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WO2016133189A1 - Composition pour former un film de revêtement biocompatible - Google Patents

Composition pour former un film de revêtement biocompatible Download PDF

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Publication number
WO2016133189A1
WO2016133189A1 PCT/JP2016/054799 JP2016054799W WO2016133189A1 WO 2016133189 A1 WO2016133189 A1 WO 2016133189A1 JP 2016054799 W JP2016054799 W JP 2016054799W WO 2016133189 A1 WO2016133189 A1 WO 2016133189A1
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WO
WIPO (PCT)
Prior art keywords
coating film
group
substrate
composition
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/054799
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English (en)
Japanese (ja)
Inventor
高広 岸岡
横山　義之
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Toyama Prefecture
Nissan Chemical Corp
Original Assignee
Toyama Prefecture
Nissan Chemical Corp
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Publication date
Application filed by Toyama Prefecture, Nissan Chemical Corp filed Critical Toyama Prefecture
Priority to JP2017500748A priority Critical patent/JP6706728B2/ja
Publication of WO2016133189A1 publication Critical patent/WO2016133189A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

Definitions

  • the present invention relates to a composition for forming a biocompatible coating film.
  • coating materials having biocompatibility that are harmless to biological substances have attracted attention.
  • examples of the use include a coating material for forming a coating film having an ability to suppress adhesion of biological substances, a coating material used for a cell culture substrate that improves cell culture efficiency, and the like.
  • Patent Document 1 describes a method for producing a plate for cell culture, which includes using a photosensitive resin composition containing an alcohol-based organic solvent (S).
  • biocompatible fibers and the like can be produced using a composition containing a specific polymer compound capable of forming a crosslinked structure using an acid as a catalyst (international patent).
  • synthetic resins plastics
  • the solvent that can dissolve the polymer compound is limited.
  • An object of the present invention is to provide a coating film forming composition or the like that can form a biocompatible coating film without eroding the substrate.
  • the present invention is as follows.
  • a biocompatible coating film-forming composition comprising (A) an organic polymer and (D) methoxy alcohol having 2 to 5 carbon atoms as a solvent.
  • (D) the methoxy alcohol having 2 to 5 carbon atoms is 2-methoxyethanol.
  • the organic polymer (A) is (A1) General formula (1):
  • R 1 represents a hydrogen atom or a methyl group
  • Q 1 represents an ester bond or an amide bond
  • R 2 is an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a hydroxymethyl group or an alkoxymethyl group having 1 to 5 carbon atoms.
  • An aromatic hydrocarbon group is shown.
  • the (A1) organic polymer is General formula (2):
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 and R 5 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group or a carboxy group.
  • [8] The base material according to [7], wherein the base material includes polystyrene.
  • a method for producing a substrate having a coating film on the surface comprising a step of forming a coating film on the surface of the substrate using the composition according to any one of [1] to [6].
  • a substrate having on the surface a pattern formed using the composition according to [6].
  • a pattern including a step of forming a coating film on the surface of the substrate using the composition according to [6], a step of irradiating the coating film with light, and a step of developing the coating film after exposure A manufacturing method of a substrate with a mark.
  • the composition for forming a biocompatible coating film of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is used, the biocompatible coating is performed without eroding the substrate (particularly, the resin substrate).
  • a film can be formed.
  • the composition of this invention contains a photo-acid generator, it can form the coating film which has photosensitivity.
  • a biocompatible coating film pattern can be formed by photolithography.
  • the said base material with a pattern can be manufactured.
  • the composition of this invention can form the coating film which has temperature responsiveness, for example, when the temperature responsive organic polymer containing the structural unit represented by following General formula (2) is used. In this case, a specific patterned substrate having temperature responsiveness can be manufactured and provided.
  • FIG. 2 is a graph showing the results of a sensitivity test of the composition for forming a coating film obtained in Example 1.
  • the vertical axis represents the film thickness (nm) of the coating film
  • the horizontal axis represents the exposure dose (mJ / cm 2 ).
  • 3 is a graph showing the results of a patterning test of the coating film forming composition obtained in Example 1.
  • FIG. The vertical axis shows the thickness (nm) of the part with the pattern (coating film) and the part without the pattern (nm)
  • the horizontal axis shows the width ( ⁇ m) of the part with the pattern (coating film) and the part without the pattern.
