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WO2006035807A1 - Materiau, dispositif et procede de formation de motif - Google Patents

Materiau, dispositif et procede de formation de motif Download PDF

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Publication number
WO2006035807A1
WO2006035807A1 PCT/JP2005/017825 JP2005017825W WO2006035807A1 WO 2006035807 A1 WO2006035807 A1 WO 2006035807A1 JP 2005017825 W JP2005017825 W JP 2005017825W WO 2006035807 A1 WO2006035807 A1 WO 2006035807A1
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WO
WIPO (PCT)
Prior art keywords
group
pattern forming
nucleus
meth
forming material
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.)
Ceased
Application number
PCT/JP2005/017825
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English (en)
Japanese (ja)
Inventor
Masanobu Takashima
Hirotaka Matsumoto
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.)
Fujifilm Holdings Corp
Fujifilm Corp
Original Assignee
Fujifilm Corp
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp, Fuji Photo Film Co Ltd filed Critical Fujifilm Corp
Priority to CN2005800401843A priority Critical patent/CN101124516B/zh
Priority to JP2006537769A priority patent/JPWO2006035807A1/ja
Publication of WO2006035807A1 publication Critical patent/WO2006035807A1/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
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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

  • the present invention relates to a pattern forming material suitable for dry film resist (DFR), etc., a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.
  • DFR dry film resist
  • a pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support has been used.
  • a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer.
  • the permanent pattern is formed by exposing to light, developing the light-sensitive layer to form a pattern after the exposure, and then performing an etching process or the like.
  • the pattern forming material is a compound having a phenolic hydroxyl group, an aromatic sensation, a heterocyclic ring, an imino group, or the like in the photosensitive resin composition for the purpose of improving storage stability or improving the resolution.
  • a polymerization inhibitor see Patent Documents 1 to 4.
  • nothing is disclosed about the point that the decrease in sensitivity can be suppressed by adding a sensitizer to the photosensitive resin composition (the photosensitive layer), and no highly sensitive dry resist film.
  • a pattern forming material capable of suppressing a decrease in sensitivity of the photosensitive layer and capable of forming a high-definition pattern
  • a pattern forming apparatus including the pattern forming material, and the pattern forming material are used.
  • a pattern formation method has not been provided yet, and further improvement and development are desired.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-268211
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-29399
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-4527
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-4528
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention provides a pattern forming material capable of effectively suppressing a decrease in sensitivity of a photosensitive layer and capable of forming a higher definition pattern, a pattern forming apparatus provided with the pattern forming material, and the pattern forming material. It is an object of the present invention to provide a pattern forming method used.
  • At least a photosensitive layer on a support and the support has a haze value of 5.0% or less, and the photosensitive layer has a dye having an acidic nucleus or a dye having a basic nucleus as a sensitizer. And at least one selected from a fluorescent brightening agent, and when the photosensitive layer is exposed and developed, the thickness of the exposed portion of the photosensitive layer is adjusted after the exposure and development.
  • the pattern forming material is characterized in that the minimum energy of light used for the exposure that is not changed in this way is 0.1 to 20 (mjZcm 2 ).
  • ⁇ 3> The pattern forming material according to any one of ⁇ 1> to ⁇ 2>, wherein the dye having an acidic nucleus is a mouth dashianine dye.
  • ⁇ 4> The pattern forming material according to any one of ⁇ 1> to ⁇ 3>, wherein the dye having an acidic nucleus has a maximum absorption wavelength power of 500 nm or less.
  • the dye having a basic nucleus is at least one selected from cyanine dyes, hemicyanine dyes, styryl dyes, and streptocyanine dye powers.
  • ⁇ 6> The pattern forming material according to any one of ⁇ 1> to ⁇ 5> above, wherein the basic nucleus is! /, Which is a benzoxazole nucleus, benzothiazole nucleus and indolenine nucleus .
  • ⁇ 7> The pattern forming material according to any one of ⁇ 1>, force ⁇ 6>, wherein the maximum absorption wavelength of the dye having a basic nucleus is 500 nm or less.
  • Nonionic nuclear force of the above ⁇ 8> which is at least one selected from a stilbene nucleus, a distyrylbenzene nucleus, a distyrylbiphenyl nucleus, a divinylstilbene nucleus, a vinylvirazoline nucleus, and a styrylpyrazoline nucleus
  • a stilbene nucleus which is at least one selected from a stilbene nucleus, a distyrylbenzene nucleus, a distyrylbiphenyl nucleus, a divinylstilbene nucleus, a vinylvirazoline nucleus, and a styrylpyrazoline nucleus
  • ⁇ 11> The pattern forming material according to any one of ⁇ 1> to ⁇ 10>, wherein the fluorescent whitening agent has a maximum absorption wavelength of 500 nm or less.
  • ⁇ 12> The pattern forming material according to any one of ⁇ 1> to ⁇ 11>, wherein the support has a total light transmittance of 86% or more.
  • ⁇ 13> The pattern forming material according to any one of ⁇ 1> to ⁇ 12>, wherein the haze value of the support and the light wavelength when determining the total light transmittance of the support are 405 nm. .
  • ⁇ 14> The pattern forming material according to any one of ⁇ 1> to ⁇ 13>, wherein the exposure wavelength force is 405 ⁇ m when the minimum energy amount of light used for exposure is obtained.
  • ⁇ 16> The pattern forming material according to any one of ⁇ 1> to ⁇ 15>, wherein the photosensitive layer contains a polymerization inhibitor, a binder, a polymerizable compound, and a photopolymerization initiator.
  • the above-mentioned 16 wherein the polymerizable compound has at least one selected from a compound containing a propylene oxide group, a compound containing an ethylene oxide group, a compound containing a urethane group, and a compound containing an aryl group. It is a pattern formation material of description.
  • the polymerizable compound contains a compound containing a propylene oxide group or a urethane group
  • the pattern forming material according to any one of the above ⁇ 16> forces and ⁇ 18>, comprising at least a compound and a compound containing an aryl group.
  • the polymerization inhibitor is selected from a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imino group, a compound having a heterocyclic ring substituted with an imino group, and a hindered amine compound.
  • ⁇ 21> The pattern forming material according to any one of the above items 16) to 20>, wherein the polymerization inhibitor is at least one selected from catechol, phenothiazine, phenoxazine, hindered amine, and derivatives thereof. .
  • ⁇ 23> The pattern forming material according to any one of ⁇ 16>, ⁇ 22>, wherein the binder has an acidic group.
  • ⁇ 24> The pattern forming material according to any one of ⁇ 16> to ⁇ 23>, wherein the binder contains a bull copolymer.
  • ⁇ 26> The pattern forming material according to any one of ⁇ 16>, ⁇ 25>, wherein the binder has an acid value of 70 to 250 mgKOHZg.
  • ⁇ 27> The pattern forming material according to any one of ⁇ 16> and ⁇ 26>, wherein the binder has an IZO value of 0.30 to 0.70.
  • the polymerizable compound is at least one polymerizable compound having two polymerizable groups in the molecule, at least one polymerizable compound having three or more polymerizable groups in the molecule, and
  • the photopolymerization initiator is a halogenated hydrocarbon derivative, hexaryl biimidazole, an oxime derivative, an organic peroxide, a thio compound, a ketone compound, or an aromatic onium salt.
  • the pattern forming material according to any one of the above 16> Karaku 29> which includes at least one kind selected for meta-octane power.
  • Photopolymerization initiator power The pattern forming material according to any one of ⁇ 16> to ⁇ 30> above, which contains hexaryl biimidazole.
  • Pattern forming material force The pattern forming material according to any one of the above items 1> force ring 34>, which is long and wound in a roll shape.
  • ⁇ 36> The pattern forming material according to any one of ⁇ 1>, ⁇ 35>, which has a protective film on the photosensitive layer in the pattern forming material.
  • a protective film on the photosensitive layer wherein the protective film contains at least one selected from polypropylene resin, ethylene-propylene copolymer resin, polyethylene resin and polyethylene terephthalate resin 1
  • the pattern forming material according to any one of ⁇ 1> to ⁇ 37>, comprising: a light irradiation unit capable of irradiating light; and modulating light from the light irradiation unit,
  • a pattern forming apparatus comprising at least light modulation means for exposing the photosensitive layer in the pattern forming material.
  • the pattern forming apparatus described in 38> thus, the light irradiation means irradiates light toward the light modulation means.
  • the light modulation means modulates light received from the light irradiation means.
  • the light modulated by the light modulation means is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a highly precise pattern is formed.
  • the light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the light generated from the light irradiation means is generated by the pattern signal generation means.
  • the pattern forming apparatus according to ⁇ 38> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
  • the light modulation means includes n pixel portions, and forms any less than n of the pixel portions continuously arranged from the n pixel portions.
  • the pattern forming apparatus according to any one of ⁇ 38> to ⁇ 39>, which can be controlled according to pattern information.
  • n in the light modulation unit Light of the light irradiation means power is modulated at high speed by controlling any less than n pixel parts arranged continuously from the individual picture element parts according to the pattern information.
  • ⁇ 41> The pattern forming apparatus according to any one of ⁇ 38> and ⁇ 40>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 42> The pattern forming apparatus according to ⁇ 41>, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 44> The pattern forming apparatus according to any one of the above ⁇ 38> and ⁇ 43>, wherein the light irradiation means can synthesize and irradiate two or more lights.
  • the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth.
  • the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses and couples the laser beams irradiated with the plurality of laser forces, respectively, to the multimode optical fiber.
  • the pattern forming device according to any one of the above 38> Karaku 44>, which has In the pattern forming apparatus according to ⁇ 45>, the light irradiating means can collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
  • a pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of ⁇ 1> to ⁇ 37>.
  • exposure is performed on the pattern forming material. For example, by developing the photosensitive layer thereafter, a highly precise pattern is formed.
  • the control signal is generated based on the pattern information to be formed, and the control signal is generated using light modulated in accordance with the control signal.
  • This is a pattern forming method.
  • a control signal is generated based on the pattern formation information to be formed, and light is modulated in accordance with the control signal.
  • the exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed.
  • the light modulated by the light modulation means passes through the aspheric surface in the microlens array, so that the aberration due to the distortion of the exit surface in the pixel portion is corrected.
  • the as a result distortion of an image formed on the pattern forming material is suppressed, and exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
  • ⁇ 52> The pattern forming method according to ⁇ 51>, wherein the aspherical surface is a toric surface.
  • the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and the image formed on the noturn forming material is imaged. Is efficiently suppressed.
  • the pattern forming material is exposed with extremely high precision. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 53> The pattern forming method according to any one of ⁇ 46>, ⁇ 52>, wherein exposure is performed through an aperture array.
  • the extinction ratio is improved by performing exposure through the aperture array.
  • the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 54> The pattern forming method according to any one of ⁇ 46>, ⁇ 53>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • the exposure is performed at a high speed by performing the exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • ⁇ 56> The pattern forming method according to any one of ⁇ 46> to ⁇ 55>, wherein the photosensitive layer is developed after the exposure.
  • the photosensitive layer is developed to obtain a high-definition pattern. Is formed.
  • ⁇ 58> The pattern formation method according to ⁇ 57>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
  • the present invention it is possible to solve conventional problems, to effectively suppress a decrease in sensitivity of the photosensitive layer, and to form a pattern with higher definition, and A pattern forming apparatus including the pattern forming material and a pattern forming method using the pattern forming material can be provided.
  • FIG. 1 is an example of a partially enlarged view showing the configuration of a digital micromirror device (DMD).
  • DMD digital micromirror device
  • FIG. 2A is an example of an explanatory diagram for explaining the operation of the DMD.
  • FIG. 2B is an example of an explanatory diagram for explaining the operation of the DMD.
  • FIG. 3A is an example of a plan view showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined.
  • FIG. 3B is an example of a plan view showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined.
  • FIG. 4A is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 4B is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 5 is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by one scanning by a scanner.
  • FIG. 6A is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by a plurality of scans by a scanner.
  • FIG. 6B is an example of a plan view for explaining an exposure method for exposing a photosensitive layer by a plurality of scans by a scanner.
  • FIG. 7 is an example of a schematic perspective view showing an appearance of an example of a pattern forming apparatus.
  • FIG. 8 is an example of a schematic perspective view showing the configuration of the scanner of the pattern forming apparatus.
  • FIG. 9A is an example of a plan view showing an exposed region formed in the photosensitive layer.
  • FIG. 9B is an example of a diagram showing an arrangement of exposure areas by each exposure head.
  • FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means.
  • FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG.
  • FIG. 12 shows an example of a controller that controls DMD based on pattern information.
  • FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system.
  • FIG. 13B is an example of a plan view showing an optical image projected onto the exposure surface when a microlens array or the like is not used.
  • FIG. 13C is an example of a plan view showing an optical image projected onto an exposed surface when a microlens array or the like is used.
  • FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines.
  • FIG. 15A is an example of a graph showing distortion of the reflecting surface of the micromirror in two diagonal directions of the mirror.
  • FIG. 15B is an example of a graph showing distortion of the reflecting surface of the micromirror similar to that in FIG. 15A in two diagonal directions of the mirror.
  • FIG. 16A is an example of a front view of a microlens array used in the pattern forming apparatus.
  • FIG. 16B is an example of a side view of the microlens array used in the pattern forming apparatus.
  • FIG. 17A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 17B is an example of a side view of a microlens constituting the microlens array.
  • FIG. 18A is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 18B is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 19A is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention.
  • FIG. 19B is an example of a diagram showing the same simulation results as in FIG. 19A but at different positions.
  • FIG. 19C is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 19D is an example of a diagram showing a simulation result similar to FIG. 19A at another position.
  • FIG. 20A is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method.
  • FIG. 20B is an example of a diagram showing the same simulation results as in FIG. 20A but at different positions.
  • FIG. 20C is an example of a diagram illustrating the simulation result similar to FIG. 20A at another position.
  • FIG. 20D is an example of a diagram showing a simulation result similar to FIG. 20A at another position.
  • FIG. 21 is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 22A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 22B is an example of a side view of a microlens constituting a microlens array.
  • FIG. 23A is a cross-sectional view of the condensing state by the microlens of FIGS. 22A and 22B It is an example of the schematic shown about the inside.
  • FIG. 23B is an example of a schematic diagram showing another cross section of the example of FIG. 23A.
  • FIG. 24A is an example of an explanatory diagram of the concept of correction by the light quantity distribution correcting optical system.
  • FIG. 24B is an example of an explanatory diagram of the concept of correction by the light quantity distribution correcting optical system.
  • FIG. 24C is an example of an explanatory diagram of the concept of correction by the light quantity distribution correction optical system.
  • FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means is a Gaussian distribution and the light amount distribution is not corrected.
  • FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system.
  • FIG. 27A is a perspective view showing the configuration of the fiber array light source
  • FIG. 27A (B) is an example of a partially enlarged view of FIG. 27A (C)
  • FIG. (D) is an example of a plan view showing an array of light emitting points in the laser emitting section.
  • FIG. 27B is an example of a front view showing an array of light emitting points in a laser emitting section of a fiber array light source.
  • FIG. 28 is an example of a diagram showing a configuration of a multimode optical fiber.
  • FIG. 29 is an example of a plan view showing a configuration of a combined laser light source.
  • FIG. 30 is an example of a plan view showing a configuration of a laser module.
  • FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 30.
  • FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. 30.
  • FIG. 33 is an example of a perspective view showing a configuration of a laser array.
  • FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser.
  • FIG. 34B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 34A are arranged in an array.
  • FIG. 35 is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 36A is an example of a plan view showing another configuration of the combined laser light source.
  • FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. 36A.
  • FIG. 37A shows the depth of focus in the conventional exposure apparatus and the pattern forming method of the present invention.
  • FIG. 3 is an example of a cross-sectional view along an optical axis showing a difference from a depth of focus by a (pattern forming device).
  • FIG. 37B is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.
  • the pattern forming material of the present invention has at least a photosensitive layer on a support, the haze value of the support is 5.0% or less, and the photosensitive layer has a dye having an acidic nucleus as a sensitizer.
  • a dye having a basic nucleus, and at least one selected from a fluorescent brightening agent and when the photosensitive layer is exposed and developed, the thickness of the exposed portion of the photosensitive layer is determined by the exposure and development.
  • the minimum energy of light used for the exposure which is not changed later is 0.1 to 20 (miZcm 2 ).
  • the thickness of the exposed portion of the photosensitive layer is not changed before and after the exposure and development.
  • it is ⁇ 20 (miZcm 2 )
  • it can be appropriately selected according to the purpose for which there is no particular restriction.For example, 0.5 to 10 (mjZcm 2 ) is preferred, but 1 to 8 (mjZcm 2 ) is preferred. More preferable.
  • capri may be generated in the processing step. If it exceeds 20 (mjZcm 2 ), the time required for exposure becomes longer and the processing speed is increased. May slow down.
  • the minimum energy of light used in the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. . The thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer has not changed due to exposure and development.
  • a method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.
  • Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.
  • the support can be appropriately selected depending on the purpose without particular limitation if the haze value is 5.0% or less, but the photosensitive layer can be peeled off and has good light transmittance. Some are preferred and the surface smoothness is more favorable.
  • the haze value of the support is preferably 5.0% or less with respect to 405 nm light, more preferably 4.0% or less, and 3.0% or less. Is particularly preferred. When the haze value exceeds 5.0%, the amount of light scattering in the photosensitive layer increases, and the resolution when obtaining a fine pitch may be reduced.
  • the total light transmittance of the support with respect to 405 nm light is preferably 86% or more, more preferably 87% or more.
  • the method for measuring the haze value and total light transmittance is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the methods described below.
  • the method for measuring the total light transmittance can be appropriately selected according to the purpose for which there is no particular limitation. For example, an integrating sphere and a spectrophotometer capable of emitting light of 405 ⁇ m (for example, Shimadzu Corporation) And UV-2400) manufactured by the company.
  • the parallel light transmittance is measured in the same manner as the measurement method of the total light transmittance except that the integrating sphere is not used.
  • the total light transmittance, the parallel light transmittance, or (4) The following calculation formula, the diffuse light transmittance Z, the total light transmittance X 100, and the force can also determine the haze value.
  • the wavelength for obtaining the total light transmittance and the haze value is 405 nm, and the thickness of the measurement sample at that time is 16 ⁇ m.
  • the support may have at least one surface coated with inert fine particles.
  • the inactive fine particles are preferably applied on the surface opposite to the surface on which the photosensitive layer is formed.
  • Examples of the inert fine particles include crosslinked polymer particles; calcium carbonate, phosphoric acid strength, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, fluoride power, lithium fluoride, lithium fluoride, zeolite, sulfur Inorganic particles such as molybdenum; organic particles such as hexamethylene bisbehenamide, hexamethylene bisstearylamide, N, N, monodistearyl terephthalamide, silicone, calcium oxalate; precipitated particles formed during polyester polymerization Of these, silica, calcium carbonate, and hexamethylenbisbehenamide are preferred.
  • the precipitated particles are, for example, particles precipitated in a reaction system by polymerizing a system using an alkali metal or alkaline earth metal compound as a transesterification catalyst by a conventional method. It may be the one precipitated by adding terephthalic acid during the polycondensation reaction.
  • phosphoric acid trimethyl phosphate, triethyl phosphate, tributyl phosphate, acidic ethyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, etc.
  • One or more of the phosphorus compounds may be present.
  • the average particle size of the inert fine particles is preferably 0.01-2.0 ⁇ m, more preferably 0.02-1.5 m force S, 0.03: L 0 m force S More preferably, 0.04 to 0.5 m force S is particularly preferable.
  • the pattern forming material may have poor transportability.
  • the inert fine particles are contained in a large amount. By doing so, the haze value of the support may increase.
  • the average particle size of the inert fine particles exceeds 2.0 m, the resolution is caused by scattering of exposure light. Force S may decrease.
  • the method for applying the inert fine particles can be appropriately selected depending on the purpose without particular limitation.
  • a method of applying a coating solution containing the inert fine particles by a known method after the production of the synthetic resin film as the support is mentioned.
  • the synthetic resin containing the inert fine particles may be melted and discharged from a die cutter to be molded on a synthetic resin film to be the support. Further, it may be formed by the method described in JP-A-2000-221688.
  • the thickness of the coating layer containing the inert fine particles in the support is from 0.02 to 3.
  • the synthetic resin film used as the support is preferably a transparent film, for example, a biaxially stretched polyester film, which is preferably a polyester resin film.
  • polyester resin examples include polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate copolymer, poly (meth) acrylate alkyl ester, polyethylene 2,6 naphthalate, polytetramethylene terephthalate, poly Examples include tetramethylene 1, 2, 6 naphthalate. These may be used alone or in combination of two or more.
  • Examples of the resin other than the polyester resin include polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polychlorinated butyl, polybutyl alcohol, polycarbonate, polystyrene, cellophane, and polysalt vinylidene copolymer.
  • Examples include coalescides, polyamides, polyimides, butyl chloride butyl acetate copolymers, polytetrafluoroethylene, polytrifluoroethylene, cellulosic resin, and nylon resin. These may be used alone or in combination of two or more.
  • the synthetic resin film may be composed of one layer or may be composed of two or more layers. In the case of comprising two or more layers, it is preferred that the inert fine particles are contained in a layer located farthest from the photosensitive layer.
  • the synthetic resin film has two characteristics from the viewpoint of mechanical strength characteristics and optical characteristics.
  • An axially stretched polyester film is preferred.
  • the biaxial orientation method of the biaxially stretched polyester film can be appropriately selected according to the purpose without particular limitation.
  • the polyester resin is melt-extruded into a sheet shape, rapidly cooled to form an unstretched film, and when the unstretched film is biaxially stretched, the stretching temperature is 85 to 145 ° C., stretching in the machine and transverse directions. It can be prepared by setting the magnification to 2.6 to 4.0 times and heat-fixing the film after biaxial stretching as necessary at 150 to 210 ° C.
  • the biaxial stretching is a sequential biaxial stretching method in which an unstretched film is stretched in the longitudinal direction or the transverse direction to form a uniaxially stretched film, and then the -axially stretched film is stretched in the transverse direction or the longitudinal direction.
  • a simultaneous biaxial stretching method may be used in which the unstretched film is stretched simultaneously in the machine direction and the transverse direction.
  • the biaxially stretched film can be further stretched in at least one of the longitudinal direction and the transverse direction as necessary.
  • the thickness of the support may be appropriately selected depending on the purpose for which there is no particular limitation.
  • Force f row; t is a force of 2-150 ⁇ m, S girls, 5-: LOO ⁇ m force SJ-like girls, 8-50 ⁇ m force S Particularly preferred.
  • the shape of the support can be appropriately selected depending on the purpose without any particular limitation, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include those having a length of 10 m to 20, OOOm.
  • the photosensitive layer contains at least one selected from a dye having an acidic nucleus, a dye having a basic nucleus, and a fluorescent brightener as a sensitizer, and includes a polymerization inhibitor, a binder, a polymerizable compound, and photopolymerization initiation. In addition, it may contain other components appropriately selected as necessary.
  • the pattern forming material of the present invention when exposing and developing the photosensitive layer, improves the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer before and after the development. Therefore, it is particularly preferable to use the sensitizer together.
  • the sensitizer together for example, the sensitivity of the photosensitive layer is adjusted to 0.1 to 20 (mjZcm Z ) can also be adjusted very easily.
  • the sensitizer is not particularly limited as long as it is a dye having an acidic nucleus, a dye having a basic nucleus, or a fluorescent brightener (for example, visible light, ultraviolet light, and visible light). It can be selected appropriately according to the optical laser or the like.
  • the maximum absorption wavelength of the sensitizer is preferably 500 nm or less, more preferably 480 nm or less, and particularly preferably 450 nm or less. Better ,.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • the dye having an acidic nucleus examples include merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, oral dacyanine dyes, and oxonol dyes.
  • merocyanine dyes and oral dacyanine dyes are preferable. More preferred are merocyanine dyes.
  • the acidic nucleus is, for example, “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., 1977. , Chapter 8, “Sensitizing and Desensitizing Dyes”, U.S. Pat.Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862 4, 0 02, 480, 4, 925, 777, JP-A-3-167546, and the like.
  • the end of the methine bond is malono-tolyl, alkanesulfonylacetonitrile, cyanomethylbenzofuranyl ketone, cyanomethylphenylketone, malonate, and isylaminomethyl. It is preferably a group such as an active methylene compound such as a substituted ketone.
  • nitrogen-containing heterocycle that preferably forms a nitrogen heterocycle
