WO2011105011A1 - Procédé de formation d'image et composition photosensible utilisée dans ledit procédé - Google Patents

Procédé de formation d'image et composition photosensible utilisée dans ledit procédé Download PDF

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Publication number
WO2011105011A1
WO2011105011A1 PCT/JP2011/000572 JP2011000572W WO2011105011A1 WO 2011105011 A1 WO2011105011 A1 WO 2011105011A1 JP 2011000572 W JP2011000572 W JP 2011000572W WO 2011105011 A1 WO2011105011 A1 WO 2011105011A1
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Prior art keywords
image
exposure
photosensitive composition
light
acid
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Ceased
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PCT/JP2011/000572
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English (en)
Japanese (ja)
Inventor
英和 宮部
健太郎 大渕
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Filing date
Publication date
Application filed by Taiyo Holdings Co Ltd filed Critical Taiyo Holdings Co Ltd
Priority to JP2012501664A priority Critical patent/JP5916600B2/ja
Priority to KR1020127021921A priority patent/KR101844087B1/ko
Priority to CN201180010804.4A priority patent/CN102770805B/zh
Publication of WO2011105011A1 publication Critical patent/WO2011105011A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/08—Photoprinting; Processes and means for preventing photoprinting
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • the present invention relates to an image forming method and a photosensitive composition used in the method, and specifically, an image forming method capable of achieving both high contrast and excellent image stability without using a wet development method, and
  • the present invention relates to a photosensitive composition used in the method.
  • an image forming method by a photolithography method is widely used in the printing industry and the electronics industry because it is excellent in fine workability and suitable for mass production due to its good workability.
  • the wet development method using an alkaline aqueous solution has been widely used in the production of printed wiring boards, the formation of solder resists, and further the production of semiconductor-related members from the viewpoint of reducing the environmental load.
  • an image forming method based on photothermography using photocuring and heat melting is expected as a dry type image forming method free from the problem of waste from the viewpoint of reducing the environmental load.
  • a color developing type thermal recording method using coloring by a dye As one of the image forming methods by this method, there is a color developing type thermal recording method using coloring by a dye.
  • This method is further classified into two types: a diazo type thermal recording method using a coupling reaction of a diazo group and a leuco type thermal recording method using an electron donating dye such as a leuco dye.
  • the challenges of these methods include the compatibility of high contrast (high color development) and quality stability after image formation. Technologies related to quality stabilization after leuco-type image formation with excellent color development or image stability Many techniques relating to high contrast of a diazo type having superior properties have been studied (see Patent Documents 1 and 2).
  • the present invention has been made in view of the above-described problems of the prior art, and its purpose is a dry process capable of realizing high contrast properties, high image stability, and excellent coating film properties without using a developer.
  • An object of the present invention is to provide a type of image forming method and a photosensitive composition used in the method.
  • the inventors of the present invention separate the wavelength range of the exposure process for forming the contrast of the image from the wavelength range of the exposure process for photocuring, and color by performing multiple exposures. It has been found that the image can be fixed on the uncolored portion and the uncolored portion, and has been filed earlier.
  • the image forming method of this application is such that a colored part and an uncolored part are exposed to a coating film of a photosensitive composition containing a photoacid generator and an electron-donating dye at a plurality of different wavelength ranges.
  • both the colored and uncolored parts are photocured, and therefore, the contrast stability after image formation is excellent, which cannot be achieved by the conventional method. Compatibility with the physical properties of the coating film is also possible.
  • the inventors of the present invention have a new problem of inactivation of the photoacid generator remaining in the system after image formation depending on the application. Turned out to be. In other words, in a usage environment such as exposure to light such as sunlight, there is a problem that an acid is generated from the photoacid generator remaining in the coating film and an unintentional coloring (coloring) reaction occurs. It was.
  • the inventors of the present invention pay attention to the ultraviolet component of sunlight reaching the ground for the image stability after the image pattern formation, and consider the influence of the ultraviolet component on the image stability. It came to solve. That is, the inventors of the present invention, as a result of earnestly examining the separation region of the exposure wavelength in this method, in order to reduce the influence of the ultraviolet component of sunlight on the image stability, an exposure process for forming an image pattern It has been found that by setting the exposure wavelength range of A to less than 280 nm, and setting the exposure wavelength range of the exposure step B for photo-curing and image fixing to a wavelength range of 280 nm or more, the image stability can be drastically improved. It came to be completed.
