WO2012043109A1 - Method for producing porous plate for microarray or the like, photosensitive composition used for the method, porous plate for microarray or the like, and substrate for microarray - Google Patents

Method for producing porous plate for microarray or the like, photosensitive composition used for the method, porous plate for microarray or the like, and substrate for microarray Download PDF

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Publication number
WO2012043109A1
WO2012043109A1 PCT/JP2011/069418 JP2011069418W WO2012043109A1 WO 2012043109 A1 WO2012043109 A1 WO 2012043109A1 JP 2011069418 W JP2011069418 W JP 2011069418W WO 2012043109 A1 WO2012043109 A1 WO 2012043109A1
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Prior art keywords
photosensitive film
pore
polymer
photosensitive
film
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PCT/JP2011/069418
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French (fr)
Japanese (ja)
Inventor
聡子 安孫子
石川　悟司
宏文 後藤
光 水野
利治 新木
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Jsr株式会社
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Priority to JP2012536287A priority Critical patent/JP5682627B2/en
Publication of WO2012043109A1 publication Critical patent/WO2012043109A1/en

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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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—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
    • G03F7/027—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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer

Definitions

  • the present invention relates to a method for producing a microporous plate and the like, a photosensitive composition used in the above method, a microporous plate and a microarray substrate.
  • a substrate for microarrays is equipped with a substance such as a nucleic acid, protein, peptide, sugar chain, low molecular weight compound, cell, or tissue as a probe molecule on a substrate, and measures the interaction with a biological substance that is the target molecule. It is a device for making use of reaction.
  • the microarray substrate is used, for example, as a device for DNA sequencing that determines the sequence of nucleotides (nucleobases) constituting DNA.
  • One technique for DNA sequencing is a technique using protein nanopore technology. This is because DNA passes through a through hole (diameter of 500 nm or less) slightly larger than its molecular diameter, and when DNA passes through the through hole, the current flowing through the through hole depends on the nucleobase of the DNA. This is a technique for performing DNA sequencing using this method.
  • a microarray pore plate having pores and a polymer membrane having a through-hole having a diameter of 500 nm or less are formed, and the polymer membrane is a thin film of the microarray pore plate.
  • a microarray substrate formed so as to cover the holes is required.
  • Various studies have been made on methods for producing microplates and other microporous plates (see, for example, Patent Documents 1 and 2).
  • the present invention provides a method for producing a microporous plate or the like without using a mechanical process or a dry process, and is used in the method. It is an object of the present invention to provide a photosensitive composition, a microplate manufactured for the microarray manufactured by the method, and a microarray substrate having the microporous plate.
  • the present invention is as follows. [1] (1) Forming a first photosensitive film on a base substrate, and forming a second photosensitive film containing a lipophilic component on the first photosensitive film, (2) The first A step of selectively exposing the photosensitive film and the second photosensitive film; and (3) a step of developing the first photosensitive film after exposure and the second photosensitive film after exposure. A method for producing a pore plate having pores, wherein at least part of the side wall surface of the pores has lipophilicity. [2] The method for producing a pore plate according to [1], wherein the lipophilicity-imparting component is (E2) a silicone-based surfactant.
  • the second photosensitive film before exposure is (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond, (D2) a solvent, and (E2 )
  • the hydrophilicity-imparting component is (A1) a polymer having a hydroxyl group.
  • the first photosensitive film before exposure is (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, (C1) a compound having at least one ethylenically unsaturated bond, and (D1) a solvent.
  • A1 a polymer having a hydroxyl group
  • B1 a photoradical generator
  • C1 a compound having at least one ethylenically unsaturated bond
  • D1 a solvent.
  • a photosensitive composition comprising a compound having an unsaturated bond, (D2) a solvent, and (E2) a silicone-based surfactant.
  • the photosensitive composition containing the compound which has two ethylenically unsaturated bonds, and (D1) solvent is a photosensitive composition used in the method for producing a pore plate according to [3] or [7]
  • a photosensitive composition comprising a compound having an unsaturated bond, (D2) a solvent, and (E2) a silicone-based surfactant.
  • [10] Having at least one pore produced by the method for producing a pore plate according to any one of [1] to [7], wherein at least a part of the side wall surface of the pore is lipophilic.
  • a pore plate having [11] A pore plate having at least one pore, wherein at least a part of the side wall surface of the pore has lipophilicity, and the surface of the lipophilic side wall surface contains silicon atoms. .
  • a microporous plate or the like can be easily produced without using a mechanical process or a dry process.
  • step (1) A step of forming a first photosensitive film on a base substrate and forming a second photosensitive film containing a lipophilic component on the first photosensitive film (hereinafter also referred to as “step (1)”). ), (2) a step of selectively exposing the first photosensitive film and the second photosensitive film (hereinafter also referred to as “step (2)”), and (3) the first photosensitive film and exposure after exposure.
  • step (3) A step of developing the subsequent second photosensitive film.
  • step (1) as shown in (1) of FIG. 1, a first photosensitive film 112 is formed on a base substrate 111, and a second lipophilicity-imparting component is contained on the first photosensitive film 112. In this step, the photosensitive film 113 is formed.
  • the base substrate 111 may be a substrate formed from an inorganic material such as a silicon substrate or a glass substrate, a substrate formed from an organic material, or a substrate formed from a composite material thereof.
  • the base substrate 111 may be a substrate having a sensor for confirming that a nucleobase or the like has passed through the polymer film.
  • the first photosensitive film 112 may be a positive photosensitive film or a negative photosensitive film as long as the solubility of the first photosensitive film 112 changes in the developer upon exposure.
  • the polymer film described later is formed so as to cover the pores 134, when the buffer solution is hydrophilic, the buffer solution can be efficiently taken into the pores 134.
  • the side wall surface 131 of the pores 134 formed by the first photosensitive film 112 has hydrophilicity. In order to impart hydrophilicity to the side wall surface 131 of the pores 134, it is usually sufficient to include a hydrophilicity imparting component in the first photosensitive film 112.
  • hydrophilicity-imparting component examples include compounds having a polar group such as a hydroxyl group or a carboxyl group.
  • a polymer (A1) having a hydroxyl group In order to efficiently impart hydrophilicity to the side wall surface 131 of the pore 134, it is preferable to use a polymer (A1) having a hydroxyl group.
  • the polymer (A1) having a hydroxyl group refer to “3-1. It is described in “Polymer having hydroxyl group (A1)”.
  • a composition containing a compound whose properties are changed by light such as a photo radical generator (B1), a photo acid generator, and a naphthoquinone diazide compound.
  • a method for forming the first photosensitive film 112 on the base substrate 111 for example, a composition containing a compound whose properties are changed by light, such as a photo radical generator (B1), a photo acid generator, and a naphthoquinone diazide compound.
  • a method for a composition containing a compound whose properties are changed by light such as a photo radical generator (B1), a photo acid generator, and a naphthoquinone diazide compound.
  • the first photosensitive film 112 is formed by coating on the base substrate 111 by a technique such as spin coating, roll coating, or inkjet.
  • the method is preferable because the flat first photosensitive film 112 can be formed.
  • the composition containing the photoradical generator (B1) is preferable because it is difficult to dissolve
  • the first photosensitive film 112 includes (A1) a polymer having a hydroxyl group as a hydrophilicity-imparting component, (B1) a photoradical generator, and (C1) a compound having at least one ethylenically unsaturated bond. And (D1) a coating film obtained from a composition containing a solvent (hereinafter also referred to as “first photosensitive composition”) is preferred.
  • first photosensitive composition a composition containing a solvent
  • the second photosensitive film 113 may be a positive type photosensitive film or a negative type photosensitive film as long as it contains a lipophilicity-imparting component and changes its solubility in a developer upon exposure.
  • the lipophilicity-imparting component is used to impart lipophilicity to the side wall surface 132 of the pores 134 formed by the second photosensitive film 113, as shown in (3) of FIG.
  • Examples of the lipophilic component include compounds having a structure that contributes to lipophilicity, such as a compound having a dimethyl silicone structure and a compound having a fluorine atom.
  • the silicone surfactant (E2) is preferable, and the silicone surfactant (E2) having a dimethylsilicone structure. Is particularly preferred.
  • the silicone surfactant (E2) refer to “2-5. “Silicone-based surfactant (E2)”.
  • Examples of the method for forming the second photosensitive film 113 on the first photosensitive film 112 include a compound whose properties are changed by light, such as a photoradical generator (B2), a photoacid generator, and a naphthoquinonediazide compound. Examples thereof include a method of forming the second photosensitive film 113 by applying the composition onto the first photosensitive film 112 by a technique such as a spin coating method, a roll coating method, or an ink jet method. The method is preferable because the flat second photosensitive film 113 can be formed.
  • the second photosensitive film 113 includes (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond, (D2) a solvent, and a parent
  • a coating film obtained from a composition containing (E2) a silicone-based surfactant as an oiliness-imparting component (hereinafter also referred to as “second photosensitive composition”) is preferred.
  • E2 a silicone-based surfactant as an oiliness-imparting component
  • the first photosensitive film and the second photosensitive film need to be of the same type (positive type or negative type) in order to form fine pores. That is, when the first photosensitive film is a negative photosensitive film, the second photosensitive film is also a negative photosensitive film, and when the first photosensitive film is a positive photosensitive film, the second photosensitive film is used.
  • the photosensitive film also needs to be a positive photosensitive film.
  • the heating conditions for forming each of the first photosensitive film and the second photosensitive film are appropriately set according to these components, film thickness, etc., but for example, at 50 to 250 ° C. for 30 seconds to 1 hour, Preferably, it is 80 to 200 ° C. for 60 seconds to 0.5 hours.
  • the film thicknesses of the first photosensitive film and the second photosensitive film are appropriately determined according to the depth of the pores and the polymer film described later.
  • the thickness of the first photosensitive film is usually 0.1 to 50 ⁇ m, preferably 1 to 30 ⁇ m.
  • the film thickness of the second photosensitive film is usually 0.1 to 50 ⁇ m, preferably 1 to 30 ⁇ m.
  • Step (2) In the step (2), as shown in FIG. 1 (2) (FIG. 1 shows a case where the photosensitive film is a positive type), the first photosensitive film 112 and the second photosensitive film 112 formed in the step (1) are used.
  • the exposure film 123 is selectively exposed to the photosensitive film 113 through a mask 124 as necessary to form a latent image 121 on the first photosensitive film 112 and a latent image 122 on the second photosensitive film 113. It is a process.
  • “selectively exposing” the first photosensitive film and the second photosensitive film means forming a patterned coating film, and therefore, depending on the pattern shape, specific portions of these photosensitive films are defined. It means exposing.
  • the exposure light examples include ultraviolet rays from a semiconductor laser, excimer laser, metal halide lamp, etc .; g rays, h rays, i rays, etc. from a high-pressure mercury lamp; extreme ultraviolet rays, and electron beams.
  • g-line or i-line is preferable because a pattern can be formed with high resolution.
  • the exposure amount of the exposure light is appropriately selected according to the type of exposure light and the thickness and type of the first photosensitive film and the second photosensitive film. In the case of a high-pressure mercury lamp, it is usually 100 to 1500 mJ / cm 2 .
  • a method of selectively exposing the exposure light 123 to the first photosensitive film and the second photosensitive film a method of selectively exposing directional exposure light such as an electron beam is also possible.
  • the mask 124 is appropriately selected depending on whether the first photosensitive film and the second photosensitive film are a positive photosensitive film or a negative photosensitive film. In other words, when the first photosensitive film and the second photosensitive film are negative photosensitive films, the portion corresponding to the target pore is designed to have a lower transmittance for exposure light than the other portions.
  • a mask 124 is used.
  • the first photosensitive film and the second photosensitive film are positive type photosensitive films, the portion corresponding to the target pore is designed to have a higher transmittance for exposure light than the other portions.
  • a mask 124 is used.
  • the exposure method can be appropriately selected depending on the size of the pores.
  • exposure is usually performed by a reduction projection method.
  • heat treatment hereinafter also referred to as “PEB”
  • the PEB condition can be appropriately selected depending on the type and content of each component in each photosensitive film, but is usually 30 to 300 ° C. for 1 minute to 5 hours.
  • step (3) As shown in (3) of FIG. 1 (FIG. 1 shows a case where the photosensitive film is a positive type), the first photosensitive film after exposure formed in step (2) is formed. Then, the developer is brought into contact with the second photosensitive film to remove a portion having a relatively high solubility in the developer, that is, the latent image 121 and the latent image 122 are developed, and the patterned coating film 133 is developed. And forming the pores 134 having the side wall surface 132 having lipophilicity.
  • Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4] .3.0] -5-nonane can be used as an aqueous solution of a basic compound.
  • an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the basic compound can also be used as a developer.
  • a method for contacting the developer for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be used.
  • the patterned coating film 133 is usually washed with water. Further, for the purpose of sufficiently curing the patterned coating film 133, the entire surface can be irradiated (post-exposure). The exposure amount in the post-exposure is usually 1 to 1500 mJ / cm 2 . Furthermore, for the purpose of sufficiently curing the patterned coating film 133, a heat treatment (post-bake) can be performed.
  • the post-baking conditions can be appropriately selected depending on the type and content of each component in each photosensitive film, but are usually 30 to 300 ° C. for 1 minute to 5 hours.
  • the pores 134 are formed by the patterned coating film 133.
  • the pores 134 have a lipophilic side wall surface 132 formed by the second photosensitive film 113.
  • the pores 134 preferably have a lipophilic side wall surface 132 formed by the second photosensitive film 113 and a hydrophilic side wall surface 131 formed by the first photosensitive film 112.
  • the depth of the pores 134 is usually 0.2 to 100 ⁇ m.
  • the shape of the pore 134 when viewed from the upper surface of the pore plate is usually circular or elliptical. When the pores 134 are circular, the diameter is usually 10 to 300 ⁇ m. Further, the number of pores 134 in the pore plate is one or more.
  • At least one pore 134 is provided, and at least a part of the side wall surface of the pore 134 is lipophilic.
  • a perforated plate preferably a perforated plate in which at least another part of the side wall surface of the fine pore 134 is hydrophilic, can be produced.
  • the pore plate can be suitably used for a microarray.
  • the second photosensitive composition of the present invention comprises (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond (hereinafter “ethylenic”). (Also referred to as “compound (C2)”), (D2) a solvent, and (E2) a silicone-based surfactant.
  • the second photosensitive film obtained from the second photosensitive composition When the second photosensitive film obtained from the second photosensitive composition is exposed, active species such as radicals are generated from the photoradical generator (B2) at the exposed portion of the second photosensitive film, and this active species.
  • the ethylenic compound is polymerized by acting on the ethylenic compound (C2).
  • the exposed portion of the second photosensitive film is hardly soluble in the developer in step (3).
  • the unexposed portion of the second photosensitive film is soluble in the developer in the step (3). Therefore, a pattern can be formed by exposure / development processing.
  • a polymer (A2) is used as a structural component of a pattern.
  • the polymer (A2) is not particularly limited as long as it is soluble in the solvent (D2) and soluble in the developer in the step (3).
  • a novolac resin an epoxy resin, a melamine resin, Thermosetting resins such as urea resin, unsaturated polyester polymer, alkyd resin, polyurethane; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin (acrylonitrile / butadiene / styrene copolymer resin), AS resin ( (Acrylonitrile / styrene copolymer resin), poly (meth) acrylate polymer, fluororesin, polyamide, polyacetal, polycarbonate, polyethylene terephthalate, cyclic polyolefin, polyimide, and other thermoplastic resins; polyphenylene sulfonitrile /
  • the polymer (A2) is preferably a polymer that is highly permeable to exposure light.
  • a poly (meth) acrylic acid ester polymer is preferable, and when an alkali developer is used as the developer in the step (3), it is excellent in solubility in an alkali developer.
  • a poly (meth) acrylic acid ester polymer having a carboxyl group is more preferred.
  • the “(meth) acrylic acid” is a general term for “methacrylic acid” and “acrylic acid”.
  • a poly (meth) acrylic acid ester polymer is a compound having a (meth) acrylic group (hereinafter also referred to as “(meth) acrylic monomer”) and, if necessary, polymerized with a (meth) acrylic monomer.
  • Possible monomers (hereinafter also referred to as “other monomers”) are polymerized by a known method described in JP-A Nos. 2003-241372 and 2005-274920. It is a coalescence.
  • Examples of the (meth) acrylic monomer include monomers described in JP2003-241372A, JP2005-274920A, JP2007-272087A, and the like, methyl (meth) acrylate, ethyl (Meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meta ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate , Allyl (meth) acrylate, cyclohexyl (meth)
  • Examples of (meth) acrylic monomers and other monomers that can introduce carboxyl groups into poly (meth) acrylic acid ester polymers include (meth) acrylic acid, crotonic acid, ⁇ -chloroacrylic acid Cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid.
  • Other monomers include, for example, monomers described in JP-A-2003-241372, JP-A-2005-274920, JP-A-2007-272087, etc., p-isopropenylphenol, indene, 1- Examples include methylindene and acenaphthylene.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A2) is preferably 5,000 to 20,000, more preferably 7 from the viewpoint of solubility in a developer. , 15,000 to 15,000. Only 1 type may be used for a polymer (A2) and it may use 2 or more types together.
  • the content ratio of the polymer (A2) is appropriately selected according to the depth of the pores, the area of the pores having a lipophilic surface, the coatability of the second photosensitive composition, and the like.
  • the photo radical generator (B2) is a compound that can generate active species such as radicals by exposure light.
  • Examples of the photoradical generator (B2) include photoradical generators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, O-acyloxy compounds And the like.
