WO2016052026A1 - Procédé de fabrication d'un article ayant une structure en creux et en saillie, et article ayant une structure en creux et en saillie - Google Patents

Procédé de fabrication d'un article ayant une structure en creux et en saillie, et article ayant une structure en creux et en saillie Download PDF

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WO2016052026A1
WO2016052026A1 PCT/JP2015/074307 JP2015074307W WO2016052026A1 WO 2016052026 A1 WO2016052026 A1 WO 2016052026A1 JP 2015074307 W JP2015074307 W JP 2015074307W WO 2016052026 A1 WO2016052026 A1 WO 2016052026A1
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layer
mass
article
concavo
polymerizable compound
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PCT/JP2015/074307
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English (en)
Japanese (ja)
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均 並河
竜二 実藤
福重　裕一
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富士フイルム株式会社
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Priority claimed from JP2015167014A external-priority patent/JP6424150B2/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 WO2016052026A1 publication Critical patent/WO2016052026A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • the present invention relates to a method for manufacturing an article having a concavo-convex structure, and an article having a concavo-convex structure manufactured by this manufacturing method.
  • the technology for forming a concavo-convex structure on an article by patterning is used in various applications and fields such as flat panel display applications such as liquid crystal display devices, semiconductor manufacturing fields, bi-technology, and pharmaceutical fields.
  • a photoresist that forms an uneven structure on the surface of an article through pattern exposure and development processes is widely used.
  • a type in which a pattern-exposed portion (exposed portion) becomes a convex portion is called a negative type
  • a type in which an exposed portion becomes a concave portion is called a positive type.
  • the solubility of the exposed area in the developing solution is reduced by pattern exposure, so that the unexposed area (unexposed area) in the pattern exposure is dissolved and removed by the developing solution in the developing process, and the exposed area does not dissolve.
  • a concavo-convex structure in which the exposed portion becomes a convex portion is formed.
  • Patent Document 1 forms a concavo-convex structure without passing through a development process by pattern exposure of an energy-sensitive negative resin composition layer formed on a substrate and subsequent heat treatment.
  • a method for forming surface irregularities is disclosed.
  • Patent Document 1 the film thickness of the portion irradiated with the active energy ray is increased as compared with the film thickness of the portion not irradiated with the active energy beam, and the active energy beam is irradiated by performing post-heating. It is described that the difference in film thickness between the exposed portion and the non-irradiated portion becomes significant (see paragraph 0006 of Patent Document 1).
  • the surface unevenness forming method described in Patent Document 1 can form an uneven structure without going through a development process. Therefore, compared to the above-described photoresist, the process is simplified, the cost is reduced by not using a developer, and the like. This can be said to be a preferable method.
  • the surface of the film is formed with a concavo-convex structure whose size is less than or equal to the wavelength of light, thereby reducing the reflectance to light. (Anti-reflection).
  • the concavo-convex structure in order to prevent reflection of light having a shorter wavelength, it is required to form a fine concavo-convex structure with a larger elevation difference on the film surface.
  • fine in the concavo-convex structure means that the interval between the convex portions is narrow.
  • the fine unevenness can provide antireflection performance in both a convex structure and a concave structure.
  • the depth of the concavo-convex structure (the distance between the highest part and the lowest part) is preferably 50 to 1000 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm.
  • the height of the convex portion is 50 nm or more, the reflectance is sufficiently low and the wavelength dependence of the reflectance is small. If the height of a convex part is 1000 nm or less, the scratch resistance of a convex part will become favorable.
  • the average distance between convex portions or concave portions is preferably 50 to 400 nm, more preferably 100 to 300 nm, and particularly preferably 150 to 200 nm. If the height of the convex portion is 50 nm or more, the reflectance is sufficiently low and the wavelength dependence of the reflectance is small. If the average interval is 400 nm or less, iridescent coloring due to diffracted light can be suppressed. If the average distance is 50 nm or less, the scratch resistance is good. However, with the conventional method, it has been difficult to form a fine concavo-convex structure with a required large elevation difference.
  • An object of the present invention is to provide a method for producing an article having a concavo-convex structure that has a fine concavo-convex structure and has a large concavo-convex height difference (the height of the convex part is large), and an article having the concavo-convex structure.
  • the present inventors have determined that at least one polymerization initiator selected from a polymerizable compound, an oxime ester photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. And a step of forming a layer containing cellulose acylate, a step of pattern exposure on the surface of the layer, and a step of heating the layer after the pattern exposure. It was found that a concavo-convex structure having a large height difference can be formed.
  • the step of pattern exposure on the surface of the layer, the polymerizable compound is polymerized and cured in the exposed portion of the surface of the layer.
  • the layer contains a specific photopolymerization initiator having high sensitivity to ultraviolet rays, and the pattern-exposed region is polymerized and cured at a high rate, or is cured to the inside of the film. It is possible to make it difficult for large shape changes to occur. Therefore, the shrinkage difference between the pattern-exposed region and the heat-polymerized region can be increased, and a concavo-convex structure with a large difference in level (step) can be formed even when a fine pattern is used.
  • the large difference in level (step) between the convex portion and the concave portion enables the formation of a concave / convex shape that is recognized as a clear concave / convex portion. It is effective for forming a concavo-convex structure.
  • the above description includes inferences by the present inventors and does not limit the present invention.
  • [1] Forming a layer comprising a polymerizable compound, at least one photopolymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator, and cellulose acylate; Pattern exposure on the surface of the layer; Heating the layer after the pattern exposure; A method for producing an article having a concavo-convex structure, wherein the concavo-convex structure in which the non-exposed part of the pattern exposure is a concave part is formed.
  • the step of forming the layer comprises, on the support, a polymerizable compound, at least one photopolymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator, and cellulose acylate. And forming a layer by casting a composition comprising: Next, the step of peeling the layer from the support, The method for producing an article having a concavo-convex structure according to [1], wherein the pattern exposure step is performed on the peeled layer.
  • a first layer comprising a polymerizable compound, at least one photopolymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator, and cellulose acylate; and Forming a laminate having a second layer containing a resin; Pattern exposure on the surface of the first layer; Heating the first layer after the pattern exposure; A method for producing an article having a concavo-convex structure, wherein the concavo-convex structure in which the non-exposed part of the pattern exposure is a concave part is formed.
  • the step of forming the first layer comprises, on the support, a polymerizable compound, at least one photopolymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator, A step of casting a composition comprising cellulose acylate to form a first layer; Then, the step of peeling the first layer from the support, The method for producing an article having an uneven structure according to [5], wherein the pattern exposure step is performed on the peeled first layer.
  • the polymerizable group containing an ethylenically unsaturated bond is a polymerizable group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an acryloyl group, and a methacryloyl group.
  • Method. [12] The method for producing an article having an uneven structure according to any one of [1] to [11], wherein the polymerizable compound is a polyfunctional polymerizable compound having two or more functions. [13] The method for producing an article having an uneven structure according to any one of [1] to [12], wherein the article is a long film.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the method for producing an article having a concavo-convex structure according to the first aspect of the present invention includes a polymerizable compound, at least one photopolymerization initiation selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator.