  • examples of the nitrogen-containing heterocycle that preferably forms a nitrogen heterocycle include 2- Pyrazolin-5-one, pyrazolidine-3, 5-dione, imidazoline-5-one, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazolin-5 -One, 2-thioxazoline-2, 4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2, 4-dione, rhodanine, thiazolidin-2, 4 -Dithione, isorhodanine, indan-1,3-dione, thiophen-3-one,
  • Examples of the acidic nucleus include the acidic heterocyclic rings shown below.
  • Specific examples of the dye having an acidic nucleus include compounds represented by the following structural formulas (1) to (8).
  • I ⁇ to L 4 represent a methine group.
  • ⁇ represents 0 or 1.
  • Z and Z represent an atomic group necessary for forming a nitrogen-containing heterocycle.
  • the ring may be either an aromatic ring or a non-aromatic ring.
  • An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
  • R and R each represents an alkyl group, an aryl group, or a heterocyclic group.
  • M represents a counter ion for charge balance
  • m represents a number of 0 or more necessary to neutralize the charge of the molecule.
  • R, R, Z, Z, and L to L are cations when the structural formula (1) is a cationic dye.
  • the structural formula (1) is a betaine dye, it has one cationic substituent and one anion substituent, and the structural formula (1) is a non-one dye. In the case of having no cationic substituent and no ionic substituent.
  • the cationic dye may be any dye as long as the charge of the dye is cationic except for the counter ion, but is preferably a dye having no ionic substituent.
  • the terion dye may be any terion other than the counter ion, as long as the ionic dye has a terion charge. is there.
  • the above-mentioned betaine dye is a dye that has a charge in the molecule but forms an inner salt, and the molecule has no charge as a whole.
  • the non-ion dye is a dye having no charge in the molecule.
  • a substituent having a negative charge include, for example, proton-dissociative acid group dissociated 90% between the P H5 ⁇ 8.
  • a sulfo group and a carboxyl group More preferred are a sulfo group and a carboxyl group. Particularly preferred is a sulfo group.
  • the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.
  • R is preferably a group having an aromatic ring.
  • L to L represent methine groups.
  • Z and Z represent an atomic group necessary for forming a nitrogen-containing heterocycle.
  • the ring may be either an aromatic ring or a non-aromatic ring.
  • An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
  • R and R each represents an alkyl group, an aryl group, or a heterocyclic group.
  • M represents the counter ion for charge balance
  • m is necessary to neutralize the charge of the molecule 0
  • At least one of R and R has a terionic substituent.
  • nitrogen-containing heterocycle examples include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenin.
  • Nucleus eg, 3,3-dimethylindolenine
  • imidazoline nucleus imidazole nucleus
  • benzimidazole nucleus 2-pyridin nucleus
  • 4-pyridine nucleus 2-quinoline nucleus
  • 4-quinoline nucleus 1-isoquinoline nucleus
  • 3- Isoquinoline nucleus imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, Forces that can include tolazole nucleus, pyrimidine nucleus, etc.
  • benzothiazole nucleus Preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindolenine), benzimidazole nucleus, 2 pyridine nucleus, 4 pyridine nucleus, 2 quinoline nucleus, 4 quinoline nucleus, 1 isoquinoline nucleus, and 3 isoquinoline nucleus, such as benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindole nucleus) Renin), and benzoxazole nucleus, benzothiazole nucleus, and benzoxazole nucleus, and benzothiazole nucleus, more preferred are benzoxazole nucleus, benzothiazole nucleus, and benzoxazole nucleus.
  • the substituent represented by V is not particularly limited.
  • a halogen atom for example, chlorine, bromine, iodine, fluorine
  • a mercapto group for example, a cyano group
  • carboxy group Groups for example, phosphate groups, sulfo groups, hydroxy groups, strong rubamoyl groups (eg methylcarbamoyl, ethylcarbamoyl, morpholinocarbole), sulfamoyl groups (eg methylsulfamoyl, ethylsulfamoyl, piberidinosulfol) ), -Toxic groups, alkoxy groups (eg methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), aryloxy groups (eg phenoxy, p-methylphenoxy, p chlorophenoxy, naphthoxy),
  • alkoxy groups eg methoxy, ethoxy
  • Sulfo-amino groups for example, methane sulfo-amino-containing ethane sulfo-amino groups, benzene sulfo-amino groups
  • amino groups substituted amino groups (for example, methyl-amino-containing dimethylamino, benzylamino-containing amino-lino, diphenylamino), ammonia Group (eg trimethylammonium, triethylammonium), hydrazino group (eg trimethylhydrazino group), ureido group (eg ureido group, N, N dimethylureido group), imide group (eg succinimide group), Alkylthio groups (e.g.
  • arylthio groups for example, phenylthio, p-methylphenolthio, p-chlorophenolthio, 2-pyridylthio, naphthylthio
  • alkoxycarbonyl groups for example, methoxycarbon, ethoxycarbonyl, 2- Benzyloxycarbonyl
  • aryloxycarbonyl Groups eg phenoxycarbol
  • unsubstituted alkyl groups eg methyl, ethyl, propyl, butyl
  • substituted alkyl groups eg hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylamino
  • Methyl and also here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (e.g.
  • substituted alkyl group ⁇ substituted or unsubstituted aryl groups (for example, phenyl, naphthyl, ⁇ -carboxyphenyl, p--trophenyl, 3, 5 — Dichlorophole, p-cyanophyl, m-fluorophenol, ⁇ -tolyl) and substituted or unsubstituted heterocycles (eg pyridyl, 5 —Methylpyridyl, chael, furyl, morpholine-containing tetrahydrofurfuryl), etc., among them, alkyl groups, aryl groups, alkoxy groups, halogen atoms, aromatic ring condensation, sulfo groups, carboxy groups, A hydroxy group is preferred.
  • aryl groups for example, phenyl, naphthyl, ⁇ -carboxyphenyl, p--trophenyl, 3, 5 — Dichlorophole, p-cyanophy
  • a structure in which a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a quinoline ring) is condensed can also be used.
  • V is further substituted! /, May! /.
  • Z in the structural formula (1) and the substituent V on the Z in the structural formula (2) may be aromatic.
  • An aromatic group and aromatic ring condensation are preferred.
  • aromatic group examples include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic fused ring structure in which a hydrocarbon aromatic ring and a polycyclic fused ring obtained by condensing heteroaromatic rings, or a combination of an aromatic hydrocarbon ring and an aromatic heterocycle. It may be substituted with the substituent V or the like.
  • the aromatic rings contained in the aromatic group include benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, Pyridazine, indolizine, indole, benzofuran, benzothiene phen, isobenzofuran, quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthorin, thianthrene, chromene , Xanthene, phenoxathiin, phenothiazine, phenazine and the like.
  • Such as hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, 2-thioxazoline-2,4-dione, thiazolidine-2,4-dione, oral danine, Thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid include hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, and barbituric acid.
  • 2-thiohydantoin, 4-thiohydantoin, 2-oxazolin-5-one, rhodanone, and barbituric acid are more preferred! /.
  • R and R in the structural formula (1) and R and R in the structural formula (2) are alkyl groups
  • an aryl group and a heterocyclic group Specifically, for example, an unsubstituted alkyl group having 1 to 18 carbon atoms (preferably 1 to 7 and particularly preferably 1 to 4) (for example, methyl, ethyl) , Propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups of 1 to 18 carbon atoms (preferably 1 to 7, particularly preferably 1 to 4) (for example, as substituents Examples thereof include an alkyl group substituted with V.
  • an aralkyl group for example, benzyl, 2-phenylethyl
  • an unsaturated hydrocarbon group for example, aralkyl group
  • a hydroxyalkyl group for example, 2 hydroxyethyl, 3 hydroxypropyl
  • a carboxyalkyl group for example, carboxy Methyl, 2 carboxyethyl, 3 carboxypropyl, 4 carboxybutyl
  • alkoxyalkyl groups eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl
  • aryloxyalkyl groups eg, 2-phenoxychetyl, 2- (1 naphthoxy) ethyl
  • alkoxycarbonylalkyl groups eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl
  • aryl-polyalkylalkyl groups eg 3-phenoxycarbonylpropyl
  • acylalkyls A group e
  • An unsubstituted heterocyclic group having a number of 1 to 20 (preferably 3 to 10, more preferably 4 to 8) e.g., 2 furyl group, 2 chel group, 2 pyridyl group, 3 pyrazolyl group, 3 isoxazolyl group, 3 isothiazolyl group
  • a substituted heterocyclic group having 1 to 20 carbon atoms preferably 3 to 10, more preferably 4 to 8) (for example, a heterocyclic group substituted with the above substituent V)
  • the aromatic ring 2 is preferably a group having an aromatic ring.
  • the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, which further include a hydrocarbon aromatic ring, a polycyclic condensed ring obtained by condensing heteroaromatic rings, and an aromatic hydrocarbon ring. It may be a polycyclic fused ring combined with an aromatic heterocycle, which may be substituted with the substituent V or the like.
  • the group having an aromatic ring can be represented by Lb-A. Where Lb is a single bond
  • A represents an aromatic group.
  • It is preferably composed of an atom or atomic group containing at least one of carbon atom, nitrogen atom, sulfur atom and oxygen atom.
  • the linking group is an alkylene group (for example, methylene, ethylene, propylene, Butylene, pentylene;), arylene groups such as' phenylene, naphthylene;), anoregenylene groups (eg, etylene, probelene), alkylene groups (eg, ethylene, propylene), amides Group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfol group, sulfier group, thioether group, ether group, carbo ol group, —N (V a) one (Va is a hydrogen atom, or Represents a monovalent substituent, such as V described later), a heterocyclic divalent group (for example, 6 chloro-1,3,5 triazine-2,4 diyl group, pyrimidine) 2, 4 diyl group, quinoxaline 2,3 diyl group) or a combination group having 0 or more and
  • the linking group may further contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring) that may have a substituent represented by V.
  • Examples of the linking group include an alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, butylene), an arylene group having 6 to 10 carbon atoms (for example, phenylene, naphthylene), and carbon.
  • Alkylene group having 2 to 10 carbon atoms for example, etylene, probelene
  • Alkylene group having 2 to 10 carbon atoms for example, ethylene, propylene
  • ether group preferably an amide group, an ester group, a sulfoamide group, or a sulfonic acid ester group is preferably a divalent linking group having 1 to 10 carbon atoms. These may be substituted with V.
  • the La is a linking group even though energy transfer or electron transfer is caused by a through-bond interaction.
  • Through-bond interaction includes tunnel interaction, super-exchange interaction, etc. Among them, through-bond interaction based on super-exchange interaction is preferred. Through-bond and super-exchange interactions are described in the Chemical 'review (Chem. By Shammai suprar).
  • R and R in the structural formula (1) include hydrocarbon aromatic rings.
  • alkyl group include an aralkyl group (for example, benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), an aryloxyalkyl group (for example, 2-phenoloxyl, 2- (1— Naphthoxy) ethyl, 2- (4 biphenyl-ethyl) ethyl, 2- (o, m or p halophenoxy) ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), aryloxycarbonylalkyl
  • the groups (3 phenoxycarbopropyl, 2- (1-naphthoxycarbo) ethyl) and the like are preferred.
  • alkyl group having a heteroaromatic ring examples include 2- (2 pyridyl) ethyl, 2- (4 pyridyl) ethyl, 2 1- (2-furyl) ethyl, 2- (2-chelyl) ethyl, 2- (2-Pyridylmethoxy) ethyl is preferred.
  • hydrocarbon aromatic group 4-methoxyphenyl, phenyl, naphthyl, biphenyl and the like are preferable.
  • heteroaromatic group a 2-chell group, 4-chloro 1-chenyl, 2-pyridyl, 3-pyrazolyl and the like are preferable.
  • alkyl group having the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring is more preferable than the alkyl group having the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring or heteroaromatic ring. Especially preferred.
  • R and R in the structural formula (2) at least one group having an aromatic ring is preferable.
  • the aromatic ring examples include a hydrocarbon aromatic ring and a heteroaromatic ring, which further include a hydrocarbon aromatic ring and a polycyclic condensed ring obtained by condensing heteroaromatic rings, or an aromatic hydrocarbon. It may be a polycyclic fused ring in which a ring and an aromatic heterocycle are combined, and may be substituted with the substituent V or the like. As the aromatic ring, those shown as examples of the aromatic ring in the description of the aromatic group are preferable.
  • the group having an aromatic ring can be represented by LcA. Where Lc is a single connection
  • A represents an aromatic group.
  • Lc linking group
  • Preferable examples include the linking group described for La and the like. Preferred as an aromatic group of A
  • At least one of Lc or A At least one of Lc or A
  • the ionic substituent is substituted.
  • an aralkyl group substituted with any of a sulfo group, a phosphate group, and a carboxyl group for example, 2 sulfobenzyl, 4-acetate
  • An aryloxyalkyl group substituted by either an acid group or a carboxyl group eg, 2- (4
  • alkyl groups having a heteroaromatic ring examples include 3- (2 pyridyl) 3 sulfopropyl, 3- (2 furyl) -3-sulfopropyl, 2- (2 chael) -2-sulfopropyl pills, etc. Is preferred.
  • aryl groups substituted with any of sulfo group, phosphate group and carboxyl group for example, 4 sulfophenyl, 4 sulfonaphthyl
  • heteroaromatic groups include sulfo group, phosphorus group
  • a heterocyclic group substituted with either an acid group or a carboxyl group for example, 4-sulfo-2 chayl group, 4-sulfo-2-pyridyl group
  • a hydrocarbon aromatic ring substituted with any one of the sulfo group, phosphoric acid group, and carboxyl group, or an alkyl group having a heteroaromatic ring is more preferable.
  • the sulfo group, phosphoric acid group, and carboxyl group are more preferable.
  • base! Particularly preferred are alkyl groups with a hydrocarbon aromatic ring substituted by either one. 2 Sulfobenzyl, 4 Sulfobenzyl, 4-Sulfopheneyl, 3-Fe-Lu 3-Sulfopropyl, and 4-Ferulu 4 Sulfobutyl Is most preferred.
  • L and L in the structural formula (2) are each independently
  • It is preferably an unsubstituted methine group.
  • Examples of the substituent that may be substituted on the methine group include V.
  • M in the structural formula (1) and M in the structural formula (2) make the ionic charge of the dye neutral.
  • Typical cations include inorganic ions such as hydrogen ions (H +), alkali metal ions (eg sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg calcium ions), ammonia ions (eg , Organic ions such as ammonium ions, tetraalkyl ammonium ions, pyridinium ions, ethyl pyridinium ions).
  • H + hydrogen ions
  • alkali metal ions eg sodium ions, potassium ions, lithium ions
  • alkaline earth metal ions eg calcium ions
  • ammonia ions eg
  • Organic ions such as ammonium ions, tetraalkyl ammonium ions, pyridinium ions, ethyl pyridinium ions.
