WO2009113615A1 - Composition de résine photosensible, film durci de résine photosensible, et procédé de formation d'image photorésistante - Google Patents

Composition de résine photosensible, film durci de résine photosensible, et procédé de formation d'image photorésistante Download PDF

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Publication number
WO2009113615A1
WO2009113615A1 PCT/JP2009/054765 JP2009054765W WO2009113615A1 WO 2009113615 A1 WO2009113615 A1 WO 2009113615A1 JP 2009054765 W JP2009054765 W JP 2009054765W WO 2009113615 A1 WO2009113615 A1 WO 2009113615A1
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Prior art keywords
group
photosensitive resin
composition
acrylate
meth
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PCT/JP2009/054765
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English (en)
Japanese (ja)
Inventor
守正 佐藤
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富士フイルム株式会社
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Priority claimed from JP2008064540A external-priority patent/JP2009222792A/ja
Priority claimed from JP2008064535A external-priority patent/JP2009222791A/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2009113615A1 publication Critical patent/WO2009113615A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive resin cured film, and a light-shielding image forming method.
  • the present invention relates to a photosensitive resin composition and a photosensitive resin cured film suitable for a liquid crystal display member, and further, a black matrix for a liquid crystal display device.
  • CMOS complementary metal-oxide-semiconductor
  • CF color filters
  • BM black matrix
  • the resin BM is usually formed by a photolithography process using a black photosensitive resin composition comprising a black pigment, an alkali-soluble binder, and a polymerizable monomer.
  • the current problem of the resin BM is that the film thickness becomes thicker than the BM of the Cr film, the flatness of the completed CF is poor, and a flattening process by surface polishing that was not performed in the Cr film BM is necessary. Moreover, due to its light shielding properties, there are still problems in pattern formation and profile. Although a further thinning has been studied from the review of the black pigment, the film thickness is limited from the viewpoint of patterning properties. In particular, when the film thickness is 1 ⁇ m or less, the ratio of light-shielding components such as carbon contained in the solid text increases, and there are problems such as adhesion and developability, which is difficult to realize.
  • the embossing technology well-known in optical disc production, and pressed the resist on a die mold (generally called mold, stamper, template) with a concave / convex pattern, and mechanically deformed it. Then, a technique (nanoimprint method) for precisely transferring a fine pattern is being developed.
  • the nanoimprint method is economical because it can be easily repetitively molded with fine structures such as nanostructures once a mold is fabricated, and it is a nanofabrication technology with less harmful waste and emissions. Application to the field is expected.
  • Non-patent Document 1 a thermal nanoimprint method using a thermoplastic resin as a material to be processed
  • Non-patent Document 2 an optical nanoimprint method using a curable composition for optical nanoimprint lithography
  • Patent Document 1 and Patent Document 2 disclose a nanoimprint method in which a nanopattern is formed at low cost using a thermoplastic resin.
  • the second is to build a laminated structure by simultaneously forming a microstructure and a nanostructure, or by simple alignment between layers, and try to apply it to the production of ⁇ -TAS and biochips.
  • the third is to apply high-precision alignment and high integration to the production of a high-density semiconductor integrated circuit in place of the conventional lithography, the production of a liquid crystal display in a transistor, and the like.
  • a silicon wafer is used as a stamper, and a nanoimprint in which a fine structure of 25 nanometers or less is formed by transfer. Technology is disclosed.
  • Patent Document 4 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography.
  • studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as micro mold fabrication technology, mold durability, mold fabrication cost, mold releasability from resin, imprint uniformity and alignment accuracy, inspection technology, etc. It started to become active. These are mainly developments in nano-scale patterning, and no efforts related to BM pattern formation have been disclosed so far.
  • the composition used in optical nanoimprinting although there is a description of a demand for viscosity, there has been no report on a composition having a black pigment.
  • the main technical issues as a black matrix include many issues such as thinning, pattern accuracy, adhesion, and solvent resistance. Especially for thinning, it is necessary to contain a black pigment such as carbon black at a high concentration.
  • a black pigment such as carbon black at a high concentration.
  • the coloring pigment component such as carbon black
  • the formation of a black matrix by the conventional photolithography method has a limitation that it is not possible to limit the binder type and the amount of addition due to its development suitability.
  • Patent Document 5 discloses a method of forming fine irregularities on the surface of the black matrix by the imprint method to develop ink repellency, but does not disclose forming the black matrix itself.
  • the present invention has been accomplished in view of the above prior art, and provides a photosensitive resin composition and a photosensitive resin cured film suitable for a liquid crystal display member, and further, a black matrix for a liquid crystal display device. Objective. In particular, it is an object of the present invention to provide a photosensitive resin composition which is a thin film and has a high optical density and which is comprehensively excellent in pattern accuracy, peelability, hardness, chipping defect and solvent resistance.
  • an object of the present invention is to provide a composition capable of forming an image by a conventionally known image forming method.
  • composition (2) It is characterized by containing at least 10% by weight or more of a colorant and a polymerizable monomer in a state substantially free of solvent after drying, and having a viscosity of 3 to 50 mPa ⁇ s.
  • Photosensitive resin composition It is characterized by containing at least 10% by weight or more of a colorant and a polymerizable monomer in a state substantially free of solvent after drying, and having a viscosity of 3 to 50 mPa ⁇ s.
  • the viscosity is A photosensitive resin composition having a composition of 3 to 50 mPa ⁇ s, wherein the cured film having a thickness of 1 ⁇ m obtained by curing the composition has an optical density of 3.5 or more.
  • At least one of Y in the general formula (1) is a vinyl ether group, an allyl ether group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group, a methacryloylamide group, or an acrylamide group.
  • the photosensitive resin composition according to (6) selected from the group consisting of vinyl silane group, N-vinyl heterocyclic group and maleimide group.
  • the photosensitive resin composition as described in (6) whose at least 1 of Y in General formula (1) is an isocyanate group or a nitrile group.
  • (11) A cured product obtained by curing the photosensitive resin composition according to any one of (1) to (10).
  • the viscosity is A cured photosensitive resin film having an optical density of 3.5 or more and a thickness of 1 ⁇ m or less, obtained by curing a composition of 3 to 50 mPa ⁇ s.
  • the cured photosensitive resin film according to (12), wherein the colorant is a black colorant.
  • the cured photosensitive resin film according to (12), wherein the colorant is silver or a black colorant containing silver.
  • At least one of Y in the general formula (1) is a vinyl ether group, an allyl ether group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group, a methacryloylamide group, or an acrylamide group.
  • a light-shielding image forming method comprising the following steps. (1) Step of providing a photosensitive resin layer on the substrate using the photosensitive resin composition according to any one of (1) to (10) (2) Heat treatment at 50 to 150 ° C.
  • the method according to the steps (20) and (19) of heat-treating the photosensitive resin layer at 160 to 250 ° C. if necessary A cured cured photosensitive resin film.
  • (21) The cured photosensitive resin film according to any one of (12) to (18) and (20), wherein the cured photosensitive resin film is a member for a liquid crystal display device.
  • a photosensitive resin composition and a cured photosensitive resin film suitable for a liquid crystal display member, and further a black matrix for a liquid crystal display device it is possible to obtain a photosensitive resin composition and a cured photosensitive resin film suitable for a liquid crystal display member, and further a black matrix for a liquid crystal display device.
  • a cured photosensitive resin film having a high optical density even in a thin film and excellent in overall pattern accuracy, peelability, hardness, chipping defect, and solvent resistance can be obtained.
  • the viscosity of the composition after removing the solvent exceeds 1000 mPa ⁇ s, a sufficient image cannot be formed by the imprint method, but the viscosity is set to 3 to 50 mPa ⁇ s.
