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WO2006129800A1 - Agent de traitement de surface pour la formation d'un dessin - Google Patents

Agent de traitement de surface pour la formation d'un dessin Download PDF

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Publication number
WO2006129800A1
WO2006129800A1 PCT/JP2006/311111 JP2006311111W WO2006129800A1 WO 2006129800 A1 WO2006129800 A1 WO 2006129800A1 JP 2006311111 W JP2006311111 W JP 2006311111W WO 2006129800 A1 WO2006129800 A1 WO 2006129800A1
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Prior art keywords
group
monomer
surface treatment
fluorine
treatment agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2006/311111
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English (en)
Japanese (ja)
Inventor
Masamichi Morita
Takuji Ishikawa
Tsuneo Yamashita
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2007519089A priority Critical patent/JP4924424B2/ja
Publication of WO2006129800A1 publication Critical patent/WO2006129800A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

  • the present invention relates to a surface treatment agent for producing a pattern surface having lyophilic area and liquid repellent area force by a photolithography method.
  • Rf groups fluoroalkyl groups
  • JP-A-203-03300323 copolymers of Rf group-containing monomers and crosslinkable functional group-containing monomers
  • Rf group-containing monomer if a long-chain Rf group having 8 or more carbon atoms is used for the Rf group-containing monomer, there is a concern about the problem of accumulation in the environment and living body.
  • Rf group-containing compounds having long chain Rf groups with 8 to 12 carbon atoms which have been widely used as surface treatment agents to impart high water and oil repellency to substrates, have recently been Problems with accumulation in the living body have been pointed out.
  • telomers are synonymous with long-chain Rf groups. We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. And
  • an Rf group-containing compound having a short-chain Rf group having 1 to 6 carbon atoms is used as a water / oil repellent.
  • An object related to the first gist of the present invention is to provide a pattern forming surface treatment agent that has a sufficiently high water and oil repellency in a liquid repellent region even if it has a short-chain Rf group having 6 or less carbon atoms. Is to provide.
  • the purpose of the second aspect of the present invention is to form a small liquid repellent region on a substrate by a non-contact microdroplet discharge method, and the liquid repellent region must use a long-chain Rf group-containing compound.
  • Another object of the present invention is to provide a method for producing a patterned substrate having high liquid repellency.
  • the present invention provides a surface treatment agent for photolithography which also has a specific fluorine-based monomer and Z or a specific fluorine-based polymer power.
  • the present invention provides a surface treatment agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of the following fluorine-based monomer (A) and fluorine-based polymer (B). .
  • (A-2) a fluorine-containing cinresesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group
  • the fluoroalkyl group having 1 to 6 carbon atoms and the polymerizable group are SO (CH 3) (where n is 1 to 1
  • the fluorine monomer may be a mixture of the above two types (for example, a combination of monomer (A-1) and monomer (A-4))! /.
  • the present invention provides an electromagnetic wave curable composition
  • a pattern consisting of at least two different areas of different surface free energy is formed on the substrate by discharging it onto the substrate using a contact microdroplet discharge method and irradiating and curing the fine coating film with electromagnetic waves.
  • a method of manufacturing a pattern substrate to be formed is also provided.
  • the surface treatment agent of the present invention forms a patterned film exhibiting high water and oil repellency on a substrate.
  • ⁇ -substituted attalylate having a fluoroalkyl group having 1 to 6 carbon atoms (A-1), a polymerizable monomer having a perfluoropolyether group (3-3), a fluoroalkyl group having 1 to 6 carbon atoms And the polymerizable group are linked by SO (CH) (where n is 1 to 10, especially 3 to 6)
  • X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 ⁇ group (where X 1 and X 2 are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom ), Ciano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or straight chain having 1 to 20 carbon atoms Or branched alkyl group
  • Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group.
  • Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or at least selected from the group consisting of repeating units: —CFO—, —CFO and —CF 2 O—force.
  • a polymerizable group for example, a carbon-carbon double bond group
  • a fluoroalkyl group that is, instead of 0—Y—
  • Y 1 is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or cyclic.
  • An alkyl group, a is 0 or 1; ), -CH CH (OR U ) CH— group (where R U is a hydrogen atom)
  • n is O to 10
  • p is 0 or 1.
  • the monomers (A-1), (A-3), and (A-4) are represented by the formula:
  • examples of X are hydrogen and a methyl group in addition to the above atoms and groups.
  • the polymerizable monomer (A-3) and the polymerizable monomer (A-4) are monomers having a polymerizable group.
  • the polymerizable group may be a carbon-carbon group (for example, an ethenyl group) bonded by a double bond.
  • the polymerizable monomers (A-2) to (A-4) are atalates that are substituted at the ⁇ -position (that is, the ⁇ -position is not hydrogen or an alkyl group) [similar to the monomer (A-1)]. May be. Alternatively, it may be an acrylate having a hydrogen atom or a methyl group at the ⁇ -position.
  • the Rf group has 1 to 6, for example, 1 to 5, preferably 4.
  • the number of carbons having both liquid repellency and compatibility is 4. From the viewpoint of bioaccumulation, 4 is preferable to 6 carbon atoms.
  • F column of Rf group is one CF, -CF CF, -CF CF CF, one CF (CF), one CF CF CF C
  • Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or a cyclic fat.
  • Group or araliphatic group CH CH N (Ri) SO— group (where R 1 is an alkyl group having 1 to 4 carbon atoms), C
  • Aliphatic groups are alkylene groups (especially 1 to 4 carbon atoms, for example
  • aromatic group and the cycloaliphatic group may be either substituted or unsubstituted. -CH CH NCR ⁇ SO—group and
  • the atom bonded to Rf is the carbon atom in the methylene group.
  • a sulfur atom in a sulfone group but generally a sulfur atom in a sulfone group.
  • Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms or a small number selected from the group consisting of repeating units: —C F O, C F O and —CF O—
  • the fluorine-containing silsesquioxane monomer (A-2) containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group comprises (i) a fluorine-containing incompletely condensed silsesquioxane and (ii) a polymerizable functional group. It is obtained by reacting with a reactive silane having a group.
  • the fluorine-containing incompletely condensed silsesquioxane (i) is an incompletely condensed silsesquioxane having a fluoroalkyl group.
  • Silsesquioxane is also called POSS (Polyhedral Oligomeric Silsesquioxane).
  • silanol group of incompletely condensed silsesquioxane (i) is highly reactive and generally there are 1 to 3 silanol groups in the molecule.
  • the reactive silane (ii) having a polymerizable functional group has a polymerizable functional group and a reactive group.
  • examples of the polymerizable functional group include a (meth) acryl group, an alpha-substituted acryl group, an epoxy group, and a bur group.
  • examples of the reactive group are a trichlorosilyl group and a trialkoxysilyl group (the alkoxy group has 1 to 5 carbon atoms).
  • the reactive silane (ii) is, for example, represented by the general formula:
  • a 11 is a polymerizable functional group
  • a 21 is a direct bond or an alkyl group having 1 to 20 carbon atoms (for example, 1 to 10), and A 31 is a halogen atom (for example, chlorine atom and bromine atom) or an alkoxy group (the number of carbon atoms in the alkoxy group). Is 1-5.) ]
  • fluorine-containing silsesquioxane monomer (a) examples are as follows.
  • the fluoropolymer (B) is a copolymer
  • the fluoromonomer (B-1) unsaturated organic acids (B-2) and high softening point monomers (B-3) can be mentioned as copolymerization monomers to be copolymerized with the same fluorine-based monomer (A).