  • Anions are inorganic anions, organic anions, halogen anions (eg fluorine ions, chlorine ions, iodine ions), substituted aryl sulfonate ions (eg p-toluene sulfonate ions) , P-chlorobenzenesulfonate ion), aryl disulfonate ion (eg, 1,3-benzensulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate Examples thereof include ions (for example, methyl sulfate ion), sulfate ions, thiocynate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, and trifluoromethanesulfonate ions. Furthermore, an ionic polymer or other dye having
  • Z to Z represent a group of atoms necessary to form a 5-membered or 6-membered nitrogen-containing heterocycle.
  • D and D ′ represent a group of atoms necessary to form an acyclic or cyclic acidic nucleus
  • R 1 to R and R represent an alkyl group.
  • R is alkyl group, aryl group or complex
  • L to L represent a methine group.
  • M to M represent charge neutralization counter ions, and m to m neutralize charges in the molecule.
  • n, n, n, n and n are 0 or 1, and n, n, n and n are each 0 or more
  • R 1 to R and R 2 are preferably unsubstituted alkyl groups having 18 or less carbon atoms (for example,
  • an unsubstituted alkyl group for example, methyl group, ethyl group, ⁇ -propyl group, ⁇ -butyl group, ⁇ -pentyl group, ⁇ -hexyl group
  • carboxyalkyl group for example 2-carboxyethyl group
  • Carboxymethyl group for example, 2-carboxyethyl group
  • a sulfoalkyl group for example, 2 sulfoethyl group, 3 sulfopropyl group, 4 sulfobutyl group, 3-sulfobutyl group
  • methanesulfolcarbamoylmethyl group for example, methyl group, ethyl group, ⁇ -propyl group, ⁇ -butyl group, ⁇ -pentyl group, ⁇ -hexyl group
  • carboxyalkyl group for example 2-carboxyethyl group
  • Carboxymethyl group for example 2-carboxyeth
  • M m is a cation or an anion when needed to neutralize the ionic charge of the dye.
  • a dye is a cation, an anion, or has a net ionic charge depends on its auxiliary color groups and substituents.
  • Typical cations are inorganic or organic ammonium ions and alkali metal ions, while anions can be either inorganic anions or organic anions, for example halogen anions (eg fluorine anions).
  • Ions chloride ions, bromine ions, iodine ions), substituted aryl sulfonate ions (eg p-toluene sulfonate ion, p chlorobenzene sulfonate ion), aryl disulfonate ions (eg 1, 3 benzene disulfonic acid) Ions, 1, 5 naphthalenedisulfonic acid ions, 2, 6 naphthalenedisulfonic acid ions), alkyl sulfate ions (eg methyl sulfate ions), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroboric acid Ions, picric acid ions, acetate ions, trifluoromethanesulfonic acid ions are preferable. Ammonium ions, iodine ions, and p-toluenesulfonic acid ions are preferable.
  • Nuclei formed by Z to Z and Z include thiazole nucleus ⁇ thiazole nucleus (example
  • thiazole 4-methylthiazole, 4-phenolthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole
  • benzothiazole nucleus for example, benzothiazonore, 4-clobenzozozonole, 5-clobobenzothiazonole
  • 6-clobenzobenzothiazole 5-nitrobenzothiazole
  • 4 methylbenzothiazole 5-methylthiobenzothiazole, 5-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5 bromobenzothiazole, 6-bromobenzothiazole, 5-oodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenzothiazole, 5 ethoxy Carbonylbenzothiazole, 5-ca Boxybenzothiazole, 5-phenethylenobenzothiazo
  • a methyl group and an ethyl group are particularly preferred.
  • the aforementioned aryl group represents a file, a halogen (eg, black) substituted file, an alkyl (eg, methyl) substituted file, or an alkoxy (eg, methoxy) substituted file.
  • quinoline nuclei eg, 2 pyridine, 4 pyridine, 5-methinole-2-pyridine, 3-methinore-4-pyridine
  • quinoline nuclei eg quinoline nuclei (eg 2 quinoline, 3-methyl 2 quinoline, 5 ethyl 2 — Quinoline, 6-methyl 2 quinoline, 6-tro-2-quinoline, 8 fluoro-2 quinoline, 6-methoxy-2 quinoline, 6 hydroxy-2 quinoline, 8 chloro-2 quinoline, 4 quinoline, 6-ethoxy-4 quinoline, 6- -tallow 4-quinoline, 8-chloro-4 quinoline, 8-fluoro 1-quinoline, 8-methyl 4-quinoline, 8-methoxy 1-quinoline, 6-methyl 4-quinoline, 6-methoxy 1-quinoline, 6- 4-quinoline), isoquinoline nucleus (eg 6-tro 1-isoquinoline, 3, 4 dihydro 1-isoquinoline 6-tro 1-isoquinoline)
  • 4 5 6 is not an oxazole nucleus or an imidazole nucleus. Shaped by Z ⁇ Z and Z
  • the nuclei formed are benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, 2 quinoline nucleus, 4-quinolyl nucleus.
  • the core is benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, 2 quinoline nucleus, 4-quinolyl nucleus.
  • D and D ′ represent an atomic group necessary for forming an acidic nucleus, but V can also take the form of an acidic nucleus of a general merocyanine dye.
  • Preferable substituents involved in the resonance of D are, for example, a carbo group, a cyan group, a sulfo group, and a sulfo group.
  • Said D ' represents the remaining atomic group required in order to form an acidic nucleus.
  • D and D ′ are cyclic, they form a 5- or 6-membered heterocycle that also contains carbon, nitrogen, and chalcogen (typically oxygen, ion, selenium, and tellurium) atomic power.
  • the substituent bonded to the nitrogen atom contained in the nucleus and the R is a hydrogen atom, carbon
  • An alkyl group having a prime number of 1 to 18 (preferably 1 to 7, particularly preferably 1 to 4) ⁇ for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl ⁇ , substituted alkyl group (
  • an aralkyl group eg, benzyl, 2-phenylethyl
  • a hydroxyalkyl group eg, 2 hydroxyethyl, 3 hydroxypyr
  • a carboxyalkyl group eg, 2 carboxyethyl, 3 carboxypropyl, 4 carboxybutyl, carboxy Methyl
  • an alkoxyalkyl group eg, 2-methoxy) Shetyl, 2- (2-methoxyethoxy) ethyl
  • sulfoalkyl groups eg, 2-sulfochinole, 3-
  • an unsubstituted alkyl group eg, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl
  • a carboxyalkyl group eg, carboxymethyl, 2-carboxyethyl, A sulfoalkyl group (eg 2-snorechechinole).
  • the 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by the Z is the D and the D,
  • the cyclic heterocyclic force represented by is also in the proper position, excluding the oxo group or thixo group. More preferably, the thioxo group of the rhodanine nucleus is removed.
  • L to L are methine groups or substituted methine groups ⁇ for example, substituted
  • an unsubstituted alkyl group for example, methyl, ethyl, 2-carboxyethyl
  • a substituted or unsubstituted aryl group for example, phenyl, o-carboxyphenyl
  • a heterocyclic group for example, barbitur tool) Acid
  • halogen atom for example, chlorine atom, bromine atom
  • alkoxy group for example, methoxy, ethoxy
  • amino group for example, N, N diphenylamine-containing N-methyl-1-N-phenylamine-containing N-methylbiperazino
  • alkylthio Group substituted with a group (for example, methylthio, ethylthio), etc. ⁇ , and may form a ring with other methine groups.
  • L and L in (5) are preferably unsubstituted methine groups.
  • L and L form trimethine, pentamethine and heptamethine dyes. Said Repeated force when unit n of L and L in structural formula (3) is 2 or 3, respectively
  • L to L may each independently have a substituent.
  • the substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring.
  • Z forms a 5- or 6-membered heterocycle
  • a 5-membered or 6-membered heterocyclic ring which may be condensed with an aromatic ring or a heterocyclic ring, and an aromatic ring condensed with the heterocyclic ring or The heterocycle may have a substituent.
  • Y represents N (R) R, OR, or S (0) R, and R to R
  • R 1 and R 2 are each independently a hydrogen atom, an aliphatic group, an aromatic group,
  • Q 1 Q3 independently represents an oxygen atom or a sulfur atom.
  • Q 1 and Q 2 are preferably oxygen atoms.
  • Q 3 is preferably a sulfur atom.
  • L to L each independently represent a methine group optionally having a substituent
  • the substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring.
  • Y represents an aromatic group or a heterocyclic group
  • n represents 0, 1, 2, or 3.
  • Each of R 1 and R 2 independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
  • R and R represent an aliphatic group
  • the aliphatic group includes, for example,
  • Examples include a alkyl group, a substituted alkyl group, an alkyl group, a substituted alkenyl group, an alkyl group, a substituted alkynyl group, an aralkyl group, or a substituted aralkyl group.
  • a group, a substituted alkenyl group, an aralkyl group, or an alkyl group or a substituted alkyl group in which a substituted aralkyl group is preferred is particularly preferred.
  • the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.
  • Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The preferred number and range of carbon atoms in the alkyl part of the substituted alkyl group are the same as in the case of the alkyl group.
  • the alkyl group may be an alkyl group having a substituent or an unsubstituted alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, an octadecyl group, and a cyclohexyl group.
  • Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbo having 30 or less carbon atoms.
  • Groups for example, methoxycarbol group, ethoxycarboro group, benzyloxycarboro group), alkylsulfoluminocarbon group having 30 or less carbon atoms, arylosulfo-luminocarboro group, alkylsulfo group , Arylsulfonyl groups, acyl groups having 30 or less carbon atoms, alkoxy groups having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), carbon Alkylthio group having 30 or less (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.), 30 or less carbon atoms
  • the lower aryloxy group for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.),
  • Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20.
  • the preferred and range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as in the alkal group.
  • the alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group.
  • Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.
  • Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups.
  • the number of carbon atoms of the aralkyl group is preferably 7 to 35, and more preferably 7 to 25.
  • the preferred and range of the number of carbon atoms in the aralkyl portion of the substituted aralkyl group is the same as in the case of the aralkyl group.
  • the aralkyl group may be either a substituted aralkyl group or an unsubstituted aralkyl group.
  • Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.
  • R 1 and R 2 represent an aromatic group
  • examples of the aromatic group include aryl
  • the number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20.
  • the preferred range of the number of carbon atoms in the aryl moiety of the substituted aryl group is the same as that of the aryl group.
  • Examples of the aryl group include a phenyl group, an oc naphthyl group, and a ⁇ naphthyl group.
  • Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group.
  • R 1 and R 2 represent a heterocyclic group
  • the heterocyclic group includes a compound having a substituent.
  • heterocyclic group and the number of carbon atoms of the heterocyclic group is preferably 4 to 13.
  • the heterocyclic group include nitrogen-containing, oxygen-containing, and sulfur-containing heterocycles, and more specifically, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, an isoquinoline ring, and a quinoxaline.
  • a ring an atridine ring, a furan ring, a pyrrole ring, a azole ring, an imidazole ring, a pyrroline ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiazoline ring, a thiophene ring, and an indole ring.
  • substituent of the heterocyclic group having a substituent include the same substituents as in the case of the substituted alkyl group.
  • R 1 and R 2 are each an unsubstituted alkyl group (for example, a methyl group,
  • a substituted oxyalkyl group for example, methoxyethyl group, phenoxychetyl group, etc.
  • a substituted oxycarbonylalkyl group for example, butoxycarbonylmethyl group, phenoxyethoxycarbonylmethyl group, etc.
  • Examples of the ring which may be bonded to other adjacent substituents to form a ring include a 5-membered or 6-membered heterocycle.
  • L to L may each independently have a substituent.
  • the L to L have a substituent.
  • examples of the substituent include a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a dialylamino group, an acylamino group, etc.), a substituted oxy group (for example, a hydroxy group).
  • a substituted amino group for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a dialylamino group, an acylamino group, etc.
  • a substituted oxy group for example, a hydroxy group
  • An unsaturated aliphatic ring is preferred to an unsaturated heterocyclic ring in which the substituent may combine to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. Yes.
  • the ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cyclopentene ring or a cyclohexene ring.
  • halogen atom examples include fluorine. Examples thereof include an elementary atom, a bromine atom, a chlorine atom and the like, and the aliphatic group and the aromatic group have the same meanings as those of the aliphatic group and the aromatic group in R 1 and R 2 described above.
  • the substituted amino group, the substituted oxy group and the substituted mercapto group may be substituted with the R in the structural formula (7).
  • the methine group represented by L to L is an unsubstituted methine group or a substituent.
  • N 0, 1, 2, or 3.
  • Y represents an aromatic group or a heterocyclic group.
  • the aromatic group and the heterocyclic group are
  • Y 1 is particularly preferably an aromatic group from the viewpoint of photosensitivity.
  • R 1 and R 2 are each independently a hydrogen atom, an aliphatic group, an aromatic group,
  • 35 3 each independently represents a methine group which may have a substituent, and when these represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocycle.
  • a ring may be formed.
  • Y represents the following group (1), and n represents 0, 1, 2, or 3.
  • R 1 represents a hydrogen atom, an aliphatic group, or an aromatic group.
  • Z is 5 or 6
  • the aromatic ring and heterocyclic ring may have a substituent.
  • the anion wherein X- may form, For example, a halogen ion (Cl _, Br ", ⁇ ), p-toluenesulfonic acid ion, Echiru sulfate I O emissions, 1, 5-sulfo-naphthalenedicarboxylic ⁇ anion , PF-, BF-, CIO-, etc.
  • the substituent may be substituted at any substitutable position of the cation moiety.
  • Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrrole ring, a pyrroline ring, an imidazole ring, and a pyridine ring.
  • a 5-membered ring is preferred over a 6-membered ring.
  • the nitrogen-containing heterocycle may further include a nitrogen-containing heterocycle which may be condensed with an aromatic ring (benzene ring, naphthalene ring) or a heterocycle (pyridine, pyrazine, etc.) and a condensed ring thereof. You may have.
  • a nitrogen-containing heterocycle which may be condensed with an aromatic ring (benzene ring, naphthalene ring) or a heterocycle (pyridine, pyrazine, etc.) and a condensed ring thereof. You may have.
  • Examples of the dye having an acidic nucleus include, as other compounds, an aromatic ring substituted with an amino group or an alkoxy group (for example, a phenyl group or a naphthyl group) and an acidic nucleus connected by a methine chain. Compound etc. are mentioned.
  • the number of methine chains is preferably 1 to 5, and more preferably 1 to 3, and particularly preferably 1.
  • the acidic nucleus is preferably a 5-membered to 6-membered ring.
  • Examples of other compounds include compounds represented by the following (A) and (B).
  • Dye having basic nucleus examples include cyanine dyes, hemisyanine dyes, styryl dyes, and streptocyanine dyes. Each of the dyes includes bis-type, tris-type, and polymer-type dyes. Of these, cyanine dyes, hemicyanine dyes, and styryl dyes that are preferred are cyanine dyes and hemisyanine dyes are more preferable.