  • a desired pattern can be formed by the imprint method.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • a monomer and a monomer in this specification are synonymous.
  • the monomer in the present specification is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers.
  • the functional group refers to a group involved in polymerization.
  • the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several tens of ⁇ m to several tens of nm, and is not necessarily limited to nano order.
  • the photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) has high permeability before curing, excellent ability to form a fine concavo-convex pattern, and coating. It can be made excellent in aptitude and other process aptitudes. Moreover, after hardening, it is excellent in hardness, and also it can be set as the film property which was comprehensively excellent in other points. Therefore, the composition of the present invention can be widely used for optical nanoimprint lithography.
  • the composition of the present invention can have the following characteristics when used in optical nanoimprint lithography.
  • (2) The cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peeling properties between the coating film and the mold. Since pulling does not cause surface roughness, a good pattern can be formed.
  • composition of the present invention is suitably applied to semiconductor integrated circuits and liquid crystal display device members that have been difficult to develop until now (particularly for light-shielding films for liquid crystal displays and other fine processing applications for liquid crystal display device members).
  • Other applications for example, light shielding films for plasma display panels, flat screens, micro electro mechanical systems (MEMS), sensor elements, optical recording media such as high-density memory disks, optical components such as diffraction grating relief holograms, etc.
  • the viscosity of the composition of the present invention will be described.
  • the viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified.
  • the composition of the present invention has a viscosity at 25 ° C. of 3 to 50 mPa ⁇ s, preferably 3 to 30 mPa ⁇ s, and more preferably 3 to 20 mPa ⁇ s in a state substantially free of solvent after drying. s, particularly preferably 3 to 15 mPa ⁇ s.
  • the viscosity of the composition of the present invention by setting the viscosity to 3 mPa ⁇ s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application.
  • the viscosity of the composition of the present invention by setting the viscosity of the composition of the present invention to 50 mPa ⁇ s or less, even when a mold having a fine concavo-convex pattern is closely attached to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for the residue to remain after photocuring in the mold convex portion.
  • the composition of the present invention is preferably used so that the film thickness after curing is 5 ⁇ m or less. Particularly preferred is 0.5 to 3.0 ⁇ m. When the thickness exceeds 5 ⁇ m, a defect may be easily generated at the time of peeling from the mold. Even if the composition of the present invention is thinned in this way, it should have a high optical density and be a cured film that is comprehensively excellent in pattern accuracy, peelability, hardness, chipping defects, and solvent resistance. Can do. In particular, when silver or a black colorant containing silver is used as the pigment of the colorant, the present invention is extremely significant in that such a thin film can be formed. In the composition of the present invention, the optical density of a cured film having a thickness of 1 ⁇ m obtained by curing the composition is 3.5 or more, and preferably 4.0 or more.
  • composition of the present invention “in a state substantially free of solvent after drying” is, for example, a state in which the amount of residual solvent is 0.1% by weight or less and contains no solvent at all. Most preferred.
  • the composition of the present invention may contain a known organic solvent in advance. When the solvent is substantially contained in the state before drying, the amount of the solvent is selected so that the solid content concentration is 10 to 99% by mass.
  • the organic solvent that can be preferably used in the composition of the present invention is a solvent that is generally used in a curable composition for optical nanoimprint lithography and a photoresist, and dissolves and uniformly disperses the compound used in the present invention. Any material can be used as long as it does not react with these components.
  • organic solvent for example, those described in paragraph No. 0088 of JP-A No. 2008-105414 can be preferably used. These may be used alone or in combination of two or more.
  • methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable. These solvents may be used alone or in combination of two or more.
  • methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone and 2-heptanone are particularly preferable.
  • the photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) has at least 10% by mass of a colorant and a polymerizable monomer in a state substantially free of solvent after drying.
  • a photosensitive resin composition containing a monomer and having a viscosity of 3 to 50 mPa ⁇ s (hereinafter sometimes referred to as “photosensitive composition (A)”), or at least colored.
  • the viscosity is 3 to 50 mPa ⁇ s.
  • a photosensitive resin composition (hereinafter referred to as “photosensitive composition”), wherein the optical density of a cured film having a thickness of 1 ⁇ m obtained by curing the composition is 3.5 or more. (B) ").
  • the colorant and the polymerizable monomer may be only one type, or two or more types (hereinafter referred to as “the monomer in the present invention” and “the other polymerizable monomer”). Yes).
  • the composition of the present invention may contain other polymerizable monomer, photopolymerization initiator, and the like in addition to the colorant which is an essential component and the monomer in the present invention. Hereinafter, these contents will be described in detail.
  • the monomer contained in the composition of the present invention (hereinafter sometimes referred to as “monomer in the present invention”) will be described. There may be only one type of monomer in the present invention, or two or more types.
  • the composition of the present invention contains the monomer according to the present invention in a range of preferably 10 to 99% by mass, more preferably 20 to 80% by mass based on the total solid content of the composition.
  • the monomer in the present invention is preferably a monomer represented by the general formula (1).
  • R 1 represents a hydrogen atom, or a hydroxymethyl group
  • .Y X is .m represents an organic group represents an integer of 1 to 3
  • n is an integer of 1-4 Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group. (R 2 represents an alkyl group or an aryl group, respectively.)
  • the organic group represented by X preferably represents a divalent to 7-valent organic group, and may be aliphatic or aromatic, and the total number of carbon atoms is preferably 2 to 20. Further, the organic group may be blocked with an oxygen atom, a sulfur atom, an ester group, or a urethane group. Specific examples include a propanetriol skeleton, a pentaerythritol skeleton, and an aliphatic cyclic skeleton.
  • the curable functional group having a carbon-carbon unsaturated bond represented by Y may be either a double bond or a triple bond, and may have a substituent on the unsaturated bond, either a chain or a ring. It may be. The total carbon number is preferably 2-18.
  • vinyl ether group, allyl ether group, cyclohexenyl group, cyclopentenyl group, dicyclopenenyl group, styryl group, methacryloyloxy group, methacryloylamide group, acrylamide group, vinylsilane group, N-vinyl heterocyclic group and A maleimide group may be mentioned.
  • the curable functional group having a carbon-nitrogen unsaturated bond represented by Y include an isocyanate group and a nitrile group.
  • the curable functional group containing a cyclic group containing an oxygen atom represented by Y include an oxirane ring, an oxetane ring, and an ethylene carbonate group.
  • the alkyl group represented by R 2 is preferably an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms. Examples of such an aryl group include a phenyl group, a p-tolyl group, and a p-chlorophenyl group.
  • m is preferably 1 or 2
  • n is preferably 1 to 3. When m is 2 or more, the plurality of R 1 may be the same or different from each other. When n is 2 or more, the plurality of Y may be the same or different.
  • composition of the present invention may further contain other polymerizable monomers for the purpose of improving the composition viscosity, film hardness, flexibility and the like.
  • the polymerizable monomer is preferably a polymerizable monomer having a bifunctional or higher polymerizable functional group.
  • it is preferable that 50% by weight or more of the other polymerizable monomer contained in the composition of the present invention is a polymerizable monomer having a bifunctional or higher functional group.
  • other polymerizable monomers used in the present invention will be described in detail.
  • Another polymerizable monomer of the present invention includes a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer).
  • a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group monofunctional polymerizable unsaturated monomer.
  • a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups examples include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meta ) Acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di (meth)
  • neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like are preferably used in the present invention.
  • Examples of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meta) ) Acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) Acrylate, dipent
  • EO-modified glycerol tri (meth) acrylate PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.
  • a polyfunctional oligomer or polymer having a higher molecular weight than that of the other polyfunctional polymerizable monomer is blended within the range of achieving the object of the present invention.
  • the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, and polyepoxy acrylate.
  • a compound having an oxirane ring can also be employed.