  • the fluorine-based polymer (B) is, for example,
  • (B2) a copolymer of a fluorine-based monomer (B-1) and an unsaturated organic acid (B-2), or
  • the unsaturated organic acid (B-2) is a monomer having at least one carbon-carbon double bond and at least one acid group [eg, carboxyl group (COOH group)].
  • unsaturated organic acids are unsaturated carboxylic acids, such as free unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
  • unsaturated organic acids (B-2) are (meth) acrylic acid, bulacetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, and kaycin acid.
  • the unsaturated organic acid (B-2) imparts to the fluoropolymer (B) crosslinkability with a crosslinking agent in the electromagnetic wave irradiation region and solubility with an alkali developer in the nonelectromagnetic wave irradiation region.
  • a saturated alkyl group having an atomic ratio of 0.58 or more having an atomic ratio of 0.58 or more.
  • R 2 isoborn, born, phensil (all of which are C,, carbon atoms
  • a hydroxyl group or an alkyl group may be attached to the crosslinked hydrocarbon ring.
  • Examples of high softening point monomers ( ⁇ -3) are methyl methacrylate, phenol methacrylate, hexamethyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) Atta relay And adamantyl (meth) acrylate.
  • An example of norbornyl (meth) atarylate is
  • Examples of adamantyl (meth) atalylate are: 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3 hydroxy-1 1-adamantyl (meth) acrylate, 1 —Adamantyl at-trifluoromethyl (meth) acrylate.
  • the glass transition point and melting point are the extrapolated glass transition end temperature (T) and melting peak temperature (T) defined in JIS K7121-1987 “Method for measuring plastic transition temperature”, respectively.
  • a high-soft point monomer (B-3) having a glass transition point or a melting point of 100 ° C or higher in the homopolymer state is used as the repeating unit of the fluoropolymer (B)
  • the substrate is heat-treated.
  • the liquid repellency of the fluorine-based monomer (B-1) is improved.
  • Macromonomer (A-5) as fluorinated monomer (B-1) and unsaturated organic acid monomer (B
  • COO (CH2) 3S02C4F9 is exemplified.
  • the degree of polymerization n of the fluorinated monomer in the macromonomer is preferably 5 to 20, particularly preferably 5 to 10.
  • the fluorine-based polymer (B), which is the binary or ternary copolymer, is particularly preferably a composition comprising a crosslinking agent (C), a photocrosslinking catalyst (D), and a diluent ⁇ . I like it.
  • the weight ratio of the fluorine-based monomer ( ⁇ -1) to the unsaturated organic acid ( ⁇ -2) is 60:40 to 98: 2, and the special weight ratio is 80:20 to 95: 5.
  • the amount of the high soft spot monomer ( ⁇ -3) may be 0 to 90% by weight, for example 1 to 80% by weight, in particular 10 to 70% by weight, based on the copolymer. .
  • Fluoropolymer ( ⁇ ) is, for example, Fluorine monomer (B- 1) 20 to 80 weight 0/0,
  • High softening point monomer (B-3) 10-70% by weight
  • the fluorine-based monomer (B-1) is 20 to 80% by weight, the liquid repellency is high and the compatibility with other components constituting the surface treatment agent for photolithography is good.
  • the unsaturated organic acid monomer (B-2) is 5 to 30% by weight, the crosslinking property with the crosslinking agent in the electromagnetic wave irradiation region is good, and the solubility with the alkali developer in the non-electromagnetic wave irradiation region is good.
  • liquid repellency is good.
  • the high softening point monomer (B-3) is 10 to 70% by weight, the effect of dimensional stability is good and the liquid repellency is good.
  • the monomer (B-2) When a monomer having a hydroxyl group such as hydroxypropyl (meth) ate is copolymerized (for example, in the range of 0.1 to 30% by weight, particularly in the range of 0.5 to 25% by weight), the monomer (B-2) This has the effect of enhancing the cross-linking property with the cross-linking agent in the electromagnetic wave irradiation region and the solubility with the alkali developer in the non-electromagnetic wave irradiation region.
  • a monomer having a hydroxyl group such as hydroxypropyl (meth) ate
  • Fluorine-based polymer is a copolymer of (B), optionally ⁇ - methacryloxypropyl trimethoxysilane silane group-containing monomer represented (e.g., 0.1 to 30 weight 0/0) co Polymerization You may do it.
  • ⁇ - methacryloxypropyl trimethoxysilane silane group-containing monomer represented (e.g., 0.1 to 30 weight 0/0) co Polymerization You may do it.
  • the present invention uses a fluorine monomer ( ⁇ ) or a fluorine polymer ( ⁇ ) to form a plurality of regional forces having different surface free energies, for example, by the following method.
  • No pattern substrate in other words, a patterned substrate composed of a plurality of patterned lyophobic and lyophilic regions (hereinafter simply referred to as “pattern substrate”).
  • Fluoropolymer ( ⁇ ) is dissolved in Diluent C.
  • this fluoropolymer solution is applied onto a substrate to form a uniform liquid-repellent film and irradiated with electromagnetic waves (for example, vacuum ultraviolet light having a wavelength of 172 nm) through a photomask, it is generated by electromagnetic energy and electromagnetic waves. Due to the acid action of ozone, only the irradiated area is photolyzed and becomes lyophilic, and a patterned substrate is obtained.
  • a photocatalytic technique may be used in combination to promote photolysis of the liquid repellent film.
  • Method (2) A composition containing a fluorine-based monomer (A), a crosslinking agent (C), and a photocrosslinking catalyst (D) (a diluent ⁇ may be added if necessary) is applied on a substrate.
  • a fluorine-based monomer A
  • C crosslinking agent
  • D photocrosslinking catalyst
  • a pattern substrate can be obtained by removing (developing) the film in the non-irradiated region using a diluent ⁇ that is insoluble in the irradiated region and dissolves only the non-irradiated region.
  • Method (3) A fluoropolymer ( ⁇ ⁇ ⁇ ⁇ ) having a crosslinkable functional group ( ⁇ ) and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Fluoropolymer ( ⁇ ) having a crosslinkable functional group ( ⁇ ), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • the photocrosslinking catalyst (D) is dissolved in the diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated areas.
  • Method (6) Fluorine polymer ( ⁇ ) and crosslinker (C) having acid group (F), crosslinkable functional group ( ⁇ ) and silicone chain (G), photocrosslinking catalyst (D) as diluent ⁇ Dissolve in
  • F acid group
  • ⁇ crosslinkable functional group
  • G silicone chain
  • D photocrosslinking catalyst
  • Method (7) Dissolve the fluorine-containing polymer ( ⁇ ) having an acidic group (F), the crosslinking agent (C), and the photocrosslinking catalyst (D) in the diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • Unlit A pattern substrate is obtained by developing with a solvent that dissolves only the projecting region.
  • Method (8) A fluoropolymer (B) having an acidic group (F) and a silicone chain (G), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • the pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Method (9) A fluorine-based polymer ( ⁇ ) having an acidic group (F) and a crosslinkable functional group ( ⁇ ) and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Method (10) A fluorine-containing polymer ( ⁇ ) having an acidic group (F), a crosslinkable functional group ( ⁇ ), and a silicone chain (G) and a photocrosslinking catalyst (D) are dissolved in the diluent ⁇ .