  • the concavo-convex structure in which the part becomes a concave part is formed.
  • a layer containing the polymerizable compound, a photopolymerization initiator, and cellulose acylate is referred to as a monolayer.
  • the method for producing an article having an uneven structure according to the second aspect of the present invention includes a polymerizable compound, at least one light selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator.
  • the brittleness of the article can be improved in addition to increasing the level difference of the concavo-convex.
  • a layer obtained by combining the first layer and the second layer is referred to as a laminate.
  • the manufacturing method will be described in more detail.
  • the polymerizable compound is a compound having at least one polymerizable group in one molecule. Such a compound may be a monomer or a multimer such as an oligomer or a prepolymer.
  • a monofunctional polymerizable compound in which the number of polymerizable groups contained in one molecule is one may be used, and the number of polymerizable groups contained in one molecule is two or more.
  • a polyfunctional polymerizable compound may be used, and a monofunctional polymerizable compound and a polyfunctional polymerizable compound may be arbitrarily mixed and used.
  • the molecular weight of these polymerizable compounds is, for example, from 80 to 30,000, but is not particularly limited.
  • the molecular weight means a weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) for a multimer. Examples of specific measurement conditions include the following measurement conditions.
  • GPC device HLC-8120 (manufactured by Tosoh): Column: TSK gelMultiporeHXL-M (Tosoh, 7.8 mm ID (inner diameter) ⁇ 30.0 cm) Eluent: Tetrahydrofuran (THF)
  • the polymerizable group may be a radical polymerizable group or a cationic polymerizable group, and is preferably a radical polymerizable group.
  • examples of the polymerizable group that is preferable from the viewpoint of forming an uneven structure include polymerizable groups such as an ethylenically unsaturated bond-containing group, an epoxy group, an oxetane group, and a methylol group, and an ethylenically unsaturated bond-containing group is more preferable. .
  • Examples of the ethylenically unsaturated bond-containing group include (meth) acryloyloxy group, (meth) acryloyl group, vinyl group, styryl group, and allyl group, and (meth) acryloyloxy group and (meth) acryloyl group include More preferred is a (meth) acryloyloxy group.
  • the description “(meth) acryloyloxy group” is used in the meaning of at least one of an acryloyloxy group and a methacryloyloxy group. The same applies to “(meth) acryloyl group”, “(meth) acrylate”, “(meth) acryl” and the like.
  • the number of polymerizable groups contained in the polyfunctional polymerizable compound is 2 or more in one molecule, preferably in the range of 2 to 20, and more preferably in the range of 3 to 12.
  • a polyfunctional (meth) acrylate compound having two or more ethylenically unsaturated bond-containing groups in one molecule can be exemplified.
  • the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydi (meth) acrylate, bisphenol A tetrapropoxydi (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • Acrylate neopentyl glycol di (meth) acrylate, and the like.
  • NP-A neopentyl glycol diacrylate, molecular weight 212
  • the tri- or more functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and isocyanuric acid-modified tri (meth) acrylate.
  • the (meth) acrylate compound may be a compound in which a part of the molecular skeleton is modified. For example, those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol or the like can be used.
  • examples of the polyfunctional polymerizable compound include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylate polymer.
  • urethane (meth) acrylate is preferable from the viewpoint of transparency, for example.
  • Urethane (meth) acrylate can be obtained by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth) acrylate.
  • polyhydric alcohol examples include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and pentaerythritol.
  • Tricyclodecane dimethylol bis- [hydroxymethyl] -cyclohexane, etc .
  • the above polyhydric alcohols and polybasic acids for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydroanhydride
  • Polyester polyol obtained by reaction with phthalic acid, etc .
  • polycaprolactone polyol obtained by reaction of the above polyhydric alcohol with ⁇ -caprolactone
  • polycarbonate polyol for example, 1,6-hexanediol
  • Polycarbonate diols obtained by reacting diphenyl carbonate
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide-modified bisphenol A.
  • organic polyisocyanate examples include isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl isocyanate, adducts of these isocyanate compounds, or these Examples include isocyanate multimers.
  • hydroxy (meth) acrylate compound examples include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, hydroxyethyl (meth) ) Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono (meth) acrylate, hydroxycaprolactone (meth) acrylate, and the like.
  • pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable from the viewpoint of increasing the hardness of the manufactured article.
  • the urethane (meth) acrylate is preferably 6 or more functional and more preferably 6 to 15 functional.
  • urethane (meth) acrylate Commercial products may be used as urethane (meth) acrylate. Examples of commercially available products include: Nippon Synthetic Chemical Industry: UV1700B (weight average molecular weight 2000, 10 functional), UV7600B (weight average molecular weight 1500, 6 functional), Nippon Kayaku Co., Ltd .: DPHA40H (weight average molecular weight 7000, 10 Functionality), UX5003 (weight average molecular weight 700, 6 functionalities), Negami Kogyo Co., Ltd .: UN3320HS (weight average molecular weight 5000, 15 functionalities), UN904 (weight average molecular weight 4900, 15 functionalities), UN3320HC (weight average molecular weight 1500, 10 functionalities) ), UN3320HA (weight average molecular weight 1500, 6 functional), manufactured by Arakawa Chemical Industries, Ltd .: BS577 (weight average molecular weight 1000, 6 functional), and Shin Nakamura Chemical Industries, Ltd .: U15HA (weight average
  • a fluorine-containing polymerizable compound containing one or more fluorine atoms in one molecule a silicone-based polymerizable compound having one or more siloxane bonds in one molecule, or the like can also be used.
  • the fluorine-containing polymerizable compound for example, various compounds described in JP-A-2013-130865, paragraphs 0077 to 0103 can be used.
  • the silicone-based polymerizable compound reference can be made to paragraph 0141 of JP2013-130865A and JP0119-0120A of JP2012-103689A.
  • the monofunctional compound is not particularly limited.
  • a monofunctional (meth) acrylate compound described in WO2012 / 0777807A1 paragraph 0022 a monofunctional polymerizable compound having only one vinyl bond in one molecule described in JP2008-17895A, Monofunctional radically polymerizable monomers described in paragraph 0022 of 2008-119684 can be used.
  • the concentration of the polymerizable compound relative to the cellulose acylate in the layer is not particularly limited, but from the viewpoint of facilitating formation of a concavo-convex structure having a large difference in height, cellulose is used when the layer containing the polymerizable compound is a single layer. It is preferable to set it as 50 mass parts or more with respect to 100 mass parts of acylates. On the other hand, from the viewpoint of film production, the amount of the polymerizable compound with respect to 100 parts by mass of cellulose acylate is preferably 150 parts by mass or less. Moreover, in the case of the 1st layer containing a polymeric compound, it is preferable to set it as 50 masses or more with respect to 100 mass parts of cellulose acylates. On the other hand, from the viewpoint of film production, the amount of the polymerizable compound with respect to 100 parts by mass of cellulose acylate is preferably 1000 parts by mass or less.
  • the composition for forming the layer contains at least one polymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator that are highly sensitive to ultraviolet rays.
  • a commercially available thing can be used as at least 1 type of polymerization initiator selected from the oxime ester type photoinitiator and the acylphosphine oxide type photoinitiator.