  • the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.
  • epoxy compound examples include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol.
  • bisphenol A diglycidyl ether bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.
  • Examples of commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.
  • a vinyl ether compound may be used in combination.
  • the vinyl ether compound may be appropriately selected.
  • vinyl ether compounds are, for example, the method described in Stephen C. Lapin, Polymers Paint Paint, Journal 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.
  • styrene derivatives can be employed as other polymerizable monomers used in the present invention.
  • examples of the styrene derivative include p-methoxystyrene, p-methoxy- ⁇ -methylstyrene, p-hydroxystyrene, and the like.
  • trifluoroethyl (meth) acrylate pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl
  • fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc.
  • fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoro
  • propenyl ether and butenyl ether can be blended.
  • the other polymerizable monomer is preferably included in the composition of the present invention in the range of 10 to 90% by mass, and more preferably in the range of 20 to 80% by mass.
  • the polymerizable monomer having a bifunctional or higher polymerizable functional group preferably accounts for 50% by weight or more of the other polymerizable monomer.
  • the composition of the present invention has two or more kinds of curable functional groups having different reactivity in the same molecule, and at least one of the curable functional groups is an ⁇ , ⁇ -unsaturated ester group. It is preferable that the body is an essential component and contains other polymerizable monomers. Monofunctional polymerizable monomers are usually used as reactive diluents and are effective in reducing the viscosity of the composition of the present invention.
  • the amount used is adjusted in consideration of the balance between the composition viscosity and the mechanical strength of the cured film.
  • the use ratio of the monofunctional polymerizable monomer is preferably 15% by mass or more of the total polymerizable unsaturated monomer in order to suppress the viscosity reduction of the composition.
  • the content is preferably 30% by mass or less based on the total polymerizable unsaturated monomer.
  • a bifunctional and trifunctional polymerizable monomer In order to improve the mechanical strength of the cured film, it is preferable to use a bifunctional and trifunctional polymerizable monomer, and in particular, the mechanical strength can be improved by using a trifunctional polymerizable monomer.
  • the monomer having two unsaturated bond-containing groups is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less.
  • the ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. % Is added.
  • the ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered
  • colorant in the present invention The colorant contained in the composition of the present invention (hereinafter sometimes referred to as “colorant in the present invention”) will be described.
  • the content of the colorant in the solid content of the composition of the present invention is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 70% by mass from the viewpoint of light shielding properties. More preferably. If it is less than 20% by mass, the shielding properties are not sufficient, and if it exceeds 80% by mass, there is a problem that the pattern hardness is insufficient.
  • organic pigments, inorganic pigments, dyes and the like can be preferably used.
  • pigments and dyes described in paragraph numbers 0038 to 0054 of JP-A-2005-17716 The pigments described in paragraph Nos. 0068 to 0072 of JP-A No. 2004-361447 and the colorants described in paragraph Nos. 0080 to 0088 of JP-A No. 2005-17521 can be suitably used.
  • Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150 , 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36, 37, CIPigment Brown 25 28, CIPigment Black 1, 7 and carbon black.
  • pigments such as red, blue, and green other than light-shielding agents, such as metal oxide powders, such as carbon black, titanium oxide, and iron oxide, metal sulfide powder, and metal powder.
  • metal oxide powders such as carbon black, titanium oxide, and iron oxide, metal sulfide powder, and metal powder.
  • inorganic pigments are metal compounds such as metal oxides and metal complex salts.
  • metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony
  • metal composite oxides can also be mentioned as preferred examples.
  • the pigment is preferably used as a dispersion.
  • This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent or a vehicle.
  • the vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted.
  • Component organic solvent
  • the disperser used for dispersing the pigment is not particularly limited.
  • a kneader or a roll mill described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, Item 438.
  • known dispersers such as an atrider, a super mill, a dissolver, a homomixer, and a sand mill.
  • the material may be finely pulverized using frictional force by mechanical grinding described in Item 310 of the document.
  • a dispersion treatment is carried out in advance in a system containing a highly volatile (low boiling point) solvent, and then the solvent is volatilized or the monomer is gradually removed simultaneously with the solvent volatilization.
  • the colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 1 ⁇ m, more preferably 0.01 to 0.5 ⁇ m, more preferably 0.01 to 0, from the viewpoint of dispersion stability. A thickness of 0.1 ⁇ m is more preferable, and a thickness of 0.02 to 0.08 is particularly preferable. On the other hand, when the pigment number average particle size exceeds 0.1 ⁇ m, the light shielding property is lowered, which is not preferable.
  • particle size refers to the diameter when the electron micrograph image of the particle is a circle of the same area
  • number average particle size refers to the above-mentioned particle size for a large number of particles, This means the average value of 100 pieces.
  • pigments are generally roughly classified into organic pigments and inorganic pigments.
  • examples of pigments that can be suitably used in the present invention include colorants described in paragraphs 0038 to 0040 of JP-A-2005-17716, Examples thereof include pigments described in paragraph Nos. 0068 to 0072 of JP-A No. 2005-361447 and colorants described in paragraph Nos. 0080 to 0088 of JP-A No. 2005-17521.
  • pigments carbon black, titanium black or graphite is preferable.
  • at least one colorant is carbon black from the viewpoint of light shielding properties and cost.
  • carbon black Pigment Black 7 (carbon black CI No. 77266) is preferable.
  • Examples of commercially available products include Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (manufactured by Mitsubishi Chemical Corporation).
  • titanium black TiO 2 , TiO, TiN and a mixture thereof are preferable.
  • examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation.
  • the average particle size of titanium black is preferably 40 to 100 nm.
  • particles having a Stokes diameter of 3 ⁇ m or less are preferable. By using graphite of 3 ⁇ m or less, the contour shape of the light shielding pattern becomes uniform, and the sharpness is improved.
  • the abundance ratio of particles having a particle size of 0.1 ⁇ m or less is 70% by mass or more in graphite.
  • the pigments may be used alone or in combination of two or more.
  • Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. Combinations and combinations of blue, violet and black pigments can be mentioned.
  • the sphere equivalent diameter of the pigment is preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 1 ⁇ m, and particularly preferably 20 nm to 0.5 ⁇ m for color filters.
  • the composition of the present invention contains metal particles or a colorant containing metal (hereinafter sometimes referred to as “metal-based fine particles in the present invention”) as at least one black colorant. It is also preferable. Thereby, the member for display apparatuses from which a high optical density is obtained with a thin film can be formed.
  • the metal in the metal particles and the metal-containing particles is not particularly limited, and any metal may be used.
  • the metal particles may be a combination of two or more metals, or may be an alloy.
  • the metal-containing particles may be metal compound particles having at least one kind of metal, and may be composite particles of a metal and a metal compound.
  • Metal particle As the metal particle, it is preferable that a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is contained as a main component (60% by mass or more). . Further, it is preferable to contain a metal selected from the group consisting of Groups 2 to 14, and Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13 and Group More preferably, a metal selected from the group consisting of Group 14 is included as a main component. Among these metals, the metal particles are metals in the fourth period, the fifth period, or the sixth period, and are metals in Group 2, Group 10, Group 11, Group 12, or Group 14. Are more preferred.
  • preferable metals constituting the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, and tantel. And at least one selected from titanium, bismuth, antimony, lead, and alloys thereof. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium, and alloys thereof, and more preferable metals are copper, silver, gold, platinum, palladium, tin, and calcium.
  • At least one selected from these alloys, and particularly preferred metals are at least one selected from copper, silver, gold, platinum, tin, and alloys thereof.
  • silver or an alloy thereof is preferable (colloidal silver is preferable as silver), and particles having a silver-tin alloy part are most preferable.
  • grains which have a silver tin alloy part are mentioned later.