  • F acidic group
  • ⁇ crosslinkable functional group
  • G silicone chain
  • D photocrosslinking catalyst
  • Method (11) A fluorine-containing polymer ( ⁇ ) having an acid dissociable group ( ⁇ ) that is converted into an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid-repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
  • a fluorine-based polymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
  • Method (13) A fluorine-containing polymer ( ⁇ ) having an acid dissociable group ( ⁇ ) that is converted to an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into an acid and becomes soluble in an alkaline aqueous solution.
  • a noturn substrate can be obtained.
  • Method (14) Dissolve an acid dissociable group (H) that is converted into an acidic group by the action of an acid, a fluorine-based polymer (B) having a silicone chain (G), and a photoacid generator (I) in a diluent ⁇ .
  • a fluorine-based polymer B
  • G silicone chain
  • I photoacid generator
  • heat treatment at about 50 to 250 ° C may be performed before (pre-beta) or after (post-beta) irradiation of electromagnetic waves.
  • PEB Post Exposure Bake
  • the cross-linking agent is a monofunctional or preferably a compound having two or more functional groups, and may be of a type force that cures by a radical polymerization reaction or a type that cures by a cationic polymerization reaction.
  • an unsaturated double bond group, an taliloyl group, a vinyl group is a functional group
  • an epoxy group, a vinyl ether group, or an oxetane group is a functional group.
  • (A) to (l) are types that cure by a radical polymerization reaction
  • (g) to (i) are types that cure by a cationic polymerization reaction.
  • (a) to (e) are those obtained by adding a (meth) attalyloyl group to rosin, and are often expressed as oligomers, base resins, prepolymers, and the like.
  • Urethane (meth) atalylate has a urethane bond and a (meth) atalyloyl group in the molecule.
  • Tris (2-hydroxyethyl) isocyanurate diatalylate, tris (2 —Hi Examples include poly [(meth) atalylooxyalkyl] isocyanurate, which is typified by droxychetyl) isocyanurate triatalylate.
  • Epoxy (meth) atalylate is obtained by adding an epoxy group with a (meth) atalyloyl group, and bisphenol A, bisphenol F, phenol novolak, and an alicyclic compound were used as starting materials. Things are common.
  • Polyester (meth) acrylate is a product obtained by adding (meth) acrylate to a polybasic acid and an ester resin having a polybasic acidity.
  • Polyhydric alcohols include ethylene glycol, 1,4 butanediol, 1,6 hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, etc.
  • Basic acid is phthalic acid
  • Adipic acid maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alk-succinic acid, and the like.
  • Polyether (meth) acrylate is a diol polyether resin with a (meth) atrelate added to it.
  • Polyethylene glycol di (meth) acrylate and polypropylene diol diol (meth) Examples include attalylate, polyethylene glycol, polypropylene glycol di (meth) acrylate, and the like.
  • Silicone (meth) acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 modified at one end or both ends with a (meth) atallyloyl group. Is done.
  • (D (meth) acrylate monomer is a monofunctional or polyfunctional alkyl (meth) atrelate, a low viscosity polyether (meth) acrylate having a viscosity of 500 mPa s (25 ° C) or less, methyl ( Meta) Atylate, Ethyl (Meth) Atylate, n-Propyl (Meth) Atalylate, Isopropyl (Meth) Atalylate, n-Butyl (Meth) Atylate, Isobutyl (Meth) Atalylate, sec— Butyl (Meth) Atalylate, t-butyl (meth) atarylate, n-pentyl (meth) atrelate, 3-methylbutyl (meth) atarylate, n-hexyl (meth) atalylate, 2-ethylyl n-hexyl (meth) Atalylate, n-oct
  • Epoxy monomers are glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolak, cresolol novolak; alcohols such as butanediol, polyethylene glycol, and polypropylene glycol.
  • Ethers epoxy monomers such as glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid, and oligomers or alicyclic epoxides thereof.
  • bisphenol A glycidyl ether monomer or oligomer can be preferably used.
  • Epico ⁇ 828 (molecular weight 380), Epico ⁇ 834 (molecular weight 470), Epico ⁇ 1001 (molecular weight 900), Epico ⁇ 1002 (molecular weight 1,060), Epico Illustrative are 1055 (molecular weight 1,350) and Epico 100 100 (molecular weight 2,900).
  • the butyl ether monomer includes 2 hydroxyethyl vinyl ether, 4 hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, cis 1,1,3 trimethyl 5 vinyloxycyclohexane, trans 1, 1, 3 Trimethyl mono 5 -Buroxycyclohexane, 1—Isopropyl-4 methyl-2-Buroxy chlorohexane, 2 Buroxy 7—Oxabicyclo [3.2.1] octane-6one, 2 Methyl 2— Buloxiadamantane, 2-Ethyl 2—Buloxiadamantane, 1, 3 Bis (Buroxy) adamantane, 1—Buroxiadamantanol, 3—Buroxydamantanol, 1, 3 , 5 Tris (Buroxy) adamantane, 3, 5 Bis (Buroxy), 1 Adamantanol, 5 Buruoxy 1, 3 Ada Manta Diol, 1, 3,
  • oxetane-based monomers are 1,4 bis ⁇ [(3-ethyl-3-oxeta-l) methoxy] ethyl ⁇ benzene (Aronoxetane OXT-121) manufactured by Toagosei Co., Ltd., 3-ethyl 3-hydroxymethyloxetane ( Examples include Tolonsei Alonoxetane OXT-101).
  • an acid crosslinking agent may be used as the crosslinking agent.
  • the acid crosslinking agent includes a plurality of (for example, 2 to 10) reactive groups (for example, carboxylic acid, hydroxyl group, amino group, isocyanate group, N-methylol group, alkyl ether group N—) that crosslink with an acidic group in one molecule.
  • amino succinic acid examples include compounds obtained by hydroxymethylating a part or all of amino groups such as melamine compounds, guanamine compounds and urea compounds, or hydroxyl groups of the hydroxymethylated compounds.
  • various amino coffins of imino type examples include compounds obtained by hydroxymethylating a part or all of amino groups such as melamine compounds, guanamine compounds and urea compounds, or hydroxyl groups of the hydroxymethylated compounds.
  • Epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol 'novolac type epoxy resin, talesol' novolac type epoxy resin, trisphenol methane type epoxy resin, bromine Glycidyl etherols such as epoxidized epoxy resin, 3, 4 epoxycyclohexenolemethinole 3, 4-epoxycyclohexane strength ruboxylate, bis (2, 3 epoxycyclopentyl) ether, etc.
  • Glycidyl esters such as diglycidinolehexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate, glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylvalaminophenol, triglycidyl isocyanurate, etc.
  • glycidyl esters such as diglycidinolehexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate, glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylvalaminophenol, triglycidyl isocyanurate, etc.
  • glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylval
  • the oxazoline compounds include 2-bi-ro 2-oxazoline, 2-bi-ro 4-methyl lu 2--oxazoline, 2-vinyl 5--methyl-2-oxazoline, 2-isopropenyl lu 2-oxazoline, 2-iso-probe 4 methyl 2-oxazoline And a copolymer of polymerizable monomers such as
  • the curing speed is improved.
  • the amount of the multi-sensitive thiol may be, for example, 0.1 to 20 parts by weight, for example 1 to 10 parts by weight with respect to 100 parts by weight of the crosslinking agent.