  • oxime ester photopolymerization initiator Irgacure Oxe01 (manufactured by BASF Japan), Irgacure Oxe02 (manufactured by BASF Japan), Irgacure Oxe03 (manufactured by BASF Japan), NCI 930 (manufactured by ADEKA), NCI 831 ( ADEKA Co., Ltd.), and examples of the acylphosphine oxide photopolymerization initiator include Irgacure 819 (BASF Japan Co.) and LUCILIN TPO (BASF Japan Co.).
  • the photopolymerization initiators described above may be used alone or in a combination of two or more at any ratio.
  • the mass of the photopolymerization initiator relative to the mass of the polymerizable compound in the layer is preferably 5% by mass or more and 25% by mass or less from the viewpoint of favorably causing the polymerization reaction by pattern exposure to proceed favorably.
  • the mass of the photoinitiator with respect to the mass of a polymeric compound is 5 mass% or more and 25 mass% or less.
  • a sensitizer in the present invention, can be used in the composition for forming the layer.
  • the sensitizer can be appropriately used when, for example, the photopolymerization initiator does not have proper absorption with respect to the exposure light source.
  • Any sensitizer that can be used in the present invention can be used without particular limitation as long as it absorbs actinic rays and sensitizes the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.
  • anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
  • Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
  • acridone derivative acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
  • thioxanthone derivative thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are preferable.
  • coumarin derivatives coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
  • Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
  • Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
  • a sensitizer can be used individually by 1 type or in combination of 2 or more types.
  • the sensitizer is preferably 20 to 300 parts by weight, particularly preferably 30 to 200 parts by weight, based on 100 parts by weight of the photopolymerization initiator, from the viewpoint of achieving both sensitivity and transparency.
  • the photopolymerization initiator may be mixed with the composition together with other components such as a polymerizable compound, and added by infiltrating by applying the pattern-exposed portion of the layer formed from the composition in a spot shape. May be.
  • cellulose acylate is contained as a binder.
  • the film productivity (and brittleness) of the article can be improved.
  • JP, 2012-215812, A paragraph 0017 can be referred to for the details of the acyl group which the cellulose hydroxyl group substitutes in cellulose acylate.
  • they are an acetyl group, a propionyl group, and a butanoyl group, More preferably, they are an acetyl group and a propionyl group, More preferably, it is an acetyl group.
  • cellulose acylate having an acetyl substitution degree of 2.7 or more is preferable, more preferably 2.75 or more, and still more preferably 2.82 or more.
  • cellulose acylate having an acetyl substitution degree of 2.95 or less is preferable, more preferably 2.90 or less, and still more preferably 2.89 or less.
  • the total acyl substitution degree of the cellulose acylate is also preferably in the above-described range for the acetyl substitution degree.
  • the total acyl substitution degree and acetyl substitution degree can be measured according to the method prescribed in ASTM-D817-96.
  • the portion not substituted with an acyl group usually exists as a hydroxyl group.
  • the details of cellulose acylate can also be referred to paragraphs 0018 to 0020 of JP2012-215812A.
  • the cellulose acylate is preferably contained in an amount of 25 parts by mass or more, more preferably 50 parts by mass or more based on 100 parts by mass of the total composition forming the layer. Moreover, from a viewpoint of uneven
  • the second layer is a layer containing at least one kind or two or more kinds of resins.
  • the resin contained in the second layer may be an organic solvent soluble resin or an organic solvent insoluble resin. From the viewpoint of film forming suitability of the coating layer, an organic solvent-soluble resin is preferable.
  • the layer can be preferably formed by casting film formation, and it is preferable from the viewpoint of film forming property of casting film formation to contain an organic solvent-soluble resin.
  • organic solvent soluble means that 1% by mass or more dissolves in an organic solvent having a liquid temperature of 25 ° C.
  • the organic solvent referred to here is, for example, a composition in which one or a plurality selected from the group consisting of organic compounds having 1 to 8 carbon atoms is mixed at an arbitrary ratio and is a liquid at 25 ° C. and 1 atm. .
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane, octane and isooctane
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • methanol ethanol
  • 1-propanol 2-propanol and 1-butanol
  • Alcohols such as 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-hexanol, cyclohexanol, 1-octanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • Ketones esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol monomethyl ether acetate (PGMEA), ethers such as diethyl ether, tetrahydrofuran and dioxane Dichloromethane, chloroform, alkyl halides and 1,2-dichloroethane, and compositions obtained by mixing them at an arbitrary ratio can be mentioned.
  • the composition for forming a layer in the present invention contains a solvent, the solvent is not limited to the above.
  • a polymerizable compound often exhibits organic solvent solubility, and a polymer of the polymerizable compound often does not exhibit organic solvent solubility.
  • the resin concentration in the composition for forming the second layer is, for example, in the range of 1 to 40% by mass with respect to 100% by mass of the total composition for forming the layer from the viewpoint of film forming suitability.
  • the second layer is a layer containing at least a resin (resin-containing layer), and is preferably a layer mainly composed of a resin.
  • the main component refers to a component that occupies the most in the total solid content constituting the layer.
  • the inventors of the present invention that the resin occupies the largest amount in the total solid content of the second layer contributes to a large shape change due to the shrinkage of the resin due to heating, and thereby the height difference between the convex portion and the concave portion ( I think that the step can be increased. From this point, the resin concentration in the second layer is preferably 80% by mass or more, more preferably 85% by mass with respect to 100% by mass of the total solid content (total of components excluding the solvent) of the second layer.
  • the resin concentration in the second layer may be, for example, 95% by mass or less with respect to 100% by mass of the total solid content of the second layer, and 100% by mass (that is, the solid content is only the resin). It is also preferable.
  • organic solvent-soluble resin examples include (a) cellulose acylate and cocoon (b) (meth) acrylic resin.
  • a) cellulose acylate and cocoon a) (meth) acrylic resin.
  • (B) (Meth) acrylic resin (Meth) acrylic resin is a concept including both a methacrylic resin and an acrylic resin.
  • the (meth) acrylic resin also includes a copolymer of an acrylate ester and a methacrylate ester.
  • the repeating structural unit of the (meth) acrylic resin is not particularly limited.
  • the (meth) acrylic resin preferably has a repeating structural unit derived from a (meth) acrylic acid ester monomer as a repeating structural unit.
  • the (meth) acrylic resin is obtained by polymerizing at least one selected from a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer represented by the following general formula (201) as a repeating structural unit.
  • the repeating structural unit may be included.
  • R 201 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a —CN group, a —CO—R 202 group, or O—CO.
  • —R 203 group, and R 202 and R 203 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • (Meth) acrylic acid ester is not particularly limited.
  • JP, 2013-099875, A paragraph 0034 can be referred to.
  • the hydroxyl group-containing monomer is not particularly limited.
  • JP, 2013-099875, A paragraph 0035 can be referred to.
  • the unsaturated carboxylic acid is not particularly limited.
  • JP, 2013-099875, A paragraph 0036 can be referred to.
  • the (meth) acrylic resin may contain one or more lactone ring structures.
  • a lactone ring structure represented by the following general formula (401) can be given.
  • R 401 , R 402, and R 403 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain an oxygen atom.