  • the biocompatible coating film-forming composition of the present invention is mainly characterized in that it contains (A) an organic polymer and (D) methoxy alcohol having 2 to 5 carbon atoms as a solvent.
  • the organic polymer is not particularly limited as long as it can be used in the composition for forming a coating film, but is preferably at least one selected from a hydroxy group, a hydroxymethyl group, and an alkoxymethyl group having 1 to 5 carbon atoms. It is an organic polymer containing a structural unit having a seed organic group in the side chain.
  • Examples of the (A) organic polymer include vinyl polymer polymer reacted with olefin, polyamide, polyester, polycarbonate, polyurethane, (meth) acryl polymer polymerized (meth) acrylate compound, and the like. Not limited.
  • (A) organic polymers are preferably those obtained by radical polymerization, but those obtained by polycondensation or polyaddition reaction can also be used.
  • a vinyl polymer polymer reacted with an olefin or a (meth) acryl polymer polymerized with a (meth) acrylate compound is particularly desirable.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • alkoxymethyl group having 1 to 5 carbon atoms may be either linear or branched, and specific examples thereof include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, Propoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl group, n-pentoxymethyl group, isopentoxymethyl group, neopentoxymethyl group, tert-pentoxy Examples thereof include a methyl group, 1-ethylpropoxymethyl group, 2-methylbutoxymethyl group and the like.
  • the number of carbon atoms of the alkoxymethyl group is preferably 1 to 4, more preferably 1 to 3.
  • Component A1 (A)
  • the organic polymer is preferably represented by the general formula (1):
  • R 1 represents a hydrogen atom or a methyl group
  • Q 1 represents an ester bond or an amide bond
  • R 2 is an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a hydroxymethyl group or an alkoxymethyl group having 1 to 5 carbon atoms.
  • An aromatic hydrocarbon group is shown.
  • R 1 represents a hydrogen atom or a methyl group.
  • Q 1 represents an ester bond or an amide bond.
  • R 2 is an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a hydroxymethyl group or an alkoxymethyl group having 1 to 5 carbon atoms.
  • An aromatic hydrocarbon group is shown.
  • the “alkoxymethyl group having 1 to 5 carbon atoms” may be linear or branched, and specific examples thereof are the same as those described above, and suitable carbon atoms are the same as described above. It is.
  • alkyl group having 1 to 10 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, 1,1-dimethylbutyl group 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, hexyl group, pentyl group, octyl group, nonyl group, decyl group and the like.
  • the number of carbon atoms of the alkyl group is preferably 1-6, more preferably 1-4.
  • Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R 2 include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 2 is formed using the composition of the present invention when the composition of the present invention contains a photoacid generator (B) described later and imparts photosensitivity to a coating film formed using the photo acid generator.
  • a photoacid generator (B) described later and imparts photosensitivity to a coating film formed using the photo acid generator.
  • at least one hydrogen atom is a hydroxy group, a hydroxymethyl group, or a carbon atom from the viewpoint of allowing (B) a photoacid generator as a catalyst to act as a reactive crosslinking reaction site after exposure of the applied coating film.
  • An alkyl group having 1 to 10 (more preferably 1 to 6, particularly preferably 1 to 4) carbon atoms substituted by an alkoxymethyl group having 1 to 5 carbon atoms (more preferably a hydroxy group), or at least one A phenyl group in which a hydrogen atom is substituted with a hydroxy group, a hydroxymethyl group or an alkoxymethyl group having 1 to 5 carbon atoms (more preferably a hydroxy group).
  • R 1 is a hydrogen atom or a methyl group
  • Q 1 is an ester bond
  • R 2 is substituted with at least one hydrogen atom by a hydroxy group.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6, particularly preferably 1 to 4).
  • the structural unit represented by the general formula (1) is preferably a structural unit represented by the general formula (1A).
  • Component A1 may contain one type of structural unit represented by general formula (1), or may contain two or more types.
  • Component A1 may contain structural units other than the structural unit represented by general formula (1) as long as the object of the present invention is not impaired, and is represented by general formula (1) for all structural units of component A1.
  • the content of the structural unit is preferably 5 mol% or more, more preferably 15 mol% or more, from the viewpoint of efficiently performing the crosslinking reaction.
  • Component A1 is further represented by general formula (2):
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 and R 5 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group or a carboxy group.
  • Component A1 may contain one type of structural unit represented by general formula (2), or may contain two or more types.