  • the cross-linking agent When used in combination with a fluorinated monomer, the cross-linking agent is 1 to LOO, 000 parts by weight, particularly 10 to L00, 000 parts by weight with respect to 100 parts by weight of the fluorinated monomer.
  • the fluorine-based polymer When used in combination with a fluorine-based polymer, it is 1 to L00 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the fluorine-based polymer.
  • the photocrosslinking catalyst examples include a radical photopolymerization initiator and a photoacid generator.
  • Radical photopolymerization initiators are compounds that generate radicals by light, such as OC-diketones such as benzyl and diacetyl, acyloines such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • Thiaxanthones such as thixanthone, 2, 4 jetylthioxanthone, thixanthone 4-sulfonic acid, benzophenone, 4, 4, monobis (dimethylamino) benzophenone, 4, Benzophenones such as 4, 1-bis (jetylamino) benzophenone, acetophenone, 2- (4 toluenesulfo-ruxoxy) 2 pheulacetophenone, p dimethylaminoacetophenone, 2, 2, -dimethoxy 2-phenol-lucacetophenone, p-methoxya Cetofenones such as cetophenone, 2 methyl [4 (methylthio) phenol] 2 morpholino 1 propanone, 2 benzil 2-dimethylamino 1- (4-morpholinophenol) 1-butane 1-one, To quinones such as anthraquinone and 1,4 naphthoquinone, 2 ethyl dimethylaminobenzoate
  • a photoacid generator is a material that generates acid by reacting with light.
  • PAG is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating light of a specific wavelength to PAG with such a structure, PAG is excited and the acid precursor part begins. Generates acid.
  • PAG is, for example, diazonium salt, phospho-um salt, sulfo-um salt, iodonium salt, CF SO p—CH PhSO p—NO PhSO
  • Examples thereof include sulfonyl chloride or sulfonic acid ester.
  • the organic halogen compound is a compound forming a halogen hydrohydroacid, and such compounds are disclosed in US Pat. No. 3,515,551, US Pat. No. 3,536,489, US Pat. , 779, 778 and West German Patent Publication No. 2,243,621, etc. (the disclosures of which are incorporated herein).
  • the amount of the photocrosslinking catalyst is 0.1 to 20 parts by weight, particularly 1 to 100 parts by weight of the fluorine monomer and the crosslinking agent, or the fluorine polymer, or the fluorine polymer and the crosslinking agent in total. ⁇ 10 parts by weight.
  • the fluoropolymer (B) When used in combination with a photocrosslinking catalyst, the fluoropolymer (B) comprises a crosslinkable functional group (E), an acidic group (F), and an acid dissociable functional group (H) that is converted into an acidic group by the action of an acid. It preferably has at least one group selected from the group consisting of The fluoropolymer (B) may further have a silicone chain (G).
  • the crosslinkable functional group imparted to the fluorine-based polymer is an unsaturated double bond group such as an allyloyl group or a buyl group as a type that cures by radical polymerization reaction, and an epoxy type that cures by a cationic polymerization reaction.
  • Group, oxetane group and the like are exemplified. It may also be a reactive group that crosslinks with an acidic group, for example, a carboxylic acid, a hydroxyl group, an amino group, an isocyanate group, an N-methylol group, an alkyl etherified N-methylol group, etc.
  • the method of imparting a crosslinkable functional group is: (1) A method in which a monomer having a crosslinkable functional group is synthesized in advance and copolymerized with a fluorinated monomer.
  • the amount of the crosslinkable functional group in the fluoropolymer is generally from 0.1 to 20 mol%, particularly from 1 to LOm, based on the total number of the repeat units in the polymer. ol%.
  • acidic groups are carboxyl groups, hydroxyl groups (particularly phenolic hydroxyl groups), and sulfonic acid groups.
  • a method for adding an acidic group to a fluorine-based polymer includes:
  • examples of the monomer having an acidic group include the following.
  • examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
  • examples of the monomer having a hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • one or more hydrogen atoms of these benzene rings alkyl groups such as methyl, ethyl and n -butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms and one or more hydrogen atoms of alkyl groups Haloalkyl group substituted with a halogen atom, nitro group, cyano group, and compounds substituted with amide group.
  • Examples of monomers having a sulfonic acid group include butyl sulfonic acid, styrene sulfonic acid, (meth) aryl sulfonic acid, 2-hydroxy-3- (meth) aryloxypropane sulfonic acid, (Meth) acrylic acid—2-sulfoethyl, (meth) acrylic acid—2-sulfopropyl, 2-hydroxy-3— (meth) talyloxypropane sulfonic acid, 2 -— (meth) acrylamide—2-methylpropane
  • Examples include sulfonic acids and their salts. These may be used alone or in combination of two or more.
  • a composition distribution occurs in the copolymer due to the difference in reactivity between the fluorine-based monomer and the monomer having an acidic group, which may adversely affect the patterning.
  • a structure in which the structure of the bull group of the fluorinated monomer is the same as that of the monomer having an acidic group For example, when a-C1 acrylate containing an Rf group is used as a fluorine-based monomer, it is preferable to use a-C1 acrylic acid as a monomer having an acidic group.
  • the amount of acidic groups in the fluoropolymer is generally 0.1 to 20 mol%, particularly 1 to LOmol%, based on the total number of repeating units in the polymer.
  • the silicone chain (G) is dimethylpolysiloxane having a molecular weight of 1,000 to 10,000.
  • the method of adding a silicone chain to the fluoropolymer is as follows:
  • the silicone (meth) phthalate described in the crosslinking agent (C) may be used.
  • the amount of silicone chain in the fluoropolymer is generally 0.1 to 50 mol%, especially 1 to LOmol%, based on the total number of repeating units in the polymer.
  • Acid-dissociable functional groups that can be converted to acidic groups by the action of acid are t-butoxycarbol (t-BOC), isopropoxycarbol, tetrahydrobiral, trimethylsilyl, t-butoxycarboromethyl Group or protected with these acid-dissociable functional groups Examples include phenolic hydroxyl groups.
  • a method for imparting an acid-dissociable functional group to a fluoropolymer is as follows.
  • the amount of acid-dissociable functional groups in the fluoropolymer is generally 0.1 to 50 mol%, particularly 1 to 10 mol%, based on the total number of repeating units in the polymer. .
  • a water-soluble organic solvent an organic solvent (especially an oil-soluble organic solvent), water
  • the diluent is the same as that used for producing the fluoropolymer.
  • the diluent is inert and dissolves in the fluorinated monomer (A) or the fluorinated polymer (B).
  • Examples of diluents include water-soluble organic solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ethenore acetate, dipropylene glycol.
  • the diluent is used in a range of 50 to 2000 parts by weight, for example, 50 to L000 parts by weight, with respect to 100 parts by weight of the total of the fluorine-based monomer (A) or fluorine-based polymer (B).
  • a fluorine-type polymer can be manufactured as follows. A method is adopted in which a monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization catalyst is added and the mixture is stirred in the range of 20 to 120 ° C. for 1 to 20 hours.
  • the solvent an organic solvent, a water-soluble organic solvent, water or the like can be used, and it is the same as the diluent ⁇ .
  • the solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of monomers.
  • a chain transfer agent such as mercaptans and alkyl halides may be added.