  • the classification according to the wavelength of ultraviolet rays can be divided into near ultraviolet rays having a wavelength of 380 to 200 nm, far ultraviolet rays having a wavelength of 200 to 10 nm, and extreme ultraviolet rays having a wavelength of 10 to 1 nm.
  • Sunlight includes near ultraviolet rays having wavelengths of UVA (400 to 315 nm), UVB (315 to 280 nm), and UVC (end of 280 nm). Among them, only UVA and UVB pass through the ozone layer and reach the ground surface, and UVC is remarkably absorbed by substances and cannot pass through the atmosphere.
  • a photoacid generator that is active only at this wavelength is used for image pattern formation. This is characterized in that the image stability after the image pattern formation can be dramatically improved.
  • a coating film of a photosensitive composition containing a photoacid generator and an electron donating dye is partially exposed to light having a wavelength range of less than 280 nm.
  • the photosensitive composition used in the image forming method of the present invention comprises a photoacid generator that generates an acid by light having a wavelength range of less than 280 nm, an electron-donating dye, a photopolymerization initiator, It is preferable to contain a saturated group-containing compound.
  • the photopolymerization initiator is preferably one that can be sensitized with light in a wavelength region in which the photoacid generator does not generate an acid, that is, a wavelength region of 280 nm or more.
  • the image pattern is formed with a wavelength of less than 280 nm, which is the UVC wavelength range, which is the ultraviolet ray of sunlight that does not reach the ground, the image stability after the contrast is formed by the ultraviolet ray contained in the sunlight.
  • An effect peculiar to the present invention that it does not affect sex is manifested.
  • it can be used not only for conventional thermal recording paper and proof materials, but also for a wide range of applications, such as marking and shading in electronic substrates and display-related fields where harsh environments are used. Since it is possible to form an image on an aluminum wiring that cannot be dealt with due to a problem, it can be expected to be applied to MEMS applications such as a light receiving element and a displacement sensor.
  • a coating film of a photosensitive composition containing a photoacid generator that generates an acid by light in a wavelength region of less than 280 nm and an electron donating dye is exposed multiple times in different wavelength regions.
  • an image pattern (hereinafter also referred to as “image contrast” or the like) composed of a colored portion and an uncolored portion is formed and fixed, respectively.
  • the photoacid generator in the exposed portion generates an acid, and this acid and the electron donating dye react to develop a color, A colored part is formed.
  • the colored portion and the uncolored portion are fixed by photocrosslinking while suppressing the color development reaction by exposing the entire surface with light having a wavelength range of 280 nm or more where the photoacid generator does not generate acid. Fix the image contrast.
  • the order and number of steps are not particularly limited as long as the exposure wavelengths are separated.
  • the photosensitive composition contains an electron donating dye and a photoacid generator.
  • a photo-acid generator is used as an electron-accepting compound which shows the effect as a color developer with respect to the electron-donating dye which is a color former in a photosensitive composition.
  • the reaction between the acid generated from the photoacid generator during exposure and the electron donating dye, that is, the color is generated when the electron donating dye and the acid come into contact with each other in the coating film.
  • the exposure wavelength is separated at 280 nm, and the image is composed of a colored portion and an end colored portion by exposure at less than 280 nm (exposure step A). Contrast is formed. Therefore, the electron donating dye and the photoacid generator constituting the photosensitive composition of the present invention are compounds that develop color at less than 280 nm.
  • At least one kind can be appropriately selected from known compounds according to a desired color tone.
  • electron donating dyes can be used alone or in combination of two or more. Further, as a known means for improving the image stability, an electron donating dye may be encapsulated and used. In addition, these electron donating dyes may be blended with a photooxidant such as carbon tetrabromide for improving color developability and an additive such as quinolinol for preventing dark color development.
  • a photooxidant such as carbon tetrabromide for improving color developability
  • an additive such as quinolinol for preventing dark color development.
  • any known photoacid generator that generates an acid upon exposure in a wavelength range of less than 280 nm and does not generate an acid upon exposure in a wavelength range of 280 nm or more can be used.