  • As the photoradical generator (B2) one or more selected from acylphosphine oxide compounds and acetophenone compounds are preferable because a pattern can be formed with high accuracy.
  • acylphosphine oxide compound examples include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dichlorobenzoyl) -2.
  • acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 4- (2 -Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-1,2-diphenylethane-1-one.
  • the photo radical generator (B2) only one type may be used, or two or more types may be used in combination.
  • the content of the photo radical generator (B2) is appropriately selected depending on the exposure wavelength, but is usually 1 to 30 parts by weight, preferably 2 to 25 parts by weight with respect to 100 parts by weight of the polymer (A2). It is.
  • Ethylene compound (C2) The ethylenic compound (C2) is a compound that is polymerized by generating active species such as radicals from the photoradical generator (B2) by exposure light and acting on the active species. Specific examples include compounds having at least one ethylenically unsaturated bond group such as a (meth) acrylate group or a vinyl group.
  • Examples of the ethylenic compound (C2) include compounds described in JP-A-2006-285035 and JP-A-2009-192613, di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; polyethylene glycol, Poly (alkylene glycol) di (meth) acrylates such as polypropylene glycol; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc.
  • polyester Epoxy (meth) acrylates such as epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin; both-end hydroxypoly-1,3-butadiene, both-end hydroxypoly Puren, di (meth) acrylate at both terminals hydroxylated polymers such as hydroxy-terminated polycaprolactone, tris [2- (meth) acryloyloxyethyl] phosphate compounds and the like.
  • Epoxy (meth) acrylates such as epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin
  • di (meth) acrylate at both terminals hydroxylated polymers such as hydroxy-terminated polycaprolactone, tris [2- (meth) acryloyloxyethyl] phosphate compounds and the like.
  • poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferable, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and Dipentaerythritol hexaacrylate is particularly preferable because it can form a pattern with high accuracy.
  • the ethylenic compound (C2) only one type may be used, or two or more types may be used in combination.
  • the content of the ethylenic compound (C2) is appropriately selected depending on the exposure light, but is usually 30 to 80 parts by weight, preferably 40 to 70 parts by weight with respect to 100 parts by weight of the polymer (A2). is there.
  • Solvent (D2) The solvent (D2) is used for uniformly mixing components other than the solvent (D2) contained in the second photosensitive composition to form a uniform coating film.
  • the solvent (D2) a component that uniformly mixes components other than the solvent (D2) and does not chemically react with these components is selected. Further, since the second photosensitive composition is applied on the first photosensitive film to form a coating film, the solvent (D2) is selected so as not to dissolve the first photosensitive film.
  • Examples of the solvent (D2) include alcohols such as ethylene glycol; cyclic ethers such as tetrahydrofuran; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether; alkyl ether acetates of polyhydric alcohols such as propylene glycol monomethyl ether acetate; toluene Aromatic ketones such as; ketones such as methyl ethyl ketone; esters such as ethyl acetate. Only 1 type may be used for a solvent (D2) and it may use 2 or more types together.
  • High-boiling solvents such as propylene and phenyl cellosolve acetate are also included.
  • the content of the solvent (D2) is appropriately selected according to the coating method and the depth of the pores (pattern height).
  • the solvent (D2) is used so that the content ratio of all components other than the solvent (D2) in the second photosensitive composition is usually 30 to 70% by weight, preferably 40 to 60% by weight.
  • Silicone surfactant (E2) The silicone-based surfactant (E2) is used for imparting lipophilicity to the surface of the second photosensitive film.
  • the surface of the second photosensitive film is used.
  • the lipophilicity of the silicone surfactant (E2) is imparted to the surface of the second photosensitive film and further to part of the side wall surface of the pores.
  • silicone surfactant (E2) examples include, for example, JP-A-5-295354, JP-A 2010-181865, JP-A 2009-258619, JP-A 2009-255314, and JP-A 2009-168900. And the like, a silicone surfactant having a dimethylsilicone structure, such as a compound described in No. 1, side chain modified polydimethylsiloxane, both end modified polydimethylsiloxane, one end modified polydimethylsiloxane, and side chain both ends modified polydimethylsiloxane.
  • the modifying group include polyether groups such as a polyoxyethylene group, a polyoxyethylene polyoxypropylene group, and a polyglycerin group. Among these, a silicone-based surfactant having a dimethyl silicone structure is preferably used.
  • silicone surfactants examples include FZ-2122, FZ-2110, FZ-7006, SH28PA, FZ-2166, FZ-2164, FZ-7001, FZ-2120, and SH8400.
  • FZ-7002, FZ-2104 manufactured by Toray Dow Corning
  • Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, Polyflow KL-402 Shina Chemical Co., Ltd.
  • the silicone surfactant (E2) only one type may be used, or two or more types may be used in combination.
  • the content of the silicone-based surfactant (E2) is appropriately selected depending on the lipophilicity of the pore side wall surface and the coating property to the first photosensitive film. That is, the degree of lipophilicity on the side wall surface of the pore increases when the content ratio of the silicone surfactant (E2) is large, and decreases when the content is small.
  • membrane may be influenced also by the content rate of a silicone type surfactant (E2).
  • the content of the silicone surfactant (E2) is appropriately selected depending on these balances, but is usually 0.01 to 1 part by weight, preferably 0.05 with respect to 100 parts by weight of the polymer (A1). ⁇ 0.5 parts by weight.
  • a surfactant other than the silicone-based surfactant (E2) an adhesion assistant, a thermal polymerization inhibitor, a solubility adjuster, and a viscosity adjuster are included as necessary. Etc.
  • Surfactants other than the silicone-based surfactant (E) are components used for improving the coating property, defoaming property, and leveling property when applied to the substrate of the second photosensitive composition of the present invention.
  • the surfactant include commercially available FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218F, FTX-220D, FTX-222D (manufactured by Neos Co., Ltd.) ), MegaFuck F142D, F172, F173, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (above, Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, and S-145 (above, manufactured by Asahi Glass Co., Ltd.).
  • the content of the surfactant other than the silicone-based surfactant (E) is appropriately selected depending on the applicability to the first photosensitive film, but is usually based on 100 parts by weight of the polymer (A1). 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight.
  • the second photosensitive composition of the present invention is prepared , for example, by dispersing and mixing a predetermined amount of each of the above components using a disperser such as a dissolver, a homogenizer, or a three roll mill. it can. Moreover, you may filter a 2nd photosensitive composition using a mesh membrane filter etc. as needed.
  • a disperser such as a dissolver, a homogenizer, or a three roll mill. it can.
  • the first photosensitive composition of the present invention comprises (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, (C1) a compound having at least one ethylenically unsaturated bond (hereinafter referred to as “the first photosensitive composition”). (Also referred to as “ethylenic compound (C1)”), and (D1) a solvent.
  • the first photosensitive film obtained from the first photosensitive composition is exposed, active species such as radicals are generated from the photoradical generator (B1) at the exposed portion of the first photosensitive film, and this active species.
  • the ethylenic compound is polymerized by acting on the ethylenic compound (C1).
  • the exposed portion of the first photosensitive film is hardly soluble in the developer in step (3).
  • the unexposed portion of the first photosensitive film is soluble in the developer in step (3). Therefore, a pattern can be formed by exposure / development processing.
  • Polymer having a hydroxyl group (A1)
  • the polymer (A1) having a hydroxyl group is used for imparting hydrophilicity to the first photosensitive film, that is, used as the hydrophilicity imparting component.
  • hydrophilicity By imparting hydrophilicity to the first photosensitive film, it is possible to prevent mixing with the second photosensitive film (mixing), and when forming a polymer film to be described later so as to cover the pores, When the buffer solution is hydrophilic, the buffer solution can be efficiently taken into the pores.
  • the hydroxyl group means an alcoholic hydroxyl group and a phenolic hydroxyl group. That is, as the polymer (A1) having a hydroxyl group, a polymer (A1-1) having an alcoholic hydroxyl group, a polymer having a phenolic hydroxyl group ( A1-2).
  • the polymer (A1-1) having an alcoholic hydroxyl group for example, a (meth) acrylic resin obtained using 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or the like as a monomer component is used.
  • by having an ethylenically unsaturated bond as with the ethylenic compound (C1), it is polymerized by active species generated by exposure, and it is easy to form a pattern by a lithography method. preferable.
  • the epoxy acrylate resin is a resin obtained by a ring-opening addition reaction between an epoxy resin and an unsaturated monobasic acid and / or an unsaturated polybasic acid.
  • the epoxy resin include bisphenol type epoxy resins; biphenyl type epoxy resins; alicyclic epoxy resins; polyfunctional glycidyl amine resins such as tetraglycidylaminodiphenylmethane; and polyfunctional glycidyl ether resins such as tetraphenyl glycidyl ether ethane.
  • a phenol novolac type epoxy resin or a cresol novolak type epoxy resin a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, m-cresol, naphthol and an aromatic aldehyde having a phenolic hydroxy group;
  • a reaction product with epichlorohydrin a polyphenol compound obtained by addition reaction of a phenol compound with a diolefin compound such as divinylbenzene or dicyclopentadiene; Reaction product with lorhydrin; ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracid; epoxy resin having heterocycle such as triglycidyl isocyanurate; phenol aralkyl type epoxy resin; .
  • the epoxy resin may be used alone or in combination of two or more.
  • Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, and cinnamic acid.
  • examples of the unsaturated polybasic acid include malonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3 -Aliphatic saturated polybases such as methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Acids: aromatic saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid; het acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid,
  • Examples of the polymer (A1-2) having a phenolic hydroxyl group include phenol resins obtained by condensation of phenol and derivatives thereof with a condensing agent; monomer components such as p-hydroxystyrene and p-isopropenylphenol Aromatic vinyl resin used as Among these, a phenol resin is preferable because a first photosensitive film having excellent hydrophilicity can be obtained.
  • phenol and derivatives thereof examples include phenol, o-cresol, m-cresol, p-cresol, p-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4- Examples include xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 1-naphthol, 2-naphthol, and 2,7-dihydroxynaphthalene.
  • the said phenol and its derivative (s) may use only 1 type, and may use 2 or more types together.
  • condensing agent examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.
  • the condensing agent may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A1) having a hydroxyl group is preferably 1,000 to 100,000, more preferably 3,000 to 50,000. is there. Only 1 type may be used for the polymer (A1) which has a hydroxyl group, and 2 or more types may be used together.
  • the content ratio of the polymer (A1) having a hydroxyl group is appropriately selected depending on the depth of the pores, the coating property of the first photosensitive composition, and the like.
  • the photoradical generator (B1) is a compound that can generate active species such as radicals by exposure light.
  • Examples of the photo radical generator (B1) include photo radical generators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, O-acyloxy compounds And the like.
  • As the photoradical generator (B1) one or more selected from acylphosphine oxide compounds and acetophenone compounds are preferable because a pattern can be formed with high accuracy.
  • acylphosphine oxide compound and the acetophenone compound examples include those described in “2-2. And compounds described in “Photoradical generator (B2)”.
  • photo radical generator (B1) only one type may be used, or two or more types may be used in combination.
  • the content of the photo radical generator (B1) is appropriately selected depending on the exposure wavelength, but is usually 1 to 30 parts by weight, preferably 2 to 2 parts per 100 parts by weight of the polymer (A1) having a hydroxyl group. 25 parts by weight.
  • Ethylene compound (C1) The ethylenic compound (C1) is a compound that is polymerized by generating active species such as radicals from the photoradical generator (B1) by exposure light and acting on the active species. Specific examples include compounds having at least one ethylenically unsaturated bond group such as a (meth) acrylate group or a vinyl group.
  • Examples of the ethylenic compound (C1) include the above-mentioned “2-3. And compounds described in “Ethylene Compound (C2)”. Of these ethylenic compounds (C1), poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferred, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and Dipentaerythritol hexaacrylate is particularly preferable because a pattern can be formed with high accuracy.
  • the ethylenic compound (C1) only one type may be used, or two or more types may be used in combination.
  • the content of the ethylenic compound (C1) is appropriately selected depending on the exposure light, but is usually 5 to 80 parts by weight, preferably 10 to 70 parts per 100 parts by weight of the polymer (A1) having a hydroxyl group. Parts by weight.
  • Solvent (D1) The solvent (D1) is used for uniformly mixing components other than the solvent (D1) contained in the first photosensitive composition to form a uniform coating film.
  • the solvent (D1) is selected so that components other than the solvent (D1) are uniformly mixed and do not chemically react with these components.
  • Examples of the solvent (D1) include those described in “2-4. And the compound described in “Solvent (D2)”. Only 1 type may be used for a solvent (D1) and it may use 2 or more types together.
  • the content of the solvent (D1) is appropriately selected according to the coating method and the depth of the pores (pattern height).
  • the solvent (D1) is used so that the content of components other than the solvent (D1) in the first photosensitive composition is usually 30 to 70% by weight, preferably 40 to 60% by weight.
  • the first photosensitive composition of the present invention contains a surfactant, an adhesion assistant, a thermal polymerization inhibitor, a solubility modifier, a viscosity modifier, and the like as necessary.
  • surfactant examples include those described in “2-6.
  • the compound as described in “other components” is mentioned.
  • the content of the surfactant is appropriately selected depending on the coatability on the base substrate, but is usually 0.01 to 1 part by weight, preferably 100 parts by weight of the polymer (A1) having a hydroxyl group. 0.05 to 0.5 parts by weight.
  • the adhesion assistant is a component used to improve adhesion with the base substrate.
  • a functional silane coupling agent is preferable.
  • a functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
  • the functional silane coupling agent include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, and ⁇ -glycid.
  • the content of the adhesion assistant is appropriately selected depending on the adhesion between the first photosensitive film and the base substrate, but is usually 0.1 to 100 parts by weight based on 100 parts by weight of the polymer (A1) having a hydroxyl group.
  • the amount is 10 parts by weight, preferably 1 to 5 parts by weight.
  • the first photosensitive composition of the present invention is prepared , for example, by dispersing and mixing a predetermined amount of each of the above components using a disperser such as a dissolver, a homogenizer, or a three roll mill. it can. Moreover, you may filter a 1st photosensitive composition using a mesh membrane filter etc. as needed.
  • a disperser such as a dissolver, a homogenizer, or a three roll mill. it can.
  • Porous plate The porous plate of the present invention has at least one pore, and at least a part of the side wall surface of the pore has lipophilicity.
  • the surface of the side wall surface having the new oil property usually contains silicon atoms.
  • the pore plate of the present invention is, for example, “1. It is obtained by “a manufacturing method of a pore plate” and is suitably used for microarray applications.
  • at least a part of the side wall surface of the pore, preferably the side wall surface near the opening of the pore has lipophilicity, so that the pore can be covered with the polymer film.
  • the polymer film can be formed so as to close the vicinity of the opening of the pore.
  • the location 301 that becomes lipophilic on the side wall surface of the pore of the microarray pore plate is a location 301 that becomes the thickness of the polymer membrane and the new oil property in order to cover the pores with the polymer membrane.
  • the thickness of the polymer film is preferably approximately the same, and the width of the polymer film and the width of the pores at the location 301 where the oil is new are preferably approximately the same.
  • the lipophilic portion 301 on the side wall surface of the pore is formed on the side close to the opening 302.
  • the depth 303 of the pores is usually 0.2 to 100 ⁇ m.
  • the shape of the pores when viewed from the upper surface of the pore plate is usually a circle or an ellipse.
  • its diameter 304 is usually 10 to 300 ⁇ m.
  • the number of pores in the pore plate is one or more.
  • microarray substrate of the present invention has the above-described pore plate and a polymer film having at least one through-hole having a diameter of 500 nm or less, and the polymer film covers the pores of the pore plate. It is formed as follows.
  • Microarray substrates are disclosed in International Publication No. 2005-071405 and Anal. Chem. 2006, 78, pages 8169-8174, “Lipid Bilayer Formation by Contacting Monolayers in a Mclflldlc Development for Membrane Protein Analysis”. That is, as shown in (4) of FIG. 2, the buffer solution 211 is filled into the pores of the microarray pore plate. Next, as shown in FIG. 2 (5), the polymer film 221 is floated on the buffer solution, and the end of the polymer film 221 is allowed to act on the lipophilic side wall surface 132, whereby pores are formed by the polymer film 221.
  • a microarray substrate can be manufactured by covering.
  • the polymer film having penetrating light having a diameter of 500 nm or less is a polymer film described in JP-T-2008-545518.
  • the microarray substrate of the present invention is disclosed in J. Org. Am. Chem. Soc. 2007, 129, pages 16142 to 16148, Current Opinion in Chemical Biology 2006, 10, pages 628 to 637, Nature 2001, 413, pages 636 to 640, and DNA sequencing using protein nanopores. .
  • the polymer solution of Synthesis Example 1 was obtained by carrying out polymerization at 80 ° C. for 6 hours.
  • the polymer of Synthesis Example 1 had a weight average molecular weight in terms of polystyrene as determined by gel permeation column chromatography of 10,000.
  • Example 2 As the polymer (A2), 100 parts of the polymer of Synthesis Example 1, and as the photoradical generator (B2), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, Ciba 19 parts by Specialty Chemicals) and 4 parts 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name “Lucirin LR8953X”, manufactured by BASF), dipentaerythritol hexa as an ethylenic compound (C1) 60 parts of acrylate and 0.3 part of a silicone surfactant (trade name “SH28PA”, manufactured by Toray Dow Corning) as a silicone surfactant (E2) and propylene glycol monomethyl ether acetate as a solvent (D2) A uniform solution was prepared by mixing at 95 parts. This solution was filtered through a capsule filter having a pore size of 10 ⁇ m to obtain a photosensitive composition of Example 2.