  • the number of methine groups is preferably 1, and when the dye is a myanine dye, the number of methine groups is preferably 5 or less. Further, in the case of a styryl dye and having an alin nucleus, the number of methine chains is preferably 4 or less.
  • the basic nucleus is, for example, “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., 1977. Year, defined in Chapter 8 “Sensitizing and Desensitizing Dyes”, U.S. Pat.Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862 No. 4,002,480, No. 4,925,777, JP-A-3-167546, and the like.
  • Preferred examples of the basic nucleus include a benzoxazole nucleus, a benzothiazole nucleus, and an indolenine nucleus.
  • the basic nucleus is preferably a basic nucleus substituted with an aromatic group or a basic nucleus fused with three or more rings.
  • the number of condensed rings of the basic nucleus is, for example, 2 for the benzoxazole nucleus and 3 for the naphthoxazole nucleus. Even if the benzoxazole nucleus is substituted with a phenol group, the number of condensed rings is 2.
  • the basic nucleus fused to three or more rings may be any polycyclic condensed heterocyclic basic nucleus fused to three or more rings, but is preferably a tricyclic condensed heterocyclic ring, and 4 Examples thereof include cyclic condensed ring heterocycles.
  • Examples of the tricyclic fused ring heterocycle include naphtho [2,3-d] oxazole, naphtho [1,2d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] Thiazole, naphtho [1, 2-d] thiazole, naphtho [2, 1-d] thiazole, naphtho [2, 3-d] imidazole, naphth K1, 2-d] imidazole, naphtho K2, 1-d] Imidazole, naphth K2, 3—d] Lenazole, naphtho [1, 2-d] selenazole, naphtho [2, 1-d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3-d] Oxazole, indolo [5, 6-d] thiazole, indo
  • examples of the tetracyclic condensed heterocyclic ring include anthra [2, 3-d] oxazole, anthra [1, 2-d] oxazole, anthra [2, 1-d] oxazole, anthra [2, 3— d] thiazole, anthra [1, 2— d] thiazole, phenant mouth [2, l-d] thiazole, phenanthro [2, 3— d] imidazole, anthra [1, 2— d] imidazole, anthra [2, 1—d] imidazole, anthra [2, 3—d] selenazole, phenant mouth [1, 2—d] selenazole, phenant mouth [2, 1—d] selenazole, carbazolo [2, 3—d ] Oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, carb
  • the basic nucleus fused with three or more rings is naphtho [2,3d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d ] Thiazole, naphtho [1,2-d] thiazole, naphtho [2, 1-d] thiazole, indolo [5,6d] oxazole, indolo [6,5-d] oxazole, indolo [2,3-d ] Oxazole, indolo [5, 6- d] thiazole, indolo [2, 3-d] thiazole, benzofuro [5, 6 d] oxazole, benzofuro [6, 5-d] oxazole, benzofuro [2, 3-d ] Sazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d
  • Examples of the basic nucleus include the basic heterocyclic rings shown below.
  • R represents a hydrogen atom, an aliphatic group, or an aromatic group.
  • the dye having a basic nucleus includes compounds represented by the following structural formula (10).
  • the dye having the basic nucleus is a hemicyanine dye compound and has a function of spectrally sensitizing the radical generator. Therefore, when irradiated with ultraviolet to visible light corresponding to the absorption of the dye having the basic nucleus, it has no absorption in this region! / ⁇ radical generator Even when it contains, radical generation from the radical generator can be promoted.
  • the hemithianian dye compound may be a bis-type, tris-type, or polymer-type dye via the Y portion in the following structural formula (10).
  • R represents an aliphatic group or an aromatic group.
  • R is an aliphatic group
  • examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group.
  • the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group.
  • the chain aliphatic group may have a branch.
  • Examples of the alkyl group represented by R include linear, branched, and cyclic alkyl groups.
  • the number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20.
  • the preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group.
  • the alkyl group may be shifted between an alkyl group having a substituent and an unsubstituted alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, an octadecyl group, and a cyclohexyl group.
  • Examples include xyl group, cyclopentyl group, neopentyl group, isopropyl group, and isobutyl group.
  • Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbo having 30 or less carbon atoms.
  • Groups e.g., methoxycarbol groups, ethoxycarboro groups, Benzyloxycarbonyl group
  • alkylsulfocarbonamino group having 30 or less carbon atoms e.g., methoxycarbol groups, ethoxycarboro groups, Benzyloxycarbonyl group
  • alkylsulfocarbonamino group having 30 or less carbon atoms e.g., methoxycarbol groups, ethoxycarboro groups, Benzyloxycarbonyl group
  • alkylsulfocarbonamino group having 30 or less carbon atoms e.g., methoxycarbol groups, ethoxycarboro groups, Benzyloxycarbonyl group
  • alkylsulfocarbonamino group having 30 or less carbon atoms e.g., arylsulfol-aminoamino group
  • alkylsulfol group e.g., arylyls
  • an alkoxy group having 30 or less carbon atoms for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.
  • an alkylthio group having 30 or less carbon atoms for example, methylthio group, ethylthio group, Methylthioethylthioethyl group
  • aryloxy group having 30 or less carbon atoms for example, phenoxy group, p-trioxy group, 1-naphthoxy group, 2-naphthoxy group, etc.
  • -toxyl group 30 carbon atoms or less
  • An alkyl group, an alkoxycarboxoxy group, an aryloxycarbonyloxy group, an acyloxy group having 30 or less carbon atoms for example, Acetyloxy group, propio-loxy group, etc.
  • an acyl group having 30 or less carbon atoms for example,
  • Examples of the alkenyl group represented by R include linear, branched, and cyclic alkenyl groups.
  • the alkenyl group is preferably a range of carbon atoms in the alkenyl part of the substituted alkenyl group which may be shifted from a substituted alkenyl group having a substituent and an unsubstituted alkenyl group. Is the same as in the case of an alkenyl group.
  • substituent for the substituted alkenyl group include the same substituents as those for the substituted alkyl group.
  • Examples of the alkynyl group represented by R include linear, branched, and cyclic alkynyl groups.
  • the alkyl group includes a substituted alkyl group having a substituent and an unsubstituted alkyl group.
  • the preferred number of carbon atoms in the alkyl moiety of the substituted alkyl group, which may be shifted, is the same as in the case of the alkynyl group.
  • the substituent for the substituted alkyl group include the same substituents as those for the substituted alkyl group.
  • Examples of the aralkyl group represented by R include linear, branched, and cyclic aralkyl groups.
  • the aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group, and the number of carbon atoms in the aralkyl part of the substituted aralkyl group is preferred. It is the same.
  • the substituent of the substituted aralkyl group include the same substituents as in the case of the substituted alkyl group.
  • R represents an aromatic group
  • examples of the aromatic group include an aryl group and a substituted alkyl group.
  • the number of carbon atoms in the aryl group is preferably 6 to 30 forces, more preferably 6 to 20 forces.
  • the preferred aryl moiety of the substituted aryl group is the same as the aryl group in the range of the number of carbon atoms.
  • R for example,
  • each L is independently a methine which may have a substituent.
  • L represents a methine group having a substituent
  • the substituent is bonded to be unsaturated.
  • a Japanese aliphatic ring or an unsaturated heterocyclic ring may be formed.
  • Examples of the substituent of the methine group include a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an allylamino group, a dialylamino group, and an acylamino group), a substituted oxy group (for example, a hydroxy group, Alkoxy group, acyloxy group, aryloxy group, alkoxycarboxoxy group, aryloxycarboxoxy group, etc.), substituted mercapto group (eg, alkyl mercapto group, aryl mercapto group, etc.), halogen atom, aliphatic Group and aromatic group.
  • a substituted amino group for example, an amino group, an alkylamino group, a dialkylamino group, an allylamino group, a dialylamino group, and an acylamino group
  • a substituted oxy group for example, a hydroxy group, Alkoxy group, acyloxy
  • halogen atom examples include a fluorine atom, a bromine atom, and a chlorine atom.
  • aliphatic group and the aromatic group examples include an aliphatic group and an aromatic group represented by R. Same
  • the methine group represented by L is an unsubstituted methine group or a substituent.
  • those substituted by a halogen atom or an aliphatic group, or those in which the substituents are bonded to each other to form a cyclopentene ring or a cyclohexene ring are particularly preferable.
  • m 0, 1, 2, or 3.
  • Z represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring.
  • the nitrogen-containing heterocyclic ring may have an aromatic ring or a heterocyclic ring condensed with the nitrogen-containing heterocyclic ring and the aromatic ring or heterocyclic ring condensed with the nitrogen-containing heterocyclic ring has a substituent. You may do it.
  • the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrrole ring, a pyrroline ring, an imidazole ring, and a pyridine ring.
  • a 5-membered ring is preferred over a 6-membered ring.
  • the nitrogen-containing heterocycle may be further substituted with a nitrogen-containing heterocycle which may be condensed with an aromatic ring (benzene ring or naphthalene ring) and the condensed ring.
  • a nitrogen-containing heterocycle which may be condensed with an aromatic ring (benzene ring or naphthalene ring) and the condensed ring.
  • the substituent are the same as those of the substituted alkyl represented by R.
  • Y in the structural formula (10) represents N (R) R, OR, or S (0) nR, where R, R, R
  • R and R each independently represents a hydrogen atom or a monovalent substituent, and n is 0, 1 or 2
  • Examples of the monovalent substituent represented by 31 32 33 include an aliphatic group, an aromatic ring group, a heterocyclic group, C (0) R, and S (0) R.
  • R 1 and R 2 are independently hydrogen atoms p 35 q 36 35 36
  • R represents a hydrogen atom, an aliphatic group, an aromatic ring group, or a heterocyclic group.
  • the heterocyclic group represented by R 1 to R 4 includes a heterocyclic group having a substituent, an unsubstituted group.
  • a heterocyclic group is mentioned.
  • the heterocyclic group include a nitrogen-containing atom, an oxygen-containing atom, and a sulfur-containing heterocycle, such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, Examples include an ataridin ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, pyrroline ring, oxazole ring, thiazole ring, oxadiazole ring, thiazoline ring, thiophene ring, and indole ring.
  • the substituent of the heterocyclic group having a substituent include the same substituents
  • X— represents a group capable of forming an anion.
  • Anions include, for example, halogen ions (Cl—, Br—, ⁇ ), p-toluenesulfonic acid ions, ethyl sulfate ions, 1,5-disulfonaphthalenedanion, PF—, BF—, and CIO. — Etc. Ma
  • X— may be a substituent that replaces the position of the cation moiety of the structural formula (10), which can be substituted at any position.
  • X— may be represented by the structural formula (10). The resulting compound forms an internal salt.
  • R and R represent an aliphatic group or an aromatic group.
  • L 1, L 2, L 3 and L 4 each independently represents a methine group which may have a substituent, , L 1, and L 2 represent a methine group having a substituent, the substituent is bonded to the unsaturated fat
  • An aromatic ring or an unsaturated heterocyclic ring may be formed.
  • the other benzene rings are condensed on the benzene ring z.
  • the benzene ring z and the condensed ring which may be combined may have a substituent.
  • Z represents an atomic group that forms a heterocyclic ring, and the heterocyclic ring may have a substituent.
  • Y independently represent —CR R—, —NR—, —O—, —S, or —Se.
  • R 1, R 2 and R 3 each independently represents a hydrogen atom, an aliphatic group or an aromatic group.
  • R 1 and R 2 may be an atomic group that is bonded to each other to form a ring.
  • m is 0, 1, 2,
  • X— represents a group capable of forming an anion.
  • R and R in the structural formula (11) and the structural formula (12) are the same as R in the structural formula (10).
  • L 1, L 2 and L 3, L are each the structure
  • the benzene ring Z in the structural formula (11) may be condensed with another benzene ring.
  • the zen ring and the condensed ring thereof may have a substituent. Examples of substituents
  • an electron-withdrawing substituent is preferable because sensitivity can be improved.
  • An electron-withdrawing substituent is one having a positive Hammet's ⁇ (sigma) value.
  • those having a value of ⁇ ⁇ (sigma meta) or ⁇ ⁇ (sigma para) are preferably 0.2 or more, and more preferably 0.4 or more.
  • Examples of the electron-withdrawing substituent include a halogen group, an acyloxy group, an acyl group, a strong rubamoyl group, a sulfamoyl group, an aryl group, an alkoxycarbo group, an acylamino group, an alkylsulfo-lumino group, and an arylsulfo group.
  • a halogen group an acyloxy group, an acyl group, a strong rubamoyl group, a sulfamoyl group, an aryl group, an alkoxycarbo group, an acylamino group, an alkylsulfo-lumino group, and an arylsulfo group.
  • ⁇ in the structural formula (12) represents an atomic group forming a heterocyclic ring, and the heterocyclic ring is a substituent.
  • substituents include a substituent of the substituted alkyl represented by R.
  • R represents an aliphatic group or an aromatic group.
  • Y and Y in Structural Formula (11) and Structural Formula (12) are each independently a sulfur atom.
  • Oxygen atom, C (R) R, selenium atom, tellurium atom, R and R are independently water
  • the aliphatic group and the aromatic group are an aliphatic group represented by R and
  • the aliphatic group is particularly preferably an alkyl group or a substituted alkyl group.
  • Y and Y are oxygen atom, sulfur atom, C (R) R
  • R 11 21 33 34 Particularly preferred is a sulfur atom, and C (R) R is preferred.
  • R and R are preferably alkyl groups.
  • the m is preferably 1 or 2, and particularly preferably 1.
  • X— represents a group capable of forming an anion and has the same meaning as X— in the structural formula (10), and preferred examples thereof are also the same.
  • the compounds represented by the structural formulas (10) to (12) may be used alone or in combination of two or more.
  • Examples of the dye having a basic nucleus further include compounds represented by the following structural formulas (13) to (18). [0148] [Chemical 30]
  • 1 ⁇ , 1 ⁇ , 1 ⁇ , 1 ⁇ , 1 ⁇ , 1 ⁇ , and L represent a methine group.
  • n 0, 1, 2, 3 or 4.
  • Z and Z are nitrogen-containing heterocycles
  • R 1 and R 2 represent an aliphatic group, an aromatic group, or a heterocyclic group.
  • M is a counterbalance for charge balancing
  • M represents a number of 0 or more necessary for neutralizing the charge of the molecule.
  • Z 1, Z 2, and L to L represent a ionic substituent when the structural formula (13) is a cationic dye.
  • the structural formula (13) is a betaine dye, it has one anionic substituent.
  • L 1, L 2, L 3 and L 4 represent a methine group.
  • p represents 0 or 1;
  • n 0, 1, 2, 3 or 4.
  • Z and Z are raw materials necessary for forming a nitrogen-containing heterocycle.
  • the structural formula (14) is a betaine dye, it has one cationic substituent and one ionic substituent, and when the structural formula (14) is a non-one dye, No substituents and no ionic substituents.