  • Metal Compound Particle is a compound of the metal and an element other than the metal.
  • the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles.
  • sulfide particles are preferred because of their color tone and ease of fine particle formation.
  • the metal compound include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), and titanium black. From the viewpoint of color tone, ease of fine particle formation and stability, silver sulfide is particularly preferable. preferable.
  • Composite Particles are those in which a metal and a metal compound are combined into one particle.
  • a metal and a metal compound are combined into one particle.
  • grains united can be mentioned.
  • each of the metal compound and the metal may be one type or two or more types.
  • the composite fine particles of the metal compound and the metal preferably include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.
  • the metal fine particles in the present invention may be core-shell type composite particles (core-shell particles). Core-shell type composite particles (core-shell particles) are obtained by coating the surface of a core material with a shell material. Specific examples of the core-shell type composite particles (core-shell particles) described in paragraphs 0024 to 0027 of JP-A-2006-18210 -Shell fine particles are mentioned.
  • Particles having a silver-tin alloy part At least one of the metal-based fine particles in the present invention is preferably particles having a silver-tin alloy part.
  • the particles having a silver-tin alloy part include those made of a silver-tin alloy part, those made of a silver-tin alloy part and another metal part, and those made of a silver-tin alloy part and another alloy part.
  • At least a part is composed of a silver-tin alloy.
  • a silver-tin alloy for example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X) manufactured by Noran Co., Ltd. And a spectrum measurement of the center 15 nm ⁇ area of each particle with an acceleration voltage of 200 kV.
  • Particles having a silver-tin alloy part have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability, so that they do not impair the black density at high temperatures (for example, 200 degrees or more). ), And a high degree of light shielding properties can be stably secured.
  • a light-shielding film so-called black matrix
  • a color filter that is required to have a high light-shielding property and is generally subjected to a baking process.
  • the particles having a silver-tin alloy part are preferably obtained by combining (for example, alloying) Ag and tin (Sn) at a silver (Ag) ratio of 30 to 80 mol% with respect to tin (Sn). .
  • Ag ratio in the above-described range, it is possible to obtain a high black density with high thermal stability at a high temperature range and low light reflectance.
  • particles having an Ag ratio of 75 mol%, that is, AgSn alloy particles are easy to produce, and the obtained particles are also stable and preferable.
  • Particles having a silver-tin alloy part can be formed by alloying by a general method such as heating, melting and mixing in a crucible or the like, but the melting point of Ag is around 900 ° C. Since the melting point of Sn is around 200 ° C. and there is a large difference between the melting points of the two, and an extra fine particle forming step after compounding (for example, alloying) is required, it is preferable to use the particle reduction method. . That is, the Ag compound and the Sn compound are mixed and reduced, and the metal Ag and the metal Sn are simultaneously precipitated at a position close to each other, thereby achieving composite (for example, alloying) and micronization at the same time. It is. Since Ag tends to be reduced and tends to precipitate before Sn, it is preferable to control the precipitation timing by making Ag and / or Sn a complex salt.
  • Preferred examples of the Ag compound include silver nitrate (AgNO 3 ), silver acetate (Ag (CH 3 COO)), silver perchlorate (AgClO 4 .H 2 O), and the like. Of these, silver acetate is particularly preferred.
  • Preferred examples of the Sn compound include stannous chloride (SnCl 2 ), stannic chloride (SnCl 4 ), and stannous acetate (Sn (CH 3 COO) 2 ). Of these, stannous acetate is particularly preferable.
  • a method using a reducing agent As the reduction, a method using a reducing agent, a method of reducing by electrolysis, and the like can be cited as preferable reduction methods.
  • the former method using a reducing agent is preferable in that fine particles can be obtained.
  • the reducing agent include cetyltrimethylammonium bromide (CTAB), ascorbic acid, hydroquinone, catechol, paraaminophenol, paraphenylenediamine, and hydroxyacetone.
  • CTAB cetyltrimethylammonium bromide
  • ascorbic acid hydroquinone
  • catechol catechol
  • paraaminophenol paraphenylenediamine
  • hydroxyacetone is particularly preferable because it is easily volatilized and does not adversely affect the display device.
  • the metal-based fine particles in the present invention can be commercially available, and can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
  • rod-shaped silver fine particles can be obtained by adding spherical silver fine particles as seed particles and then adding a silver salt and using a reducing agent having a relatively low reducing power such as ascorbic acid in the presence of a surfactant such as CTAB.
  • a surfactant such as CTAB.
  • Silver bars and wires can be obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.
  • the metal-based fine particles in the present invention can be obtained by combining various types of particles so as to be closer to an achromatic color. For example, a higher transmission density can be obtained by combining particles whose shape is changed from spherical or cubic to flat (hexagonal, triangular) or rod-like. By using such metal-based fine particles, a thin film can be achieved when the light shielding layer is formed.
  • the particle size distribution of the metal-based fine particles it is preferable that the particle distribution is approximated to a normal distribution, and the particle size distribution width D 90 / D 10 of the number average particle size is 1.2 or more and less than 50.
  • the particle size is the major axis length L as the particle diameter
  • D 90 is the particle diameter at which 90% of particles close to the average particle size are found
  • D 10 is the particle diameter close to the average particle size. 10% is the particle diameter found.
  • the particle size distribution width is preferably 2 to 30, more preferably 4 to 25, from the viewpoint of color tone. If the distribution width is less than 1.2, the color tone may be close to a single color, and if it is 50 or more, turbidity may occur due to scattering by coarse particles.
  • the measurement of the particle size distribution width D 90 / D 10 is specifically performed by measuring 100 metal particles in the film at random by a method of measuring a triaxial diameter to be described later, and determining the major axis length L. and particle diameter, the particle size distribution was a normal distribution approximation, the average particle diameter in the range of 90% by the number of close particle particle size and D 90, a particle diameter in the range number of 10% from the average grain size with D 10, it is possible to calculate the D 90 / D 10.
  • the metal-based fine particles in the present invention are captured as a rectangular parallelepiped by the following method, and each dimension is measured. That is, a rectangular parallelepiped box in which one metal-based fine particle fits exactly (tightly) is considered, and the longest length of the box is defined as the long axis length L, and the thickness t, width b Is defined as the size of the metal-based fine particles.
  • the dimensions have a relationship of L> b ⁇ t, and the larger of b and t is defined as the width b unless otherwise the same.
  • metal-based fine particles are placed on a flat surface so that the center of gravity is the lowest and remains stable.
  • metal-based fine particles are sandwiched between two parallel flat plates standing at right angles to the plane, and the flat plate interval at the position where the flat plate interval is the shortest is maintained.
  • metal-based fine particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the flat plate interval and are also perpendicular to the flat surface, and the distance between the two flat plates is maintained.
  • the top plate is placed parallel to the plane so as to come into contact with the highest position of the metal-based fine particles.
  • the major axis length L is preferably 10 nm to 1000 nm, more preferably 10 nm to 800 nm, and 20 nm to 400 nm (shorter than the wavelength of visible light). Most preferred.
  • L is 10 nm or more, there is an advantage that preparation in production is simple and heat resistance and color are good, and when L is 1000 nm or less, there are advantages that there are few planar defects.
  • the ratio between width b and thickness t is defined as the average value of values measured for 100 rod-shaped metal fine particles.
  • the ratio (b / t) between the width b and the thickness t of the rod-like metal-based fine particles is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.3 or less. preferable. If the b / t ratio exceeds 2.0, it may be nearly flat and heat resistance may be reduced.
  • the relationship between the major axis length L and the width b and thickness t The major axis length L is preferably 1.2 to 100 times the width b, more preferably 1.3 to 50 times. It is particularly preferably 1.4 to 20 times.