  • Example 1 Manufacture of microarray pore plate
  • the photosensitive composition of Example 1 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a first photosensitive film having a thickness of 10 ⁇ m.
  • the contact angle (23 ° C., 1 atm) of the first photosensitive film surface with water was 35 °.
  • Example 2 The photosensitive composition of Example 2 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a second photosensitive film having a thickness of 13 ⁇ m.
  • the contact angle (23 ° C., 1 atm) of the second photosensitive film surface with water was 85 °.
  • membrane surface was less than 10 degrees.
  • Example 3 The photosensitive composition of Example 1 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a first photosensitive film having a thickness of 10 ⁇ m.
  • the photosensitive composition of Example 2 was applied on the first photosensitive film by a spin coating method, and then heated at 110 ° C. for 5 minutes on a hot plate to form a second film having a thickness of 13 ⁇ m.
  • a photosensitive film was obtained.
  • the first photosensitive film and the second photosensitive film are exposed to exposure light of 150 mJ / cm 2 under a nitrogen atmosphere using an exposure machine (trade name “MA200e” manufactured by Suss) through a patterned mask. did.
  • the first photosensitive film and the second photosensitive film were developed at room temperature for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution, and then washed with running water. Further, nitrogen blowing was performed to obtain a microarray pore plate for Example 3 having a plurality of pores having a diameter of 80 ⁇ m and a width between pores of 150 ⁇ m. A photograph taken with an electron microscope of the microarray pore plate of Example 3 is shown in FIG. Further, the contact angle (23 ° C., one atmospheric pressure) of the surface of the microarray pore plate of Example 3 with water was 100 °.
  • the second photosensitive film contains the silicone-based surfactant (E2), the contact angle with water has increased from 85 ° to 100 °, so that a highly lipophilic region is present in the vicinity of the opening of the pore. It was confirmed that it was formed.
  • E2 silicone-based surfactant
  • Example 4 In Example 3, except that the development processing was performed at room temperature for 45 seconds, the method of Example 4 having a plurality of pores having a diameter of 80 ⁇ m and a width between pores of 150 ⁇ m was obtained in the same manner as in Example 3. A microplate pore plate was obtained. A photograph taken with an electron microscope of the microarray pore plate of Example 4 is shown in FIG. In addition, the contact angle (23 ° C., one atmospheric pressure) of the surface of the microarray pore plate of Example 4 with water was 100 °.
  • Example 5 having a plurality of pores having a diameter of 80 ⁇ m and a width between pores of 150 ⁇ m in the same manner as in Example 3 except that exposure light of 200 mJ / cm 2 was exposed in Example 3.
  • a microarray pore plate was obtained.
  • a photograph taken with an electron microscope of the microarray pore plate of Example 5 is shown in FIG. Further, the contact angle (23 ° C., 1 atm) of the surface of the microarray pore plate of Example 5 with water was 100 °.
  • Example 6 In Example 3, except that exposure light of 200 mJ / cm 2 was exposed and development processing was performed at room temperature for 45 seconds, the same method as in Example 3 was used, and the diameter was 80 ⁇ m and the width between pores was 150 ⁇ m. Thus, a microarray pore plate of Example 6 having a plurality of pores was obtained. A photograph taken with an electron microscope of the microarray pore plate of Example 6 is shown in FIG. Further, the contact angle (23 ° C., 1 atm) of the surface of the microarray pore plate of Example 6 with water was 100 °.

Abstract

[Problem] To provide a method for producing a porous plate without using a mechanical process or a dry process. [Solution] A method for producing a porous plate that has at least one pore which has a side wall surface that is at least partially lipophilic. The method for producing a porous plate comprises: (1) a step wherein a first photosensitive film is formed on a base substrate and a second photosensitive film that contains a lipophilicity-imparting component is formed on the first photosensitive film; (2) a step wherein the first photosensitive film and the second photosensitive film are selectively exposed to light; and (3) a step wherein the first photosensitive film after the light exposure and the second photosensitive film after the light exposure are developed.

Description

マイクロアレイ用等の細孔板の製造方法、前記方法に用いられる感光性組成物、マイクロアレイ用等の細孔板およびマイクロアレイ用基板Method for producing microporous plate, etc., photosensitive composition used in said method, microporous plate, etc. and microarray substrate
　本発明は、マイクロアレイ用等の細孔板の製造方法、前記方法に用いられる感光性組成物、マイクロアレイ用等の細孔板およびマイクロアレイ用基板に関する。 The present invention relates to a method for producing a microporous plate and the like, a photosensitive composition used in the above method, a microporous plate and a microarray substrate.
　マイクロアレイ用基板とは、例えば、基体に、核酸、タンパク質、ペプチド、糖鎖、低分子化合物、細胞、組織などの物質をプローブ分子として搭載し、ターゲット分子である生体関連物質との相互作用を計測したり、反応を利用したりするためのデバイスである。 For example, a substrate for microarrays is equipped with a substance such as a nucleic acid, protein, peptide, sugar chain, low molecular weight compound, cell, or tissue as a probe molecule on a substrate, and measures the interaction with a biological substance that is the target molecule. It is a device for making use of reaction.
　マイクロアレイ用基板は、例えば、ＤＮＡを構成するヌクレオチド（核酸塩基）の配列を決定するＤＮＡシーケンシング用のデバイスとして用いられる。
　ＤＮＡシーケンシングの一手法として、タンパク質ナノポア技術を用いた手法がある。これはＤＮＡをその分子直径より少し大きな貫通孔（直径５００ｎｍ以下の大きさ）を通過させ、ＤＮＡが貫通孔を通過する際に、貫通孔に流れる電流が、ＤＮＡの核酸塩基に依存する性質を利用して、ＤＮＡシーケンシングを行う手法である。
　タンパク質ナノポア技術を用いたＤＮＡシーケンシングには、細孔を有するマイクロアレイ用細孔板と、直径５００ｎｍ以下の貫通孔を有するポリマー膜とから構成され、前記ポリマー膜が前記マイクロアレイ用細孔板の細孔を覆うように形成されたマイクロアレイ用基板が必要となってくる。
　そして、マイクロアレイ用等の細孔板の製造方法に関しては、種々の検討がなされている（例えば、特許文献１および２参照）。 The microarray substrate is used, for example, as a device for DNA sequencing that determines the sequence of nucleotides (nucleobases) constituting DNA.
One technique for DNA sequencing is a technique using protein nanopore technology. This is because DNA passes through a through hole (diameter of 500 nm or less) slightly larger than its molecular diameter, and when DNA passes through the through hole, the current flowing through the through hole depends on the nucleobase of the DNA. This is a technique for performing DNA sequencing using this method.
In DNA sequencing using protein nanopore technology, a microarray pore plate having pores and a polymer membrane having a through-hole having a diameter of 500 nm or less are formed, and the polymer membrane is a thin film of the microarray pore plate. A microarray substrate formed so as to cover the holes is required.
Various studies have been made on methods for producing microplates and other microporous plates (see, for example, Patent Documents 1 and 2).
ヨーロッパ特許公開公報２１０７０４０号公報European Patent Publication No. 2107040 米国特許公開公報２００４／０１２０８５４号公報US Patent Publication No. 2004/0120854
　上記特許文献に記載の方法でマイクロアレイ用等の細孔板を製造する場合、リソグラフィープロセスや、剥離工程などの力学的なプロセス、化学的気相成長法やプラズマエッチングなどのドライプロセスなど、手法が大きくことなるプロセスを複数用いる必要があり、その製造が容易でなかった。
　本発明は上述の課題を解決するためになされたものであり、つまり、力学的なプロセスやドライプロセスを用いずに、マイクロアレイ用等の細孔板を製造する方法の提供、前記方法に用いられる感光性組成物の提供、前記方法により製造されるマイクロアレイ用等の細孔板の提供および前記細孔板を有するマイクロアレイ用基板の提供を目的とする。 In the case of manufacturing microplates and the like by the method described in the above-mentioned patent document, there are techniques such as lithography process, mechanical process such as peeling process, dry process such as chemical vapor deposition and plasma etching. It was necessary to use a plurality of different processes, and the manufacture thereof was not easy.
The present invention has been made in order to solve the above-described problems. That is, the present invention provides a method for producing a microporous plate or the like without using a mechanical process or a dry process, and is used in the method. It is an object of the present invention to provide a photosensitive composition, a microplate manufactured for the microarray manufactured by the method, and a microarray substrate having the microporous plate.
　本発明は以下のとおりである。
［１］（１）ベース基板上に第１感光性膜を形成し、前記第１感光性膜上に親油性付与成分を含有する第２感光性膜を形成する工程、（２）前記第１感光性膜および前記第２感光性膜を選択的に露光する工程、ならびに（３）露光後の第１感光性膜および露光後の第２感光性膜を現像する工程を有する、少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板の製造方法。
［２］前記親油性付与成分が、（Ｅ２）シリコーン系界面活性剤である前記［１］の細孔板の製造方法。
［３］前記露光前の第２感光性膜が、（Ａ２）重合体、（Ｂ２）光ラジカル発生剤、（Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物、（Ｄ２）溶剤および（Ｅ２）シリコーン系界面活性剤を含有する感光性組成物から得られる塗膜である前記［２］の細孔板の製造方法。
［４］前記露光前の第１感光性膜が、親水性付与成分を含有する前記［１］～［３］のいずれか一項の細孔板の製造方法。
［５］前記親水性付与成分が、（Ａ１）水酸基を有する重合体である前記［４］の細孔板の製造方法。
［６］前記露光前の第１感光性膜が、（Ａ１）水酸基を有する重合体、（Ｂ１）光ラジカル発生剤、（Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物および（Ｄ１）溶剤を含有する感光性組成物から得られる塗膜である前記［５］の細孔板の製造方法。
［７］前記細孔板が、マイクロアレイ用である前記［１］～［６］のいずれか一項の細孔板の製造方法。
［８］前記［３］または［７］の細孔板の製造方法に用いられる感光性組成物であり、（Ａ２）重合体、（Ｂ２）光ラジカル発生剤、（Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物、（Ｄ２）溶剤、および（Ｅ２）シリコーン系界面活性剤を含有する感光性組成物。
［９］前記［６］または［７］の細孔板の製造方法に用いられる感光性組成物であり、（Ａ１）水酸基を有する重合体、（Ｂ１）光ラジカル発生剤、（Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物、および（Ｄ１）溶剤を含有する感光性組成物。
［１０］前記［１］～［７］のいずれか一項の細孔板の製造方法によって製造される、少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板。
［１１］少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板であり、親油性を有する側壁面の表面がシリコン原子を含有する細孔板。
［１２］前記［１０］または［１１］の細孔板と、直径５００ｎｍ以下の貫通孔を少なくとも一つ有するポリマー膜とを有し、前記ポリマー膜が、前記細孔板の細孔を覆うように形成されているマイクロアレイ用基板。 The present invention is as follows.
[1] (1) Forming a first photosensitive film on a base substrate, and forming a second photosensitive film containing a lipophilic component on the first photosensitive film, (2) The first A step of selectively exposing the photosensitive film and the second photosensitive film; and (3) a step of developing the first photosensitive film after exposure and the second photosensitive film after exposure. A method for producing a pore plate having pores, wherein at least part of the side wall surface of the pores has lipophilicity.
[2] The method for producing a pore plate according to [1], wherein the lipophilicity-imparting component is (E2) a silicone-based surfactant.
[3] The second photosensitive film before exposure is (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond, (D2) a solvent, and (E2 ) The method for producing a pore plate according to the above [2], which is a coating film obtained from a photosensitive composition containing a silicone surfactant.
[4] The method for producing a pore plate according to any one of [1] to [3], wherein the first photosensitive film before exposure contains a hydrophilicity imparting component.
[5] The method for producing a pore plate according to [4], wherein the hydrophilicity-imparting component is (A1) a polymer having a hydroxyl group.
[6] The first photosensitive film before exposure is (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, (C1) a compound having at least one ethylenically unsaturated bond, and (D1) a solvent. [5] The method for producing a pore plate according to [5] above, which is a coating film obtained from a photosensitive composition containing.
[7] The method for producing a pore plate according to any one of [1] to [6], wherein the pore plate is for microarrays.
[8] A photosensitive composition used in the method for producing a pore plate according to [3] or [7], wherein (A2) a polymer, (B2) a photoradical generator, and (C2) at least one ethylenic compound. A photosensitive composition comprising a compound having an unsaturated bond, (D2) a solvent, and (E2) a silicone-based surfactant.
[9] A photosensitive composition used in the method for producing a porous plate according to [6] or [7], wherein (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, and (C1) at least one. The photosensitive composition containing the compound which has two ethylenically unsaturated bonds, and (D1) solvent.
[10] Having at least one pore produced by the method for producing a pore plate according to any one of [1] to [7], wherein at least a part of the side wall surface of the pore is lipophilic. A pore plate having
[11] A pore plate having at least one pore, wherein at least a part of the side wall surface of the pore has lipophilicity, and the surface of the lipophilic side wall surface contains silicon atoms. .
[12] The pore plate according to [10] or [11] and a polymer film having at least one through-hole having a diameter of 500 nm or less, and the polymer film covers the pores of the pore plate. A substrate for microarray formed on the substrate.
　本発明のマイクロアレイ用等の細孔板の製造方法によれば、力学的なプロセスやドライプロセスなどを用いず容易にマイクロアレイ用等の細孔板を製造することができる。 According to the method for producing a microporous plate for a microarray of the present invention, a microporous plate or the like can be easily produced without using a mechanical process or a dry process.
本発明の「細孔板の製造方法」の一例を模式的に示した図である。It is the figure which showed typically an example of the "manufacturing method of a pore board" of this invention. 本発明の「マイクロアレイ用基板」の製造方法の一例を模式的に示した図である。It is the figure which showed typically an example of the manufacturing method of the "microarray substrate" of this invention. 「細孔」の一例を模式的に示した図である。It is the figure which showed an example of the "pore" typically. 実施例１～４のマイクロアレイ用細孔板の写真（電子顕微鏡にて撮影）である。2 is a photograph (taken with an electron microscope) of a microarray pore plate of Examples 1 to 4.
　以下、本発明のマイクロアレイ用途に好適に用いられる細孔板の製造方法、前記細孔板の製造に用いられる感光性組成物、マイクロアレイ用途に好適に用いられる細孔板、およびマイクロアレイ用基板について、詳細に説明する。 Hereinafter, a method for producing a pore plate suitably used for the microarray application of the present invention, a photosensitive composition used for producing the pore plate, a pore plate suitably used for the microarray application, and a substrate for microarray, This will be described in detail.
１．細孔板の製造方法
　本発明の細孔板の製造方法は、
（１）ベース基板上に第１感光性膜を形成し、前記第１感光性膜上に親油性付与成分を含有する第２感光性膜を形成する工程（以下「工程（１）」ともいう。）、
（２）前記第１感光性膜および前記第２感光性膜を選択的に露光する工程（以下「工程（２）」ともいう。）、ならびに
（３）露光後の第１感光性膜および露光後の第２感光性膜を現像する工程（以下「工程（３）」ともいう。）
を有する。 1. Production method of pore plate
(1) A step of forming a first photosensitive film on a base substrate and forming a second photosensitive film containing a lipophilic component on the first photosensitive film (hereinafter also referred to as “step (1)”). ),
(2) a step of selectively exposing the first photosensitive film and the second photosensitive film (hereinafter also referred to as “step (2)”), and (3) the first photosensitive film and exposure after exposure. A step of developing the subsequent second photosensitive film (hereinafter also referred to as “step (3)”).
Have
１－１．工程（１）
　工程（１）は、図１の（１）に示すように、ベース基板１１１上に第１感光性膜１１２を形成し、前記第１感光性膜１１２上に親油性付与成分を含有する第２感光性膜１１３を形成する工程である。 1-1. Process (1)
In step (1), as shown in (1) of FIG. 1, a first photosensitive film 112 is formed on a base substrate 111, and a second lipophilicity-imparting component is contained on the first photosensitive film 112. In this step, the photosensitive film 113 is formed.
　ベース基板１１１としては、シリコン基板やガラス基板などの無機材料から形成された基板でも、有機材料から形成された基板でもよく、またこれらの複合材料から形成された基板であってもよい。また、ベース基板１１１は、核酸塩基などがポリマー膜を通過したことを確認するためにセンサーを有する基板であってもよい。 The base substrate 111 may be a substrate formed from an inorganic material such as a silicon substrate or a glass substrate, a substrate formed from an organic material, or a substrate formed from a composite material thereof. The base substrate 111 may be a substrate having a sensor for confirming that a nucleobase or the like has passed through the polymer film.
　第１感光性膜１１２としては、露光により現像液に対する溶解性が変化する膜であれば、ポジ型の感光性膜でもネガ型の感光性膜でもよい。後述するポリマー膜を細孔１３４に蓋をするように形成するとき、バッファー液が親水性の場合、効率よく細孔１３４内にバッファー液を取り込むことができることから、図１の（３）に示すように、細孔１３４の、第１感光性膜１１２により形成される側壁面１３１が、親水性を有することが好ましい。
　細孔１３４の側壁面１３１に親水性を付与するには、通常、第１感光性膜１１２中に親水性付与成分を含有させればよい。前記親水性付与成分としては、例えば、水酸基やカルボキシル基などの極性基を有する化合物が挙げられる。細孔１３４の側壁面１３１に効率よく親水性を付与するには、水酸基を有する重合体（Ａ１）を用いることが好ましい。なお、水酸基を有する重合体（Ａ１）の詳細については、『３－１．水酸基を有する重合体（Ａ１）』で記載する。 The first photosensitive film 112 may be a positive photosensitive film or a negative photosensitive film as long as the solubility of the first photosensitive film 112 changes in the developer upon exposure. When the polymer film described later is formed so as to cover the pores 134, when the buffer solution is hydrophilic, the buffer solution can be efficiently taken into the pores 134. As described above, it is preferable that the side wall surface 131 of the pores 134 formed by the first photosensitive film 112 has hydrophilicity.