  • Mercaptans include ⁇ -butyl mercaptan, ⁇ -dodecyl mercaptan, t-butyl mercaptan, thioglycolic acid ethyl, 2-glycolyl thioglycolate, 2-mercaptoethanol, isooctyl mercapto acid, thioglycolic acid, 3-
  • the halogenated alkyls such as mercaptopropionic acid, methoxybutyl thioglycolate, and silicone mercaptan (KF-2001, manufactured by Shin-Etsu Chemical) include black mouth form, carbon tetrachloride, and carbon tetrabromide. These may be used alone or in combination of two or more.
  • the weight average molecular weight of the fluoropolymer may be, for example, 1,000 to 500,000, particularly 2,000 to 100,000, and the special IJ may be 3,000 to 20,000.
  • the weight average molecular weight of the fluorinated positive mer is determined by GPC (gel permeation chromatography) (standard polystyrene conversion).
  • GPC gel permeation chromatography
  • a monomer having a fluoroalkyl group having 8 to 12 carbon atoms as required for example, perfluorooctylethyl acrylate
  • a polymer having this monomer as a repeating unit may be blended.
  • Non-fluorine polymer may be used in combination with the surface treatment agent for photolithography of the present invention.
  • Non-fluorinated polymers are, for example, alkali-soluble resins, such as Japanese Patent No. 2505033, Japanese Patent Application Laid-Open No. 3-170554, Japanese Patent Application Laid-Open No. 6-118646, Novolak type phenol resin, Japanese Patent Application Laid-Open No. No.
  • black pigments include carbon black, graphite, titanium black, iron oxide, bismuth sulfide, and perylene black.
  • an acid scavenger may be added to the photolithography surface treatment agent of the present invention to control the diffusion of the acid generated from the acid generator in the film.
  • organic amines, basic ammonium salts, basic sulfo salt, etc. are used, so long as they do not sublimate or deteriorate the resist performance.
  • organic amines are preferred because of their excellent image performance.
  • JP-A-63-149640 JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683 JP-A-5-289340, JP-A-5-232706, JP-A-5-257282, JP-A-6-24 2605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110.
  • the acid scavenger is preferably 1,5 diazabicyclo [4. 3. 0] — 5 nonene, 1, 8-diazabicyclo [5. 4. 0] — 7 undecene, 1, 4 diazabici [2. 2.
  • octane 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4, 4, diaminodiphenyl ether, Pyridinium p-toluenesulfonate, 2, 4, 6 trimethylpyridium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine, etc. Can be mentioned. Among these, 1,5 diazabicyclo [4. 3.
  • octane 4 dimethylamino Organic amines such as pyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine, and tributylamine are preferred.
  • additives are used in the surface treatment agent for photolithography of the present invention as necessary.
  • fluorine-based, silicone-based, hydrocarbon-based surfactants for improving film smoothness for improving film smoothness
  • silane coupling agents for improving film adhesion for improving film adhesion
  • titanate coupling agents etc.
  • Heat polymerization inhibitors for improving film adhesion
  • UV absorbers for improving film adhesion
  • antioxidants for suppressing dark reactions
  • antifoaming agents are used in the surface treatment agent for photolithography of the present invention as necessary.
  • the base material used for the substrate of the present invention is silicon, synthetic resin, glass, metal, ceramics, etc. It is.
  • the synthetic resin may be either a thermoplastic resin or a thermosetting resin, for example, polyolefins such as polyethylene, polypropylene, ethylene prepylene copolymer, ethylene butyl acetate copolymer (EVA), Cyclic polyolefin, modified polyolefin, polychlorinated butyl, polychlorinated polyvinylidene, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly (4 methylbenten 1), ionomer, acrylic resin, polyethylene methacrylate, Acrylic styrene copolymer (AS resin), butadiene styrene copolymer, Polio copolymer (EVOH), Polyethylene terephthalate (PET), Polypropylene terephthalate (PBT), Polycyclohexane terephthalate (PCT), etc.
  • polyolefins such as polyethylene, polypropylene, ethylene prepylene cop
  • TEL polyetherketone
  • PEEK Reether ether ketone
  • polyetherimide polyacetal
  • polyphenylene oxide modified polyphenylene oxide
  • polyarylate aromatic polyester (liquid crystal polymer)
  • fluoroelastomers styrenes, polyolefins, polyvinyl chlorides, polyurethanes, fluororubbers, chlorinated polyethylenes, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, Melamine resin, unsaturated polyester, silicone resin, polyurethane, etc., or their main copolymers, blends, polymer alloys, etc. are mentioned, and one or more of these are combined. (For example, as a laminate of two or more layers). If a synthetic resin substrate is used, the substrate can be provided with features such as light weight, transparency, low cost, and bending.
  • Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda ash glass, potassium lime glass, lead (alkali) glass, norium glass, borosilicate glass, and the like.
  • Ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), sulfites ( Examples thereof include carbide (eg, cadmium sulfate), carbide (eg, carbide), and a mixture thereof may be used.
  • pretreatment such as plasma treatment or UV ozone treatment is performed. It is okay.
  • lyophilic functional groups for example, OH groups, COOH groups, NH groups
  • the shape of the pattern surface may be a circle, a rectangle, a triangle, a straight line, a curve, etc., as long as an appropriate one is selected according to the purpose of the element to be finally manufactured.
  • the patterns can be touching or distant.
  • the line width and line spacing may be 0.5 to: LOO m, for example, 120 m.
  • the line widths may be equally spaced or the widths may vary.
  • the shape of the line may be a straight line or a curve.
  • the surface treatment agent (fluorine-containing compound) is uniformly treated on the surface of these substrates in a liquid phase or a gas phase.
  • a known coating method can be adopted as long as the film thickness can be controlled.
  • roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted.
  • the substrate is heated at 150 ° C for 1 second to 10 minutes (eg, 110 ° C for 1 minute) to dry the solvent from the fluorine-containing compound film. Yes.
  • Pattern substrate production method (1 (11) to (14) provides a uniform liquid-repellent surface with a water contact angle of 60 ° or more, particularly 80 ° or more, without irradiation with light.
  • a liquid repellent surface having a water contact angle of 60 ° or more, particularly 80 ° or more is formed in the irradiated region.
  • the electromagnetic wave irradiated to the film in the present invention is light having a wavelength of 10 to 400 nm, such as ultraviolet (UV, 200 to 400 nm), vacuum ultraviolet (VUV, 150 to 200 nm), extreme ultraviolet (EUV, 10 to 120 nm), etc.
  • UV ultraviolet
  • VUV vacuum ultraviolet
  • EUV extreme ultraviolet
  • a commercially available xenon excimer lamp that can emit VUV with a wavelength of 172 nm can be used.
  • UV is used, a mercury xenon lamp, mercury-silver lamp, xenon lamp, or xenon excimer lamp can be used as the light source.
  • a 248 nm Kr F excimer laser, a 193 nm ArF excimer laser, and a 157 nm F2 excimer laser may be used.
  • the exposure dose may be from 1 to 10,000 mj / cm 2 , in particular from 1 to L000 mj / cm 2 .
  • X-rays with a wavelength of 0.1 to 10 nm, electron beams with a wavelength of 0.001 to 0.01 nm, and electromagnetic waves of a laser beam with a wavelength of 10 to 3 OO nm may be used!
  • the film may be irradiated with light through a photomask, or a DMD (digital micromirror device) developed by Texas Instruments, Inc.
  • DMD digital micromirror device
  • a simple semiconductor may be used to irradiate light in a pattern without a mask.
  • DMD lays out 480,000 to 1,130,000 micron-sized ultra-fine mirrors, reflects the lamp light to the mirror, and irradiates the film with light in a pattern.