  • the “alkyl group having 1 to 4 carbon atoms” in R 4 and R 5 in the general formula (2) may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group and isobutyl group can be mentioned.
  • “may be substituted with a hydroxy group or a carboxy group” means that part or all of the hydrogen atoms contained in the above “alkyl group having 1 to 4 carbon atoms” are substituted with a hydroxy group or a carboxy group. Indicates that it may be.
  • R 3 is more preferably a hydrogen atom or a methyl group
  • both R 4 and R 5 are more preferably a methyl group.
  • the weight average molecular weight of component A1 is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 5,000 to 500,000, particularly from the viewpoint of forming an appropriate coating film thickness.
  • the range is preferably 10,000 to 200,000.
  • “weight average molecular weight” means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • Component A1 may be used alone or in combination of two or more.
  • Component A1 can be produced by a method known per se or a method analogous thereto.
  • a monomer corresponding to each structural unit (a monomer corresponding to the structural unit represented by the general formula (1), a structural unit other than the structural unit represented by the general formula (1) (preferably the general formula The monomer corresponding to the structural unit represented by (2)) in a suitable solvent (eg, propylene glycol monoethyl ether, etc.) and a suitable polymerization initiator (eg, 2,2′-azobis).
  • a suitable solvent eg, propylene glycol monoethyl ether, etc.
  • a suitable polymerization initiator eg, 2,2′-azobis
  • Examples of the monomer corresponding to the structural unit represented by the general formula (1) include 2-hydroxyethyl (meth) acrylate (for example, a compound having CAS number: 868-77-9), 2-hydroxypropyl ( (Meth) acrylate (for example, a compound having CAS number: 923-26-2), 4-hydroxybutyl (meth) acrylate (for example, a compound having CAS number: 2478-10-6), N-hydroxymethyl (meth) acrylamide ( For example, a compound having CAS number: 923-02-4), N- (2-hydroxyethyl) (meth) acrylamide (for example, a compound having CAS number: 5238-56-2), N- (2-hydroxypropyl) ( (Meth) acrylamide (for example, a compound having CAS number: 26099-09-2), p-hydroxy (meth) actyl Examples include ruanilide (for example, a compound having CAS number: 19243-95-9), N-methoxymethyl (meth) acryl
  • 2-hydroxyethyl (meth) acrylate 2-hydroxy Propyl (meth) acrylate, N-methoxymethyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide is preferred, and 2-hydroxyethyl (meth) acrylate is most preferred.
  • Examples of the monomer corresponding to the structural unit represented by the general formula (2) include N-isopropyl (meth) acrylamide, N- (1-methylpropyl) (meth) acrylamide, and N- (1-ethylpropyl). ) (Meth) acrylamide, N- (1-propylbutyl) (meth) acrylamide, N- (1-butylpentyl) (meth) acrylamide, 2-carboxyisopropyl (meth) acrylamide, 2-hydroxyisopropyl (meth) acrylamide, etc.
  • N-isopropyl (meth) acrylamide, 2-carboxyisopropyl (meth) acrylamide or 2-hydroxyisopropyl (meth) acrylamide is most preferable.
  • component A1 has a structural unit represented by general formula (2)
  • the coating film formed using the composition of the present invention has temperature responsiveness.
  • the content ratio of the structural unit represented by the general formula (2) with respect to all the structural units of the component A1 is preferably 60 to 95 mol%.
  • the coating film formed using the composition of the present invention has temperature responsiveness, so that, for example, a coating film pattern whose size changes with temperature can be formed.
  • a drug delivery system that allows water or a drug to stay in or release from the coating film or application to a drug sheet, and (ii) control the hydrophobicity / hydrophilicity of the surface. This is advantageous in that application to devices that can control the adhesion of substances is expected.
  • Component A1 may further contain an arbitrary structural unit in addition to the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
  • Such an arbitrary structural unit does not impair the performance of the coating film formed using the composition of the present invention, and the monomer corresponding to the structural unit represented by the general formula (1) and the general formula (2) If it is a structural unit derived from the monomer which can superpose
  • Examples of such monomers include (meth) acrylic acid esters having 1 to 10 carbon atoms in the alkyl group, benzyl (meth) acrylate, acrylamides (eg, acrylamide, N-alkylacrylamide, N- Arylacrylamide, N, N-dialkylacrylamide, N, N-diarylacrylamide, N-methyl-N-phenylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc.), methacrylamides (eg, methacrylamide, N -Alkyl methacrylamide, N-aryl methacrylamide, N, N-dialkyl methacrylamide, N, N-diaryl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, etc.) It is done.