In order to impart hydrophilicity to the side wall surface 131 of the pores 134, it is usually sufficient to include a hydrophilicity imparting component in the first photosensitive film 112. Examples of the hydrophilicity-imparting component include compounds having a polar group such as a hydroxyl group or a carboxyl group. In order to efficiently impart hydrophilicity to the side wall surface 131 of the pore 134, it is preferable to use a polymer (A1) having a hydroxyl group. For details of the polymer (A1) having a hydroxyl group, refer to “3-1. It is described in “Polymer having hydroxyl group (A1)”.
　第１感光性膜１１２をベース基板１１１上に形成する方法としては、例えば、光ラジカル発生剤（Ｂ１）、光酸発生剤およびナフトキノンジアジド化合物などの光により性質が変わる化合物を含有する組成物を、スピンコート法、ロールコート法またはインクジェット法などの手法によりベース基板１１１上に塗布して、第１感光性膜１１２を形成する方法が挙げられる。前記方法は、平坦な第１感光性膜１１２を形成できることから好ましい。
　特に、光ラジカル発生剤（Ｂ１）を含有する組成物は、バッファー液に溶解しにくく、物理的にも強靱な第１感光性膜１１２を形成できることから好ましい。 As a method for forming the first photosensitive film 112 on the base substrate 111, for example, a composition containing a compound whose properties are changed by light, such as a photo radical generator (B1), a photo acid generator, and a naphthoquinone diazide compound. Examples thereof include a method in which the first photosensitive film 112 is formed by coating on the base substrate 111 by a technique such as spin coating, roll coating, or inkjet. The method is preferable because the flat first photosensitive film 112 can be formed.
In particular, the composition containing the photoradical generator (B1) is preferable because it is difficult to dissolve in the buffer solution and the first photosensitive film 112 that is physically tough can be formed.
　以上のことから、第１感光性膜１１２としては、親水性付与成分として（Ａ１）水酸基を有する重合体、（Ｂ１）光ラジカル発生剤、（Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物、および（Ｄ１）溶剤を含有する組成物（以下「第１感光性組成物」ともいう。）から得られる塗膜が好ましい。なお、第１感光性組成物の詳細については、『３．第１感光性組成物』にて記載する。 From the above, the first photosensitive film 112 includes (A1) a polymer having a hydroxyl group as a hydrophilicity-imparting component, (B1) a photoradical generator, and (C1) a compound having at least one ethylenically unsaturated bond. And (D1) a coating film obtained from a composition containing a solvent (hereinafter also referred to as “first photosensitive composition”) is preferred. For details of the first photosensitive composition, refer to “3. It is described in “First photosensitive composition”.
　第２感光性膜１１３としては、親油性付与成分を含有し、且つ、露光により現像液に対する溶解性が変化する膜であれば、ポジ型の感光性膜でもネガ型の感光性膜でもよい。前記親油性付与成分は、図１の（３）に示すように、細孔１３４の、第２感光性膜１１３により形成される側壁面１３２に親油性を付与するために用いられる。
　親油性付与成分としては、例えば、ジメチルシリコーン構造を有する化合物や、フッ素原子を有する化合物など、親油性に寄与する構造を有する化合物が挙げられる。これらの中でも露光・現像処理後に細孔１３４の側壁面１３２の親油性が大幅に向上することから、シリコーン系界面活性剤（Ｅ２）が好ましく、ジメチルシリコーン構造を有するシリコーン系界面活性剤（Ｅ２）が特に好ましい。なお、シリコーン系界面活性剤（Ｅ２）の詳細については、『２－５．シリコーン系界面活性剤（Ｅ２）』で記載する。 The second photosensitive film 113 may be a positive type photosensitive film or a negative type photosensitive film as long as it contains a lipophilicity-imparting component and changes its solubility in a developer upon exposure. The lipophilicity-imparting component is used to impart lipophilicity to the side wall surface 132 of the pores 134 formed by the second photosensitive film 113, as shown in (3) of FIG.
Examples of the lipophilic component include compounds having a structure that contributes to lipophilicity, such as a compound having a dimethyl silicone structure and a compound having a fluorine atom. Among these, since the lipophilicity of the side wall surface 132 of the pores 134 is greatly improved after exposure / development processing, the silicone surfactant (E2) is preferable, and the silicone surfactant (E2) having a dimethylsilicone structure. Is particularly preferred. For details of the silicone surfactant (E2), refer to “2-5. “Silicone-based surfactant (E2)”.
　第２感光性膜１１３を第１感光性膜１１２上に形成する方法としては、例えば、光ラジカル発生剤（Ｂ２）、光酸発生剤およびナフトキノンジアジド化合物などの光により性質が変わる化合物を含有する組成物を、スピンコート法、ロールコート法またはインクジェット法などの手法により第１感光性膜１１２上に塗布して、第２感光性膜１１３を形成する方法が挙げられる。前記方法は、平坦な第２感光性膜１１３を形成できることから好ましい。 Examples of the method for forming the second photosensitive film 113 on the first photosensitive film 112 include a compound whose properties are changed by light, such as a photoradical generator (B2), a photoacid generator, and a naphthoquinonediazide compound. Examples thereof include a method of forming the second photosensitive film 113 by applying the composition onto the first photosensitive film 112 by a technique such as a spin coating method, a roll coating method, or an ink jet method. The method is preferable because the flat second photosensitive film 113 can be formed.
　以上のことから、第２感光性膜１１３としては、（Ａ２）重合体、（Ｂ２）光ラジカル発生剤、（Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物、（Ｄ２）溶剤、および親油性付与成分として（Ｅ２）シリコーン系界面活性剤を含有する組成物（以下「第２感光性組成物」ともいう。）から得られる塗膜が好ましい。なお、第２感光性組成物の詳細については、『２．第２感光性組成物』にて記載する。 From the above, the second photosensitive film 113 includes (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond, (D2) a solvent, and a parent A coating film obtained from a composition containing (E2) a silicone-based surfactant as an oiliness-imparting component (hereinafter also referred to as “second photosensitive composition”) is preferred. For details of the second photosensitive composition, refer to “2. It is described in “Second photosensitive composition”.
　また、第１感光性膜および第２感光性膜は、良好な形状の細孔を形成するには同じ型（ポジ型またはネガ型）である必要がある。つまり、第１感光性膜がネガ型の感光性膜の場合、第２感光性膜もネガ型の感光性膜であり、第１感光性膜がポジ型の感光性膜の場合、第２感光性膜もポジ型の感光性膜である必要がある。
　第１感光性膜および第２感光性膜をそれぞれ形成する際の加熱条件は、これらの含有成分・膜厚等に応じて適宜設定されるが、例えば５０～２５０℃で３０秒～１時間、好ましくは８０～２００℃で６０秒～０．５時間である。
　第１感光性膜および第２感光性膜の膜厚は、細孔の深さや、後述するポリマー膜に応じて適宜決定される。第１感光性膜の膜厚は、通常０．１～５０μｍ、好ましくは１～３０μｍである。第２感光性膜の膜厚は、通常０．１～５０μｍ、好ましくは１～３０μｍである。 Further, the first photosensitive film and the second photosensitive film need to be of the same type (positive type or negative type) in order to form fine pores. That is, when the first photosensitive film is a negative photosensitive film, the second photosensitive film is also a negative photosensitive film, and when the first photosensitive film is a positive photosensitive film, the second photosensitive film is used. The photosensitive film also needs to be a positive photosensitive film.
The heating conditions for forming each of the first photosensitive film and the second photosensitive film are appropriately set according to these components, film thickness, etc., but for example, at 50 to 250 ° C. for 30 seconds to 1 hour, Preferably, it is 80 to 200 ° C. for 60 seconds to 0.5 hours.
The film thicknesses of the first photosensitive film and the second photosensitive film are appropriately determined according to the depth of the pores and the polymer film described later. The thickness of the first photosensitive film is usually 0.1 to 50 μm, preferably 1 to 30 μm. The film thickness of the second photosensitive film is usually 0.1 to 50 μm, preferably 1 to 30 μm.
１－２．工程（２）
　工程（２）は、図１の（２）に示すように（図１は感光性膜がポジ型の場合である）、前記工程（１）で形成された第１感光性膜１１２および第２感光性膜１１３に、必要に応じてマスク１２４を介して、選択的に露光光１２３を露光し、第１感光性膜１１２における潜像１２１および第２感光性膜１１３における潜像１２２を形成する工程である。
　なお、本発明において第１感光性膜および第２感光性膜を「選択的に露光する」とは、パターン化塗膜を形成するため、パターン形状に応じて、これら感光性膜の特定箇所を露光することをいう。 1-2. Step (2)
In the step (2), as shown in FIG. 1 (2) (FIG. 1 shows a case where the photosensitive film is a positive type), the first photosensitive film 112 and the second photosensitive film 112 formed in the step (1) are used. The exposure film 123 is selectively exposed to the photosensitive film 113 through a mask 124 as necessary to form a latent image 121 on the first photosensitive film 112 and a latent image 122 on the second photosensitive film 113. It is a process.
In the present invention, “selectively exposing” the first photosensitive film and the second photosensitive film means forming a patterned coating film, and therefore, depending on the pattern shape, specific portions of these photosensitive films are defined. It means exposing.
　露光光としては、例えば、半導体レーザー、エキシマレーザー、メタルハライドランプ等による紫外線等；高圧水銀灯によるｇ線、ｈ線、ｉ線等；極端紫外線が挙げられ、また、電子線を挙げることもできる。これらの中でも、高解像度でパターンを形成できる点から、ｇ線またはｉ線が好ましい。
　露光光の露光量は、露光光の種類、第１感光性膜および第２感光性膜の膜厚および種類により適宜選択されるが、高圧水銀灯の場合、通常１００～１５００ｍＪ／ｃｍ2である。 Examples of the exposure light include ultraviolet rays from a semiconductor laser, excimer laser, metal halide lamp, etc .; g rays, h rays, i rays, etc. from a high-pressure mercury lamp; extreme ultraviolet rays, and electron beams. Among these, g-line or i-line is preferable because a pattern can be formed with high resolution.
The exposure amount of the exposure light is appropriately selected according to the type of exposure light and the thickness and type of the first photosensitive film and the second photosensitive film. In the case of a high-pressure mercury lamp, it is usually 100 to 1500 mJ / cm 2 .
　第１感光性膜および第２感光性膜に、選択的に露光光１２３を露光する方法としては、電子線など指向性のある露光光を選択的に露光する方法も可能であるが、細孔板の製造を大量に行う場合は、通常、マスク１２４を介して行われる。マスク１２４は、第１感光性膜および第２感光性膜がポジ型の感光性膜か、ネガ型の感光性膜かにより適宜選択される。つまり、第１感光性膜および第２感光性膜がネガ型の感光性膜の場合、目的とする細孔に対応する箇所がそれ以外の箇所よりも露光光に対する透過率が小さくなるよう設計したマスク１２４を用いる。一方、第１感光性膜および第２感光性膜がポジ型の感光性膜の場合、目的とする細孔に対応する箇所がそれ以外の箇所よりも露光光に対する透過率が大きくなるよう設計したマスク１２４を用いる。 As a method of selectively exposing the exposure light 123 to the first photosensitive film and the second photosensitive film, a method of selectively exposing directional exposure light such as an electron beam is also possible. When a large number of plates are manufactured, it is usually performed through a mask 124. The mask 124 is appropriately selected depending on whether the first photosensitive film and the second photosensitive film are a positive photosensitive film or a negative photosensitive film. In other words, when the first photosensitive film and the second photosensitive film are negative photosensitive films, the portion corresponding to the target pore is designed to have a lower transmittance for exposure light than the other portions. A mask 124 is used. On the other hand, when the first photosensitive film and the second photosensitive film are positive type photosensitive films, the portion corresponding to the target pore is designed to have a higher transmittance for exposure light than the other portions. A mask 124 is used.
　細孔の大きさによって露光方法は適宜選択可能であり、微細な細孔を形成する際は、通常、縮小投影法により露光する。
　また、露光後、必要に応じて、加熱処理（以下「ＰＥＢ」ともいう。）をすることも可能である。ＰＥＢ条件は、各感光性膜中の各成分の種類および含有量等によって適宜選択可能であるが、通常３０～３００℃で１分間～５時間である。 The exposure method can be appropriately selected depending on the size of the pores. When forming fine pores, exposure is usually performed by a reduction projection method.
In addition, after exposure, heat treatment (hereinafter also referred to as “PEB”) may be performed as necessary. The PEB condition can be appropriately selected depending on the type and content of each component in each photosensitive film, but is usually 30 to 300 ° C. for 1 minute to 5 hours.
１－３．工程（３）
　工程（３）は、図１の（３）に示すように（図１は感光性膜がポジ型の場合である）、前記工程（２）で形成された露光後の前記第１感光性膜および前記第２感光性膜に、現像液を接触させることにより、相対的に現像液への溶解性の高い箇所を除去、つまり、潜像１２１および潜像１２２を現像し、パターン化塗膜１３３を形成し、親油性を有する側壁面１３２を有する細孔１３４を形成する工程である。 1-3. Process (3)
In step (3), as shown in (3) of FIG. 1 (FIG. 1 shows a case where the photosensitive film is a positive type), the first photosensitive film after exposure formed in step (2) is formed. Then, the developer is brought into contact with the second photosensitive film to remove a portion having a relatively high solubility in the developer, that is, the latent image 121 and the latent image 122 are developed, and the patterned coating film 133 is developed. And forming the pores 134 having the side wall surface 132 having lipophilicity.
　前記現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア、エチルアミン、ｎ－プロピルアミン、ジエチルアミン、ジエチルアミノエタノール、ジ－ｎ－プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン、１，５－ジアザビシクロ［４．３．０］－５－ノナンなどの塩基性化合物の水溶液を用いることができる。また、前記塩基性化合物の水溶液にメタノール、エタノール等の水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。現像液を接触する方法としては、例えば液盛り法、ディッピング法、揺動浸漬法、シャワー法等の適宜の方法を利用することができる。 Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4] .3.0] -5-nonane can be used as an aqueous solution of a basic compound. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the basic compound can also be used as a developer. As a method for contacting the developer, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be used.
　その後、パターン化塗膜１３３は、通常、水により洗浄処理する。また、パターン化塗膜１３３を充分に硬化させることを目的に、光を全面に照射（後露光）することもできる。前記後露光における露光量は、通常１～１５００ｍＪ／ｃｍ2である。さらに、パターン化塗膜１３３を充分に硬化させることを目的に、加熱処理（後ベーク）をすることも可能である。後ベークの条件は、各感光性膜中の各成分の種類および含有量等によって適宜選択可能であるが、通常３０～３００℃で１分～５時間である。 Thereafter, the patterned coating film 133 is usually washed with water. Further, for the purpose of sufficiently curing the patterned coating film 133, the entire surface can be irradiated (post-exposure). The exposure amount in the post-exposure is usually 1 to 1500 mJ / cm 2 . Furthermore, for the purpose of sufficiently curing the patterned coating film 133, a heat treatment (post-bake) can be performed. The post-baking conditions can be appropriately selected depending on the type and content of each component in each photosensitive film, but are usually 30 to 300 ° C. for 1 minute to 5 hours.
　パターン化塗膜１３３により、細孔１３４は形成されている。
　細孔１３４は、第２感光性膜１１３により形成される親油性を有する側壁面１３２を有することになる。細孔１３４は、第２感光性膜１１３により形成される、親油性を有する側壁面１３２と、第１感光性膜１１２により形成される、親水性を有する側壁面１３１とを有することが好ましい。
　細孔１３４の深さは、通常０．２～１００μｍである。細孔板の上面から見たときの細孔１３４の形状は、通常、円形もしくは楕円形である。細孔１３４が円形の場合、その直径は、通常１０～３００μｍである。また、細孔板にある細孔１３４の数は１つ以上である。
　上記工程（１）～工程（３）により、力学的なプロセスやドライプロセスを用いずに、少なくとも１つの細孔１３４を有し、細孔１３４の側壁面の少なくとも一部が親油性を有する細孔板、好ましくは細孔１３４の側壁面の少なくとも他の一部が親水性を有する細孔板を製造することができる。前記細孔板は、マイクロアレイ用に好適に用いることができる。 The pores 134 are formed by the patterned coating film 133.
The pores 134 have a lipophilic side wall surface 132 formed by the second photosensitive film 113. The pores 134 preferably have a lipophilic side wall surface 132 formed by the second photosensitive film 113 and a hydrophilic side wall surface 131 formed by the first photosensitive film 112.
The depth of the pores 134 is usually 0.2 to 100 μm. The shape of the pore 134 when viewed from the upper surface of the pore plate is usually circular or elliptical. When the pores 134 are circular, the diameter is usually 10 to 300 μm. Further, the number of pores 134 in the pore plate is one or more.
By the above steps (1) to (3), without using a mechanical process or a dry process, at least one pore 134 is provided, and at least a part of the side wall surface of the pore 134 is lipophilic. A perforated plate, preferably a perforated plate in which at least another part of the side wall surface of the fine pore 134 is hydrophilic, can be produced. The pore plate can be suitably used for a microarray.