  • the intensity (sensitivity) of the photosensitive wavelength region depends on the concentration, even if the bottom of the photosensitive wavelength region of the photoacid generator is about 280 nm, the amount is limited to 280 nm by limiting the blending amount. Such an intensity can be reduced, and it can be used as a photoacid generator that does not generate acid upon exposure in a wavelength region of 280 nm or longer.
  • photoacid generators examples include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, onium salts such as ferrocene, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethane compounds, and the like.
  • a disulfonylmethane compound etc. can be mentioned, It can use individually or in combination of 2 or more types.
  • triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluorobutanesulfonate, tris (4-methylphenyl) sulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium hexafluorophosphate, diphenyl-4- Methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate Bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis
  • the photosensitive wavelength range is shorter than 280 nm, such as bis (cyclohexylsulfonyl) diazomethane and bis (t-butylsulfonyl) diazomethane, It is more desirable to have little photosensitivity.
  • an acid generated from the photoacid generator is used as necessary for the purpose of improving color developability.
  • An acid proliferating agent that newly generates an acid and causes the acid to proliferate can be blended.
  • an acid is generated by the action of an acid generated from a photoacid generator, and the acid has an acid strength sufficient to act as a developer of an electron donating dye. If it does not specifically limit. Examples thereof include phenol derivatives and carboxylic acid derivatives, sulfonic acid esters and phosphoric acid esters having a protecting group such as t-butyl group and acetal group that can be dissociated by acid.
  • the exposure wavelength in the exposure step A is less than 280 nm
  • a known light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, or an excimer laser can be used as the light source.
  • a light source in which the exposure areas of the exposure process A and the exposure process B do not overlap is preferable.
  • an ArF excimer laser (193 nm), a KrBr excimer laser (207 nm), a KrCl excimer laser (223 nm), and a KrF excimer laser (248 nm) are more preferable.
  • the photopolymerization initiator constituting the photosensitive composition to be described later may be exposed to light to generate radicals, and photopolymerization of the ethylenically unsaturated group-containing compound may start. At the same time, a fixed fixing takes place.
  • the exposure step A when fixed fixing is performed simultaneously with the formation of the colored portion, it is preferable not to give priority to photopolymerization in order to prevent insufficient color development.
  • the photoacid generator is not subjected to oxygen inhibition unlike the photopolymerization initiator, there is an advantage that an acid can be stably supplied even in exposure under an oxygen atmosphere, so that a known vacuum contact method, etc.
  • the contact exposure method, non-contact exposure method such as proximity exposure, and direct imaging method can be freely selected.
  • a direct imaging method using a laser that does not require a photomask is more preferable.
  • the step of fixing the image contrast which will be described later, it is preferable to photopolymerize the entire coating film while suppressing the color development reaction, in order not to reduce the degree of photocrosslinking and physical properties of the cured coating film.
  • post-exposure heat treatment (Post Bake: PEB) can be performed in order to diffuse the acid generated by the exposure in the coating film.
  • PEB post-exposure heat treatment
  • known methods and conditions can be applied.
  • the exposure step B in order to fix the image contrast formed on the coating film of the photosensitive composition as described above, a wavelength region different from that in the exposure step A, that is, 280 nm or more where the uncolored portion does not develop color.
  • the entire coating film is cured by photocrosslinking.
  • the color-forming reaction of the electron-donating dye is an equilibrium reaction with the acid generated by the photoacid generator being exposed to light. Therefore, in order to ensure excellent image stability, the acid supply source should be cut off. Is essential, and it is preferable to suppress contact between the dye and the acid in the coating film by a crosslinking reaction.
  • the photoacid generator is not sensitized and exposure in the wavelength region of 280 nm or more where only the photopolymerization initiator is sensitized prevents the generation of acid related to color development and proceeds only photocrosslinking of the entire coating film.
  • Image contrast can be fixed.
  • it is particularly effective to select a photopolymerization initiator constituting the photosensitive composition. That is, as the photopolymerization initiator, a photopolymerization initiator having a photosensitive wavelength range that does not overlap with the photosensitive wavelength range of the photoacid generator, that is, a photosensitizer that is sensitive in a wavelength range of 280 nm or more where no acid is generated is used. preferable.