  • Electron beam exposure is 10 to 10,000 ⁇ for raster drawing In shot drawing, it may be 100 to 100,0001 C / dot, particularly l, 000 to 10,000 fC / dot.
  • the solvent-soluble region may be removed, that is, so-called “development” may be performed using the contrast of solubility in the solvent after irradiation with the electromagnetic wave.
  • the solvent (developer) used for development the one used for the production of a fluoropolymer or an alkaline aqueous solution is used.
  • Alkaline aqueous solutions include inorganic alkaline aqueous solutions such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine.
  • Secondary amines such as jetylamine and di-n-pylamine; tertiary amines such as triethylamine, methyljetylamine and N-methylpyrrolidone; dimethylethanolamine and triethanolamine Any alcohol amines; quaternary ammonium salts such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, etc .; using an organic alkaline aqueous solution consisting of alkalis of cyclic amines such as pyrrole and piperidine . These can be used alone or in combination of two or more! Also, a surfactant may be added.
  • the developing method may be performed in the range of 10 seconds to 10 minutes by an immersion method, a liquid filling method, or the like.
  • the following method for producing a patterned substrate can be used.
  • an electromagnetic wave curable composition comprising a fluoromonomer-containing fluoromonomer (A), a crosslinking agent (B), and a photocrosslinking catalyst (C) is applied onto a substrate by a non-contact microdroplet discharge method.
  • a film having a microstructure is formed by discharging, and the film is cured by irradiation with electromagnetic waves.
  • Examples of the non-contact minute droplet discharge method include an ink jet method and a microdispenser method.
  • a piezo method can be used.
  • the piezo method is also used in inkjet printers because of its excellent droplet controllability and high degree of freedom in ink selection.
  • the piezo method has MLP (Multi Layer Piezo) type and MLChip (Multi Layer Ceramic Hyper Integrated Piezo segments).
  • the thermal method ink jet generates heat and generates bubbles to push out ink liquid.
  • the volume per droplet discharged by the ink jet method is 0.1 pL to ln L.
  • the physical properties at 25 ° C. of the electromagnetic wave curable composition (ink) suitable for the ink jet method are as follows. Viscosity: 1-50 mPa's, surface tension: 19-30 mN / m, boiling point: 100-250 ° C.
  • microdispenser method a tubing method or an air compression method can be used.
  • the volume per droplet discharged by the microdispenser method is generally [In 1 to 1 ⁇ m].
  • electromagnetic waves may be irradiated in an atmosphere of an inert gas such as nitrogen or argon.
  • a liquid-repellent film is formed on the surface of the substrate, and the surface free energy
  • a pattern substrate composed of a plurality of (at least two) different region forces in other words, a pattern substrate composed of at least one lyophobic region that has been turned into one and at least one lyophilic region force (hereinafter simply referred to as “pattern”).
  • pattern a pattern substrate composed of at least one lyophobic region that has been turned into one and at least one lyophilic region force
  • substrate Abbreviated as “substrate”.
  • the thickness of the liquid repellent film may generally be from lnm to 1000 ⁇ m, such as from 10 nm to 200 ⁇ m, in particular from 50 nm to 100 / ⁇ ⁇ .
  • the liquid repellent region exhibits liquid repellency of, for example, a water contact angle of 70 ° or more, particularly 80 ° or more.
  • Examples of the shape of the pattern of the liquid repellent region include straight lines, curves, circles, squares, triangles, and the like that can be selected according to the purpose of the element to be finally manufactured. Mutual patterns may be in contact or separated.
  • the width of the line may be 10 to: LOOO / zm, for example, 100 to 500 / ⁇ ⁇ .
  • the ratio of the line and the space is arbitrary, for example, 1/10 to 10/1.
  • the shape of the line can be straight or curved.
  • the functional compound solution or dispersion is applied to the substrate on which the pattern is formed.
  • the functional compound solution can be applied by spin coating, dip coating, casting, roll coating, printing, transfer, ink jet [P. Calvert, Chem. Mater., 13, 3299 (2001)], the bar code method, the one-way method.
  • a layer of the functional compound is formed on the patterned fluorine-containing compound film.
  • the layer of the functional compound can be formed by applying a solution obtained by dissolving a functional compound in a solvent on the pattern surface and removing the solvent.
  • a functional compound solution When a functional compound solution is applied to multiple areas with different surface free energies, the functional compound solution avoids areas with a water contact angle of 60 ° or more, especially 80 ° or more, and has a water contact angle of 50 ° or less, especially 3 Adheres only to areas below 0 °.
  • a layer of functional compound is formed on the lyophilic region patterned on the substrate.
  • Examples of the functional compound include a semiconductor compound, a conductive compound, a dye or pigment for forming a display pixel, a photochromic compound, a thermochromic compound, a lens material, a life science drug, and the like.
  • Organic compounds are preferred as semiconductor compounds, for example, pentacene derivatives, polythiophene derivatives, phthalocyanine derivatives, polyfluorene derivatives, poly (p-fluoro-lenbi-re). And layered herosky toy compounds.
  • the conductive compound has a conductivity of 10 2 S / cm or more at room temperature.
  • a conductivity 10 2 S / cm or more at room temperature.
  • polyacetylene derivatives, polythiophene derivatives, polypyrrole, poly p-phenylene vinylene, polyarine and the like can be mentioned. Conductivity may be improved by doping these compounds.
  • nanoparticles in which nanoparticles such as gold, silver and copper are dispersed in a liquid can be mentioned.
  • the photochromic compound is preferably an organic compound, for example, an azobenzene derivative, a spiropyran derivative, a fulgide derivative, a diarylethene derivative, or the like.
  • a thermochemical compound is a general term for compounds in which the color of a substance changes reversibly with changes in temperature.For example, salicylidene dilins, polythiophene derivatives, tetrahalogeno complexes, ethylene diamine derivative complexes, dinitrodiammine copper complexes. 1,4-diazasic octane (daco) complex, hexamethylenetetramine (hmta) complex, saltyl aldehyde (sa len) complex and the like.
  • the thickness of the functional compound layer may be 0.1 nm to 100 ⁇ m, for example, 1 nm to 1 ⁇ m.
  • Examples of the solvent that dissolves the functional compound are an organic solvent (particularly an oil-soluble organic solvent), a water-soluble organic solvent, and water.
  • an organic solvent especially an oil-soluble organic solvent
  • a water-soluble organic solvent especially an oil-soluble organic solvent
  • water especially an oil-soluble organic solvent
  • the solvent that dissolves the functional compound is preferably an organic solvent having a surface tension of 40 mNZm or less, for example, 30 mN / m or less.
  • the surface tension is 40 mNZm or less, the solution can easily spread along the pattern shape.
  • Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (for example, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvents are not allowed to be fluorinated. But either is fine.
  • Specific examples of the organic solvent include perfluorodecalin, hydrated fluoroether, HCFC225, chloroformated form, 1,1,2,2-tetrachloroethane, tetrachloroethylene, cyclobenzene, butyl acetate, hexane, Examples include isopentane, toluene, xylene, and tetrahydrofuran.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl caffeosolve, cellosolve Examples thereof include acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl acetate, isopropyl alcohol, methanol, and ethanol.
  • the surface tension may be reduced by adding a surfactant or the above water-soluble organic solvent.
  • the concentration of the functional compound in the solution of the functional compound may be 0.1 to 20% by weight, for example, 1 to 10% by weight.