  • the organic residue having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like.
  • the content of the lactone ring structure represented by the general formula (401) in the structure of the lactone ring-containing (meth) acrylic resin is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably. It is 10 to 60% by mass, particularly preferably 10 to 50% by mass.
  • the content of the lactone ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably. It is 10 to 60% by mass, particularly preferably 10 to 50% by mass.
  • the method for producing the lactone ring-containing (meth) acrylic resin there is no particular limitation on the method for producing the lactone ring-containing (meth) acrylic resin.
  • the resulting polymer (p) is heat treated to introduce a lactone ring structure into the polymer.
  • the (lactone cyclization condensation step) a lactone ring-containing (meth) acrylic resin can be obtained.
  • JP, 2012-250535, A paragraphs 0040-0047 can be referred to for details, such as a preferred physical property of a lactone ring containing (meth) acrylic resin.
  • the weight average molecular weight Mw of the (meth) acrylic resin is preferably 80000 or more.
  • the weight average molecular weight Mw of the (meth) acrylic resin is 80000 or more, the mechanical strength is high and the handling suitability during production is excellent.
  • the (meth) acrylic resin preferably has a weight average molecular weight Mw of 100,000 or more.
  • the (meth) acrylic resin commercially available products or those synthesized by a known synthesis method can be used.
  • commercially available products include, but are not limited to, Delpet (Japan registered trademark) 60N, 80N (Asahi Kasei Chemicals), Dialnal (Japan registered trademark) BR80, BR85, BR88, BR102 (Mitsubishi Rayon).
  • KT75 manufactured by Denki Kagaku Kogyo).
  • composition for forming the layer contains at least the polymerizable compound described above, a photopolymerization initiator, and cellulose acylate, and can further contain one or more optional components. Below, an arbitrary component is demonstrated.
  • the composition forming the monolayer may contain a resin in addition to the cellulose acylate.
  • the first layer may also contain a resin.
  • resin the resin mentioned above can be contained.
  • the resin contained in the first layer and the resin contained in the second layer may be the same or different. Good adhesion between the first layer and the second layer is preferable from the viewpoint of durability of the formed article. From this point, it is preferable that the first layer includes the same type of resin as the second layer. In the present invention, since the first layer contains cellulose acylate, the second layer preferably also contains cellulose acylate.
  • the composition for forming the layer can optionally contain a solvent. Including a solvent is preferable from the viewpoint of adjusting the viscosity of the composition for forming the layer and improving the coating suitability.
  • the solvent is preferably an organic solvent.
  • organic solvents include ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,2-dimethoxyethane, formic acid Esters such as methyl, ethyl formate, methyl acetate, ethyl acetate, amyl acetate, ⁇ -butyrolactone, methyl cellosolve, dimethylimidazolinone, dimethylformamide, dimethylacetamide, acetonitrile, dimethyl sulfoxide, sulfolane, nitroethane, methylene
  • 1,3-dioxolane, THF, methyl ethyl ketone, acetone, methyl acetate and methylene chloride are preferred.
  • the organic solvent exemplified above is the main solvent occupying the largest proportion (for example, 50% by mass or more and less than 99% by mass with respect to 100% by mass of the mixed solvent). Is preferred.
  • alcohol having 1 to 4 carbon atoms is preferable.
  • examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and propylene glycol monomethyl.
  • One type or two or more types of ethers can be mentioned.
  • the sub-solvent can be contained in the mixed solvent at a ratio of, for example, 1% by mass to less than 50% by mass, preferably 1% by mass to 40% by mass with respect to 100% by mass of the total amount of the mixed solvent.
  • the composition may contain a small amount of water in addition to the organic solvent.
  • the concentration of water with respect to 100% by mass of the total solvent can be, for example, 0.1 to 5% by mass, preferably 0.1 to 3% by mass, and more preferably 0.2 to 2% by mass.
  • the organic solvent is 5 to 30% by mass with respect to 100% by mass of the total amount of the solvent, More preferably, the content of alcohol is 7 to 25% by mass, and more preferably 10 to 20% by mass, because peeling of the laminate from the support is facilitated when film formation is performed on the support.
  • the proportion of the total amount of the solvent is, for example, in the range of 60 to 95% by mass, and preferably in the range of 70 to 85% by mass.
  • a composition containing a solvent in the above range is preferred because it hardly causes changes in concentration and composition due to volatilization of the solvent and precipitation of solids, and a viscosity suitable for stable film formation is obtained.
  • the composition for forming the layer can optionally contain a surfactant.
  • the surfactant can function as a leveling agent, for example.
  • the silicone compound include those having a substituent at at least one of a terminal end and a side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units.
  • the compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.
  • the substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group or these groups.
  • the molecular weight is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less, and most preferably 3,000 to 30,000.
  • the molecular weight refers to a weight average molecular weight.
  • the silicone atom content of the silicone compound is not particularly limited, but is preferably 18.0% by mass or more, more preferably 25.0 to 37.8% by mass, and 30.0 to 37. More preferably, it is 0% by weight.
  • silicone compounds examples include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, and X-22 manufactured by Shin-Etsu Chemical. 1821 (named above); Chisso FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (named above). However, it is not limited to these.
  • the fluorine compound a compound having a fluoroalkyl group is preferable.
  • the fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (eg, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.), but branched structures (eg, CH (CF 3 ) 2 , CH 2 CF (CF 3 ) 2 , CH (CH 3) ) CF 2 CF 3 , CH (CH 3 ) (CF 2 ) 5 CF 2 H, etc.), even alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups, per It may be a fluorocyclopentyl group or an alkyl group substituted with these.
  • ether bond e.g., CH 2 OCH 2 CF 2 CF 3 , CH 2 CH 2 OCH 2 C 4 F 8 H, CH 2 CH 2 OCH 2 CH 2 C 8 F 17, CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.
  • Multiple fluoroalkyl groups may be contained in the same molecule.
  • the fluorine compound further has one or more substituents such as an acryloyl group, a methacryloyl group, a vinyl group, an aryl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. May be included.
  • the fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited.
  • the fluorine atom content of the fluorine-based compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and further preferably 40 to 70% by mass.
  • preferable fluorine-based compounds include R-2020, M-2020, R-3833, M-3833 (trade name) manufactured by Daikin Chemical Industries, Ltd .; MegaFac (Japan registered trademark) F-784, F-171 manufactured by DIC F-172, F-179A, F-114, F-251, F-281, F-410, F-430, F-444, F-477, F-510, F-511, F-552, F -553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-563, F-567 , F-567, F-569, F-570, F-571, R-40, R-41, R-43, R-94, RS-72-K
  • a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like may be added as appropriate.
  • These dustproof agent and antistatic agent may contain the structural unit in the above-mentioned silicone compound or fluorine compound. Examples of preferred compounds include, but are not limited to, Megafac F-150 manufactured by DIC and SH-3748 manufactured by Toray Dow Corning.
  • Surfactants may be used singly or in combination of two or more at an arbitrary ratio.
  • the amount of the surfactant in the composition for forming the layer is not particularly limited. For example, 0.001 to 10 mass with respect to 100 mass parts of the solid content in the composition for forming the layer. Part.