  • acrylamides eg, acrylamide, N-alkylacrylamide, N- Arylacrylamide, N
  • component A1 may be used alone or in combination of two or more.
  • a (meth) acrylic acid ester having 1 to 10 carbon atoms in the alkyl group having a hydrophobic side chain or benzyl (meth) acrylate is used, the hydrophilicity / hydrophobicity balance of component A1 can be adjusted. it can.
  • the content of component A in the coating film forming composition of the present invention is suitable for forming a coating film with an appropriate thickness and for coating film formation excluding the solvent from the viewpoint of storage stability of the coating film forming composition of the present invention.
  • the amount is preferably 60 to 95% by weight, more preferably 70 to 90% by weight, based on the solid content of the composition.
  • the coating film forming composition of the present invention may contain (B) a photoacid generator (hereinafter also simply referred to as “component B”).
  • Component B is not particularly limited as long as it is a compound that generates an acid directly or indirectly upon exposure.
  • a diazomethane compound, an onium salt compound, a sulfonimide compound, a nitrobenzyl compound, an iron arene complex, a benzoin tosylate compound, Examples include halogen-containing triazine compounds, cyano group-containing oxime sulfonate compounds, and naphthalimide compounds.
  • diazomethane compound examples include bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2,4-dimethylphenylsulfonyl) diazomethane. .
  • onium salt compound examples include bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and the like.
  • sulfonimide compound examples include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-normalbutanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) naphthalimide, and the like. Is mentioned.
  • nitrobenzyl compound examples include 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, and the like.
  • iron arene complex examples include biscyclopentadienyl- ( ⁇ 6-isopropylbenzene) -iron (II) hexafluorophosphate.
  • benzoin tosylate compound examples include benzoin tosylate and ⁇ -methylbenzoin tosylate.
  • halogen-containing triazine compound examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis. (Trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- ( 5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.
  • Examples of the cyano group-containing oxime sulfonate compound include ⁇ - (methylsulfonyloxyimino) -4-methoxybenzyl cyanide, ⁇ - (trifluoromethylsulfonyloxyimino) -4-methoxybenzyl cyanide, ⁇ - (ethyl And sulfonyloxyimino) -4-methoxybenzyl cyanide, ⁇ - (propylsulfonyloxyimino) -4-methylbenzyl cyanide, and the like.
  • naphthalimide compounds include 6- (n-butylthio) -2- (perfluorobutylsulfonyloxy) -2-aza-2H-phenalene-1,3-dione, 6- (n-butylthio) -2 -(Trifluoromethylsulfonyloxy) -2-aza-2H-phenalene-1,3-dione and 6- (isopropylthio) -2- (trifluoromethylsulfonyloxy) -2-aza-2H-phenalene-1, 3-dione and the like can be mentioned.
  • the photoacid generator is preferably a naphthalimide compound, more preferably 6- (n-butylthio) -2- (perfluorobutylsulfonyloxy) -2-aza-2H-phenalene-1,3. -Dione, 6- (n-butylthio) -2- (trifluoromethylsulfonyloxy) -2-aza-2H-phenalene-1,3-dione and 6- (isopropylthio) -2- (trifluoromethylsulfonyloxy) ) -2-aza-2H-phenalene-1,3-dione.
  • the content of (B) the photoacid generator is such that the coating film forming composition of the present invention obtains good patterning performance by exposure.
  • the solid content of the composition for forming a coating film excluding the solvent it is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and still more preferably 1 to 13% by weight.
  • composition for forming a coating film of the present invention contains (B) a photoacid generator, only one type of (B) photoacid generator may be used, or two or more types may be used in combination.
  • the composition for forming a coating film of the present invention preferably contains (C) a cross-linking agent (hereinafter also simply referred to as “component C”) that reacts with a reactive group in the presence of an acid.
  • component C a cross-linking agent
  • a crosslinking agent may use only 1 type and may use 2 or more types together.
  • the organic polymer can be crosslinked without a crosslinking agent (self-crosslinking).
  • the composition for forming a coating film of the present invention may not contain (C) a crosslinking agent.