  • L L L L L L L L L L and L represent a methine group.
  • n and n represent 0 1 2 3 or 4; Z Z and Z are
  • R R and R represent an aliphatic group, an aromatic group, or a heterocyclic group
  • L L L L L L and L represent a methine group.
  • n 0 1 2 3 or 4; Z and Z are nitrogen-containing heterocycles
  • R R represents an aliphatic group, an aromatic group, or a heterocyclic group.
  • M is a counterbalance for charge balancing
  • R 1 Structural formula (17) In the structural formula (17), L 1, L 2, L 3 and L represent a methine group. p represents 0 or 1
  • n 0, 1, 2, 3 or 4.
  • Z and Z are necessary to form a nitrogen-containing heterocycle
  • M and m are as defined in the structural formula (16). However, R
  • R 1 have a terionic substituent.
  • L 1, L 2, L 3, L 4, L 3, L 4, L 3, L 4, and L 5 represent a methine group.
  • n and n represent 0, 1, 2, 3 or 4.
  • the ring may be condensed.
  • M and m are as defined in the structural formula (16). However, at least one of R, R and R
  • At least one of nine, preferably two, more preferably three are groups having an aromatic ring.
  • One is a group having an aromatic ring, preferably two are groups having an aromatic ring, more preferably three are groups having an aromatic ring, and particularly preferably four or more are aromatic rings. It is group which has.
  • the fluorescent whitening agent also known as a “fluorescent whitening agent” is capable of absorbing light having a wavelength in the vicinity of 300 to 450 nm, which is visible in the ultraviolet to shortwave, and 400 to 400 It is a colorless or weakly colored compound capable of emitting fluorescence having a wavelength around 500 nm.
  • suitable optical brighteners contain a ⁇ electron system comprising a carbocyclic or heterocyclic nucleus.
  • a compound having a nonionic nucleus is preferred.
  • the nonionic nucleus is preferably at least one selected from, for example, a stilbene nucleus, a distyrylbenzene nucleus, a distyrylbiphenyl nucleus, and a divinylstilbene nucleus force.
  • the compound having a nonionic nucleus is not particularly limited and can be appropriately selected according to the purpose.
  • pyrazolines triazines, stilbenes, distyrylbenzenes, distyrylbiphenyls, divinylstilbene , Triazylamino stilbenes, stilbyl triazoles, stilbyl naphthotriazoles, bis-triazole stilbenes, benzoxazoles, bisphenol benzoxazoles, stilbene pentoxazoles, bis Benzoxazoles, furans, benzofurans, bis-monobenzimidazoles, diphenylvirazolines, diphenyloxadiazoles, naphthalimides, xanthenes, carbostyrils, pyrenes and 1,3,5 triazines -Lu derivatives and the like.
  • those having at least one kind selected from styryl group, benzoxazolyl group, and benzothiazolyl group are preferable.
  • distyrylbenzenes, distyrylbiphenyls, ethenyl groups, aromatic ring groups, heterocyclic group groups are preferred.
  • Bisbenzoxazoles and bisbenzothiazoles linked by a divalent linking group are particularly preferred.
  • the fluorescent brightening agent may have a substituent.
  • substituents include an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and a carbon number of 30 or less.
  • Alkoxy power of the group for example, methoxy carbo ol group, ethoxy carbo ol group, benzyloxy carbo ol group
  • alkylsulfo carboamino group having 30 or less carbon atoms for example, aryl sulfo lumino carbo ol group, Alkyl sulfonyl group, aryl sulfonyl group, isylaminosulfonyl group having 30 or less carbon atoms, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group) Etc.), an alkylthio group having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methyl group) Thioethylthioethyl group, etc.), aryloxy group having 30 or less carbon atoms (
  • Examples of each of the above representative optical brighteners include, for example, those described in Okawara "Dye Handbook", Kodansha, pages 84 to 145, pages 432 to 439.
  • the triazines can be appropriately selected according to the purpose without any particular restrictions.
  • Examples of typical optical brighteners are shown in the following structural formulas (19) to (25).
  • the present invention is suitable for the use of the fluorescent brightener power S having any of the following partial structures.
  • nuclei in each of the above formulas are replaced by It may be.
  • substituents include an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and a carbon number of 30 or less.
  • Alkoxycarbon groups for example, methoxycarbon groups, ethoxycarbon groups, benzyloxycarboro groups
  • alkylsulfo-luminocarbol groups having 30 or less carbon atoms
  • arylsulfo-luminocarbon groups alkyls Sulfo group, aryl hydrocarbon group
  • acyl group having 30 or less carbon atoms
  • alkoxy group having 30 or less carbon atoms for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group) Etc.
  • an alkylthio group having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.)
  • carbon Aryloxy group having a prime number of 30 or less for example, phenoxy group, p-triloxy group, 1-naphthoxy group, 2-naph
  • the fluorescent whitening agent is preferably a compound that can be dissolved in an organic solvent, water, or an alkaline aqueous solution. Moreover, the compound which can be disperse
  • the optical brightener can be used as a single compound or as a mixture of several substances.
  • optical brighteners those having the following partial structures are particularly preferred, but are not limited to these for the present invention! /.
  • R 2 : H
  • R 3 : SO 2 CH 2 CH 2 OCH (CH 2) CH NMe
  • the fluorescent brightening agent used in the present invention one containing at least one compound represented by the following structural formula (26) or structural formula (27) may be used.
  • the fluorescent whitening agent is a spectral sensitizing dye, and has a function of spectrally sensitizing a compound capable of generating radicals or cations (radical or cation generator). Therefore, when visible to infrared light corresponding to the absorption of the spectral sensitizing dye is irradiated, even if it contains a radical or a cation generator without absorption in this region, a radical from the generator is generated. Can promote the generation of cations.
  • I ⁇ to R 12 are each independently a hydrogen atom, a saturated or unsaturated alkyl group, aralkyl group, or aryl group that may have a substituent.
  • ⁇ 2 represents an unsaturated nitrogen-containing heterocyclic group, and the nitrogen atom in the ring is bonded to the benzene ring.
  • each group of RR 12 may form a saturated or unsaturated ring together with the adjacent group.
  • X, ⁇ , and ⁇ each independently represent an oxygen atom, a sulfur atom, or a monosubstituted nitrogen atom.
  • ⁇ and LL 3 represent a divalent linking group having an aromatic ring or heteroaromatic ring which may have a substituent.
  • Q represents a 1, 3, 5-benzenetriyl group or a nitrogen atom.
  • n represents an integer of 1 or more.
  • a, b, and c represent 0 and an integer of 1 or more, but when Q is a nitrogen atom, it represents an integer of 1 or more.
  • Examples of the saturated alkyl radical RR 12 represents a linear, branched, and cyclic alkyl groups, more preferably 1 to 30 preferably tool 20 as the number of carbon atoms.
  • Examples of such alkyl groups are methyl, ethyl, n-propyl, n-butyl, 2-ethyl.
  • Examples include a hexyl group, a cyclohexyl group, and an octadecyl group.
  • examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, a carbon Alkoxycarbo groups having a carbon number of 30 or less (for example, methoxycarbon groups, ethoxycarbon groups, benzyloxycarboro groups), alkylsulfo-carbomino groups having no more than 30 carbon atoms, and arylsulfo-luminocarbo- groups.
  • a carboxyl group for example, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, a carbon Alkoxycarbo groups having a carbon number of 30 or less (for example, methoxycarbon groups, ethoxycarbon groups
  • alkoxy group having 30 or less carbon atoms for example, methoxy group, ethoxy group,
  • An acyl group having 30 or less carbon atoms for example, acetyloxy group, propio-oxy group, etc.
  • an acyl group having 30 or less carbon atoms for example, acetyl group, propiol group, benzoyl group, etc.
  • strong rubamoyl group for example, rubamoyl group, N, N dimethylcarbamoyl group, morpholinocarbol group, piperidinocarbol group, etc.
  • sulfamoyl group for example, sulfamoyl group, N, N dimethylsulfamoyl group, morpholinosulfol group, Pyridinosulfol group, etc.
  • aryl group having 30 or less carbon atoms eg, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, naphthyl group, etc.
  • substituted amino group eg, amino group, alkyl group
  • Examples of the unsaturated alkyl group represented by Ri to R 12 include linear, branched, and cyclic alkenyl groups.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 30. 2 to 20 is more preferable.
  • the alkenyl group is a carbon atom of the alkenyl part of the substituted alkenyl group which may be shifted from a substituted alkenyl group having a substituent or an unsubstituted alkenyl group.
  • the preferred number range is the same as in the case of the alkenyl group.
  • Examples of the substituent for the substituted alkenyl group include the same substituents as those for the substituted alkyl group.
  • examples of the unsaturated alkyl group represented by include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30. ⁇ 20 is more preferred.
  • the alkyl group is preferably a substituted alkynyl group having a substituent or an unsubstituted alkyl group, and the number of carbon atoms in the alkyl part of the substituted alkyl group may be shifted. The range is the same as in the case of the alkynyl group.
  • examples of the substituent of the substituted alkyl group include the same substituents as those of the substituted alkyl group.
  • Examples of the aralkyl group represented by RR 12 include linear, branched, and cyclic aralkyl groups, and the number of carbon atoms is preferably 7 to 30, and more preferably 7 to 20. Specific examples include a benzyl group and a phenethyl group. Further, the aralkyl group may be shifted between a substituted aralkyl group having a substituent and an unsubstituted aralkyl group! /.
  • the aryl group represented by Ri to R 12 preferably has 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Examples of such aryl groups include a phenol group, a naphthyl group, and 13 naphthyl group.
  • the saturated alkyloxy group represented by Ri to R 12 preferably has 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms.
  • Examples of such an alkyloxy group include a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, a phenoxyethoxy group, and the like.
  • examples of the unsaturated alkyloxy group include an alkyloxy group and an alkyloxy group, and the alkyl group and the alkyl group have the same meanings as those of the aforementioned unsaturated alkyl group.
  • Ararukiruokishi group Ri ⁇ R 12 represents, preferably Ri preferred instrument 7-10 force C7-12.
  • examples of such aralkyloxy groups include benzyloxy groups and phenoxy groups.
  • the aryloxy group represented by Ri to R 12 preferably has 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Examples of such aryloxy groups include phenoxy group, 4-methylphenoxy group, oc-naphthyloxy group and the like.
  • the saturated alkylthio group represented by Ri to R 12 preferably has 1 to 30 carbon atoms.
  • alkylthio groups include methylthio groups, ethylthio groups , N-butylthio group, 2-ethylhexylthio group and the like.
  • unsaturated alkylthio group include an alkenylthio group and an alkylthio group, and the alkyl group and the alkyl group have the same meanings as those of the aforementioned unsaturated alkyl group.
  • the aralkylthio group represented by Ri to R 12 preferably has 7 to 20 carbon atoms, more preferably 7 to 20 carbon atoms.
  • Examples of such an aralkylthio group include a benzylthio group and a phenethylthio group.
  • the arylothio group represented by Ri to R 12 preferably has 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Examples of such an arylthio group include a phenylthio group, a 4-methylphenolthio group, an ⁇ -naphthylthio group, and the like.
  • the dialkylamino group Ri ⁇ R 12 represents may be any 2 Tsuga ⁇ conversion to amino groups of the alkyl group described above, the number of carbon atoms is preferably 1 to 30.
  • Examples of such a dialkylamino group include a dimethylamino group, a jetylamino group, a dibutylamino group, a dioctylamino group, and a didecylamino group.
  • the Jiariruamino group Ri ⁇ R 12 represents are any two of the amino group substituted in Ariru groups described above, the number of carbon atoms is 6 to 30 is preferred.
  • Examples of such diarylamino groups include diphenylamino groups, ditolylamino groups, dixylylamino groups, di-di-naphthylamino groups, di- ⁇ -naphthylamino groups, and the like.
  • halogen atom RR 12 represents, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
  • ⁇ 2 represents an unsaturated nitrogen-containing heterocyclic group, and the nitrogen atom in the ring is bonded to the benzene ring.
  • the nitrogen-containing heterocyclic ring is a 5- to 7-membered unsaturated nitrogen-containing heterocyclic group which may have a substituent, and specific examples are shown below.
  • the substitution position of the nitrogen-containing heterocycle is the following in the structural formula (26) and the structural formula (27): Any one of R 1Q and R 11 is preferred.
  • Preferred examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a dialkylamino group, and a diarylamino group.
  • the base of the RR 12 is but it may also be formed respectively saturated or unsaturated with an adjacent group ring.
  • saturated or unsaturated rings include a tetrahydroquinoline ring and a julolidine ring.
  • X, Y, the mono-substituted nitrogen atom represented by ⁇ is a nitrogen atom which alkyl or Ariru group is substituted, alkyl group and Ariru groups on nitrogen atom, before represented by RR 12 It is synonymous with the alkyl group and aryl group.
  • the divalent heteroaromatic groups shown below are particularly preferable.
  • R 13 , R 15 and R 16 in the above formulas represent a lower alkyl group, and R "represents 1 ⁇ -
  • n represents an integer of 1 or more, and 1, 2, and 3 are particularly preferable. Further, when n represents an integer of 2 or more, the P may be a combination of an aromatic ring and a heteroaromatic ring. a, b, c are integers greater than or equal to 1 When represents, the substituents represented by to may be different from each other.
  • the content of the sensitizer is preferably from 0.01 to 4% by mass, more preferably from 0.02 to 2% by mass, based on all components of the photosensitive resin composition. .05 to 1% by mass is particularly preferred. When the content is less than 0.01% by mass, the sensitivity may be lowered, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.
  • the polymerization inhibitor can be appropriately selected according to the purpose without particular limitation.
  • the polymerization inhibitor provides hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to the radical component of polymerization initiation generated from the photopolymerization initiator by the exposure. ) And the like to deactivate polymerization initiation radicals and to inhibit polymerization initiation.
  • Examples of the polymerization inhibitor include compounds having a lone electron pair (for example, compounds having oxygen, nitrogen, sulfur, metal, etc.), compounds having pi electrons (for example, aromatic compounds), and the like.
  • a compound having a phenolic hydroxyl group, a compound having an imino group, a compound having an aromatic ring, and a compound having a heterocyclic ring are preferable.