  • the polymerizable compound contained in the composition for forming the layer is partially polymerized and cured by pattern exposure.
  • the present inventors consider that a polymerizable compound that has not been reacted in pattern exposure is polymerized by heating performed after pattern exposure.
  • the present inventors speculate that a large difference in shrinkage between polymerization by pattern exposure and polymerization by heating helps to form a concavo-convex structure having a large difference in elevation.
  • the composition for forming the layer may contain a thermal polymerization initiator in order to enable polymerization by heating.
  • the polymerizable group contained in the polymerizable compound upon heating may generate a radical and function as an initiator.
  • a polymerization reaction (thermal polymerization) of a polymerizable compound that has not been reacted in pattern exposure can be allowed to proceed without including a thermal polymerization initiator in the composition for forming the layer. it can.
  • the structure of the thermal polymerization initiator is not particularly limited.
  • the thermal polymerization initiator include azo compounds, hydroxylamine ester compounds, organic peroxides, hydrogen peroxide, and the like.
  • Specific examples of the organic peroxide include those described in Japanese Patent No. 5341155, paragraph 0031.
  • the azo compound may contain at least one azo bond, and may contain various substituents together with the azo bond.
  • 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylisobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1- Azonitrile compounds such as [(1-cyano-1-methylethyl) azo] formamide, dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate), etc.
  • hydroxylamine ester compound examples include a hydroxylamine ester compound represented by the formula I described in JP-A-2012-521573. Specific compounds are shown below. However, it is not limited to these.
  • the second layer may contain one or more polymerizable compounds as optional components.
  • the polymerizable compound is as described above.
  • the polymerizable compound concentration in the second layer is lower than the polymerizable compound concentration in the first layer.
  • the shrinkage of the resin by heating tends to have a larger shrinkage rate than the polymerization shrinkage by heating of the polymerizable compound. Therefore, from the viewpoint of greatly changing the shape (shrinking) of the second layer by heating, the resin shrinkage is as described above.
  • the polymerizable compound concentration in the second layer is, for example, 5% by mass or less, preferably 3% by mass or less, and 0% by mass with respect to 100% by mass of the total composition for forming the second layer. It may be.
  • the laminate including the single layer body and the first layer and the second layer may be composed of only these layers, and includes a support such as a base film and one or more other layers. May be. Moreover, it is also possible to form the said single layer body or laminated body on the surface of the article which should form an uneven structure. Since the coating layer can be formed not only on a flat surface but also on a curved surface, the surface shape of the support or article on which the layer is provided does not matter. Moreover, as an example of said other layer, the easily bonding layer and adhesive layer for improving the adhesiveness of a single layer body or a 2nd layer, and a support body and articles
  • the article which has an uneven structure on both surfaces can also be obtained by heating this.
  • an article having a concavo-convex structure on both surfaces by forming the first layer on both surfaces of the second layer and heating the laminate after performing pattern exposure to be described later on each first layer.
  • the layer containing a polymerizable compound, a photopolymerization initiator, and cellulose acylate may be formed as a single layer or a laminate formed with a layer containing a resin.
  • a composition (dope) containing a polymerizable compound, a photopolymerization initiator, and cellulose acylate in desired ratios is prepared.
  • the dope is extruded from a casting giusa and cast.
  • a layer can be formed by a well-known film forming method.
  • a coating method it can be performed by using a coating device such as a bar coater, a blade coater, a die coater, or a gravure coater, or by a method such as curtain coating or dip coating. From the viewpoint of productivity, the casting film forming method is preferable.
  • a manufacturing method can be simplified compared with the case where a laminated body is formed.
  • a polymerizable compound instead of forming the monolayer, a polymerizable compound, at least one polymerization initiator selected from an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator, and a cellulose acylate are used.
  • the laminate may be formed by a step of forming a first layer containing a rate and a second layer containing a resin. In this case, the surface of the first layer is subjected to pattern exposure and heated to form a concavo-convex structure.
  • the second layer may contain a polymerizable compound, but the content is preferably lower than the content of the polymerizable compound in the first layer.
  • the first layer and the second layer are formed by a casting film forming method, more specifically, a co-casting method or a sequential casting method, or a film forming method such as a coating method using a known coating apparatus. By doing so, it can be manufactured.
  • a casting dope having the composition for forming the first layer and the second layer are formed on a casting support (band or drum).
  • the dope for casting having the composition to be extruded is extruded using a casting gussa that is simultaneously extruded from another slit, etc., and each layer is simultaneously cast, peeled off from the support at an appropriate time, and dried to form a film. This is a casting method for molding.
  • the casting dope for the second layer is first extruded from the casting giusa on the casting support, cast, dried, or dried, On top of that, the dope for casting for the first layer is extruded from the casting giusa to cast and laminate the dope successively, peeled off from the support at an appropriate time, and dried to form a film.
  • the coating method can be performed using a coating device such as a bar coater, a blade coater, a die coater, or a gravure coater, and can also be performed by a method such as curtain coating or dip coating.
  • the composition for forming the first layer is prepared by using a suitable coating apparatus. It is applied to the surface of the layer and dried to produce a laminate. From the viewpoint of productivity, the casting film forming method is preferable, and the co-casting method is more preferable.
  • both the casting film forming method and the coating method include an aspect in which the second layer is laminated while the second layer is wet, and an aspect in which the first layer is laminated after the second layer is dried. Any aspect may be used. From the viewpoint of the adhesion of the laminate, the former mode is preferred.
  • the first layer Either the layer or the second layer may be on the support side.
  • pattern exposure can also be performed after laminating
  • the bonding can be performed by a known bonding method such as bonding with an adhesive layer.
  • the second layer is so positioned that the first layer subjected to pattern exposure is located on the air interface side and the second layer is located on the support side.
  • the layers may be stacked in the order of the first layer and the first layer.
  • the layer formed as a single layer or a laminate is optionally subjected to a drying step as necessary.
  • a drying process can be performed by arrangement
  • the heating temperature at the time of drying is preferably a temperature at which the polymerization reaction of the polymerizable compound does not progress and the resin does not undergo large thermal shrinkage, for example, a temperature of 50 ° C. or more and 100 ° C. or less.
  • the heating temperature refers to the temperature of warm air or the atmospheric temperature in the heating furnace. The same applies to the heating step after pattern exposure described later.
  • the method for producing an article having a concavo-convex structure of the present invention preferably has a step of peeling the layer from the support between the layer forming step and the pattern exposure step. By stripping the layer from the support and then pattern exposure, the average height of the convex portions can be increased.
  • the timing at which the layer is peeled off is not particularly limited, but is preferably performed when the solvent is dried to some extent.
  • the method for producing an article having an uneven structure according to the present invention includes a step of forming a layer on a support, a polymerizable compound, an oxime ester photopolymerization initiator, and an acylphosphine oxide photopolymerization.
  • the peeled layer is preferably subjected to a pattern exposure step described later.
  • the step of forming the first layer includes a polymerizable compound, an oxime ester photopolymerization initiator, and an acyl phosphine oxide system on the support.
  • Pattern exposure process After the drying step, the layer is pattern exposed.