  • the photopolymerization initiator since it is an essential condition that the photoacid generator has a photosensitive region in a wavelength region where no acid is generated, the selection greatly depends on the combination with the photoacid generator. That is, the wavelength region where the photopolymerization initiator is sensitive and the wavelength region where the photoacid generator generates acid do not overlap with each other, or the wavelength region where the photopolymerization initiator is sensitive and the photoacid generation. There is no particular limitation as long as there is a photosensitive wavelength region possessed only by the photopolymerization initiator in addition to the wavelength region where the agent overlaps with the wavelength region where the acid is generated.
  • the photoacid generator uses an acid that generates an acid upon exposure in a wavelength range of less than 280 nm
  • the photoinitiator since the photoacid generator uses an acid that generates an acid upon exposure in a wavelength range of less than 280 nm, the photoinitiator generates a radical upon exposure in a wavelength range of 280 nm or more. Available.
  • photopolymerization initiators examples include known radical photopolymerization such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, oxime ester, and titanocene.
  • An initiator is used, and the photoacid generator used in combination uses a photopolymerization initiator that exhibits absorption and photoactivity in a wavelength region of 280 nm or more where photoactivity is not exhibited and has high photosensitivity in such a wavelength region. Is particularly preferred.
  • These photopolymerization initiators can be used alone or in combination of two or more.
  • These photopolymerization initiators can be used alone or in combination of two or more known photopolymerization accelerators such as benzoic acid type and tertiary amine type.
  • a known bimolecular complex starting system in which a dye such as coumarin, cyanine, squalium and a radical generator is combined can be used.
  • a combination of various dyes, a combination of a triazine compound as a radical generator and an aromatic ketone derivative as a dye, and the like are known.
  • Alkyl borates of pigments such as cyanine, rhodamine and safranin are also known as effective visible light initiators, and these known photopolymerization initiator systems can also be used.
  • the exposure step B for fixing the image contrast only the ethylenically unsaturated group-containing compound constituting the photosensitive composition and the photopolymerization initiator are reacted, and coloring in this step (of the photoacid generator) is performed.
  • the photocrosslinking of the entire coating film proceeds while suppressing (photosensitivity).
  • photosensitivity photosensitivity
  • the wavelength region used in the exposure step B is preferably a wavelength region in which the photoacid generator in the photosensitive composition does not generate an acid as described above. In order to prevent fogging of uncolored portions in this step, it is preferable to separate the exposure wavelength range as much as possible from the wavelength range in which the photoacid generator generates acid. Since the photoacid generator used in the present invention generates an acid in the UVC region, that is, a wavelength region of less than 280 nm, it may be a single wire or a mixed wire as long as it is longer in this step.
  • any light source capable of oscillating an active ray in a wavelength region according to the purpose of image fixing by photocrosslinking can be appropriately selected and used.
  • known low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps or metal halide lamps as well as known argon ion lasers, helium neon lasers, helium cadmium lasers, dye lasers, semiconductor lasers, YAG lasers, etc. Laser.
  • the separation method of the wavelength region in the exposure step B it is possible to directly separate with various lasers, and further, exposure is performed through a filter that cuts light of 300 nm or less, a film such as PET or PEN, or glass. As a result, even an exposure source with a wide oscillation wavelength distribution can easily separate the wavelength range.
  • the photosensitive composition used is not particularly limited as long as it is photosensitive and photocrosslinkable.
  • the above-described photopolymerization initiator and ethylenically unsaturated group-containing compound are used. It is preferable to contain.
  • Examples of the ethylenically unsaturated group-containing compound include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris- Polyhydric alcohols such as hydroxyethyl isocyanurate or polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide additions of these phenols Polyacrylates such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylo Le propane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half such as isophorone diisocyanate on the hydroxyl group of this epoxy acrylate resin.
  • a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate half such as isophorone diisocyanate on the hydroxyl group of this epoxy acrylate resin.
  • an epoxy urethane acrylate compound obtained by reacting a urethane compound.
  • Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
  • Such ethylenically unsaturated group-containing compounds can be used alone or in any combination of two or more depending on the intended use.
  • the acid generation efficiency may decrease due to exposure. Therefore, for example, since a compound having an aromatic group exhibits a large absorption in any of the regions less than 280 nm, by using a composition composed of a non-aromatic base resin, light having a short wavelength can be obtained. Transparency can be improved and sensitivity can be improved.