  • the compound having a phenolic hydroxyl group is not particularly limited, and can be appropriately selected according to the purpose.
  • a compound having at least two phenolic hydroxyl groups is preferable.
  • at least two phenolic hydroxyl groups may be substituted with different aromatic rings in the same molecule, which may be substituted with the same aromatic ring.
  • the compound having at least two phenolic hydroxyl groups is more preferably a compound represented by the following structural formula (28), for example.
  • Z represents a substituent
  • m represents an integer of 2 or more
  • n represents an integer of 0 or more.
  • Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, and a halogen atom.
  • alkoxy carboxylic group having 30 or less carbon atoms for example, methoxy carbo yl group, ethoxy carbo yl group, benzyl oxy carboxy group), carbon number 30 or less aryloxycarbonyl groups (for example, phenoxycarbon groups), alkylsulfo-carbomino groups having 30 or less carbon atoms (for example, methylsulfo-aminocarbonyl groups, octylsulfo-luminocarboro groups), Arylsulfo-carboamino group (for example, toluenesulfo-luminocarbon group), acyl group having 30 or less carbon atoms (for example, benzoylaminosulfol group, acetylaminosulfol group, Bevaloylaminosulfol group), alkoxy group having 30 or less carbon atoms
  • arylsulfol group for example, benzenesulfol group, toluenesulfol group, naphthalenesulfol group, pyridinesulfol group
  • aryl group having 30 or less carbon atoms for example, a phenyl group, a dichlorophenol group, a tolyl group, a methoxyphenyl group.
  • a jetylaminophenol group an acetylaminophenol group, a methoxycarbol group, a hydroxyphenyl group, a t-octylphenol group, a naphthyl group, etc.
  • a substituted amino group for example, Amino group, alkylamino group, dialkylamino group, arylylamino group, diarylamino group, acylamino group, etc.
  • substituted phosphono group eg, phosphono group, jetylphosphono group, diphenylphosphono group
  • heterocyclic group eg, pyridyl group
  • Examples of the compound represented by the structural formula (28) include alkyl catechol (for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3 methyl force teconole, 4-methinore force teconole, 2 ethinore Force Teconole, 3 Ethinore Force Teconole, 4-Ethylcatechol, 2 Propylcatechol, 3 Propylcatechol, 4 Propinore Force Teconole, 2—n-Butinore Force Teconole, 3—n—Butinore Force Teconole, 4 n—Butinore Force Teconole, 2 tert-butinoleic power Teconole, 3 tert-butinoleic power Teconole, 4-tert-butylcatechol, 3,5-ditert-butylcatechol, etc.), alkylresorcinol (for example, 2-methylresorcinol, 4 —Methyl), alkyl
  • the compound having a phenolic hydroxyl group is also preferably a compound in which aromatic rings having at least one phenolic hydroxyl group are linked to each other by a divalent linking group.
  • Examples of the divalent linking group include groups having 1 to 30 carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, SO, SO and the like.
  • Examples of the substituent on which the carbon atom and oxygen atom may have a substituent include Z in the structural formula (28) described above.
  • the aromatic ring may have a substituent.
  • Examples of the substituent include Z in the structural formula (28) described above.
  • Specific examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol S, bisphenol M, a known bisphenol compound used as a color developer for thermal paper, and Japanese Patent Application Laid-Open No. 2003-305945. And hindered phenolic compounds used as acid-proofing agents.
  • monophenolic compounds having substituents such as 4-methoxyphenol, 4-methoxy-2-hydroxybenzophenone, 13-naphthol, 2,6-di-tert-butyl-4-cresol, methyl salicylate, jetylaminophenol, etc. Can be mentioned.
  • Examples of commercially available compounds having a phenolic hydroxyl group include bisphenol compounds manufactured by Honshu Chemical Co., Ltd.
  • the compound having an imino group is not particularly limited and can be appropriately selected depending on the purpose.
  • a compound having a molecular weight of 50 or more is preferable, and a compound having a molecular weight of 70 or more is more preferable.
  • the compound having an imino group preferably has a cyclic structure substituted with an imino group.
  • the cyclic structure is more preferably one in which at least one of an aromatic ring and a heterocyclic ring is condensed, and a preferable aromatic ring is condensed.
  • the annular structure In the annular structure,
  • Specific examples of the compound having an imino group include phenothiazine, phenoxazine, dihydrophenazine, hydroquinoline, or a compound obtained by substituting these compounds with Z in the above structural formula (28). Can be mentioned.
  • a hindered amine derivative having a hindered amine as a moiety is preferable.
  • hindered amine examples include hindered amines described in JP-A-2003-246138.
  • the compound having a nitro group or the compound having a nitroso group is not particularly limited, and can be appropriately selected according to the purpose.
  • a molecular weight having a molecular weight of 50 or more is preferable. Is more preferably 70 or more.
  • Specific examples of the compound having a nitro group or the compound having a nitroso group include nitrobenzene, a chelate compound of nitroso compound and aluminum, and the like.
  • the compound having an aromatic ring is not particularly limited and may be appropriately selected depending on the purpose.
  • the aromatic ring has a lone pair of electrons (for example, an oxygen atom, a nitrogen atom). And those substituted with a substituent having a sulfur atom or the like.
  • Specific examples of the compound having an aromatic ring include, for example, the above-described compound having a phenolic hydroxyl group, the above-described compound having an imino group, and a compound partially having an aniline skeleton (for example, methylene blue, crystal Violet).
  • the compound having a heterocyclic ring is not particularly limited and may be appropriately selected depending on the purpose.
  • the heterocyclic ring may include an atom having a lone pair of electrons such as nitrogen, oxygen, and sulfur. What has is preferable.
  • Specific examples of the compound having a heterocyclic ring include pyridine and quinoline.
  • the compound having a metal atom is appropriately selected depending on the intended purpose without any limitation.
  • the metal atom is not particularly limited as long as it is a metal atom having an affinity for a radical generated from the polymerization initiator, and can be appropriately selected according to the purpose. Examples thereof include copper, aluminum, and titanium. Can be mentioned.
  • compounds having at least two phenolic hydroxyl groups, compounds having an aromatic ring substituted with an imino group, and compounds having a heterocyclic ring substituted with an imino group are preferred.
  • Particularly preferred are compounds in which the imino group constitutes part of the cyclic structure, and hindered amine compounds.
  • catechol, phenothiazine, phenoxazine, hindered amine, or derivatives thereof are preferable.
  • the polymerization inhibitor is generally contained in a trace amount in a commercially available polymerizable compound, but in the present invention, it is contained in the commercially available polymerizable compound from the viewpoint of improving the resolution.
  • the polymerization inhibitor described above is included. Therefore, the polymerization inhibitor is preferably a compound other than monophenolic compounds such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.
  • the polymerization inhibitor may be added in advance to the photosensitive resin composition solution in the production process of the pattern forming material.
  • the content of the polymerization inhibitor is about 0. 0 with respect to the polymerizable compound of the photosensitive layer.
  • the resolution may decrease, and when it exceeds 0.5% by mass, the sensitivity to active energy rays may decrease.
  • the content of the polymerization inhibitor represents a content excluding monophenolic compounds such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.
  • the noinder is more preferably soluble in an alkaline liquid, preferably swellable in an alkaline liquid.
  • Suitable examples of the binder exhibiting swellability or solubility with respect to the alkaline liquid include those having an acidic group.
  • the acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyxenore group is preferable. .
  • binder having a carboxyl group examples include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin.
  • solubility in a coating solvent Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties.
  • Vinyl copolymers having a carboxyl group are preferred. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.
  • the vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.
  • Examples of the bull monomer having a carboxyl group include (meth) acrylic acid and vinyl. -Lebenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid
  • (meth) acrylic acid is particularly preferred from the viewpoint of copolymerization cost and solubility.
  • monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
  • the other copolymerizable monomer is not particularly limited and can be appropriately selected according to the purpose.
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid.
  • vinyl esters examples include vinyl acetate, vinyl propionate, butyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
  • maleic diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
  • Examples of the itaconic acid diesters include dimethyl itaconate, dimethyl itaconate, and dibutyl itaconate.
  • Examples of the (meth) acrylamides include (meth) acrylamide, ⁇ ⁇ ⁇ -methyl (meth) acrylamide, ⁇ ethyl (meth) acrylamide, ⁇ ⁇ ⁇ ⁇ propyl (meth) acrylamide, ⁇ ⁇ ⁇ ⁇ ⁇ isopropyl (meth) acrylamide, and ⁇ ⁇ ⁇ butyl.
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropylino styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, Examples thereof include dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl benzoate, a-methylstyrene, and the like.
  • an acidic substance for example, t-Boc, etc.
  • butyl ethers examples include methyl butyl ether, butyl benzene ether, hexyl butyl ether, methoxyethyl butyl ether, and the like.
  • Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group and a hydroxyl group Addition reaction with a compound containing 1 or a compound with 1 primary or secondary amino group, addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group and a monoisocyanate Is mentioned.
  • Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (29) to (31).
  • R 1 represents a hydrogen atom or a methyl group.
  • Examples of the monoisocyanate include cyclohexylenoisocyanate, n-butynoleisocyanate, tolylisocyanate, benzylisocyanate, phenylisocyanate, and the like.
  • Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (32) to (40).
  • R 1 represents a hydrogen atom or a methyl group
  • n represents an integer of 1 or more.
  • Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n -propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-xanol).
  • alcohols for example, methanol, ethanol, n -propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-xanol.
  • Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.
  • Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexylamine).
  • the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate.
  • Suitable examples include (meth) acrylic acid 2-ethylhexyl, styrene, chlorostyrene, bromostyrene, hydroxystyrene and the like.
  • the other copolymerizable monomers may be used alone or in combination of two or more.
  • the vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Further, it can be prepared by utilizing polymerization such as so-called emulsion polymerization in a state where the monomer is dispersed in an aqueous medium.
  • the suitable solvent used in the solution polymerization method is not particularly limited and can be appropriately selected depending on the monomer to be used and the solubility of the copolymer to be produced.
  • solvents may be used alone or in combination of two or more.
  • the radical polymerization initiator is not particularly limited.
  • 2, 2'-azobis isobutyoritol-tolyl) (AIBN)
  • peracids such as benzoyl peroxide
  • persulfates such as potassium persulfate and ammonium persulfate.
  • [0325] is the content of the polymerizable compound having a carboxyl group in the vinyl copolymer, a force such as especially limited can be appropriately selected depending on the Nag purpose, preferably 5 to 50 mol 0/0 ingredients 10 to 40 mole 0/0, more preferably tool 15-35 mole 0/0 are particularly preferred. If the content is less than 5 mol%, developability in alkaline water may be insufficient.
  • the developer resistance of the cured part (image part) may be insufficient.
  • the molecular weight of the binder having a carboxyl group is a force that can be appropriately selected according to the purpose without any particular limitation.
  • the mass average molecular weight is 2,000 to 3
  • the mass average molecular weight is less than 2,000, the strength of the film may be insufficient and stable production may be difficult immediately. If it exceeds 300,000, developability may be deteriorated.
  • the above-mentioned noder having a carboxyl group may be used alone or in combination of two or more.
  • two or more binders are used in combination include, for example, two or more binders having different copolymer component forces, two or more binders having different mass average molecular weights, two or more binders having different dispersities, And the like.
  • the binder having a carboxyl group a part or all of the carboxyl group may be neutralized with a basic substance.
  • the binder is polyester You may use together resin with different structures, such as resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.
  • binder for example, a resin soluble in an alkaline solution described in Japanese Patent No. 2873889 and the like can be used.
  • the content of the binder in the photosensitive layer is not particularly limited, and can be appropriately selected according to the purpose. For example, 10 to 90% by mass is preferable 20 to 80% by mass
  • the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced.
  • the above content may be the total content of the binder and the polymer binder used in combination as necessary.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne un matériau de formation de motif permettant de supprimer ou de réduire efficacement la sensibilité d'une couche photosensible, et de former un motif précis. L'invention concerne également un dispositif et un procédé de formation de motif mettant en oeuvre ledit matériau. Au moins une couche photosensible est disposée sur un corps support, ce dernier présentant une valeur de flou non supérieure à 5 %. La couche photosensible comprend comme agent sensibilisant au moins un agent choisi dans le groupe constitué par un pigment contenant un noyau acide, un pigment contenant un noyau basique, et un agent de blanchiment fluorescent. Lorsque la couche photosensible est exposée et développée, l'épaisseur de la partie exposée de la couche photosensible ne change pas avant et après le développement. L'énergie minimum de la lumière utilisée pour l'exposition est comprise entre 0,1 et 20 (mJ/cm2).
PCT/JP2005/017825 2004-09-28 2005-09-28 Materiau, dispositif et procede de formation de motif Ceased WO2006035807A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2005800401843A CN101124516B (zh) 2004-09-28 2005-09-28 图案形成材料、以及图案形成装置和图案形成方法
JP2006537769A JPWO2006035807A1 (ja) 2004-09-28 2005-09-28 パターン形成材料、並びにパターン形成装置及びパターン形成方法