  • a non-exposed portion of pattern exposure is a concave portion, and an exposed portion exposed by pattern exposure is a convex portion. Therefore, the pattern exposure is performed so that a portion where a convex portion on the surface of the layer is to be formed is exposed.
  • Pattern exposure methods are already known in the field of photoresists and the like, and those known techniques can be applied to the pattern exposure in the manufacturing method without any limitation.
  • a method of pattern exposure by placing a photomask (exposure mask) between the light source and the layer surface a method of directly irradiating the layer surface with laser light in a spot form without using a photomask (so-called direct drawing) Or a pattern direct exposure method) may be used.
  • a method of performing pattern exposure by arranging a photomask is roughly divided into a non-contact method in which the photomask is arranged at a distance from the surface of the layer and a contact method in which the photomask is arranged on the layer surface. Any method may be used, but the non-contact method is preferable from the viewpoint that there is no change in the surface property of the layer due to contact with the photomask and no adhesion of dust / dust.
  • Non-contact methods include proximity exposure and projection exposure, but either exposure method may be adopted.
  • the surface of the first layer is subjected to pattern exposure, whereby the polymerizable compound is polymerized and cured in the exposed portion.
  • the subsequent heating causes polymerization of the polymerizable compound that has not been reacted in the pattern exposure in the first layer, so that so-called polymerization shrinkage occurs.
  • the resin contained in this layer contracts due to heat. In this way, shrinkage occurs in portions other than the exposed portion, whereas the exposed portion is already polymerized and cured, so that it is considered that no significant shape change occurs during heating.
  • the present inventors speculate that an uneven shape in which the exposed portion becomes a convex portion can be formed.
  • the present inventors have contributed to increasing the height difference (step) between the convex part and the concave part as a result of a large shape change called heat shrinkage of the resin in the second coating layer. It is presumed that a fine uneven structure having a height difference can be formed.
  • the large difference in level (step) between the convex portion and the concave portion enables the formation of a concave / convex shape that is recognized as a clear concave / convex portion. It is effective for forming a concavo-convex structure.
  • the photomask 2 is arranged at a predetermined interval from the surface of the layer 1 after the drying process. Thereafter, light 3 is irradiated from above the photomask 2 toward the surface of the layer 1. Thereby, only the light irradiation area
  • the light used for pattern exposure may be determined according to the type of polymerizable compound and photopolymerization initiator contained in the layer, and in particular, ultraviolet rays (i-line, 365 nm) and laser light (405 nm) are preferable.
  • the light source for light irradiation include a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and an LED. be able to.
  • the light irradiation amount is preferably 50 mJ / cm 2 or more and 1000 mJ / cm 2 or less, but may be a light irradiation amount at which the polymerization reaction proceeds at the convex portion and the convex portion is cured, and is limited to the above range. It is not something.
  • a heat treatment for heating the layer 1 is performed.
  • the heat treatment can be performed by placing in the heating furnace, transporting in the heating furnace, blowing hot air, or the like.
  • the heating temperature in the heat treatment is preferably 140 to 200 ° C., and the heating time is preferably 2 to 200 minutes.
  • the thickness of the article manufactured by the manufacturing method of the present invention depends on the thickness of the layer formed in the layer forming step, and is, for example, 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more. . According to the study by the present inventors, there was a tendency that the height difference (step) between the convex portion and the concave portion becomes larger as the thickness of the layer formed in the layer forming step is thicker. This point is preferable from the viewpoint of forming a fine relief structure. Therefore, the upper limit of the layer thickness is not particularly limited.
  • the thickness of the layer may be a set film thickness at the time of application or an actual measurement value.
  • the layer in which the concavo-convex structure is formed can be used as an article having the concavo-convex structure as it is or by cutting into a shape according to the application.
  • an article having a concavo-convex structure can be obtained by laminating the layer to the article surface by a known laminating method.
  • the article having a concavo-convex structure can be, for example, a long film.
  • the film-like layer may be bonded to an article having an arbitrary shape, and the shape of the article is not limited.
  • One or more of the other layers can be arbitrarily formed on one or both of the surface having the concavo-convex structure and the other surface.
  • the article manufactured by the above manufacturing method is not limited to the article having the concavo-convex structure on the outermost surface of the article. Are also included. Thus, having an uneven structure at the interface can contribute to, for example, improving the adhesion of the interface between the two layers.
  • articles having uneven structures of various shapes and sizes including a fine uneven structure can be manufactured.
  • the size for example, it is possible to form a fine uneven structure as shown in the examples.
  • the above manufacturing method is also suitable as a method for manufacturing an article having a concavo-convex structure larger than the concavo-convex structure shown in the examples.
  • the shape of the concavo-convex structure to be formed is not particularly limited.
  • the concavo-convex structure is formed by two-dimensionally arranging a shape selected from the group consisting of a polygonal cone-like shape, a cone-like shape, a partial spheroid-like shape, and a partial sphere-like shape. Is formed.
  • the concavo-convex structure is formed by one-dimensionally arranging a shape selected from the group consisting of a partial columnar shape, a partial elliptical columnar shape, and a prismatic shape.
  • the term “one-dimensionally arranged” means that the shape is arranged only in one direction of the laminate surface (pattern-exposed surface), that is, in parallel. Such an uneven structure is sometimes called a line and space pattern.
  • the two-dimensional arrangement means that the shape is arranged in two or more directions on the surface of the laminate. For example, it is formed in two directions, that is, a certain direction and a direction orthogonal to this direction, and is not limited to a regularly formed aspect, but also includes an irregularly (randomly) formed aspect. Is done.
  • the uneven structure may be a fine uneven structure called a moth-eye structure.
  • the shape is a convex shape.
  • the shape is a concave shape. For example, by performing pattern exposure using an exposure mask having an opening corresponding to the above shape, a concavo-convex structure having a convex portion having the above shape can be formed.
  • FIG. 4 are schematic views showing the shapes of patterning photomasks that can be used in the present invention.
  • a black area indicates an exposed portion
  • a white area indicates a light shielding portion.
  • the shape of the opening of the exposed portion is a square and a photomask having a houndstooth shape
  • FIG. 5 the shape of the exposed portion of the opening is square and the light shielding portion.
  • the shape of the photomask is not limited to the shape shown in FIGS. 4 to 7, and any shape of photomask can be used.
  • the size of the exposed portion and the distance between adjacent exposed portions can also be arbitrarily set. Can be set. In the present invention and the present specification, descriptions relating to angles such as orthogonal and parallel include the range of errors allowed in the technical field to which the present invention belongs.
  • the angle is within the range of strict angle ⁇ 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.
  • the “polygonal pyramid shape” is used to mean not only a perfect polygonal pyramid shape but also a shape that approximates a polygonal pyramid.
  • a further aspect of the present invention relates to an article having a concavo-convex structure produced by the above production method (hereinafter also simply referred to as an article).
  • the manufacturing method, details of the concavo-convex structure, and the like are as described above.
  • the average height of the protrusions of the concavo-convex structure is 1% or more with respect to the average length of the concavo-convex structure.
  • the average height of the convex portion indicates the average value of the maximum distance between the top surface of the convex portion and the bottom surface of the concave portion adjacent to the convex portion.