  • an organic solvent can be blended with the photosensitive composition used in the present invention as necessary for the purpose of adjusting the viscosity.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene Glycol ethers such as glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate , Propylene glycol monomethyl ether acetate
  • fillers such as inorganic fillers such as silica, alumina, talc, calcium carbonate, barium sulfate, and organic fillers such as acrylic beads and urethane beads
  • a coating additive such as a coupling agent, an antifoaming agent, and a leveling agent can be blended.
  • the coating film to be used for forming an image may be made of a photosensitive composition.
  • the photosensitive composition may be screen printed, curtain coated, or spray coated.
  • a film obtained by applying the composition on a substrate by a method such as a coating method, a roll coating method or a spin coating method, and drying by heating at a temperature of 60 to 80 ° C. for 15 to 60 minutes, or a dry film made of a photosensitive composition There are things that can be obtained using.
  • Exposure Process A image Contrast Forming Process
  • Exposure condition 1 As exposure step A, a KrF excimer laser oscillating at 248 nm was used as a light source, and patterning was performed on the test substrate at 1000 mJ / cm 2 . Thereafter, PEB treatment (post-exposure heat treatment) at 80 ° C. for 10 minutes was performed.
  • Exposure condition 2 In the exposure step A, a metal halide lamp was used as a light source, and the test substrate was irradiated with light of 1000 mJ / cm 2 in the entire light wavelength region through a negative mask on which a predetermined pattern was formed. Thereafter, PEB treatment (post-exposure heat treatment) at 80 ° C. for 10 minutes was performed.
  • Exposure Step B (Image Contrast Fixing Step) (3) Exposure condition 3 As the exposure process B, after the exposure in the exposure process A is completed, vacuum adhesion exposure is performed using a metal halide lamp through a PET film to cut the wavelength of 300 nm or less, and the entire coating film is irradiated with light at 1000 mJ / cm 2. Thus, a substrate (image forming substrate) having a coating film on which an image was formed was obtained.
  • Exposure condition 4 As exposure process B, after the exposure in exposure process A, a direct drawing exposure machine that oscillates a wavelength of 405 nm is used, and the entire coating film is irradiated with light at 1000 mJ / cm 2 to form a coating film on which an image is formed. (Image forming substrate) was obtained.
  • Image contrast The image contrast of the image forming substrates obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was visually confirmed.
  • the evaluation criteria are as follows. Colored ... Colored after exposure. No color development ... No color change before and after exposure.
  • Comparative Examples 1 to 3 using the conventional image forming method the image contrast can be formed, but it can be seen that the uncolored portion is not sufficiently cured, so that the image stability is poor and the image contrast cannot be maintained.
  • Comparative Example 4 using the image forming method previously proposed by the present inventors there was a tendency that the image stability was improved by using the composition 7 corresponding to the forming method, but this was insufficient. It can be seen that it is.
  • Comparative Example 5 using the image forming method of the present invention no image contrast can be formed because the composition corresponding to the image forming method according to the present invention is not used.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne un procédé de formation d'image de type à sec qui n'utilise pas de révélateur liquide et permet d'obtenir d'excellentes propriétés de contraste et de couchage et, en particulier, une stabilité de l'image. La présente invention concerne en outre une composition photosensible utilisée dans ledit procédé. Le procédé de formation d'image présenté est caractérisé en ce qu'il comprend : une étape d'exposition (A) qui forme un motif d'image en exposant partiellement un film en une composition photosensible à une lumière ayant une longueur d'onde inférieure à 280 nm, ladite composition photosensible contenant un générateur photo-acide et un colorant donneur d'électrons; et une étape d'exposition (B) qui fixe le motif d'image en exposant toute la surface à une lumière ayant une longueur d'onde supérieure ou égale à 280 nm.
PCT/JP2011/000572 2010-02-26 2011-02-02 Procédé de formation d'image et composition photosensible utilisée dans ledit procédé Ceased WO2011105011A1 (fr)

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CN102770805A (zh) 2012-11-07
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CN102770805B (zh) 2016-10-12
KR101844087B1 (ko) 2018-03-30
KR20120120334A (ko) 2012-11-01

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