  • the major axis length L is less than 1.2 times the width b, the characteristics of a flat plate may appear and the heat resistance may deteriorate.
  • the major axis length L exceeds 100 times the width b, the black density may become low, and the high density of the thin layer may not be achieved.
  • Measurement of length L, width b, and thickness t can be made with an electron microscope surface observation ( ⁇ 500000) and an atomic force microscope (AFM). The average value of the values measured for 100 rod-shaped metal fine particles.
  • the atomic force microscope (AFM) has several operation modes, which are selectively used depending on the application. Broadly divided into the following three. (1) Contact method: A method in which the probe is brought into contact with the sample surface and the surface shape is measured from the displacement of the cantilever. (2) A tapping method: The probe is periodically brought into contact with the sample surface, and the surface shape is determined from the change in vibration amplitude of the cantilever. (3) Non-contact method: A method for measuring the surface shape from changes in the cantilever vibration frequency without contacting the probe with the sample surface.
  • the non-contact method needs to detect extremely weak attractive force with high sensitivity. For this reason, it is difficult to detect static force by directly measuring the displacement of the cantilever, and the mechanical resonance of the cantilever is applied.
  • the above three methods can be mentioned, but any method can be selected according to the sample.
  • the electron microscope can be measured at an acceleration voltage of 200 kV using an electron microscope JEM2010 manufactured by JEOL.
  • An example of the atomic force microscope (AFM) is SPA-400 manufactured by Seiko Instruments Inc.
  • the measurement is facilitated by inserting polystyrene beads in the comparison.
  • metal particles, particles containing an alloy, or metal compound particles are preferable as the metal particles or metal-containing particles, silver particles, particles containing a silver alloy or silver compound particles are more preferable, and have a silver-tin alloy part. Particles are most preferred.
  • the number average particle size of metal particles or metal-containing particles is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, and particularly preferably 0.05 ⁇ m or less.
  • the number average particle size of the particles is 0.1 ⁇ m or less, the surface smoothness is good and the defects due to coarse particles are reduced.
  • the metal-based fine particles in the photosensitive composition (B) are preferably present in a stable dispersed state, for example, more preferably in a colloidal state.
  • the metal fine particles are substantially dispersed in the fine particle state.
  • substantially dispersed refers to a state in which primary particles are dispersed independently without being aggregated or softly aggregated.
  • the dispersant for dispersion and the additive that may be added to the composition of the present invention include the dispersants and additives described in paragraph Nos. 0027 to 0031 of JP-A-2005-17322. Are also preferred.
  • the content of the metal-based fine particles (and, if necessary, the pigment) in the photosensitive composition (B) of the present invention is, for example, metal-based fine particles (and, if necessary, at the time of post-baking such as during the production of a color filter).
  • the content of the metal-based fine particles (and the pigment as necessary) is preferably determined in consideration of the change in optical density due to the average particle size.
  • the pigment is desirably used as a dispersion.
  • This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle).
  • vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state.
  • the portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent).
  • the disperser used for dispersing the pigment is not particularly limited.
  • a dispersion treatment is carried out in advance in a system containing a highly volatile (low boiling point) solvent, and then the solvent is volatilized or the monomer is gradually removed simultaneously with the solvent volatilization. It can be added to finally remove the solvent.
  • the monomer can be used as a diluent medium and dispersed.
  • a dispersion aid may be used in combination when preparing the dispersion.
  • the colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 1 ⁇ m, more preferably 0.01 to 0.5 ⁇ m, more preferably 0.01 to 0, from the viewpoint of dispersion stability. A thickness of 0.1 ⁇ m is more preferable, and a thickness of 0.02 to 0.08 is particularly preferable. On the other hand, when the pigment number average particle size exceeds 0.1 ⁇ m, the light shielding property is lowered, which is not preferable.
  • particle size refers to the diameter when the electron micrograph image of the particle is a circle of the same area
  • number average particle size refers to the above-mentioned particle size for a large number of particles, This means the average value of 100 pieces.
  • the composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator used in the present invention contains, for example, 0.1 to 15% by mass in the total composition, preferably 0.2 to 12% by mass, and more preferably 0.3 to 10% by mass. %.
  • the total amount becomes the said range.
  • the ratio of the photopolymerization initiator is 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved.
  • the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable.
  • a photopolymerization initiator that is active with respect to the wavelength of the light source to be used is mixed to generate an appropriate active species.
  • radical photopolymerization initiator used in the present invention for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A No. 2008-105414 can be preferably used.
  • a photosensitizer may be added to the composition of the present invention to adjust the wavelength in the UV region.
  • Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymers Sci, 62, 1 (1984)], specifically pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.
  • Surfactant A surfactant may be added to the composition of the present invention, and the surfactant used in the present invention contains, for example, 0.001 to 5% by mass in the total composition, preferably It is 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass. When using 2 or more types of surfactant, the total amount becomes the said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity may be insufficient. On the other hand, if it exceeds 5% by mass, mold transfer characteristics may be deteriorated.
  • the surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant.
  • both the fluorine-based surfactant and the silicone-based surfactant or fluorine -More preferably, a silicone-based surfactant is included, and most preferably, a fluorine-silicone-based surfactant is included.
  • the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
  • Striations and scale-like patterns that occur during coating on the substrate such as alloy films, silicon nitride films, amorphous silicone films, various films such as tin oxide-doped indium oxide (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) films and tin oxide films (ITO) (ITO) films and tin oxide films (ITO) (ITO) films and tin oxide films (ITO) (ITO) films and tin oxide films (ITO) (ITO) films and tin oxide films (ITO) (ITO) films and tin oxide films (ITO) (ITO)
  • nonionic fluorosurfactant used in the present invention examples include trade names Florard FC-430 and FC-431 (manufactured by Sumitomo 3M), trade names Surflon “S-382” (manufactured by Asahi Glass Co., Ltd.), EFTOP “ EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 ”(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 ( All are OMNOVA), brand names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) ), Trade name Megafuk 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of nonionic silicon-based
  • fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.).
  • Product names, Megafuk R-08 and XRB-4 both manufactured by Dainippon Ink & Chemicals, Inc.).
  • the composition of the present invention may contain a known antioxidant. By including an antioxidant, the film thickness reduction can be further reduced.
  • the antioxidant used in the present invention contains, for example, 0.01 to 10% by mass, preferably 0.2 to 5% by mass in the total composition. When using 2 or more types of antioxidant, the total amount becomes the said range. Antioxidants have the advantage of being able to reduce film thickness reduction due to decomposition.
  • antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.
  • hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.
  • Irganox 1010, 1035, 1076, 1222 manufactured by Ciba Geigy Co., Ltd.
  • Antigene P, 3C, FR Sumilyzer S, Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
  • ADK STAB AO70, AO80, AO503 made by ADEKA Co., Ltd.
  • Binder The composition of the present invention may contain a binder.
  • Various known polymers can be used as the binder.
  • the binder used from the viewpoint of developability needs to be alkali-soluble such as an acid group, but the binder used in the present invention is not limited thereto.
  • organic polymer materials described in JP-A-5-72724 are preferable, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, and ethylene and acrylic.
  • Acid ester or saponified product thereof polyvinyl chloride, vinyl chloride copolymer such as vinyl chloride and vinyl acetate and saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene and (meth) acrylic acid ester or Styrene copolymer such as saponified product, polyvinyltoluene, vinyltoluene and (meth) acrylic ester or vinyltoluene copolymer such as saponified product, poly (meth) acrylate, butyl (meth) acrylate And (meth) acrylic acid esters such as vinyl acetate Polymers, vinyl copolymers nylon acetate, copolymer nylon, N- alkoxymethyl nylon, organic polymeric polyamide resins such as N- dimethylamino nylon and the like.