  • the average length of the unevenness indicates an average value of a distance obtained by doubling the distance from the center of the convex portion to the center of the adjacent concave portion.
  • the composition for forming a layer contains a photopolymerization initiator having high sensitivity to ultraviolet rays, so that the difference in shrinkage between the pattern-exposed region and the heat-polymerized region is large.
  • a concavo-convex structure in which the height of the convex portion is large (the level difference of the concavo-convex is large) can be formed.
  • the ratio of the average height of the projections to the average length of the projections and depressions can be obtained as follows.
  • the height of the convex portion is determined by observing the surface of the manufactured article having a concavo-convex structure with a non-contact surface / layer cross-sectional shape measuring system (VertScan 2.0 manufactured by Ryoka System Co., Ltd.). It can be obtained by measuring the maximum distance between the bottom surface of the recess adjacent to the top surface of the surface.
  • the average length of the projections and depressions can be obtained from a mask pattern design drawing or an observation image of an optical microscope, the above-described non-contact surface / layer cross-sectional shape measurement system, an atomic force microscope, or an electron microscope.
  • the ratio of the average height of the projections to the average length of the projections and depressions can be obtained by calculating the average value of the projection heights in the numerator and the average length of the projections and depressions in the denominator.
  • the article manufactured by the manufacturing method according to the second aspect of the present invention has a concentration gradient in which the concentration of the polymer of the polymerizable compound decreases from the surface having the concavo-convex structure toward the thickness direction of the article. Can be confirmed. This is because, in the above production method, when the second layer contains a polymerizable compound, the polymerizable compound concentration in the second layer is lower than the polymerizable compound concentration in the first layer.
  • the article manufactured by the above manufacturing method may have a concentration gradient in which the resin concentration increases from the surface having the concavo-convex structure toward the thickness direction of the article.
  • the concentration gradient may increase continuously or may increase intermittently.
  • a polymer of a polymerizable compound is harder and more brittle than a resin (especially an organic solvent-soluble resin), whereas a resin is softer than a polymer of a polymerizable compound, which contributes to improving the brittleness of an article. Then, the present inventors consider.
  • the concentration gradient of the polymer of the polymerizable compound in the article can be confirmed by, for example, composition analysis by Raman spectroscopy.
  • composition analysis by Raman spectroscopy For details such as analysis conditions, the following examples can be referred to.
  • the article having the concavo-convex structure described above can be used as a constituent member of a flat panel display such as a liquid crystal display device, for example, as an antireflection film, a brightness enhancement film (for example, a prism sheet) exhibiting a light collecting effect, or the like.
  • item which has said uneven structure can also be used as a cell culture sheet which has an uneven structure in order to make peeling of the cultured cell easy.
  • the above application example is merely an example, and the article having the uneven structure can be used in various applications and fields such as flat panel display applications, semiconductor manufacturing fields, biotechnology, and pharmaceutical fields.
  • Cellulose acetate (degree of substitution 2.86, degree of polymerization 350) 100 parts by weight pentaerythritol tetraacrylate (A-TMMT manufactured by Shin-Nakamura Chemical) 100 parts by mass photopolymerization initiator (Irgacure OXE-01 manufactured by BASF) 10 parts by mass Fluorine-based leveling agent (Megafac F-784 manufactured by DIC) 0.1 part by mass Methylene chloride 525 parts by mass Methanol 133 parts by mass 1-butanol 7 parts by mass (in Table 1, cellulose acetate is described as “TAC” (Pentaerythritol tetraacrylate is described as “A-TMMT”.) In Table 1, Irgacure OXE-01 is described as Irg OXE-01.
  • the dope A was used to cast on the surface of the glass (support) with an applicator whose gap was adjusted so that the film thickness (set film thickness) was 60 ⁇ m. Thereafter, it was dried at 70 ° C. for 6 minutes in a heating oven (Incubator Safety Oven SPHH-202 manufactured by Espec Corp.). After that, the film sample is peeled off from the glass surface, placed after the frame is attached so that the air side surface at the time of film production is in close contact with the quartz exposure mask, and the proximity type exposure machine (Hitachi High-Tech Electronic Engineering Co., Ltd.) with an ultra-high pressure mercury lamp.
  • Examples 1-2 to 1-6 A patterning sample was obtained in the same manner as in Example 1-1 except that the addition amount of pentaerythritol tetraacrylate and the addition amount of the initiator were the values shown in Table 1.
  • Acrylic binder a copolymer of glycidyl methacrylate adduct to methacrylic acid / cyclohexyl methacrylate / methyl methacrylate / methacrylic acid, wherein the molar ratio of methacrylic acid / cyclohexyl methacrylate / methyl methacrylate / methacrylic acid is 20 / 46/2/32 with a weight average molecular weight of 36000 and an acid value of 66.
  • Examples 2-1 to 2-4 For the film of Example 1-1, a patterning sample was obtained in the same manner as in Example 1-1 except that the exposure amount was changed to the exposure amount shown in Table 2 instead of 100 mJ / cm 2 . Evaluation was made in the same manner, and the results are shown in Table 2 below.
  • Examples 3-1 to 3-5 A patterning sample was obtained in the same manner as in Example 1-1 except that the polymerizable compounds shown in Table 3 were added instead of pentaerythritol tetraacrylate in Example 1-1. Evaluation was made in the same manner, and the results are shown in Table 3 below.
  • Dipentaerythritol hexaacrylate Kayarad DPHA, Nippon Kayaku Co., Ltd.
  • V1000 Osaka Organic Chemical Industry Co., Ltd.
  • UV1700B Nippon Synthetic Chemical Industry Co., Ltd.
  • UA306I Kyoeisha Chemical Co., Ltd.
  • UA306H Kyoeisha Chemical Co., Ltd.
  • Example 4-1 A film was produced in the same manner as in Example 1-1 except that Irg 819 (manufactured by BASF) was added instead of Irg Oxe01 in Example 1-1.
  • This film was subjected to pattern exposure using a laser beam (wavelength: 405 nm) with a spot diameter of 600 nm and an exposure interval of 600 nm, followed by heat treatment at 170 ° C. for 60 minutes to obtain a patterning sample.
  • This sample was observed with a scanning probe microscope SPA400 (manufactured by SII).
  • the average height of the convex portions of the concavo-convex structure of this sample was 30 nm, and the pattern ratio was 2.5%.
  • the laminate (co-cast sample) in which the layer of dope A (first layer) and the layer of dope B (second layer) are laminated is peeled off from the glass surface, and the dope A layer after the frame is stretched Using a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the surface facing the quartz exposure mask at an interval, a quartz exposure mask (mask pattern exposure part 600 nm) Proximity exposure (pattern exposure) was performed at a light irradiation amount of 300 mJ / cm 2 via a square, a light-shielding portion 600 nm. Thereafter, heat treatment was performed at 170 ° C. for 60 minutes in the heating oven used in the above drying treatment to obtain a patterning sample (film sample) of Example 5-1.
  • a proximity-type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • Example 5-6 A patterning sample was obtained in the same manner as in Example 5-1, except that the addition amount of pentaerythritol tetraacrylate and the addition amount of the initiator were the values shown in Table 4.