  • the solvent can be removed by evaporation or the like.
  • the solvent can be removed by heating the substrate (for example, 60 to 200 ° C.).
  • the solvent removal may be performed under reduced pressure (for example, 0.01-: LOOPa).
  • the substrate of the present invention can be used in a wide range of devices such as electronic, optical, medical and chemical analyses.
  • electronic devices can be used in integrated circuits such as transistors, memories, light emitting diodes (EL), lasers, and solar cells. With these device capabilities, flexible displays, wireless tags, and wearable computers are manufactured.
  • Optical devices include display pixels, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, and medical devices include DNA arrays. It can be used for biochips such as protein arrays.
  • As a chemical analysis device it can be used for micro chemical chips such as micro chemical plants and micro chemical analysis systems.
  • the surface treatment agent for photolithography of the present invention is extremely useful for the liquid repellency of a black matrix, which is necessary when producing a color filter for display by the inkjet method.
  • the inkjet method is expected as a technology for manufacturing color filters at a low cost, but the inkjet technology alone has a landing accuracy that accurately prints red, green, and blue ink in the black matrix (pixel area). Is lacking. For this reason, it is necessary to repel the upper part of the black matrix and draw back ink droplets that have been accidentally removed into the pixels. Also
  • red, green, and blue inks are injected in amounts exceeding the height of the black matrix in order to increase the pixel film thickness, the liquid repellent layer on the top of the black matrix is essential.
  • the former liquid repellency is indicated by the drop angle of the ink solution, and the latter liquid repellency is indicated by the static contact angle.
  • Fluorine gas such as CHF was adsorbed on the black matrix (JP 2000 353594).
  • the fluoropolymers disclosed in these documents have not been able to achieve both liquid repellency and compatibility with other materials forming the photosensitive composition.
  • the surface treatment agent for photolithography of the present invention has both extremely high liquid repellency and compatibility.
  • the black matrix is made liquid repellent by using the surface treatment agent for photolithography of the present invention. Two methods for doing this will be described.
  • the first method uses a black pigment dispersed in a lyophilic transparent substrate by a photolithography method using a surface treatment agent for photolithography of the present invention in which a black pigment is dispersed. It is a method of forming.
  • a surface treatment agent for photolithography at this time for example,
  • Fluoropolymer (B) having crosslinkable functional group (E) and acidic group (F) having crosslinkable functional group (E) and acidic group (F)
  • Photocrosslinking catalyst (D) 1—5% by weight 20% carbon black dispersion 10-20% by weight
  • the second method is to apply a photolithographic surface treatment agent of the present invention uniformly on a photosensitive resin black layer uniformly formed on a lyophilic transparent substrate.
  • One method is to form a lyophobic black matrix on a lyophilic transparent substrate.
  • surface treatment agents for photolithography at this time include, for example, a fluorine-based polymer (B) having an acidic group (F) 5 to 10% by weight
  • Photocrosslinking catalyst (D) 1—5% by weight
  • a red, black, or yellow pigment dispersion for color filter is applied by an ink jet method, and the solvent is removed to remove the color filter. Can be manufactured at an extremely low cost.
  • the static contact angle was obtained by dropping 2 L of microsyringe-powered water or n-hexadecane on a horizontally placed substrate and taking a still image 1 second after dropping with a video microscope. .
  • the sliding angle was determined by the following method. Drop 20 ⁇ L for water and 5 ⁇ L for n-hexadecane and propylene glycol monomethyl etherate (PGMEA) from a microsyringe onto a horizontally placed substrate, and add the substrate at a rate of 2 ° per second. It was tilted and recorded as a moving picture with a video microscope until the droplet started to fall. The video was replayed and the angle at which the droplet began to fall was defined as the falling angle.
  • PMEA propylene glycol monomethyl etherate
  • Fluorine monomer CH C (F) COOCH CH C F (abbreviation ⁇ -F) 100g, HCFC225 40 in a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirrer
  • the weight average molecular weights were 16,000, 9,000, and 15,000, respectively.
  • the substrate silicon wafer was cleaned with acetone, and then the surface was made superhydrophilic by irradiation with vacuum ultraviolet light.
  • a 1 wt% solution prepared by diluting the fluoropolymers of Production Examples 1 to 3 and Comparative Production Example 1 with HC FC225 was spin-coated on this substrate at 2000 rpm for 1 minute to obtain a film thickness (solvent Excluded film thickness)
  • An lOOnm film was prepared.
  • the static contact angle and rolling angle of this film were measured. The results are shown in Table 1.
  • the glass transition point shown is measured for Balta polymer.
  • the static contact angle is almost the same between the example and the comparative example, but the falling angle is much smaller in the example than in the comparative example, and the liquid tends to roll.
  • a photomask of line / space 10 ⁇ m / 10 ⁇ m was adhered to these films and irradiated with vacuum ultraviolet light for 10 minutes to make the irradiated region lyophilic, and the lyophobic region and lyophilic solution.
  • Example 4 bisphenol A-dihirochetyl ether diatalylate (crosslinking agent) 45% by weight, a-F (fluorine monomer) 25% by weight, both ends modified with methacryloyl groups and having a molecular weight of 5,000 Dimethylpolysiloxane (cross-linking agent) 25% by weight, 2-hydroxy-2-methyl-1 phenol propane (photopolymerization initiator) 5% by weight are mixed and dissolved, and this solution is deposited on the substrate using a doctor blade. The film was applied so that the film thickness (excluding the solvent) was 100 m. In Example 5 and Comparative Example 2, —F was replaced with ⁇ Cl and a—H, respectively.
  • Comparative Production Example 2 was obtained by replacing the fluorinated monomer of Production Example 4 with ⁇ -H.
  • the weight average molecular weight was 32,000.
  • Fluoropolymer 10% by weight in Production Example 4 or Comparative Production Example 2 acid generator WPAG-1 99 (Wako Pure Chemicals) 1% by weight, acid crosslinking agent Cymel 303 (Nippon Cytec Industries) 5% by weight, propylene glycol monomethyl ether a solution of 84 weight 0/0 and was spin-coated to form a film having a thickness (excluding the solvent! was ⁇ thickness) 5 mu m on a substrate same substrate as in example 1.
  • the irradiated region is cross-linked and becomes insoluble in the solvent.
  • 2.3 8 wt 0/0 tetramethylammonium - was developed by immersion for 1 minute in Umuhidorokishido aqueous solution, washed with water, to produce a patterned substrate made of liquid-repellent region and the lyophilic region.
  • Comparative Production Example 3 was obtained by replacing the fluorinated monomer of Production Example 5 with ⁇ -H.
  • the weight average molecular weight was 33,000.
  • fluoroatalylate CH C (Cl) COOCH CH C F (abbreviation ⁇ Cl) 50 g, methacrylolic acid 20 g
  • AdEMA 2-ethyl 2-adamantyl metatalylate
  • lauryl mercaptan 5 g
  • propylene glycol monomethyl ether acetate 300 g
  • 2,2′azobisisobutyl-tolyl lg 3 g
  • Residual monomer in reaction solution is analyzed by gas chromatography As a result, it was confirmed that the polymerization rate was 95% or more.
  • the obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer.
  • the weight average molecular weight was 11,000 (polystyrene conversion).
  • the glass transition point measured by DSC was 135 ° C. DSC temperature range and heating rate are 1 st RUN:-50-200 ° C (10 ° C / min), 2nd RUN:-50-200 ° C (10 ° C / min), and glass transition point Is the extrapolated glass transition end temperature of 2nd RUN.