２．第２感光性組成物
　本発明の第２感光性組成物は、（Ａ２）重合体、（Ｂ２）光ラジカル発生剤、（Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物（以下「エチレン性化合物（Ｃ２）」ともいう。）、（Ｄ２）溶剤、および（Ｅ２）シリコーン系界面活性剤を含有する。 2. Second Photosensitive Composition The second photosensitive composition of the present invention comprises (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond (hereinafter “ethylenic”). (Also referred to as “compound (C2)”), (D2) a solvent, and (E2) a silicone-based surfactant.
　第２感光性組成物から得られる第２感光性膜を露光すると、第２感光性膜の露光された箇所では、光ラジカル発生剤（Ｂ２）からラジカルなどの活性種が発生し、この活性種が、エチレン性化合物（Ｃ２）に作用することで、エチレン性化合物が重合する。その結果、第２感光性膜の露光された箇所は、工程（３）の現像液に対して難溶化する。一方、第２感光性膜の露光されていない箇所は、工程（３）の現像液に可溶である。したがって、露光・現像処理によりパターンを形成することができる。 When the second photosensitive film obtained from the second photosensitive composition is exposed, active species such as radicals are generated from the photoradical generator (B2) at the exposed portion of the second photosensitive film, and this active species. However, the ethylenic compound is polymerized by acting on the ethylenic compound (C2). As a result, the exposed portion of the second photosensitive film is hardly soluble in the developer in step (3). On the other hand, the unexposed portion of the second photosensitive film is soluble in the developer in the step (3). Therefore, a pattern can be formed by exposure / development processing.
２－１．重合体（Ａ２）
　重合体（Ａ２）は、パターンの構成成分として用いられる。
　重合体（Ａ２）は、溶剤（Ｄ２）に可溶であり、且つ、工程（３）の現像液に対して可溶であれば特に限定されず、例えば、ノボラック樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル重合体、アルキド樹脂、ポリウレタンなどの熱硬化性樹脂；ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、ＡＢＳ樹脂（アクリロニトリル／ブタジエン／スチレン共重合樹脂）、ＡＳ樹脂（アクリロニトリル／スチレン共重合樹脂）、ポリ（メタ）アクリル酸エステル重合体、フッ素樹脂、ポリアミド、ポリアセタール、ポリカーボネート、ポリエチレンテレフタレート、環状ポリオレフィン、ポリイミドなどの熱可塑性樹脂；ポリフェニレンスルファイド、ポリスルホン、ポリエーテルサルフォン、ポリエーテルケトン、液晶ポリマーなどのスーパーエンジニアリングプラスチック；が挙げられる。 2-1. Polymer (A2)
A polymer (A2) is used as a structural component of a pattern.
The polymer (A2) is not particularly limited as long as it is soluble in the solvent (D2) and soluble in the developer in the step (3). For example, a novolac resin, an epoxy resin, a melamine resin, Thermosetting resins such as urea resin, unsaturated polyester polymer, alkyd resin, polyurethane; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin (acrylonitrile / butadiene / styrene copolymer resin), AS resin ( (Acrylonitrile / styrene copolymer resin), poly (meth) acrylate polymer, fluororesin, polyamide, polyacetal, polycarbonate, polyethylene terephthalate, cyclic polyolefin, polyimide, and other thermoplastic resins; polyphenylene sulfide, polysulfone, polyethersulfone , Polyether ketone, super engineering plastics such as liquid crystal polymer; and the like.
　第２感光性膜を経て、第１感光性膜は露光されるため、第２感光性膜の露光光に対する透過性を上げることが好ましい。第２感光性膜の透過性は、重合体（Ａ２）の種類により大きく影響するため、重合体（Ａ２）は、露光光に対して透過性の高い重合体が好ましい。
　このような重合体（Ａ２）としては、ポリ（メタ）アクリル酸エステル重合体が好ましく、工程（３）の現像液としてアルカリ現像液を用いる場合、アルカリ現像液に対して可溶性に優れることから、カルボキシル基を有するポリ（メタ）アクリル酸エステル重合体が更に好ましい。前記「（メタ）アクリル酸」とは、「メタクリル酸」および「アクリル酸」の総称である。 Since the first photosensitive film is exposed through the second photosensitive film, it is preferable to increase the transparency of the second photosensitive film to the exposure light. Since the permeability of the second photosensitive film is greatly affected by the type of the polymer (A2), the polymer (A2) is preferably a polymer that is highly permeable to exposure light.
As such a polymer (A2), a poly (meth) acrylic acid ester polymer is preferable, and when an alkali developer is used as the developer in the step (3), it is excellent in solubility in an alkali developer. A poly (meth) acrylic acid ester polymer having a carboxyl group is more preferred. The “(meth) acrylic acid” is a general term for “methacrylic acid” and “acrylic acid”.
　ポリ（メタ）アクリル酸エステル重合体とは、（メタ）アクリル基を有する化合物（以下「（メタ）アクリル単量体」ともいう。）と、必要に応じて（メタ）アクリル単量体と重合可能な単量体（以下「その他単量体」ともいう。）とを、特開２００３－２４１３７２号公報、特開２００５－２７４９２０号公報等に記載の公知の方法により、重合して得た重合体のことである。 A poly (meth) acrylic acid ester polymer is a compound having a (meth) acrylic group (hereinafter also referred to as “(meth) acrylic monomer”) and, if necessary, polymerized with a (meth) acrylic monomer. Possible monomers (hereinafter also referred to as “other monomers”) are polymerized by a known method described in JP-A Nos. 2003-241372 and 2005-274920. It is a coalescence.
　（メタ）アクリル単量体としては、例えば、特開２００３－２４１３７２号公報、特開２００５－２７４９２０号公報、特開２００７－２７２０８７号公報等に記載の単量体、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、アリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシジエチレングルコール（メタ）アクリレート、メトキシトリエチレングルコール（メタ）アクリレート、メトキシプロピレングルコール（メタ）アクリレート、メトキシジプロピレングルコール（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デカジエニル（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デカニル（メタ）アクリレート、トリシクロ〔５．２．１．０2,6〕デセニル（メタ）アクリレート、イソボロニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレートが挙げられる。 Examples of the (meth) acrylic monomer include monomers described in JP2003-241372A, JP2005-274920A, JP2007-272087A, and the like, methyl (meth) acrylate, ethyl (Meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meta ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate , Allyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decadienyl (meth) acrylate, Tricyclo [5.2.1.0 2,6 ] decanyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl ( Meta) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, phenoxyethyl glycol (meth) acrylate.
　ポリ（メタ）アクリル酸エステル重合体に、カルボキシル基を導入することができる（メタ）アクリル単量体およびその他単量体としては、例えば、（メタ）アクリル酸、クロトン酸、α－クロルアクリル酸、ケイ皮酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、メサコン酸が挙げられる。
　その他単量体としては、例えば、特開２００３－２４１３７２号公報、特開２００５－２７４９２０号公報、特開２００７－２７２０８７号公報等に記載の単量体、ｐ－イソプロペニルフェノール、インデン、１－メチルインデン、アセナフチレンが挙げられる。 Examples of (meth) acrylic monomers and other monomers that can introduce carboxyl groups into poly (meth) acrylic acid ester polymers include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid Cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid.
Other monomers include, for example, monomers described in JP-A-2003-241372, JP-A-2005-274920, JP-A-2007-272087, etc., p-isopropenylphenol, indene, 1- Examples include methylindene and acenaphthylene.
　重合体（Ａ２）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算の重量平均分子量（Ｍｗ）は、現像液への溶解性の点から、好ましくは５，０００～２０，０００、より好ましくは７，０００～１５，０００である。
　重合体（Ａ２）は１種のみを用いてもよく、２種以上を併用してもよい。
　重合体（Ａ２）の含有割合は、細孔の深さ、細孔の側壁面の親油性を有する面の面積、第２感光性組成物の塗布性などにより、適宜選択される。 The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A2) is preferably 5,000 to 20,000, more preferably 7 from the viewpoint of solubility in a developer. , 15,000 to 15,000.
Only 1 type may be used for a polymer (A2) and it may use 2 or more types together.
The content ratio of the polymer (A2) is appropriately selected according to the depth of the pores, the area of the pores having a lipophilic surface, the coatability of the second photosensitive composition, and the like.
２－２．光ラジカル発生剤（Ｂ２）
　光ラジカル発生剤（Ｂ２）は、露光光によりラジカルなどの活性種を発生することができる化合物である。
　光ラジカル発生剤（Ｂ２）は、特開２００６－２８５０３５号公報および特開２００９－１９２６１３号公報に記載の光ラジカル発生剤が挙げられる。具体的には、アシルホスフィンオキサイド系化合物、ビイミダゾール系化合物、ベンゾイン系化合物、アセトフェノン系化合物、ベンゾフェノン系化合物、α－ジケトン系化合物、多核キノン系化合物、キサントン系化合物、トリアジン系化合物、Ｏ－アシルオキシム型化合物等が挙げられる。
　光ラジカル発生剤（Ｂ２）としては、精度よくパターンを形成できることから、アシルホスフィンオキサイド系化合物およびアセトフェノン系化合物から選ばれる１種以上が好ましい。 2-2. Photoradical generator (B2)
The photo radical generator (B2) is a compound that can generate active species such as radicals by exposure light.
Examples of the photoradical generator (B2) include photoradical generators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, O-acyloxy compounds And the like.
As the photoradical generator (B2), one or more selected from acylphosphine oxide compounds and acetophenone compounds are preferable because a pattern can be formed with high accuracy.
　アシルホスフィンオキサイド系化合物としては、例えば、ビス（２，６－ジクロルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－４－エトキシフェニルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－４－プロピルフェニルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－２－ナフチルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－１－ナフチルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－４－クロルフェニルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－２，４－ジメトキシフェニルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－デシルホスフィンオキサイド、ビス（２，６－ジクロルベンゾイル）－４－オクチルフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２，６－ジクロル－３，４，５－トリメトキシベンゾイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２，６－ジクロル－３，４，５－トリメトキシベンゾイル）－４－エトキシフェニルホスフィンオキサイド、ビス（２－メチル－１－ナフトイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２－メチル－１－ナフトイル）－４－エトキシフェニルホスフィンオキサイド、ビス（２－メチル－１－ナフトイル）－２－ナフチルホスフィンオキサイド、ビス（２－メチル－１－ナフトイル）－４－プロピルフェニルホスフィンオキサイド、ビス（２－メチル－１－ナフトイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２－メトキシ－１－ナフトイル）－４－エトキシフェニルホスフィンオキサイド、ビス（２－クロル－１－ナフトイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキサイドが挙げられる。 Examples of the acylphosphine oxide compound include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dichlorobenzoyl) -2. , 5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2, 6-Dichloroben Yl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -decylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4 , 6-Trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl)- 2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5- Dimethylphenylphosphine oxide, bis (2-methyl -1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis ( 2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5 -Dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.
　アセトフェノン系化合物としては、例えば、２，２－ジメトキシアセトフェノン、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オンが挙げられる。 Examples of acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 4- (2 -Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-1,2-diphenylethane-1-one.
　光ラジカル発生剤（Ｂ２）は１種のみを用いてもよく、２種以上を併用してもよい。
　光ラジカル発生剤（Ｂ２）の含有量は、露光波長により適宜選択されるが、重合体（Ａ２）の含有量１００重量部に対して、通常１～３０重量部、好ましくは２～２５重量部である。 As the photo radical generator (B2), only one type may be used, or two or more types may be used in combination.
The content of the photo radical generator (B2) is appropriately selected depending on the exposure wavelength, but is usually 1 to 30 parts by weight, preferably 2 to 25 parts by weight with respect to 100 parts by weight of the polymer (A2). It is.
２－３．エチレン性化合物（Ｃ２）
　エチレン性化合物（Ｃ２）は、露光光により光ラジカル発生剤（Ｂ２）からラジカルなどの活性種が発生し、この活性種と作用することで重合する化合物のことである。具体的には、（メタ）アクリレート基やビニル基などのエチレン性不飽和結合基を少なくとも１つ有する化合物などである。 2-3. Ethylene compound (C2)
The ethylenic compound (C2) is a compound that is polymerized by generating active species such as radicals from the photoradical generator (B2) by exposure light and acting on the active species. Specific examples include compounds having at least one ethylenically unsaturated bond group such as a (meth) acrylate group or a vinyl group.
　エチレン性化合物（Ｃ２）としては、例えば、特開２００６－２８５０３５号公報および特開２００９－１９２６１３号公報に記載の化合物、エチレングリコール、プロピレングリコール等のアルキレングリコールのジ（メタ）アクリレート；ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコールのジ（メタ）アクリレート；グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等の３価以上の多価アルコールのポリ（メタ）アクリレートやそれらのジカルボン酸変性物；ポリエステル、エポキシ樹脂、ウレタン樹脂、アルキド樹脂、シリコーン樹脂、スピラン樹脂等のオリゴ（メタ）アクリレート；両末端ヒドロキシポリ－１，３－ブタジエン、両末端ヒドロキシポリイソプレン、両末端ヒドロキシポリカプロラクトン等の両末端ヒドロキシル化重合体のジ（メタ）アクリレート；トリス〔２－（メタ）アクリロイロキシエチル〕フォスフェート類が挙げられる。 Examples of the ethylenic compound (C2) include compounds described in JP-A-2006-285035 and JP-A-2009-192613, di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; polyethylene glycol, Poly (alkylene glycol) di (meth) acrylates such as polypropylene glycol; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyester , Epoxy (meth) acrylates such as epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin; both-end hydroxypoly-1,3-butadiene, both-end hydroxypoly Puren, di (meth) acrylate at both terminals hydroxylated polymers such as hydroxy-terminated polycaprolactone, tris [2- (meth) acryloyloxyethyl] phosphate compounds and the like.
　これらのエチレン性化合物（Ｃ２）のうち、３価以上の多価アルコールのポリ（メタ）アクリレートやこれらのジカルボン酸変性物が好ましく、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレートおよびジペンタエリスリトールヘキサアクリレートが、精度よくパターンを形成できることから特に好ましい。 Among these ethylenic compounds (C2), poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferable, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and Dipentaerythritol hexaacrylate is particularly preferable because it can form a pattern with high accuracy.
　エチレン性化合物（Ｃ２）は１種のみを用いてもよく、２種以上を併用してもよい。
　エチレン性化合物（Ｃ２）の含有量は、露光光により適宜選択されるが、重合体（Ａ２）の含有量１００重量部に対して、通常３０～８０重量部、好ましくは４０～７０重量部である。 As the ethylenic compound (C2), only one type may be used, or two or more types may be used in combination.
The content of the ethylenic compound (C2) is appropriately selected depending on the exposure light, but is usually 30 to 80 parts by weight, preferably 40 to 70 parts by weight with respect to 100 parts by weight of the polymer (A2). is there.
２－４．溶剤（Ｄ２）
　溶剤（Ｄ２）は、第２感光性組成物に含まれる溶剤（Ｄ２）以外の成分を均一に混合し、均一な塗膜を形成するために用いられる。溶剤（Ｄ２）は、溶剤（Ｄ２）以外の成分を均一に混合し、且つ、これら成分と化学反応しないものが選ばれる。また、第２感光性組成物は、第１感光性膜上に塗布して塗膜を形成するため、溶剤（Ｄ２）は、第１感光性膜を溶解させないものが選ばれる。 2-4. Solvent (D2)
The solvent (D2) is used for uniformly mixing components other than the solvent (D2) contained in the second photosensitive composition to form a uniform coating film. As the solvent (D2), a component that uniformly mixes components other than the solvent (D2) and does not chemically react with these components is selected. Further, since the second photosensitive composition is applied on the first photosensitive film to form a coating film, the solvent (D2) is selected so as not to dissolve the first photosensitive film.
　溶剤（Ｄ２）としては、例えば、エチレングリコール等のアルコール；テトラヒドロフラン等の環状エーテル；エチレングリコールモノメチルエーテル等の多価アルコールのアルキルエーテル；プロピレングリコールモノメチルエーテルアセテート等の多価アルコールのアルキルエーテルアセテート；トルエン等の芳香族炭化水素；メチルエチルケトン等のケトン；酢酸エチル等のエステルが挙げられる。
　溶剤（Ｄ２）は１種のみを用いてもよく、２種以上を併用してもよい。 Examples of the solvent (D2) include alcohols such as ethylene glycol; cyclic ethers such as tetrahydrofuran; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether; alkyl ether acetates of polyhydric alcohols such as propylene glycol monomethyl ether acetate; toluene Aromatic ketones such as; ketones such as methyl ethyl ketone; esters such as ethyl acetate.
Only 1 type may be used for a solvent (D2) and it may use 2 or more types together.
　溶剤（Ｄ２）としては、また、Ｎ－メチルホルムアミド、Ｎ、Ｎ－ジメチルホルムアミド、Ｎ－メチルホルムアニリド、Ｎ－メチルアセトアミド、Ｎ、Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ－ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテートなどの高沸点の溶剤も挙げられる。 As the solvent (D2), N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid High-boiling solvents such as propylene and phenyl cellosolve acetate are also included.
　溶剤（Ｄ２）の含有量は、塗布方法や細孔の深さ（パターンの高さ）に応じて適宜選択される。例えば、第２感光性組成物において、溶剤（Ｄ２）以外の全成分の含有割合が、通常３０～７０重量％、好ましくは４０～６０重量％となるよう、溶剤（Ｄ２）は用いられる。 The content of the solvent (D2) is appropriately selected according to the coating method and the depth of the pores (pattern height). For example, the solvent (D2) is used so that the content ratio of all components other than the solvent (D2) in the second photosensitive composition is usually 30 to 70% by weight, preferably 40 to 60% by weight.