Applications Claiming Priority (6)

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JP2004282707 2004-09-28
JP2004-282707 2004-09-28
JP2004323007 2004-11-05
JP2004-323007 2004-11-05
JP2004323013 2004-11-05
JP2004-323013 2004-11-05

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WO2006035807A1 true WO2006035807A1 (fr) 2006-04-06

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PCT/JP2005/017825 Ceased WO2006035807A1 (fr) 2004-09-28 2005-09-28 Materiau, dispositif et procede de formation de motif

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JP (1) JPWO2006035807A1 (fr)
KR (1) KR20070057993A (fr)
CN (1) CN101124516B (fr)
TW (1) TW200622491A (fr)
WO (1) WO2006035807A1 (fr)

Cited By (10)

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Publication number Priority date Publication date Assignee Title
WO2007032246A1 (fr) * 2005-09-16 2007-03-22 Fujifilm Corporation Matériau de formation de motif, appareil de formation de motif, et procédé de formation de motif
JP2008116751A (ja) * 2006-11-06 2008-05-22 Asahi Kasei Electronics Co Ltd 感光性樹脂組成物及び積層体
WO2009101932A1 (fr) * 2008-02-13 2009-08-20 Fujifilm Corporation Composition colorée photosensible, filtre coloré et procédé pour produire ceux-ci
JP2009265642A (ja) * 2008-03-31 2009-11-12 Fujifilm Corp 感光性透明樹脂組成物、カラーフィルタの製造方法及びカラーフィルター
EP2096493A4 (fr) * 2006-12-19 2010-11-17 Hitachi Chemical Co Ltd Élément photosensible
EP2273315A4 (fr) * 2008-03-31 2012-01-11 Fujifilm Corp Composition durcissable, filtre de couleur et processus de production associé, et dispositif d'imagerie à semi-conducteur
WO2012111400A1 (fr) * 2011-02-18 2012-08-23 株式会社Adeka Composition colorante photosensible
WO2015072388A1 (fr) * 2013-11-13 2015-05-21 Ｄｉｃグラフィックス株式会社 Composition de vernis de revêtement durcissable aux rayons ultraviolets
WO2015098870A1 (fr) * 2013-12-27 2015-07-02 日立化成株式会社 Composition de résine photosensible, élément photosensible, procédé de formation d'un motif de réserve et procédé de fabrication d'une carte à circuit imprimé
JP2022127585A (ja) * 2021-02-19 2022-08-31 旭化成株式会社 感光性ドライフィルム

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TWI546574B (zh) * 2011-06-01 2016-08-21 Jsr股份有限公司 著色組成物、彩色濾光片及顯示元件
CN104892513B (zh) * 2015-05-21 2017-05-03 常州强力先端电子材料有限公司 一种含链烯基吡唑啉类增感剂及其制备方法和应用
WO2017110352A1 (fr) * 2015-12-25 2017-06-29 富士フイルム株式会社 Composition de résine sensible à la lumière active ou à un rayonnement, film sensible à la lumière active ou à un rayonnement, procédé de formation de motif, et procédé de production de dispositif électronique
CN110144547B (zh) * 2016-04-14 2021-06-01 凸版印刷株式会社 蒸镀掩模用基材、蒸镀掩模用基材的制造方法及蒸镀掩模的制造方法
WO2018025835A1 (fr) * 2016-08-05 2018-02-08 凸版印刷株式会社 Masque métallique de dépôt en phase vapeur, procédé de production de masque métallique de dépôt en phase vapeur, et procédé de production de dispositif d'affichage
JP7308014B2 (ja) * 2017-02-23 2023-07-13 旭化成株式会社 感光性樹脂組成物及び感光性樹脂積層体

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001042522A (ja) * 1999-05-27 2001-02-16 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
JP2001324807A (ja) * 2000-05-15 2001-11-22 Fuji Photo Film Co Ltd 光重合性組成物及びそれを用いた記録材料
JP2002268239A (ja) * 2001-03-06 2002-09-18 Fuji Photo Film Co Ltd 印刷版の製版方法
JP2002308922A (ja) * 2001-04-12 2002-10-23 Fuji Photo Film Co Ltd 光重合性組成物並びにそれを用いた記録材料
JP2003057817A (ja) * 2001-08-15 2003-02-28 Fuji Photo Film Co Ltd 光重合性組成物及びそれを用いた記録材料
JP2003295426A (ja) * 2002-03-28 2003-10-15 Agfa Gevaert Nv ３００〜４５０ｎｍの波長範囲に関して増感された光重合可能な組成物
JP2003337428A (ja) * 2002-05-20 2003-11-28 Fuji Photo Film Co Ltd 露光装置
JP2003337427A (ja) * 2002-05-20 2003-11-28 Fuji Photo Film Co Ltd 露光装置
WO2004015497A1 (fr) * 2002-08-07 2004-02-19 Mitsubishi Chemical Corporation Materiau de formation d'image comportant une couche de materiau de reserve photosensible au laser violet bleuatre et procede de formation d'image de reserve correspondant
JP2004191938A (ja) * 2002-11-27 2004-07-08 Mitsubishi Chemicals Corp 青紫色レーザー感光性組成物並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2004198446A (ja) * 2002-04-24 2004-07-15 Mitsubishi Chemicals Corp 光重合性組成物、並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2005091593A (ja) * 2003-09-16 2005-04-07 Mitsubishi Chemicals Corp 青紫色レーザー感光性組成物、並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2005274923A (ja) * 2004-03-24 2005-10-06 Fuji Photo Film Co Ltd 感光性樹脂組成物およびアクリドンオリゴマー
JP2005316174A (ja) * 2004-04-28 2005-11-10 Fuji Photo Film Co Ltd 感光性樹脂組成物およびクマリン化合物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001042522A (ja) * 1999-05-27 2001-02-16 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
JP2001324807A (ja) * 2000-05-15 2001-11-22 Fuji Photo Film Co Ltd 光重合性組成物及びそれを用いた記録材料
JP2002268239A (ja) * 2001-03-06 2002-09-18 Fuji Photo Film Co Ltd 印刷版の製版方法
JP2002308922A (ja) * 2001-04-12 2002-10-23 Fuji Photo Film Co Ltd 光重合性組成物並びにそれを用いた記録材料
JP2003057817A (ja) * 2001-08-15 2003-02-28 Fuji Photo Film Co Ltd 光重合性組成物及びそれを用いた記録材料
JP2003295426A (ja) * 2002-03-28 2003-10-15 Agfa Gevaert Nv ３００〜４５０ｎｍの波長範囲に関して増感された光重合可能な組成物
JP2004198446A (ja) * 2002-04-24 2004-07-15 Mitsubishi Chemicals Corp 光重合性組成物、並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2003337428A (ja) * 2002-05-20 2003-11-28 Fuji Photo Film Co Ltd 露光装置
JP2003337427A (ja) * 2002-05-20 2003-11-28 Fuji Photo Film Co Ltd 露光装置
WO2004015497A1 (fr) * 2002-08-07 2004-02-19 Mitsubishi Chemical Corporation Materiau de formation d'image comportant une couche de materiau de reserve photosensible au laser violet bleuatre et procede de formation d'image de reserve correspondant
JP2004191938A (ja) * 2002-11-27 2004-07-08 Mitsubishi Chemicals Corp 青紫色レーザー感光性組成物並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2005091593A (ja) * 2003-09-16 2005-04-07 Mitsubishi Chemicals Corp 青紫色レーザー感光性組成物、並びにそれを用いた画像形成材料、画像形成材、及び画像形成方法
JP2005274923A (ja) * 2004-03-24 2005-10-06 Fuji Photo Film Co Ltd 感光性樹脂組成物およびアクリドンオリゴマー
JP2005316174A (ja) * 2004-04-28 2005-11-10 Fuji Photo Film Co Ltd 感光性樹脂組成物およびクマリン化合物

Cited By (24)

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Publication number Priority date Publication date Assignee Title
WO2007032246A1 (fr) * 2005-09-16 2007-03-22 Fujifilm Corporation Matériau de formation de motif, appareil de formation de motif, et procédé de formation de motif
JP2008116751A (ja) * 2006-11-06 2008-05-22 Asahi Kasei Electronics Co Ltd 感光性樹脂組成物及び積層体
CN102707571A (zh) * 2006-12-19 2012-10-03 日立化成工业株式会社 感光性元件
EP2096493A4 (fr) * 2006-12-19 2010-11-17 Hitachi Chemical Co Ltd Élément photosensible
CN102360163A (zh) * 2006-12-19 2012-02-22 日立化成工业株式会社 感光性元件
CN102360163B (zh) * 2006-12-19 2013-06-12 日立化成株式会社 感光性元件
WO2009101932A1 (fr) * 2008-02-13 2009-08-20 Fujifilm Corporation Composition colorée photosensible, filtre coloré et procédé pour produire ceux-ci
US8980505B2 (en) 2008-02-13 2015-03-17 Fujifilm Corporation Photosensitive colored composition, color filter and method for producing the same
KR101308504B1 (ko) 2008-02-13 2013-09-17 후지필름 가부시키가이샤 감광성 착색 조성물, 컬러필터 및 그 제조방법
EP2273315A4 (fr) * 2008-03-31 2012-01-11 Fujifilm Corp Composition durcissable, filtre de couleur et processus de production associé, et dispositif d'imagerie à semi-conducteur
US8883376B2 (en) 2008-03-31 2014-11-11 Fujifilm Corporation Photosensitive transparent resin composition, production method of color filter, and color filter
US8492071B2 (en) 2008-03-31 2013-07-23 Fujifilm Corporation Curable composition, color filter and process for production thereof, and solid-state imaging device
EP2264526A4 (fr) * 2008-03-31 2011-12-28 Fujifilm Corp Composition de résine transparente photosensible, processus de production de filtres de couleur, et filtres de couleur
JP2009265642A (ja) * 2008-03-31 2009-11-12 Fujifilm Corp 感光性透明樹脂組成物、カラーフィルタの製造方法及びカラーフィルター
US20130306920A1 (en) * 2011-02-18 2013-11-21 Adeka Corporation Colored photosensitive composition
JPWO2012111400A1 (ja) * 2011-02-18 2014-07-03 株式会社Adeka 着色感光性組成物
WO2012111400A1 (fr) * 2011-02-18 2012-08-23 株式会社Adeka Composition colorante photosensible
US9239408B2 (en) 2011-02-18 2016-01-19 Adeka Corporation Colored photosensitive composition
WO2015072388A1 (fr) * 2013-11-13 2015-05-21 Ｄｉｃグラフィックス株式会社 Composition de vernis de revêtement durcissable aux rayons ultraviolets
JPWO2015072388A1 (ja) * 2013-11-13 2017-03-16 Ｄｉｃグラフィックス株式会社 紫外線硬化型コーティングニス組成物
WO2015098870A1 (fr) * 2013-12-27 2015-07-02 日立化成株式会社 Composition de résine photosensible, élément photosensible, procédé de formation d'un motif de réserve et procédé de fabrication d'une carte à circuit imprimé
JPWO2015098870A1 (ja) * 2013-12-27 2017-03-23 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
US10104781B2 (en) 2013-12-27 2018-10-16 Hitachi Chemical Company, Ltd. Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP2022127585A (ja) * 2021-02-19 2022-08-31 旭化成株式会社 感光性ドライフィルム

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CN101124516A (zh) 2008-02-13
TW200622491A (en) 2006-07-01
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JPWO2006035807A1 (ja) 2008-05-15
KR20070057993A (ko) 2007-06-07

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