  • the binder used has a weight average molecular weight of 1,000 to 100,000, and if it is 1000 or less, the effect as a binder cannot be obtained, and if it exceeds 100,000, the viscosity of the composition of the present invention becomes too high.
  • the amount of the binder added is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total solid content. When the amount is more than 10% by weight, the pigment addition amount and the monomer addition amount tend to be relatively reduced, and the strength of the cured product and the optical density may be lowered.
  • the composition of the present invention can be made free of a binder, and is extremely significant in that it enables realization of an unprecedented high pigment concentration.
  • the composition of the present invention may include a release agent, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesion promoter.
  • a release agent e.g., a silicone hydroxide, a silicone hydroxide, a silicone hydroxide, a silicone hydroxide, a silicone hydroxide, a silicone hydroxide, and a silane coupling agent, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesion promoter.
  • Thermal polymerization initiators, colorants, elastomer particles, photoacid proliferators, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants and the like may be added.
  • a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of allowing the mold pressed against the photosensitive resin layer comprising the composition of the present invention to be peeled cleanly without causing surface roughness or plate removal of the photosensitive resin layer.
  • the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used.
  • these mold release agents can be adhered to the mold.
  • Silicone mold release agent is a mold release agent having an organopolysiloxane structure as a basic structure, and includes, for example, unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, silicone acrylic resin, and the like. It is also possible to apply a silicone leveling agent generally used in hard coat compositions.
  • the modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil.
  • the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification.
  • the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification. Two or more of the above-described modification methods can be performed on one polysiloxane molecule.
  • the modified silicone oil has appropriate compatibility with the composition components.
  • a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step.
  • silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone, vinyl-modified silicone, etc., since it crosslinks with the composition of the present invention, it has excellent properties after curing.
  • Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
  • the said mold release agent can be added only in 1 type or in combination of 2 or more types.
  • a release agent When a release agent is added to the composition of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, more preferably in a range of 0.01 to 5% by mass. preferable. If the ratio of a mold release agent is less than the said range, the peelable improvement effect of the photosensitive resin layer which consists of a mold and the composition of this invention tends to become inadequate.
  • the ratio of the release agent exceeds the above range, the surface of the coating film may be rough due to repelling during coating of the composition, or the substrate itself and the adjacent layer in the product, for example, the adhesion of the vapor deposition layer It is not preferable from the viewpoint of inhibiting the properties and causing film breakage or the like during transfer (film strength becomes too weak).
  • the ratio of the release agent is 0.01% by mass or more, the effect of improving the peelability between the mold and the curable composition layer for optical nanoimprint lithography is sufficient.
  • the ratio of the release agent is within the above range of 10% by mass or less, the problem of surface roughness of the coating film due to repelling at the time of coating the composition hardly occurs, and the substrate itself and the adjacent layer in the product, for example, It is preferable in that it hardly inhibits the adhesion of the vapor-deposited layer and hardly causes film breakage or the like (film strength becomes too weak) during transfer.
  • an organic metal coupling agent may be blended in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine concavo-convex pattern.
  • the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction.
  • various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.
  • silane coupling agent used in the composition of the present invention examples include vinyl silanes such as vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ⁇ -methacryloxypropyltrimethoxysilane
  • An epoxy silane such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane; N- ⁇ - (aminoethyl)- aminosilanes such as ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -amino
  • titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, iso Ropirutori (
  • zirconium coupling agent examples include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.
  • aluminum coupling agent examples include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.
  • the organometallic coupling agent can be arbitrarily blended in a proportion of 0.001 to 10% by mass in the total solid content of the composition of the present invention.
  • the ratio of the organometallic coupling agent By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer.
  • the ratio of the organometallic coupling agent is 10% by mass or less, the stability and film forming property of the composition of the present invention tend to be suppressed, which is preferable.
  • a polymerization inhibitor may be blended in order to improve storage stability and the like.
  • the polymerization inhibitor for example, phenols such as hydroquinone, tert-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like can be used.
  • the polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.
  • UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350. 400 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.
  • the ultraviolet absorber is preferably blended arbitrarily in a proportion of 0.01 to 10% by mass with respect to the total amount of the curable composition for optical nanoimprint lithography.
  • Light stabilizers are Tinuvin® 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Chemical Industry Co., Ltd.) Etc.
  • the light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.
  • anti-aging agents include Antigene® W, S, P, 3C, 6C, RD-G, FR, AW (above, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
  • the antiaging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.
  • a plasticizer can be added to the composition of the present invention in order to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like.
  • preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.
  • Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used.
  • the adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • thermal polymerization initiator can be added as necessary.
  • thermal polymerization initiators include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.
  • a photobase generator may be added as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like.
  • elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.
  • the elastomer particles that can be added as an optional component to the composition of the present invention have an average particle size of preferably 10 nm to 700 nm, more preferably 30 to 300 nm.
  • core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used.
  • the elastomer particles may have a crosslinked structure.
  • Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resin Chemical Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.
  • elastomer particles can be used alone or in combination of two or more.
  • the content of the elastomer component in the composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.
  • a basic compound may be optionally added to the composition of the present invention for the purpose of suppressing cure shrinkage and improving thermal stability.
  • the basic compound include amines, nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like.
  • amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.
  • a chain transfer agent may be added to the composition of the present invention to improve photocurability.
  • the surface tension of the photosensitive composition of the present invention is preferably in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, surface smoothness can be improved by setting it as such a range.
  • the composition of the present invention can be prepared as a solution by mixing the above components and then filtering with a filter having a pore size of 0.05 ⁇ m to 5.0 ⁇ m, for example.
  • Mixing / dissolution of the composition of the present invention is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered.
  • Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.
  • the composition of the present invention is used for a permanent film (resist for a structural member) used in a liquid crystal display (LCD) or the like
  • an ionic impurity of a metal or an organic substance in the resist is used so as not to hinder the operation of the display. It is preferable to avoid mixing as much as possible.
  • the content of Na and K elements is particularly preferably 1000 ppm or less, and more preferably 100 ppm or less.
  • a light-shielding image by the following steps.
  • (1) A step of providing a photosensitive resin layer on the substrate using the photosensitive resin composition of the present invention
  • (2) A heat treatment at 50 to 150 ° C. is performed as necessary to remove the solvent of the photosensitive resin layer.
  • Step (3) Step of pressure-bonding the mold having an uneven surface and the photosensitive resin layer so that the uneven surface is in contact
  • Step (3) Step of pressure-bonding the mold having an uneven surface and the photosensitive resin layer so that the uneven surface is in contact
  • the uneven surface (6) A step of heat-treating the photosensitive resin layer at 160 to 250 ° C. as necessary
  • the coating of the composition is a generally well-known coating method.
  • it can be formed by coating by a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or the like.
  • the composition of the present invention may be applied in multiple layers.
  • the film thickness of the layer made of the composition of the present invention is usually 1 ⁇ m or less, and preferably 0.5 to 1.0 ⁇ m in a black matrix used for an LCD or the like.
  • a light-transmitting material as a mold material (mold material) having an uneven surface.
  • Substrates for applying the composition of the present invention are quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, polyester film
  • Polymer substrates such as polycarbonate films and polyimide films, TFT array substrates, plasma display (PDP) electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicone, silicone nitride,
  • semiconductor fabrication substrates such as polysilicone, silicone oxide, and amorphous silicone.
  • the shape of the substrate may be a plate shape or a roll shape.
  • the drying step Remove the solvent.
  • the drying step can be performed at a temperature of 50 to 150 ° C. by a known method, a method using a convection oven, a hot plate, an infrared heater, or the like. Further, drying may be performed at 500 to 10 ⁇ 6 Torr under reduced pressure as necessary.
  • a mold having a concavo-convex surface (mold) Crimp so that is in contact.