  • COOCH CH C F (abbreviation a-H) replaced with production examples 7, 8, comparative production example 3 and
  • the weight average molecular weights were 9, 000, 12,000, and 10,000, respectively.
  • the glass transition points were 115 °, 87 °, and 71 °, respectively.
  • the film was developed by immersing it in a 15% aqueous solution of alkaline developer P3 disperse M (Henkel Japan) for 1 minute, washed with water, dried, and heated at 200 ° C for 1 hour. A patterned substrate consisting of regions was produced. When the pattern was observed with a field-effect scanning electron microscope (FE—SEM), in Examples 8 to 10, the line width was 10 m. A clear line pattern was formed. On the other hand, in Comparative Example 5, disorder was observed in the line shape.
  • FE—SEM field-effect scanning electron microscope
  • a colorant for a liquid crystal display color filter was applied to these pattern substrates by an inkjet method.
  • the ink jet device used Litrex 70 manufactured by Litrex
  • a uniformly hydrophilic substrate it was observed with an optical microscope that a thin film with a diameter of about 200 m was formed after solvent drying.
  • a noturn substrate was used, in Examples 8 to 10, a color thin film that was clearly split along the lyophilic region having a line width of 10 ⁇ m was formed.
  • Comparative Example 5 there were portions where a thin film was formed not only in the lyophilic region but also in the lyophobic region, and the color thin film was not completely split.
  • Production examples 9 to 20 and comparative production example 4 were obtained by replacing the fluoroatalylate and the high soft spot monomer of Production Example 6 with those shown in Table 2.
  • the relationship between compound names and abbreviations is as follows.
  • CH CHCOOCH CH C F (abbreviation C8 a— H), 2-methyl-2-adaman
  • AdMMA Tylmetatalylate
  • MMA Methylmetatalylate
  • iBMA Isovol Metatalylate
  • PhMA Phenol Metatalylate
  • NBMA Norbornyl Methyl Metatalylate
  • CHMA Cyclohe Xylmethalate
  • Examples 11 to 22 and Comparative Example 6 were obtained by replacing the fluoropolymer of Production Example 8 (Production Example 6) with Production Examples 7 to 20 and Comparative Production Example 4.
  • Noturn was observed with FE-SEM, in Examples 11 to 22, a clear line pattern having a line width of 10 m was formed.
  • Comparative Example 6 disorder was observed in the line shape.
  • a color filter colorant was applied to these patterned substrates by an inkjet method.
  • Examples 11 to 22 a force-strength film that was clearly split along the lyophilic region having a line width of 10 / z m was formed.
  • Comparative Example 6 there was a portion where a thin film was formed not only in the lyophilic region but also in the lyophobic region.
  • a solution of 82% by weight of rumonomethyl ether acetate was spin-coated on a superhydrophilic glass substrate in the same manner as in Example 1, and a film thickness (film thickness excluding the solvent) of 2 ⁇ m was formed on the substrate.
  • a patterned substrate composed of a liquid repellent region and a lyophilic region was prepared in the same manner as in Example 8 below. When Noturn was observed with FE-SEM, a clear line pattern with a line width of 10 m was formed.
  • the graft copolymer replaced with COO (CH2) 3S02C4.F9 was used as Production Example 21.
  • the weight average molecular weight was 13,000 and the glass transition point was 125 ° C.
  • Example 24 A case where the fluoropolymer (random copolymer) of Example 16 is replaced with the graft copolymer of Production Example 21 is referred to as Example 24.
  • Example 24 When the pattern was observed with FE-SEM, a clear line pattern with a line width of 10 ⁇ m was formed.
  • a color thin film clearly divided along the lyophilic region having a line width of 10 m was formed.
  • the falling angle for n-hexadecane was 10
  • the sliding angle with respect to PGMEA was 14 °, and the performance was further improved as compared with Example 16 using a random copolymer.
  • the contact angle should be measured as it is. I can't. Therefore, in order to measure the contact angle, a large area liquid repellent region was prepared by the following method.
  • the electromagnetic wave curable composition of the present invention is uniformly applied to a 3 cm ⁇ 3 cm substrate by a spin coating method (2000 rpm, 30 seconds), and the coating film is cured by irradiating with an ultraviolet ray having an integrated illuminance lOOOmjZcm 2 in a nitrogen atmosphere. It was.
  • the contact angle was measured with a fully automatic contact angle meter after dropping 2 L of water or n-hexadecane from a microsyringe onto a horizontally placed substrate.
  • HX—2A Hexanediol ditalylate
  • Table 1 shows the contact angles of this electromagnetic wave curable composition. Even water and n-hexadecane showed high liquid repellency even in the case of liquid droplets.
  • the silicon wafer was cleaned with acetone and then irradiated with vacuum ultraviolet light to make the surface superhydrophilic.
  • the film of the electromagnetic wave curable composition was cured by irradiating the substrate with ultraviolet rays having an integrated illuminance of lOOOOmjZcm 2 in a nitrogen atmosphere.
  • Example 26 pentaerythritol tetratalate (abbreviated as PEN-4A) was used.
  • TMP-3A trimethylolpropane tritalylate
  • PEN-4A pentaerythritol tetratalate
  • Example 28 [R C6) Abbreviated as talate] was used as Example 28 when Irgacure 907 was 1% by weight. In this system, when 2% by weight or more of Irgacure 907 was added, the electromagnetic wave curable composition was not dissolved uniformly. This electromagnetic wave curable composition showed high liquid repellency, and the F8 thin film had good splitting properties with respect to the pattern substrate.
  • Example 25 Q (Laylyl atylate was used instead of C1 atylate, and HX—2A, TMP—3A, and PEN—4A were used as multifunctional acrylates. 10 and 11.
  • This electromagnetic wave curable composition had almost no liquid repellency to n-xadecane, and the F8 thin film had poor splitting ability to the pattern substrate.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention concerne un agent de traitement de surface pour la photolithographie contenant au moins un monomère fluoré (A) décrit ci-dessous et/ou un polymère fluoré (B) contenant le monomère fluoré. Le monomère fluoré (A) est au moins un monomère fluoré sélectionné entre (A-1) un acrylate substitué en a contenant un groupe fluoroalkyle ayant 1-6 atomes de carbone ; (A-2) un monomère de type silsesquioxane contenant du fluor contenant un groupe fluoroalkyle ayant 1-6 atomes de carbone et un groupe polymérisable ; (A-3) un monomère polymérisable contenant un groupe perfluoropolyéther ; (A-4) un monomère dans lequel un groupe fluoroalkyle ayant 1-6 atomes de carbone et un groupe polymérisable sont reliés par -SO2(CH2)n- (dans lequel n est 1-10) ; et (A-5) un macromonomère contenant au moins un des monomères (A-1)-(A-4) comme unité récurrente et ayant un groupe (méth)acryloyle à une extrémité du polymère. Cet agent de traitement de surface produit une région repoussant les liquides ayant un caractère hydrofuge et un caractère oléofuge suffisamment élevés bien qu'il ait un groupe Rf à chaîne courte (un groupe fluoroalkyle à chaîne courte) ayant 6 ou moins de 6 atomes de carbone.
PCT/JP2006/311111 2005-06-03 2006-06-02 Agent de traitement de surface pour la formation d'un dessin Ceased WO2006129800A1 (fr)

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