２－５．シリコーン系界面活性剤（Ｅ２）
　シリコーン系界面活性剤（Ｅ２）は、第２感光性膜の表面に親油性を付与するために用いるものであり、工程（１）～工程（３）の段階で、第２感光性膜の表面に析出し、シリコーン系界面活性剤（Ｅ２）が有する親油性を、第２感光性膜の表面、さらには、細孔の側壁面の一部に親油性を付与することになる。 2-5. Silicone surfactant (E2)
The silicone-based surfactant (E2) is used for imparting lipophilicity to the surface of the second photosensitive film. In the steps (1) to (3), the surface of the second photosensitive film is used. And the lipophilicity of the silicone surfactant (E2) is imparted to the surface of the second photosensitive film and further to part of the side wall surface of the pores.
　シリコーン系界面活性剤（Ｅ２）としては、例えば、特開平５－２９５３５４号公報、特開２０１０－１８１８６５号公報、特開２００９－２５８６１９号公報、特開２００９－２５５３１４号公報および特開２００９－１６８９００号公報記載の化合物、側鎖変性ポリジメチルシロキサン、両末端変性ポリジメチルシロキサン、片末端変性ポリジメチルシロキサン、側鎖両末端変性ポリジメチルシロキサンなどのジメチルシリコーン構造を有するシリコーン系界面活性剤が挙げられ、変性基としてはポリオキシエチレン基、ポリオキシエチレンポリオキシプロピレン基、ポリグリセリン基等のポリエーテル基が挙げられる。これらの中でも、ジメチルシリコーン構造を有するシリコーン系界面活性剤が好ましく用いられる。 Examples of the silicone surfactant (E2) include, for example, JP-A-5-295354, JP-A 2010-181865, JP-A 2009-258619, JP-A 2009-255314, and JP-A 2009-168900. And the like, a silicone surfactant having a dimethylsilicone structure, such as a compound described in No. 1, side chain modified polydimethylsiloxane, both end modified polydimethylsiloxane, one end modified polydimethylsiloxane, and side chain both ends modified polydimethylsiloxane. Examples of the modifying group include polyether groups such as a polyoxyethylene group, a polyoxyethylene polyoxypropylene group, and a polyglycerin group. Among these, a silicone-based surfactant having a dimethyl silicone structure is preferably used.
　商業的に入手可能なシリコーン系界面活性剤（Ｅ２）としては、例えば、ＦＺ－２１２２、ＦＺ－２１１０、ＦＺ－７００６、ＳＨ２８ＰＡ、ＦＺ－２１６６、ＦＺ－２１６４、ＦＺ－７００１、ＦＺ－２１２０、ＳＨ８４００、ＦＺ－７００２、ＦＺ－２１０４（以上、東レ・ダウコーニング社製）、ポリフローＫＬ－２５０、ポリフローＫＬ－２６０、ポリフローＫＬ－２７０、ポリフローＫＬ－２８０、ポリフローＫＬ－４０２（以上、共栄社化学株式会社製）が挙げられる。 Examples of commercially available silicone surfactants (E2) include FZ-2122, FZ-2110, FZ-7006, SH28PA, FZ-2166, FZ-2164, FZ-7001, FZ-2120, and SH8400. FZ-7002, FZ-2104 (manufactured by Toray Dow Corning), Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, Polyflow KL-402 (Kyoeisha Chemical Co., Ltd.) Manufactured).
　シリコーン系界面活性剤（Ｅ２）は１種のみを用いてもよく、２種以上を併用してもよい。
　シリコーン系界面活性剤（Ｅ２）の含有量は、細孔側壁面の親油性の程度、第１感光性膜への塗布性により適宜選択される。つまり、細孔側壁面の親油性の程度は、シリコーン系界面活性剤（Ｅ２）の含有割合が多いと上がり、少ないと下がる。また、第１感光性膜への塗布性は、シリコーン系界面活性剤（Ｅ２）の含有割合にも影響されうる。これらのバランスによりシリコーン系界面活性剤（Ｅ２）の含有量は適宜選ばれるが、重合体（Ａ１）の含有量１００重量部に対して、通常０．０１～１重量部、好ましくは０．０５～０．５重量部である。 As the silicone surfactant (E2), only one type may be used, or two or more types may be used in combination.
The content of the silicone-based surfactant (E2) is appropriately selected depending on the lipophilicity of the pore side wall surface and the coating property to the first photosensitive film. That is, the degree of lipophilicity on the side wall surface of the pore increases when the content ratio of the silicone surfactant (E2) is large, and decreases when the content is small. Moreover, the applicability | paintability to a 1st photosensitive film | membrane may be influenced also by the content rate of a silicone type surfactant (E2). The content of the silicone surfactant (E2) is appropriately selected depending on these balances, but is usually 0.01 to 1 part by weight, preferably 0.05 with respect to 100 parts by weight of the polymer (A1). ~ 0.5 parts by weight.
２－６．その他成分
　本発明の第２感光性組成物には、必要に応じて、シリコーン系界面活性剤（Ｅ２）以外の界面活性剤、密着助剤、熱重合禁止剤、溶解性調整剤、粘度調整剤などを含有する。 2-6. Other components In the second photosensitive composition of the present invention, a surfactant other than the silicone-based surfactant (E2), an adhesion assistant, a thermal polymerization inhibitor, a solubility adjuster, and a viscosity adjuster are included as necessary. Etc.
　シリコーン系界面活性剤（Ｅ）以外の界面活性剤は、本発明の第２感光性組成物の基板に塗布する際の塗布性、消泡性、レベリング性を向上させるために用いる成分である。前記界面活性剤としては、例えば、市販されているものとして、ＦＴＸ－２０４Ｄ、ＦＴＸ－２０８Ｄ、ＦＴＸ－２１２Ｄ、ＦＴＸ－２１６Ｄ，ＦＴＸ－２１８Ｆ、ＦＴＸ－２２０Ｄ、ＦＴＸ－２２２Ｄ（以上（株）ネオス製）、メガファックＦ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ１８３（以上、大日本インキ化学工業（株）製）、フロラードＦＣ－１３５、同ＦＣ－１７０Ｃ、同ＦＣ－４３０、同ＦＣ－４３１（以上、住友スリーエム（株）製）、サーフロンＳ－１１２、同Ｓ－１１３、同Ｓ－１３１、同Ｓ－１４１、同Ｓ－１４５（以上、旭硝子（株）製）が挙げられる。
　シリコーン系界面活性剤（Ｅ）以外の界面活性剤の含有量は、第１感光性膜への塗布性により適宜選択されるが、重合体（Ａ１）の含有量１００重量部に対して、通常０．０１～１重量部、好ましくは０．０５～０．５重量部である。 Surfactants other than the silicone-based surfactant (E) are components used for improving the coating property, defoaming property, and leveling property when applied to the substrate of the second photosensitive composition of the present invention. Examples of the surfactant include commercially available FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218F, FTX-220D, FTX-222D (manufactured by Neos Co., Ltd.) ), MegaFuck F142D, F172, F173, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (above, Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, and S-145 (above, manufactured by Asahi Glass Co., Ltd.).
The content of the surfactant other than the silicone-based surfactant (E) is appropriately selected depending on the applicability to the first photosensitive film, but is usually based on 100 parts by weight of the polymer (A1). 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight.
２－７．第２感光性組成物の調製方法
　本発明の第２感光性組成物は、例えば、所定量の上記各成分をディゾルバー、ホモジナイザー、３本ロールミルなどの分散機を用いて分散・混合することにより調製できる。また必要に応じて、メッシュメンブランフィルターなどを用いて、第２感光性組成物を濾過してもよい。 2-7. Method for Preparing Second Photosensitive Composition The second photosensitive composition of the present invention is prepared , for example, by dispersing and mixing a predetermined amount of each of the above components using a disperser such as a dissolver, a homogenizer, or a three roll mill. it can. Moreover, you may filter a 2nd photosensitive composition using a mesh membrane filter etc. as needed.
３．第１感光性組成物
　本発明の第１感光性組成物は、（Ａ１）水酸基を有する重合体、（Ｂ１）光ラジカル発生剤、（Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物（以下「エチレン性化合物（Ｃ１）」ともいう。）、および（Ｄ１）溶剤を含有する。
　第１感光性組成物から得られる第１感光性膜を露光すると、第１感光性膜の露光された箇所では、光ラジカル発生剤（Ｂ１）からラジカルなどの活性種が発生し、この活性種が、エチレン性化合物（Ｃ１）に作用することで、エチレン性化合物が重合する。その結果、第１感光性膜の露光された箇所は、工程（３）の現像液に対して難溶化する。一方、第１感光性膜の露光されていない箇所は、工程（３）の現像液に可溶である。したがって、露光・現像処理によりパターンを形成することができる。 3. First Photosensitive Composition The first photosensitive composition of the present invention comprises (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, (C1) a compound having at least one ethylenically unsaturated bond (hereinafter referred to as “the first photosensitive composition”). (Also referred to as “ethylenic compound (C1)”), and (D1) a solvent.
When the first photosensitive film obtained from the first photosensitive composition is exposed, active species such as radicals are generated from the photoradical generator (B1) at the exposed portion of the first photosensitive film, and this active species. However, the ethylenic compound is polymerized by acting on the ethylenic compound (C1). As a result, the exposed portion of the first photosensitive film is hardly soluble in the developer in step (3). On the other hand, the unexposed portion of the first photosensitive film is soluble in the developer in step (3). Therefore, a pattern can be formed by exposure / development processing.
３－１．水酸基を有する重合体（Ａ１）
　水酸基を有する重合体（Ａ１）は、第１感光性膜に親水性を付与するために用いられ、つまり、前記親水性付与成分として用いられる。第１感光性膜に親水性を付与することにより、第２感光性膜との混ざり（ミキシング）を防ぐことができ、さらに、後述するポリマー膜を細孔に蓋をするように形成するとき、バッファー液が親水性の場合、効率よく細孔内にバッファー液を取り込むことができる。 3-1. Polymer having a hydroxyl group (A1)
The polymer (A1) having a hydroxyl group is used for imparting hydrophilicity to the first photosensitive film, that is, used as the hydrophilicity imparting component. By imparting hydrophilicity to the first photosensitive film, it is possible to prevent mixing with the second photosensitive film (mixing), and when forming a polymer film to be described later so as to cover the pores, When the buffer solution is hydrophilic, the buffer solution can be efficiently taken into the pores.
　水酸基とは、アルコール性水酸基およびフェノール性水酸基のことであり、つまり、水酸基を有する重合体（Ａ１）としては、アルコール性水酸基を有する重合体（Ａ１－１）、フェノール性水酸基を有する重合体（Ａ１－２）が挙げられる。 The hydroxyl group means an alcoholic hydroxyl group and a phenolic hydroxyl group. That is, as the polymer (A1) having a hydroxyl group, a polymer (A1-1) having an alcoholic hydroxyl group, a polymer having a phenolic hydroxyl group ( A1-2).
　アルコール性水酸基を有する重合体（Ａ１－１）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートなどを単量体成分として用いて得られる（メタ）アクリル樹脂；アリルアルコールなどを単量体成分として用いるアリル樹脂；ビニルアルコールなどを単量体成分として用いるビニル樹脂；フェノキシ樹脂；エポキシアクリレート樹脂；が挙げられる。これらのなかでもエチレン性不飽和結合を有することにより、エチレン性化合物（Ｃ１）と同様に、露光により発生した活性種により重合し、リソグラフィー法によるパターンの形成が容易なことから、エポキシアクリレート樹脂が好ましい。 As the polymer (A1-1) having an alcoholic hydroxyl group, for example, a (meth) acrylic resin obtained using 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or the like as a monomer component is used. An allyl resin using allyl alcohol or the like as a monomer component; a vinyl resin using vinyl alcohol or the like as a monomer component; a phenoxy resin; an epoxy acrylate resin. Among these, by having an ethylenically unsaturated bond, as with the ethylenic compound (C1), it is polymerized by active species generated by exposure, and it is easy to form a pattern by a lithography method. preferable.
　エポキシアクリレート樹脂とは、エポキシ樹脂と、不飽和一塩基酸および／または不飽和多塩基酸を開環付加反応して得られる樹脂のことである。
　前記エポキシ樹脂としては、例えば、ビスフェノール型エポキシ樹脂；ビフェニル型エポキシ樹脂；脂環式エポキシ樹脂；テトラグリシジルアミノジフェニルメタン等の多官能性グリシジルアミン樹脂；テトラフェニルグリシジルエーテルエタン等の多官能性グリシジルエーテル樹脂；フェノールノボラック型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂；フェノール、ｏ－クレゾール、ｍ－クレゾール、ナフトール等のフェノール化合物と、フェノール性ヒドロキシ基を有する芳香族アルデヒドとの縮合反応により得られるポリフェノール化合物と、エピクロルヒドリンとの反応物；フェノール化合物とジビニルベンゼンやジシクロペンタジエン等のジオレフィン化合物との付加反応により得られるポリフェノール化合物と、エピクロルヒドリンとの反応物；４－ビニルシクロヘキセン－１－オキサイドの開環重合物を過酸でエポキシ化したもの；トリグリシジルイソシアヌレート等の複素環を有するエポキシ樹脂；フェノールアラルキル型エポキシ樹脂；が挙げられる。
　前記エポキシ樹脂は１種のみを用いてもよく、２種以上を併用してもよい。 The epoxy acrylate resin is a resin obtained by a ring-opening addition reaction between an epoxy resin and an unsaturated monobasic acid and / or an unsaturated polybasic acid.
Examples of the epoxy resin include bisphenol type epoxy resins; biphenyl type epoxy resins; alicyclic epoxy resins; polyfunctional glycidyl amine resins such as tetraglycidylaminodiphenylmethane; and polyfunctional glycidyl ether resins such as tetraphenyl glycidyl ether ethane. A phenol novolac type epoxy resin or a cresol novolak type epoxy resin; a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, m-cresol, naphthol and an aromatic aldehyde having a phenolic hydroxy group; A reaction product with epichlorohydrin; a polyphenol compound obtained by addition reaction of a phenol compound with a diolefin compound such as divinylbenzene or dicyclopentadiene; Reaction product with lorhydrin; ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracid; epoxy resin having heterocycle such as triglycidyl isocyanurate; phenol aralkyl type epoxy resin; .
The epoxy resin may be used alone or in combination of two or more.
　前記不飽和一塩基酸としては、例えば、アクリル酸、メタクリル酸、ケイ皮酸が挙げられる。
　前記不飽和多塩基酸としては、例えば、マロン酸、コハク酸、メチルコハク酸、２，２－ジメチルコハク酸、２，３－ジメチルコハク酸、ヘキシルコハク酸、グルタル酸、２－メチルグルタル酸、３－メチルグルタル酸、２，２－ジメチルグルタル酸、３，３－ジメチルグルタル酸、３，３－ジエチルグルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族飽和多塩基酸；フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸等の芳香族飽和多塩基酸；ヘット酸、１，２－ヘキサヒドロフタル酸、１，１－シクロブタンジカルボン酸、５－ノルボルネン－２，３－ジカルボン酸、１，４－シクロヘキサンジカルボン酸等の脂環族飽和多塩基酸が挙げられる。
　前記不飽和一塩基酸および前記不飽和多塩基酸は１種のみを用いてもよく、２種以上を併用してもよい。 Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, and cinnamic acid.
Examples of the unsaturated polybasic acid include malonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3 -Aliphatic saturated polybases such as methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Acids: aromatic saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid; het acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, 5-norbornene And alicyclic saturated polybasic acids such as -2,3-dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
The unsaturated monobasic acid and the unsaturated polybasic acid may be used alone or in combination of two or more.
　フェノール性水酸基を有する重合体（Ａ１－２）としては、例えば、フェノールおよびその誘導体と、縮合剤との縮合によって得られるフェノール樹脂；ｐ－ヒドロキシスチレン、ｐ－イソプロペニルフェノールなどの単量体成分として用いる芳香族ビニル樹脂；が挙げられる。これらのなかでも親水性に優れた第１感光性膜を得られることから、フェノール樹脂が好ましい。 Examples of the polymer (A1-2) having a phenolic hydroxyl group include phenol resins obtained by condensation of phenol and derivatives thereof with a condensing agent; monomer components such as p-hydroxystyrene and p-isopropenylphenol Aromatic vinyl resin used as Among these, a phenol resin is preferable because a first photosensitive film having excellent hydrophilicity can be obtained.
　前記フェノールおよびその誘導体としては、例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｐ－キシレノール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、３，４－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、１－ナフトール、２－ナフトール、２，７－ジヒドロキシナフタレンが挙げられる。
　前記フェノールおよびその誘導体は１種のみを用いてもよく、２種以上を併用してもよい。 Examples of the phenol and derivatives thereof include phenol, o-cresol, m-cresol, p-cresol, p-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4- Examples include xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 1-naphthol, 2-naphthol, and 2,7-dihydroxynaphthalene.
The said phenol and its derivative (s) may use only 1 type, and may use 2 or more types together.
　前記縮合剤としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、グリオキサール、グルタルアルデヒド、テレフタルアルデヒド、イソフタルアルデヒドが挙げられる。
　前記縮合剤は１種のみを用いてもよく、２種以上を併用してもよい。 Examples of the condensing agent include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.
The condensing agent may be used alone or in combination of two or more.