  • the mold pressure is usually preferably 10 kN or less. It is preferable that the mold pressure is 10 kN or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and because the pressure is low, the apparatus can be reduced.
  • the mold pressure is preferably selected in a range where the mold transfer uniformity can be ensured within a range in which the residual film of the composition on the mold convex portion is reduced.
  • a mold having a pattern to be transferred can be widely used.
  • the mold can be formed in a pattern according to the desired processing accuracy by, for example, photolithography or electron beam drawing method, or a replica can be taken from the finished product to be aimed at. Not limited.
  • the light-transmitting molding material used in the present invention is not particularly limited as long as it has predetermined strength and durability.
  • a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin
  • a transparent metal vapor-deposited film a transparent metal vapor-deposited film
  • a flexible film such as polydimethylsiloxane
  • a photocured film a metal film
  • the mold used in the present invention may be a mold which has been subjected to a release treatment in order to improve the peelability between the composition of the present invention and the mold.
  • a silane coupling agent such as a silicone type or a fluorine type
  • commercially available mold release agents such as those manufactured by Daikin Industries, Optool DSX, Sumitomo 3M, and Novec-EGC-1720 can also be suitably used.
  • Step of irradiating light through at least a mold having an uneven surface light irradiation is performed through a mold having at least an uneven surface to cure the composition of the present invention.
  • the light irradiation is performed with the mold attached.
  • it is preferable for light-shielding image formation that exposure is performed simultaneously or sequentially from both the substrate side and the mold side.
  • the light for curing the composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light or radiation having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared or the like.
  • a high-energy ionizing radiation source for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used.
  • an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron
  • radiation such as ⁇ rays, X rays, ⁇ rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used.
  • the ultraviolet light source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp.
  • Examples of radiation include microwaves and EUV.
  • laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention.
  • These lights may be monochromatic light, or may be light having a plurality of different wavelengths (mixed light).
  • the light irradiation may be sufficiently larger than the irradiation amount necessary for curing.
  • the amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint lithography and the tackiness of the cured film.
  • During exposure is preferably in the range of exposure intensity of 1mW / cm 2 ⁇ 50mW / cm 2.
  • the exposure time can be shortened, so that productivity is improved.
  • By setting it to 50 mW / cm 2 or less deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable.
  • the exposure dose is preferably in the range of 5 mJ / cm 2 to 1000 mJ / cm 2 . If it is less than 5 mJ / cm 2 , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, when it exceeds 1000 mJ / cm 2 , there is a risk of deterioration of the permanent film due to decomposition of the composition. Further, during exposure, in order to prevent radical polymerization from being inhibited by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.
  • an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.
  • the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
  • the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
  • a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing reactivity decrease due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography.
  • Light irradiation may be performed.
  • the preferred degree of vacuum is in the range of 10 ⁇ 1 Pa to normal pressure.
  • Step of peeling mold having uneven surface from photosensitive resin layer a mold having uneven surface is peeled from the photosensitive resin layer.
  • the composition of the present invention may be heat-treated at 160 to 250 ° C. as necessary. By adopting such means, curing can be further promoted.
  • the heat treatment may be performed before the peeling or after the peeling.
  • the heat for curing is preferably 160 to 250 ° C, more preferably 200 to 250 ° C.
  • the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • a heat treatment method a known method, a method using a convection oven, a hot plate, an infrared heater or the like is used. If necessary, it may be carried out under reduced pressure, for example, at 500 to 10 ⁇ 6 Torr.
  • Permanent films used for liquid crystal displays (LCDs) are bottled in containers such as gallon bottles and coated bottles after manufacture, and are transported and stored. In this case, the purpose is to prevent deterioration.
  • the inside of the container may be replaced with inert nitrogen, argon, or the like.
  • the room temperature may be used, but the temperature may be controlled in the range of ⁇ 20 ° C. to 0 ° C. in order to prevent the permanent film from being deteriorated. Of course, it is necessary to shield from light so that the reaction does not proceed.
  • composition of the present invention can also be applied as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays, and the like.
  • compositions of Examples and Comparative Examples were prepared by blending a black pigment dispersion, a photopolymerization initiator, a surfactant, a polymerization inhibitor, and, if necessary, a solvent so as to have the composition shown in each table.
  • Dispersion A1 (a dispersion of particles having a prepared silver-tin alloy part) was prepared by the following method. In 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, 2 g of polyethylene glycol (molecular weight 3,000), and PVP-K30 (ISP A solution 1 was obtained by dissolving 5 g of a polyvinyl pyrrolidone polymer manufactured by Japan Co., Ltd. Separately, 46.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.
  • the solution 1 was vigorously stirred while being kept at 25 ° C.
  • the solution 2 was added thereto over 2 minutes, and the stirring was gently continued for 6 hours.
  • the mixed liquid turned black, and metal particles having a silver-tin alloy part (hereinafter, sometimes referred to as “silver-tin alloy part-containing particles”) were obtained.
  • this mixed solution was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation was carried out for 30 minutes at a rotational speed of 2,000 rpm using a desktop centrifuge H-103n (manufactured by Kokusan Co., Ltd.) in small portions of 150 ml. The supernatant was discarded and the total liquid volume was 150 ml.
  • the silver-tin alloy part-containing particles obtained above were again used as a dispersion, and the dispersion was further centrifuged to precipitate the silver-tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifugation, the supernatant was discarded as described above to make the total liquid volume 150 ml, and 850 ml of pure water and 500 ml of normal propyl alcohol were added thereto, and the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. . Centrifugation was performed again in the same manner as described above to precipitate the silver-tin alloy part-containing particles.
  • the supernatant was discarded as described above to a liquid volume of 150 ml, and 150 ml of pure water and 1200 ml of normal propyl alcohol were added thereto.
  • the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid volume 70 ml, and 30 ml of normal propyl alcohol was added thereto.
  • the number average particle size of the silver-tin alloy part-containing particles in the dispersion A1 was about 40 nm. The number average particle size was determined as follows using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd., magnification: 100,000 times, acceleration voltage: 200 kV). 100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle size, and the average value of the particle sizes of 100 particles was defined as the number average particle size.
  • Dispersion B1 (silver fine particle dispersion) was prepared by the following procedure. 3.0 g of the following compound T-4 was added to 2.5 L of an aqueous solution adjusted to pH 12.0 using a 1 mol / L sodium hydroxide aqueous solution and stirred at 45 ° C. for 30 minutes until it was completely dissolved. .
  • the temperature of this solution was controlled at 45 ° C., and 700 mL of an aqueous solution containing 8.5 g of ascorbic acid, 700 mL of an aqueous solution containing 5 g of hydroquinone and 1.5 g of sodium sulfite, and 500 mL of an aqueous solution containing 30 g of silver nitrate were added simultaneously.
  • a silver nanoparticle-containing solution was prepared. The obtained silver nanoparticles were connected particles in which spherical particles having an arithmetic average particle size: 16.1 nm and an average aspect ratio of 2.2 were randomly connected.
  • Centrifugation treatment (12,000 rpm, 30 min) was performed on the prepared silver nanoparticle-containing solution, and the supernatant was discarded, followed by washing with water to which distilled water was added three times.
  • Acetone was added to the obtained silver nanoparticle-containing solution, and the mixture was stirred with a stirrer and then centrifuged (12000 rpm, 30 min). Thereafter, the supernatant was removed, cyclohexanone and propylene glycol monomethyl ether acetate were added, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson.
  • the silver nanoparticle dispersion thus obtained had the same shape and color as after the formation of the particles (silver particle concentration 25% by mass).
  • the concentration of the polymer compound T-4 obtained from loss on drying using TG-DTA (Seiko Co., Ltd.) in the solvent dispersion was 1.1% by mass.
