N-acryloyl hydrazine) and 5 g. of hexabromodimethyl sulfone are dissolved in 80 cc. of dioxane, and the solution is coated onto a grained aluminum plate. Through a microfilm negative, this lightsensitive plate is exposed to light for minutes by means of an enlarging printer. Subsequently, the plate is lightly rubbed with absorbent cotton impregnated with dioxane, whereby unexposed portion is removed to leave a pink positive image. This image is thoroughly washed with water and is then treated with damping water. When this image is subjected to an offset printing machine, more than 1000 copies excellent in image reproduction can be obtained.
  • EXAMPLE 3 6 g. of 2-tribromomethylsulfonyl benzothiazole and 6 g. of a 4:6 copolymer (M.W. about 150,000) of N-ethyl- N-phenylamino ethyl methacrylate and methacrylic acid are dissolved in 100 cc. of dioxane. The solution is coated by means of a whirler onto a polished zinc plate and is then dried. Through a negative, the zinc plate is exposed by means of a fluorescent lamp, vacuum printer, whereby a pale blue positive image is obtained. When the image is developed with a 0.05% aqueous caustic soda solution, unexposed portion is removed and the image portion becomes deep blue. The plate is etched with a Dow etching liquid and is subjected, after water-washing, to a relief printing machine to obtain many clear copies.
  • M.W. about 150,000 M.W. about 150,000
  • EXAMPLE 4 5 g. of 2-w,w,w-tribromomethylquinoline and 5 g. of a vinylmethylether-maleic acid half-p-anilinophenylamide copolymer are dissolved in 100 cc. of methylethylketone. The solution is sprayed onto an iron plate coated with a white primer and is then dried. Through a negative, the iron plate is exposed to light by means of a drafting enlarger, whereby a brown image is formed on the white iron plate. This image can withstand flame cutting.
  • a photoresist-forming composition which comprises a photoactivator having a polychlorinated or polybrominated methyl group capable of forming a free radical by action of light and a homopolymer, or a copolymer with other vinyl monomer, of a monomer represented by the general formula wherein A is a hydrogen atom, a carboxylic acid or carboxylic acid amide group; X is COOCH CH R is a hydrogen atom or a lower alkyl group; R is a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group; and R and R are individual ly a hydrogen atom or a lower alkyl group, provided that in the case of the Formula II, R and R may form a heterocyclic ring together with nitrogen and the benzene ring, and R and R may form a naphthalene ring together with the benzene ring.
  • a vinyl monomer selected from styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methyl a-ch

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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)
US721621A 1967-04-25 1968-04-16 Photoresist-forming compositions Expired - Lifetime US3579343A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2598867 1967-04-25

Publications (1)

Publication Number Publication Date
US3579343A true US3579343A (en) 1971-05-18

Family

ID=12181077

Family Applications (1)

Application Number Title Priority Date Filing Date
US721621A Expired - Lifetime US3579343A (en) 1967-04-25 1968-04-16 Photoresist-forming compositions

Country Status (4)

Country Link
US (1) US3579343A (de)
DE (1) DE1772262C3 (de)
GB (1) GB1223632A (de)
NL (1) NL6805927A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859098A (en) * 1971-07-15 1975-01-07 Konishiroku Photo Ind Photoresist composition
US3902906A (en) * 1972-10-17 1975-09-02 Konishiroku Photo Ind Photosensitive material with quinone diazide moiety containing polymer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5315153A (en) * 1976-07-27 1978-02-10 Canon Inc Hologram

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859098A (en) * 1971-07-15 1975-01-07 Konishiroku Photo Ind Photoresist composition
US3902906A (en) * 1972-10-17 1975-09-02 Konishiroku Photo Ind Photosensitive material with quinone diazide moiety containing polymer

Also Published As

Publication number Publication date
DE1772262B2 (de) 1973-07-19
GB1223632A (en) 1971-03-03
DE1772262C3 (de) 1974-02-14
DE1772262A1 (de) 1971-11-11
NL6805927A (de) 1968-10-28

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