　水酸基を有する重合体（Ａ１）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは１，０００～１００，０００、より好ましくは３，０００～５０，０００である。
　水酸基を有する重合体（Ａ１）は１種のみを用いてもよく、２種以上を併用してもよい。
　水酸基を有する重合体（Ａ１）の含有割合は、細孔の深さ、第１感光性組成物の塗布性などにより、適宜選択される。 The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A1) having a hydroxyl group is preferably 1,000 to 100,000, more preferably 3,000 to 50,000. is there.
Only 1 type may be used for the polymer (A1) which has a hydroxyl group, and 2 or more types may be used together.
The content ratio of the polymer (A1) having a hydroxyl group is appropriately selected depending on the depth of the pores, the coating property of the first photosensitive composition, and the like.
３－２．光ラジカル発生剤（Ｂ１）
　光ラジカル発生剤（Ｂ１）は、露光光によりラジカルなどの活性種を発生することができる化合物である。
　光ラジカル発生剤（Ｂ１）は、特開２００６－２８５０３５号公報および特開２００９－１９２６１３号公報に記載の光ラジカル発生剤が挙げられる。具体的には、アシルホスフィンオキサイド系化合物、ビイミダゾール系化合物、ベンゾイン系化合物、アセトフェノン系化合物、ベンゾフェノン系化合物、α－ジケトン系化合物、多核キノン系化合物、キサントン系化合物、トリアジン系化合物、Ｏ－アシルオキシム型化合物等が挙げられる。
　光ラジカル発生剤（Ｂ１）としては、精度よくパターンを形成できることから、アシルホスフィンオキサイド系化合物およびアセトフェノン系化合物から選ばれる１種以上が好ましい。 3-2. Photoradical generator (B1)
The photoradical generator (B1) is a compound that can generate active species such as radicals by exposure light.
Examples of the photo radical generator (B1) include photo radical generators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, O-acyloxy compounds And the like.
As the photoradical generator (B1), one or more selected from acylphosphine oxide compounds and acetophenone compounds are preferable because a pattern can be formed with high accuracy.
　アシルホスフィンオキサイド系化合物およびアセトフェノン系化合物としては、例えば、前記『２－２．光ラジカル発生剤（Ｂ２）』に記載の化合物が挙げられる。
　光ラジカル発生剤（Ｂ１）は１種のみを用いてもよく、２種以上を併用してもよい。
　光ラジカル発生剤（Ｂ１）の含有量は、露光波長により適宜選択されるが、水酸基を有する重合体（Ａ１）の含有量１００重量部に対して、通常１～３０重量部、好ましくは２～２５重量部である。 Examples of the acylphosphine oxide compound and the acetophenone compound include those described in “2-2. And compounds described in “Photoradical generator (B2)”.
As the photo radical generator (B1), only one type may be used, or two or more types may be used in combination.
The content of the photo radical generator (B1) is appropriately selected depending on the exposure wavelength, but is usually 1 to 30 parts by weight, preferably 2 to 2 parts per 100 parts by weight of the polymer (A1) having a hydroxyl group. 25 parts by weight.
３－３．エチレン性化合物（Ｃ１）
　エチレン性化合物（Ｃ１）は、露光光により光ラジカル発生剤（Ｂ１）からラジカルなどの活性種が発生し、この活性種と作用することで重合する化合物のことである。具体的には、（メタ）アクリレート基やビニル基などのエチレン性不飽和結合基を少なくとも１つ有する化合物などである。 3-3. Ethylene compound (C1)
The ethylenic compound (C1) is a compound that is polymerized by generating active species such as radicals from the photoradical generator (B1) by exposure light and acting on the active species. Specific examples include compounds having at least one ethylenically unsaturated bond group such as a (meth) acrylate group or a vinyl group.
　エチレン性化合物（Ｃ１）としては、例えば、前記『２－３．エチレン性化合物（Ｃ２）』に記載の化合物が挙げられる。
　これらのエチレン性化合物（Ｃ１）のうち、３価以上の多価アルコールのポリ（メタ）アクリレートやこれらのジカルボン酸変性物が好ましく、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレートおよびジペンタエリスリトールヘキサアクリレートが、精度良くパターンを形成出来ることから特に好ましい。 Examples of the ethylenic compound (C1) include the above-mentioned “2-3. And compounds described in “Ethylene Compound (C2)”.
Of these ethylenic compounds (C1), poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferred, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and Dipentaerythritol hexaacrylate is particularly preferable because a pattern can be formed with high accuracy.
　エチレン性化合物（Ｃ１）は１種のみを用いてもよく、２種以上を併用してもよい。
　エチレン性化合物（Ｃ１）の含有量は、露光光により適宜選択されるが、水酸基を有する重合体（Ａ１）の含有量１００重量部に対して、通常５～８０重量部、好ましくは１０～７０重量部である。 As the ethylenic compound (C1), only one type may be used, or two or more types may be used in combination.
The content of the ethylenic compound (C1) is appropriately selected depending on the exposure light, but is usually 5 to 80 parts by weight, preferably 10 to 70 parts per 100 parts by weight of the polymer (A1) having a hydroxyl group. Parts by weight.
３－４．溶剤（Ｄ１）
　溶剤（Ｄ１）は、第１感光性組成物に含まれる溶剤（Ｄ１）以外の成分を均一に混合し、均一な塗膜を形成するために用いられる。溶剤（Ｄ１）は、溶剤（Ｄ１）以外の成分を均一に混合し、且つ、これら成分と化学反応しないものが選ばれる。 3-4. Solvent (D1)
The solvent (D1) is used for uniformly mixing components other than the solvent (D1) contained in the first photosensitive composition to form a uniform coating film. The solvent (D1) is selected so that components other than the solvent (D1) are uniformly mixed and do not chemically react with these components.
　溶剤（Ｄ１）としては、例えば、前記『２－４．溶剤（Ｄ２）』に記載の化合物が挙げられる。
　溶剤（Ｄ１）は１種のみを用いてもよく、２種以上を併用してもよい。
　溶剤（Ｄ１）の含有量は、塗布方法や細孔の深さ（パターンの高さ）に応じて適宜選択される。例えば、第１感光性組成物において、溶剤（Ｄ１）以外の成分の含有割合が、通常３０～７０重量％、好ましくは４０～６０重量％となるよう、溶剤（Ｄ１）は用いられる。 Examples of the solvent (D1) include those described in “2-4. And the compound described in “Solvent (D2)”.
Only 1 type may be used for a solvent (D1) and it may use 2 or more types together.
The content of the solvent (D1) is appropriately selected according to the coating method and the depth of the pores (pattern height). For example, the solvent (D1) is used so that the content of components other than the solvent (D1) in the first photosensitive composition is usually 30 to 70% by weight, preferably 40 to 60% by weight.
３－５．その他成分
　本発明の第１感光性組成物には、必要に応じて、界面活性剤、密着助剤、熱重合禁止剤、溶解性調整剤、粘度調整剤などを含有する。 3-5. Other Components The first photosensitive composition of the present invention contains a surfactant, an adhesion assistant, a thermal polymerization inhibitor, a solubility modifier, a viscosity modifier, and the like as necessary.
　界面活性剤としては、例えば、前記『２－６．その他成分』に記載の化合物が挙げられる。
　界面活性剤の含有量は、ベース基板での塗布性により適宜選択されるが、水酸基を有する重合体（Ａ１）の含有量１００重量部に対して、通常０．０１～１重量部、好ましくは０．０５～０．５重量部である。 Examples of the surfactant include those described in “2-6. The compound as described in "other components" is mentioned.
The content of the surfactant is appropriately selected depending on the coatability on the base substrate, but is usually 0.01 to 1 part by weight, preferably 100 parts by weight of the polymer (A1) having a hydroxyl group. 0.05 to 0.5 parts by weight.
　密着助剤は、ベース基板との密着性を向上させるために用いる成分である。密着助剤としては、官能性シランカップリング剤が好ましい。なお、官能性シランカップリング剤とは、カルボキシル基、メタクリロイル基、イソシアネート基、エポキシ基などの反応性置換基を有するシランカップリング剤を意味する。上記官能性シランカップリング剤としては、例えば、トリメトキシシリル安息香酸、γ－メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ－イソシアナートプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランが挙げられる。
　密着助剤の含有量は、第１感光性膜とベース基板との密着性により適宜選択されるが、水酸基を有する重合体（Ａ１）の含有量１００重量部に対して、通常０．１～１０重量部、好ましくは１～５重量部である。 The adhesion assistant is a component used to improve adhesion with the base substrate. As the adhesion assistant, a functional silane coupling agent is preferable. In addition, a functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycid. And xylpropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
The content of the adhesion assistant is appropriately selected depending on the adhesion between the first photosensitive film and the base substrate, but is usually 0.1 to 100 parts by weight based on 100 parts by weight of the polymer (A1) having a hydroxyl group. The amount is 10 parts by weight, preferably 1 to 5 parts by weight.
３－６．第１感光性組成物の調製方法
　本発明の第１感光性組成物は、例えば、所定量の上記各成分をディゾルバー、ホモジナイザー、３本ロールミルなどの分散機を用いて分散・混合することにより調製できる。また必要に応じて、メッシュメンブランフィルターなどを用いて、第１感光性組成物を濾過してもよい。 3-6. Method for Preparing First Photosensitive Composition The first photosensitive composition of the present invention is prepared , for example, by dispersing and mixing a predetermined amount of each of the above components using a disperser such as a dissolver, a homogenizer, or a three roll mill. it can. Moreover, you may filter a 1st photosensitive composition using a mesh membrane filter etc. as needed.
４．細孔板
　本発明の細孔板は、少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する。前記新油性を有する側壁面の表面はシリコン原子を通常含有する。本発明の細孔板は、例えば、前記『１．細孔板の製造方法』により得られ、マイクロアレイ用途に好適に用いられる。
　本発明の細孔板は、細孔の側壁面の少なくとも一部、好ましくは細孔の開口部近辺の側壁面が親油性を有することから、細孔をポリマー膜により覆うことができる。例えば、細孔の開口部近辺を塞ぐように、ポリマー膜を形成することができる。このため、マイクロアレイ用基板を形成することができる。
　図３に示すように、マイクロアレイ用細孔板の、細孔の側壁面の親油性となる場所３０１は、細孔をポリマー膜により覆うためには、ポリマー膜の厚さと新油性となる場所３０１の厚さとがほぼ同等であり、ポリマー膜の幅と新油性となる場所３０１における細孔の幅とがほぼ同等となるように、形成されていることが好ましい。さらに、後述するバッファー液を使った手法で細孔をポリマー膜により覆う場合、細孔の側壁面の親油性となる場所３０１は、開口部３０２に近い側に形成される方が好ましい。 4). Porous plate The porous plate of the present invention has at least one pore, and at least a part of the side wall surface of the pore has lipophilicity. The surface of the side wall surface having the new oil property usually contains silicon atoms. The pore plate of the present invention is, for example, “1. It is obtained by “a manufacturing method of a pore plate” and is suitably used for microarray applications.
In the pore plate of the present invention, at least a part of the side wall surface of the pore, preferably the side wall surface near the opening of the pore, has lipophilicity, so that the pore can be covered with the polymer film. For example, the polymer film can be formed so as to close the vicinity of the opening of the pore. For this reason, a microarray substrate can be formed.
As shown in FIG. 3, the location 301 that becomes lipophilic on the side wall surface of the pore of the microarray pore plate is a location 301 that becomes the thickness of the polymer membrane and the new oil property in order to cover the pores with the polymer membrane. The thickness of the polymer film is preferably approximately the same, and the width of the polymer film and the width of the pores at the location 301 where the oil is new are preferably approximately the same. Further, when the pores are covered with a polymer film by a method using a buffer solution described later, it is preferable that the lipophilic portion 301 on the side wall surface of the pore is formed on the side close to the opening 302.
　前記細孔の深さ３０３は、通常０．２～１００μｍである。細孔板の上面から見たときの細孔の形状は、通常、円形もしくは楕円形である。細孔が円形の場合、その直径３０４は、通常１０～３００μｍである。また、細孔板にある細孔の数は１つ以上である。 The depth 303 of the pores is usually 0.2 to 100 μm. The shape of the pores when viewed from the upper surface of the pore plate is usually a circle or an ellipse. When the pore is circular, its diameter 304 is usually 10 to 300 μm. The number of pores in the pore plate is one or more.
５．マイクロアレイ用基板
　本発明のマイクロアレイ用基板は、上述の細孔板と、直径５００ｎｍ以下の貫通孔を少なくとも１つ有するポリマー膜とを有し、前記ポリマー膜が、前記細孔板の細孔を覆うように形成されている。 5. Microarray Substrate The microarray substrate of the present invention has the above-described pore plate and a polymer film having at least one through-hole having a diameter of 500 nm or less, and the polymer film covers the pores of the pore plate. It is formed as follows.
　マイクロアレイ用基板は、国際公開公報２００５－０７１４０５号公報や、Ａｎａｌ．Ｃｈｅｍ．２００６、７８、頁８１６９～８１７４「Ｌｉｐｉｄ　Ｂｉｌａｙｅｒ　Ｆｏｒｍａｔｉｏｎ　ｂｙ　Ｃｏｎｔａｃｔｉｎｇ　Ｍｏｎｏｌａｙｅｒｓ　Ｉｎ　ａ　Ｍｌｃｒｏｆｌｕｌｄｌｃ　Ｄｅｖｌｃｅ　ｆｏｒ　Ｍｅｎｂｒａｎｅ　Ｐｒｏｔｅｉｎ　Ａｎａｌｙｓｉｓ」に記載の方法により製造することができる。
　つまり、図２の（４）に示すように、マイクロアレイ用細孔板の細孔内にバッファー液２１１を充填する。次いで図２の（５）に示すように、バッファー液にポリマー膜２２１を浮かべて、ポリマー膜２２１の端部を、親油性の側壁面１３２と作用させるととにより、ポリマー膜２２１により細孔を覆い、マイクロアレイ用基板を製造することができる。 Microarray substrates are disclosed in International Publication No. 2005-071405 and Anal. Chem. 2006, 78, pages 8169-8174, “Lipid Bilayer Formation by Contacting Monolayers in a Mclflldlc Development for Membrane Protein Analysis”.
That is, as shown in (4) of FIG. 2, the buffer solution 211 is filled into the pores of the microarray pore plate. Next, as shown in FIG. 2 (5), the polymer film 221 is floated on the buffer solution, and the end of the polymer film 221 is allowed to act on the lipophilic side wall surface 132, whereby pores are formed by the polymer film 221. A microarray substrate can be manufactured by covering.
　前記、直径５００ｎｍ以下の貫通光を有するポリマー膜とは、特表２００８－５４５５１８号公報に記載されているポリマー膜のことである。
　本発明のマイクロアレイ用基板は、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．２００７，１２９、頁１６１４２～１６１４８や、Ｃｕｒｒｅｎｔ　Ｏｐｉｎｉｏｎ　ｉｎ　Ｃｈｅｍｉｃａｌ　Ｂｉｏｌｏｇｙ２００６、１０、頁６２８～６３７や、Ｎａｔｕｒｅ　２００１、４１３、頁６３６～６４０に記載のタンパク質ナノポアを用いたＤＮＡシーケンシングなどに用いることができる。 The polymer film having penetrating light having a diameter of 500 nm or less is a polymer film described in JP-T-2008-545518.
The microarray substrate of the present invention is disclosed in J. Org. Am. Chem. Soc. 2007, 129, pages 16142 to 16148, Current Opinion in Chemical Biology 2006, 10, pages 628 to 637, Nature 2001, 413, pages 636 to 640, and DNA sequencing using protein nanopores. .
　以下、実施例を挙げて、本発明の実施の形態を更に具体的に説明する。但し、本発明は、これらの実施例に何ら制約されるものではない。なお、「部」および「％」は、特記しない限り重量基準である。 Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. “Parts” and “%” are based on weight unless otherwise specified.
１．第１感光性組成物の調製
　［実施例１］
　水酸基を有する重合体（Ａ１）として、酸変性ビスフェノールＡ型エポキシアクリレート（商品名「ＫＡＹＡＲＡＤ　ＺＡＲ－２００１Ｈ」、日本化薬社製）９５部、およびｍ－クレゾール／ｐ－クレゾール＝６０／４０（モル比）からなるクレゾールノボラック樹脂（ポリスチレン換算の重量平均分子量＝８，７００）５部、光ラジカル発生剤（Ｂ１）として、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、チバ・スペシャリティ・ケミカルズ社製）１９部、および２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド（商品名「Ｌｕｃｉｒｉｎ　ＬＲ８９５３Ｘ」、ＢＡＳＦ社製）４部、エチレン性化合物（Ｃ１）として、ジペンタエリスリトールヘキサアクリレート３０部、密着助剤として、３－グリシドキプロピルトリメトキシシラン３部、ならびに界面活性剤として、フッ素系界面活性剤（商品名「ＦＴＸ－２１８Ｆ」、ネオス社製）０．１部を、溶剤（Ｄ１）として、プロピレングリコールモノメチルエーテルアセテート７５部にて混合して、均一な溶液を調製した。この溶液を孔径１０μｍのカプセルフィルターでろ過して実施例１の感光性組成物を得た。 1. Preparation of first photosensitive composition [Example 1]
As a polymer (A1) having a hydroxyl group, 95 parts of acid-modified bisphenol A type epoxy acrylate (trade name “KAYARAD ZAR-2001H”, manufactured by Nippon Kayaku Co., Ltd.) and m-cresol / p-cresol = 60/40 (mol) Cresol novolak resin (polystyrene equivalent weight average molecular weight = 8,700) 5 parts, photoradical generator (B1) as 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name) 19 parts “Irgacure 651” manufactured by Ciba Specialty Chemicals) and 4 parts 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name “Lucirin LR8953X” manufactured by BASF), ethylenic compound (C1) Dipentaerythritol hexaacrylate 30 3 parts of 3-glycidoxypropyltrimethoxysilane as an adhesion assistant and 0.1 part of a fluorosurfactant (trade name “FTX-218F”, manufactured by Neos) as a surfactant, ) Was mixed with 75 parts of propylene glycol monomethyl ether acetate to prepare a uniform solution. This solution was filtered through a capsule filter having a pore size of 10 μm to obtain a photosensitive composition of Example 1.