  • This silver nanoparticle dispersion was designated as metal-containing dispersion B1.
  • each composition was applied onto a glass substrate by a spin coat method so that the film thickness after drying was the coating film thickness described in each table.
  • drying was performed at 100 ° C. for 2 minutes after application to remove the solvent.
  • the spin-coated coating base film was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power: 2000 mW / cm 2 ) manufactured by ORC as a light source, the mold pressure was 0.8 kN, the degree of vacuum during exposure was 10 Torr, and the recess diameter was 20 ⁇ m.
  • a polydimethylsiloxane (Toray Industries, Inc.) having a pattern in which cylindrical recesses having a recess depth of 3.5 ⁇ m are two-dimensionally arranged at a pitch of 900 ⁇ m, a line width of 20 ⁇ m, a pitch of 300 ⁇ m, a depth of 1 ⁇ m, and a cross-sectionally ridged pattern.
  • a pitch of 900 ⁇ m a line width of 20 ⁇ m, a pitch of 300 ⁇ m, a depth of 1 ⁇ m, and a cross-sectionally ridged pattern.
  • the obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
  • the following evaluation was performed. The results are shown in the following table
  • ⁇ Viscosity measurement> The viscosity of the composition before curing in a substantially solvent-free state was measured at 25 ⁇ 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
  • the rotational speed during the measurement is 100 rpm for 0.5 mPa ⁇ s to less than 5 mPa ⁇ s, 50 rpm for 5 mPa ⁇ s to less than 10 mPa ⁇ s, 20 rpm for less than 30 mPa ⁇ s for 10 mPa ⁇ s, and 60 mPa ⁇ s for 30 mPa ⁇ s to 60 mPa ⁇ s.
  • Less than 10 rpm, 60 mPa ⁇ s or more and less than 120 mPa ⁇ s was 5 rpm, and 120 mPa ⁇ s or more was 1 rpm or 0.5 rpm, respectively.
  • the film thickness was measured using a contact surface roughness meter P-10 (manufactured by KLA Tencor).
  • ⁇ Evaluation of optical density> The chromaticity of the image obtained from the above was measured at a pinhole diameter of 5 ⁇ m using a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100), calculated as a result of the F10 light source field of view of 2 degrees, and the logarithm of the Y value. ( ⁇ Log (Y / 100)) was calculated.
  • the pattern shape after the transfer was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated as follows.
  • D Clearly different from the original pattern of the mold pattern shape. Or the film thickness of the pattern differs from the original pattern by 20% or more.
  • the base plate with the black matrix obtained in the above examples and comparative examples was observed on the entire surface with an optical microscope (differential interference mode, 200 times), and generation of a chip (a portion where a portion lacking 20% or more of the fine line width was present) was generated. The number was observed.
  • the number of chippings was evaluated according to the following criteria. ⁇ ... less than 20 pieces / m 2 ⁇ ... 20 pieces / m 2 or more and less than 40 pieces / m 2 , ⁇ : 40 pieces / m 2 or more and less than 80 pieces / m 2 , ⁇ ... 80 / m 2 or more and less than 120 / m 2 ⁇ ... 120 / m 2 or more
  • ITO Indium Tin Oxide
  • spacers and rib bodies were formed so that a columnar pattern was formed on BM and a bowl-shaped pattern was formed on each RGB pixel.
  • a glass substrate was prepared as a counter substrate, patterned on the transparent electrode of the color filter substrate and the counter substrate for the PVA mode, and an alignment film made of polyimide was further provided thereon.
  • a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a PVA mode liquid crystal is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant.
  • Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained.
  • FR1112H chip type LED manufactured by Stanley Electric Co., Ltd.
  • R red
  • G green
  • B blue
  • a side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.
  • ⁇ Display unevenness> For each liquid crystal display device, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
  • R-1 benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)
  • R-4 Isobornyl acrylate (Wako Pure Chemical Industries, Ltd.)
  • W-1 Fluorosurfactant (manufactured by Tochem Products: Fluorosurfactant)
  • W-2 Silicone surfactant (manufactured by Dainippon Ink and Chemicals, Inc .: MegaFuck Paint 31)
  • MFGAC represents propylene glycol monomethyl ether acetate.
  • the film thickness has shown the film thickness (unit: micrometer) after drying.
  • the composition of the present invention was excellent in all of pattern accuracy, peelability, hardness, defects, solvent resistance, and display unevenness in a liquid crystal display device.
  • MFGAC represents propylene glycol monomethyl ether acetate.
  • the film thickness has shown the film thickness (unit: micrometer) after drying.
  • the composition of the present invention When the composition of the present invention is thinned, it has a high optical density of 4.0 even when the film thickness is 0.9 ⁇ m.
  • An excellent composition was obtained for all of pattern accuracy, peelability, hardness, chipping defects, solvent resistance, and display unevenness in a liquid crystal display device.
  • the composition of the present invention When the composition of the present invention is used as a black matrix in an imprint system, it has become possible to provide a black matrix that is comprehensively excellent in mechanical strength, peelability, pattern shape, coatability, and solvent resistance. . In addition, when used as a black matrix, it is possible to provide a composition having excellent residual film properties, mechanical properties such as scratch resistance, and solvent resistance. In the present invention, it is possible to reduce the addition amount of the binder to the photosensitive resin composition for patterning, and to make addition unnecessary. As a result, an unprecedented high pigment concentration can be realized. In particular, the composition of the present invention has a high optical density even when the thickness is 1 ⁇ m or less.

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Abstract

L'invention concerne une composition photosensible permettant d'obtenir une matrice noire d'une excellente précision des motifs et dureté par lithographie à nano-impression. La composition est une composition de résine photosensible comportant au moins 10 % en masse d'un agent de coloration et un monomère polymérisable, avec une viscosité comprise entre 3 et 50 Mpa⋅s pratiquement sans solvant après séchage, ou bien est une composition comportant au moins un agent de coloration et un monomère polymérisable, avec un liant ne dépassant pas 10 % en masse sur la base du total des solides, et avec une viscosité comprise entre 3 et 50 Mpa.s pratiquement sans solvant après séchage. L'invention concerne une composition de résine photosensible, la densité optique du film durci ayant une épaisseur de 1µm de la composition durcie étant au moins égale à 3,5.
PCT/JP2009/054765 2008-03-13 2009-03-12 Composition de résine photosensible, film durci de résine photosensible, et procédé de formation d'image photorésistante WO2009113615A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2008-064535 2008-03-13
JP2008064540A JP2009222792A (ja) 2008-03-13 2008-03-13 感光性樹脂組成物および遮光性画像の形成方法。
JP2008064535A JP2009222791A (ja) 2008-03-13 2008-03-13 感光性樹脂組成物、感光性樹脂硬化膜および遮光性画像形成方法
JP2008-064540 2008-03-13

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WO2009113615A1 true WO2009113615A1 (fr) 2009-09-17

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WO (1) WO2009113615A1 (fr)

Cited By (2)

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WO2005037926A1 (fr) * 2003-10-15 2005-04-28 Toray Industries, Inc. Composition de noir, composition de revetement de noir, matrice de noir de resine, filtre a couleurs pour ecran a cristaux liquides et ecran a cristaux liquides
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040626A1 (fr) * 2009-09-30 2011-04-07 Fujifilm Corporation Composition durcissable noire pour lentille à l'échelle de la tranche, et lentille à l'échelle de la tranche
CN102483472A (zh) * 2009-09-30 2012-05-30 富士胶片株式会社 用于晶片级透镜的黑色可固化组合物和晶片级透镜
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US9229136B2 (en) 2012-09-27 2016-01-05 Toshiba Tec Kabushiki Kaisha Microlens array unit and image processing apparatus

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