  • a film was produced by the method of Example 5-1, except that Irg 819 was added instead of Irg Oxe01 of Example 5-1, and 300 parts by weight of pentaerythritol tetraacrylate was added instead of 100 parts by weight of pentaerythritol tetraacrylate. did.
  • This film was subjected to pattern exposure using a laser beam (wavelength: 405 nm) with a spot diameter of 600 nm and an exposure interval of 600 nm, followed by heat treatment at 170 ° C. for 60 minutes to obtain a patterning sample (Example 6).
  • This sample was observed with a scanning probe microscope SPA400 (manufactured by SII). The average height of the protrusions of the uneven structure of this sample was 59 nm, and the pattern ratio was 4.9%.
  • Example 6-1 ⁇ Preparation of first layer forming composition (polymerizable compound-containing cellulose acylate dope P)> The following composition was put into a mixing tank and stirred to dissolve each component to prepare a dope P.
  • An exposure mask (corresponding to the mask pattern in FIG. 7; exposure part width 20 ⁇ m, light-shielding part width 100 ⁇ m) in which the exposure pattern has a grid pattern is brought into contact with one surface of the sample, and laser light (405 nm) is irradiated from the mask side. Irradiation was performed to 100 mJ / cm 2 .
  • the grid-shaped exposure mask is removed, and the square of the exposure pattern (corresponding to the mask pattern in FIG. 6; exposure part width 20 ⁇ m, light-shielding part width 100 ⁇ m) is brought into contact with the other side of the sample.
  • the heat processing was performed at 170 degreeC for 60 minute (s) in the heating oven used by said drying process, and the patterning sample (film sample) was obtained.
  • the lattice pattern is convex on the side exposed from the lattice mask pattern side (like protruding from the film), and the square pattern is convex on the side exposed from the square mask pattern side. It was confirmed that it was formed.

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  • Spectroscopy & Molecular Physics (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de fabrication d'un article ayant une structure en creux et en saillie, lequel procédé comprend : une étape consistant à former une couche qui contient un composé polymérisable, au moins un type d'initiateur de photopolymérisation choisi parmi un initiateur de photopolymérisation à base d'ester d'oxime et un initiateur de photopolymérisation à base d'oxyde d'acyl-phosphine, et l'acylate de cellulose ; une étape consistant à réaliser une exposition à une lumière de motif sur une surface de la couche ; et une étape consistant à chauffer la couche après l'exposition à une lumière de motif, le procédé formant une structure en creux et en saillie dans laquelle une partie non exposée à la lumière dans l'exposition à une lumière de motif est une partie en creux. Le procédé est utilisé pour fournir un procédé de fabrication d'un article ayant une structure en creux et en saillie avec une grande différence entre les creux et les saillies, et un article ayant une structure en creux et en saillie.
PCT/JP2015/074307 2014-09-30 2015-08-27 Procédé de fabrication d'un article ayant une structure en creux et en saillie, et article ayant une structure en creux et en saillie WO2016052026A1 (fr)

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JP2015167014A JP6424150B2 (ja) 2014-09-30 2015-08-26 凹凸構造を有する物品の製造方法および凹凸構造を有する物品

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JPH0854734A (ja) * 1994-08-12 1996-02-27 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物およびこれを用いた感光性ドライフィルム
JPH10508882A (ja) * 1994-11-23 1998-09-02 ビーエーエスエフ アクチェンゲゼルシャフト 支持体を被覆及び印刷する方法
JP2002082428A (ja) * 2000-09-06 2002-03-22 Kyoto Elex Kk アルカリ現像型感光性ペースト組成物
JP2004037522A (ja) * 2002-06-28 2004-02-05 Hitachi Chem Co Ltd 表面凹凸形成方法、それにより得られる光学フィルム及び拡散反射板並びに拡散反射板の製造方法
WO2007144967A1 (fr) * 2006-06-13 2007-12-21 Sekisui Chemical Co., Ltd. Procédé de production de film à motif et composition de résine photosensible
JP2009192964A (ja) * 2008-02-18 2009-08-27 Fujifilm Corp 光記録用組成物およびホログラフィック記録媒体
JP2009237057A (ja) * 2008-03-26 2009-10-15 Taiyo Ink Mfg Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2010008713A (ja) * 2008-06-26 2010-01-14 Mitsubishi Chemicals Corp ホログラム記録層形成用組成物、並びにそれを用いたホログラム記録材料及びホログラム光記録媒体
JP2010501687A (ja) * 2006-08-30 2010-01-21 スティッチング ダッチ ポリマー インスティテュート ポリマーレリーフ構造の調製方法
JP2010524037A (ja) * 2007-04-11 2010-07-15 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト ホログラフィ用途用の有利な記録媒体
WO2012090532A1 (fr) * 2010-12-28 2012-07-05 太陽インキ製造株式会社 Composition de résine photodurcissable, film sec et objet durci obtenus à partir de celle-ci et carte de circuits imprimés obtenue à l'aide de ceux-ci
JP2013080020A (ja) * 2011-09-30 2013-05-02 Taiyo Holdings Co Ltd 感光性導電性樹脂組成物、感光性導電性ペーストおよび導電体パターン

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0854734A (ja) * 1994-08-12 1996-02-27 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物およびこれを用いた感光性ドライフィルム
JPH10508882A (ja) * 1994-11-23 1998-09-02 ビーエーエスエフ アクチェンゲゼルシャフト 支持体を被覆及び印刷する方法
JP2002082428A (ja) * 2000-09-06 2002-03-22 Kyoto Elex Kk アルカリ現像型感光性ペースト組成物
JP2004037522A (ja) * 2002-06-28 2004-02-05 Hitachi Chem Co Ltd 表面凹凸形成方法、それにより得られる光学フィルム及び拡散反射板並びに拡散反射板の製造方法
WO2007144967A1 (fr) * 2006-06-13 2007-12-21 Sekisui Chemical Co., Ltd. Procédé de production de film à motif et composition de résine photosensible
JP2010501687A (ja) * 2006-08-30 2010-01-21 スティッチング ダッチ ポリマー インスティテュート ポリマーレリーフ構造の調製方法
JP2010524037A (ja) * 2007-04-11 2010-07-15 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト ホログラフィ用途用の有利な記録媒体
JP2009192964A (ja) * 2008-02-18 2009-08-27 Fujifilm Corp 光記録用組成物およびホログラフィック記録媒体
JP2009237057A (ja) * 2008-03-26 2009-10-15 Taiyo Ink Mfg Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2010008713A (ja) * 2008-06-26 2010-01-14 Mitsubishi Chemicals Corp ホログラム記録層形成用組成物、並びにそれを用いたホログラム記録材料及びホログラム光記録媒体
WO2012090532A1 (fr) * 2010-12-28 2012-07-05 太陽インキ製造株式会社 Composition de résine photodurcissable, film sec et objet durci obtenus à partir de celle-ci et carte de circuits imprimés obtenue à l'aide de ceux-ci
JP2013080020A (ja) * 2011-09-30 2013-05-02 Taiyo Holdings Co Ltd 感光性導電性樹脂組成物、感光性導電性ペーストおよび導電体パターン

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