２．第２感光性組成物の調製
　［合成例１］
　窒素置換したフラスコ中に、２，２’－アゾビスイソブチロニトリルを５部、プロピレングリコールモノメチルエーテルアセテートを１５０部仕込み、重合開始剤が溶解するまで攪拌した。この溶液に、メタクリル酸を１０部、ｐ－イソプロペニルフェノールを１５部、イソボロニルアクリレートを４０部、フェノキシジエチレングリコールアクリレートを２０部、トリシクロ［５．２．１．０2,6］デカニルメタクリレートを１５部仕込み、ゆるやかに攪拌を開始し、８０℃まで昇温した。その後、８０℃で６時間保持して重合することにより、合成例１の重合体の溶液を得た。なお、合成例１の重合体のゲルバーミエーションカラムクロマトグラフィーによるポリスチレン換算の重量平均分子量は１０，０００であった。 2. Preparation of second photosensitive composition [Synthesis Example 1]
In a nitrogen-substituted flask, 5 parts of 2,2′-azobisisobutyronitrile and 150 parts of propylene glycol monomethyl ether acetate were charged and stirred until the polymerization initiator was dissolved. In this solution, 10 parts of methacrylic acid, 15 parts of p-isopropenylphenol, 40 parts of isobornyl acrylate, 20 parts of phenoxydiethylene glycol acrylate, tricyclo [5.2.1.0 2,6 ] decanyl methacrylate Was added, and stirring was started gently, and the temperature was raised to 80 ° C. Then, the polymer solution of Synthesis Example 1 was obtained by carrying out polymerization at 80 ° C. for 6 hours. The polymer of Synthesis Example 1 had a weight average molecular weight in terms of polystyrene as determined by gel permeation column chromatography of 10,000.
　［実施例２］
　重合体（Ａ２）として、合成例１の重合体１００部、光ラジカル発生剤（Ｂ２）として、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、チバ・スペシャリティ・ケミカルズ社製）１９部、および２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド（商品名「Ｌｕｃｉｒｉｎ　ＬＲ８９５３Ｘ」、ＢＡＳＦ社製）４部、エチレン性化合物（Ｃ１）として、ジペンタエリスリトールヘキサアクリレート６０部、ならびにシリコーン系界面活性剤（Ｅ２）として、シリコーン系界面活性剤（商品名「ＳＨ２８ＰＡ」、東レダウコーニング社製）０．３部を、溶剤（Ｄ２）として、プロピレングリコールモノメチルエーテルアセテート９５部にて混合して、均一な溶液を調製した。この溶液を孔径１０μｍのカプセルフィルターでろ過して実施例２の感光性組成物を得た。 [Example 2]
As the polymer (A2), 100 parts of the polymer of Synthesis Example 1, and as the photoradical generator (B2), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, Ciba 19 parts by Specialty Chemicals) and 4 parts 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name “Lucirin LR8953X”, manufactured by BASF), dipentaerythritol hexa as an ethylenic compound (C1) 60 parts of acrylate and 0.3 part of a silicone surfactant (trade name “SH28PA”, manufactured by Toray Dow Corning) as a silicone surfactant (E2) and propylene glycol monomethyl ether acetate as a solvent (D2) A uniform solution was prepared by mixing at 95 parts. This solution was filtered through a capsule filter having a pore size of 10 μm to obtain a photosensitive composition of Example 2.
３．マイクロアレイ用細孔板の製造
　［参考例１］
　シリコンウエハ上にスピンコート法にて、実施例１の感光性組成物を塗布し、次いで、ホットプレートにて１１０℃で５分間加熱して、膜厚１０μｍの第１感光性膜を得た。第１感光性膜表面の水での接触角（２３℃、一気圧）は、３５°であった。 3. Manufacture of microarray pore plate [Reference Example 1]
The photosensitive composition of Example 1 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a first photosensitive film having a thickness of 10 μm. The contact angle (23 ° C., 1 atm) of the first photosensitive film surface with water was 35 °.
　［参考例２］
　シリコンウエハ上にスピンコート法にて、実施例２の感光性組成物を塗布し、次いで、ホットプレートにて１１０℃で５分間加熱して、膜厚１３μｍの第２感光性膜を得た。第２感光性膜表面の水での接触角（２３℃、一気圧）は、８５°であった。また、第２感光性膜表面のヘキサデカンでの接触角（２３℃、一気圧）は、１０°未満であった。 [Reference Example 2]
The photosensitive composition of Example 2 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a second photosensitive film having a thickness of 13 μm. The contact angle (23 ° C., 1 atm) of the second photosensitive film surface with water was 85 °. Moreover, the contact angle (23 degreeC, 1 atmosphere) in the hexadecane of the 2nd photosensitive film | membrane surface was less than 10 degrees.
　［実施例３］
　シリコンウエハ上にスピンコート法にて、実施例１の感光性組成物を塗布し、次いで、ホットプレートにて１１０℃で５分間加熱して、膜厚１０μｍの第１感光性膜を得た。ついで、前記第１感光性膜上に、スピンコート法にて、実施例２の感光性組成物を塗布し、次いで、ホットプレートにて１１０℃で５分間加熱して、膜厚１３μｍの第２感光性膜を得た。
　第１感光性膜および第２感光性膜に、パターン化マスクを介して、露光機（Ｓｕｓｓ社製、商品名「ＭＡ２００ｅ」）を用いて、窒素雰囲気下、１５０ｍＪ／ｃｍ2の露光光を露光した。次いで、露光後の第１感光性膜および第２感光性膜を、２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液を現像液として、室温で３０秒間、現像処理を行った後、流水洗浄し、更に窒素ブローして、直径８０μｍで、細孔間の幅が１５０μｍの、複数の細孔を有する実施例３のマイクロアレイ用細孔板を得た。実施例３のマイクロアレイ用細孔板の電子顕微鏡による写真を図４（１）に示す。
　また、実施例３のマイクロアレイ用細孔板の表面の水での接触角（２３℃、一気圧）は、１００°であった。第２感光性膜がシリコーン系界面活性剤（Ｅ２）を含有することで、水での接触角が８５°から１００°に増加したことから、細孔の開口部近辺に親油性の高い領域が形成されたことが確認された。 [Example 3]
The photosensitive composition of Example 1 was applied onto a silicon wafer by spin coating, and then heated at 110 ° C. for 5 minutes on a hot plate to obtain a first photosensitive film having a thickness of 10 μm. Next, the photosensitive composition of Example 2 was applied on the first photosensitive film by a spin coating method, and then heated at 110 ° C. for 5 minutes on a hot plate to form a second film having a thickness of 13 μm. A photosensitive film was obtained.
The first photosensitive film and the second photosensitive film are exposed to exposure light of 150 mJ / cm 2 under a nitrogen atmosphere using an exposure machine (trade name “MA200e” manufactured by Suss) through a patterned mask. did. Next, after the exposure, the first photosensitive film and the second photosensitive film were developed at room temperature for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution, and then washed with running water. Further, nitrogen blowing was performed to obtain a microarray pore plate for Example 3 having a plurality of pores having a diameter of 80 μm and a width between pores of 150 μm. A photograph taken with an electron microscope of the microarray pore plate of Example 3 is shown in FIG.
Further, the contact angle (23 ° C., one atmospheric pressure) of the surface of the microarray pore plate of Example 3 with water was 100 °. Since the second photosensitive film contains the silicone-based surfactant (E2), the contact angle with water has increased from 85 ° to 100 °, so that a highly lipophilic region is present in the vicinity of the opening of the pore. It was confirmed that it was formed.
　［実施例４］
　実施例３において、現像処理を室温で４５秒間行った以外は、実施例３と同様の手法にて、直径８０μｍで、細孔間の幅が１５０μｍの、複数の細孔を有する実施例４のマイクロアレイ用細孔板を得た。実施例４のマイクロアレイ用細孔板の電子顕微鏡による写真を図４（２）に示す。
　また、実施例４のマイクロアレイ用細孔板の表面の水での接触角（２３℃、一気圧）は、１００°であった。 [Example 4]
In Example 3, except that the development processing was performed at room temperature for 45 seconds, the method of Example 4 having a plurality of pores having a diameter of 80 μm and a width between pores of 150 μm was obtained in the same manner as in Example 3. A microplate pore plate was obtained. A photograph taken with an electron microscope of the microarray pore plate of Example 4 is shown in FIG.
In addition, the contact angle (23 ° C., one atmospheric pressure) of the surface of the microarray pore plate of Example 4 with water was 100 °.
　［実施例５］
　実施例３において、２００ｍＪ／ｃｍ2の露光光を露光した以外は、実施例３と同様の手法にて、直径８０μｍで、細孔間の幅が１５０μｍの、複数の細孔を有する実施例５のマイクロアレイ用細孔板を得た。実施例５のマイクロアレイ用細孔板の電子顕微鏡による写真を図４（３）に示す。
　また、実施例５のマイクロアレイ用細孔板の表面の水での接触角（２３℃、一気圧）は、１００°であった。 [Example 5]
Example 5 having a plurality of pores having a diameter of 80 μm and a width between pores of 150 μm in the same manner as in Example 3 except that exposure light of 200 mJ / cm 2 was exposed in Example 3. A microarray pore plate was obtained. A photograph taken with an electron microscope of the microarray pore plate of Example 5 is shown in FIG.
Further, the contact angle (23 ° C., 1 atm) of the surface of the microarray pore plate of Example 5 with water was 100 °.
　［実施例６］
　実施例３において、２００ｍＪ／ｃｍ2の露光光を露光し、且つ現像処理を室温で４５秒間行った以外は、実施例３と同様の手法にて、直径８０μｍで、細孔間の幅が１５０μｍの、複数の細孔を有する実施例６のマイクロアレイ用細孔板を得た。実施例６のマイクロアレイ用細孔板の電子顕微鏡による写真を図４（４）に示す。
　また、実施例６のマイクロアレイ用細孔板の表面の水での接触角（２３℃、一気圧）は、１００°であった。 [Example 6]
In Example 3, except that exposure light of 200 mJ / cm 2 was exposed and development processing was performed at room temperature for 45 seconds, the same method as in Example 3 was used, and the diameter was 80 μm and the width between pores was 150 μm. Thus, a microarray pore plate of Example 6 having a plurality of pores was obtained. A photograph taken with an electron microscope of the microarray pore plate of Example 6 is shown in FIG.
Further, the contact angle (23 ° C., 1 atm) of the surface of the microarray pore plate of Example 6 with water was 100 °.
　１１１…ベース基板、１１２…第１感光性膜、１１３…第２感光性膜、１２１および１２２…潜像、１２３…露光光、１２４…マスク、１３１…親水性を有する側壁面、１３２…親油性を有する側壁面、１３３…パターン化膜、１３４…細孔、２１１…バッファー液、２２１…ポリマー膜、３０１…側壁面の新油性となる場所、３０２…細孔の開口部、３０３…細孔の深さ、３０４…細孔の直径 DESCRIPTION OF SYMBOLS 111 ... Base substrate, 112 ... 1st photosensitive film | membrane, 113 ... 2nd photosensitive film | membrane, 121 and 122 ... Latent image, 123 ... Exposure light, 124 ... Mask, 131 ... Side wall surface which has hydrophilic property, 132 ... Lipophilicity ,..., Patterned film, 134... Pore, 211... Buffer solution, 221... Polymer film, 301. Depth, 304 ... Diameter of pore

Claims (12)

  1. （１）ベース基板上に第１感光性膜を形成し、前記第１感光性膜上に親油性付与成分を含有する第２感光性膜を形成する工程、
    （２）前記第１感光性膜および前記第２感光性膜を選択的に露光する工程、ならびに
    （３）露光後の第１感光性膜および露光後の第２感光性膜を現像する工程
    を有する、少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板の製造方法。     (1) forming a first photosensitive film on a base substrate and forming a second photosensitive film containing a lipophilic component on the first photosensitive film;
    (2) a step of selectively exposing the first photosensitive film and the second photosensitive film, and (3) a step of developing the first photosensitive film after exposure and the second photosensitive film after exposure. A method for producing a porous plate having at least one fine pore, wherein at least a part of the side wall surface of the fine pore has lipophilicity.
  2. 　前記親油性付与成分が、（Ｅ２）シリコーン系界面活性剤である請求項１の細孔板の製造方法。 The method for producing a porous plate according to claim 1, wherein the lipophilic component is (E2) a silicone-based surfactant.
  3. 　前記露光前の第２感光性膜が、（Ａ２）重合体、（Ｂ２）光ラジカル発生剤、（Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物、（Ｄ２）溶剤および（Ｅ２）シリコーン系界面活性剤を含有する感光性組成物から得られる塗膜である請求項２の細孔板の製造方法。 The second photosensitive film before exposure is (A2) a polymer, (B2) a photoradical generator, (C2) a compound having at least one ethylenically unsaturated bond, (D2) a solvent, and (E2) a silicone system. The method for producing a pore plate according to claim 2, wherein the film is a coating film obtained from a photosensitive composition containing a surfactant.
  4. 　前記露光前の第１感光性膜が、親水性付与成分を含有する請求項１～３のいずれか一項の細孔板の製造方法。 The method for producing a perforated plate according to any one of claims 1 to 3, wherein the first photosensitive film before exposure contains a hydrophilicity imparting component.
  5. 　前記親水性付与成分が、（Ａ１）水酸基を有する重合体である請求項４の細孔板の製造方法。 The method for producing a porous plate according to claim 4, wherein the hydrophilicity-imparting component is (A1) a polymer having a hydroxyl group.
  6. 　前記露光前の第１感光性膜が、（Ａ１）水酸基を有する重合体、（Ｂ１）光ラジカル発生剤、（Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物および（Ｄ１）溶剤を含有する感光性組成物から得られる塗膜である請求項５の細孔板の製造方法。 The first photosensitive film before exposure contains (A1) a polymer having a hydroxyl group, (B1) a photoradical generator, (C1) a compound having at least one ethylenically unsaturated bond, and (D1) a solvent. The method for producing a porous plate according to claim 5, which is a coating film obtained from the photosensitive composition.
  7. 　前記細孔板が、マイクロアレイ用である請求項１～６のいずれか一項の細孔板の製造方法。 The method for producing a pore plate according to any one of claims 1 to 6, wherein the pore plate is for a microarray.
  8. 　請求項３または７の細孔板の製造方法に用いられる感光性組成物であり、
    （Ａ２）重合体、
    （Ｂ２）光ラジカル発生剤、
    （Ｃ２）少なくとも１つのエチレン性不飽和結合を有する化合物、
    （Ｄ２）溶剤、および
    （Ｅ２）シリコーン系界面活性剤
    を含有する感光性組成物。     A photosensitive composition used in the method for producing a pore plate according to claim 3 or 7,
    (A2) polymer,
    (B2) a photo radical generator,
    (C2) a compound having at least one ethylenically unsaturated bond,
    (D2) A photosensitive composition containing a solvent and (E2) a silicone-based surfactant.
  9. 　請求項６または７の細孔板の製造方法に用いられる感光性組成物であり、
    （Ａ１）水酸基を有する重合体、
    （Ｂ１）光ラジカル発生剤、
    （Ｃ１）少なくとも１つのエチレン性不飽和結合を有する化合物、および
    （Ｄ１）溶剤
    を含有する感光性組成物。     A photosensitive composition used in the method for producing a porous plate according to claim 6 or 7,
    (A1) a polymer having a hydroxyl group,
    (B1) a photo radical generator,
    (C1) A photosensitive composition containing a compound having at least one ethylenically unsaturated bond, and (D1) a solvent.
  10. 　請求項１～７のいずれか一項の細孔板の製造方法によって製造される、少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板。 A pore plate produced by the method for producing a pore plate according to any one of claims 1 to 7, having at least one pore, wherein at least a part of the side wall surface of the pore has lipophilicity.
  11. 　少なくとも１つの細孔を有し、前記細孔の側壁面の少なくとも一部が親油性を有する細孔板であり、親油性を有する側壁面の表面がシリコン原子を含有する細孔板。 A pore plate having at least one pore, wherein at least a part of the side wall surface of the pore is lipophilic and the surface of the lipophilic side wall surface contains silicon atoms.
  12. 　請求項１０または１１の細孔板と、
    　直径５００ｎｍ以下の貫通孔を少なくとも一つ有するポリマー膜と
    を有し、前記ポリマー膜が、前記細孔板の細孔を覆うように形成されているマイクロアレイ用基板。     A pore plate according to claim 10 or 11,
    And a polymer film having at least one through-hole having a diameter of 500 nm or less, wherein the polymer film is formed so as to cover the pores of the pore plate.
PCT/JP2011/069418 2010-09-30 2011-08-29 Method for producing porous plate for microarray or the like, photosensitive composition used for the method, porous plate for microarray or the like, and substrate for microarray WO2012043109A1 (en)

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