  • Component C is not particularly limited as long as it reacts with the reactive group in the presence of an acid, and those usually used in the field of photosensitive compositions can be used in the present invention.
  • component C examples include glycoluril compounds and melamine compounds.
  • glycoluril compound examples include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (ethoxymethyl) glycoluril, 1,3,4,6-tetrakis ( And propoxymethyl) glycoluril and 1,3,4,6-tetrakis (butoxymethyl) glycoluril.
  • Examples of the melamine compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine and the like.
  • Component C is preferably a glycoluril compound, more preferably 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (ethoxymethyl) glycoluril, It is at least one selected from the group consisting of 3,4,6-tetrakis (propoxymethyl) glycoluril and 1,3,4,6-tetrakis (butoxymethyl) glycoluril, more preferably 1,3,4 , 6-tetrakis (methoxymethyl) glycoluril.
  • component C When component C is used, its content is preferably 0.1 to 40, based on the solid content of the coating film forming composition excluding the solvent, in order to obtain good patterning characteristics and sufficient temperature responsiveness.
  • % By weight, more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight.
  • composition for forming a coating film of the present invention contains (D) a methoxy alcohol having 2 to 5 carbon atoms (hereinafter also simply referred to as “component D”) as a solvent.
  • component D a methoxy alcohol having 2 to 5 carbon atoms
  • the composition of the present invention can form a biocompatible coating film without particularly eroding the resin substrate.
  • methoxy alcohol having 2 to 5 carbon atoms examples include methoxymethanol (CAS number; 4461-52-3), 2-methoxyethanol (CAS number; 109-86-4), 2-methoxy-1-propanol. (CAS number; 1589-47-5), 3-methoxy-1-propanol (CAS number; 1589-49-7), 2-methoxy-1-butanol (CAS number; 15467-25-1), 3-methoxy -1-butanol (CAS number; 2517-43-3) and the like.
  • the number of carbon atoms of the methoxy alcohol is preferably 2-4, more preferably 3-4.
  • Component D is preferably 2-methoxyethanol (CAS number; 109-86-4, alternatively named ethylene glycol monomethyl ether, methyl cellosolve, methyl glycol).
  • the content of component D is Preferably, it is 50 to 99.5% by weight, more preferably 70 to 99.5% by weight, and still more preferably 85 to 99% by weight.
  • the content ratio of component A in the coating film forming composition of the present invention (that is, the content of component A based on the composition for forming a coating film) is suitable for the production of a coating film having an appropriate thickness or the coating film of the present invention. From the viewpoint of storage stability of the forming composition, 0.1 to 90% by weight is preferable, and 0.5 to 70% by weight is more preferable.
  • the content ratio of component B in the composition for forming a coating film (that is, the content of component B based on the composition for forming a coating film) is: From the viewpoint of maintaining the characteristics of the temperature-responsive resin, it is preferably 0.01 to 50% by weight, more preferably 0.05 to 40% by weight, and particularly preferably 0.1 to 20% by weight.
  • the weight ratio of component A and component B (weight of component A / weight of component B) contained in the composition for forming a coating film of the present invention is: From the viewpoint of reaction efficiency between component A and component B, 0.01 to 50 is preferable, and 0.1 to 40 is more preferable.
  • the content ratio of component C in the composition for forming a coating film of the present invention (that is, the content of component C based on the composition for forming a coating film) Is preferably from 0.01 to 15% by weight, more preferably from 0.03 to 10% by weight, particularly preferably from 0.05 to 5% by weight, from the viewpoint of reaction efficiency with Component A.
  • the coating film-forming composition of the present invention may contain additives as necessary in addition to the components A to D as long as the object of the present invention is not significantly impaired.
  • the additive include a surfactant, a rheology modifier, a drug, and fine particles.
  • composition for forming a coating film of the present invention is prepared by mixing component A and component D, and optionally mixing component B and / or component C, or further mixing the above additives.
  • the mixing method is not particularly limited, and may be mixed by a method known per se or a method analogous thereto.
  • the substrate having a coating film formed using the coating film forming composition of the present invention on at least a part of the surface is obtained by applying the coating film forming composition of the present invention by a method such as spin coating or slit coating. It can manufacture by forming a coating film in at least one part of the surface of a base material by apply
  • the present invention also provides a substrate having such a coating film.
  • the patterned substrate of the present invention is a step of forming a coating film on at least a part of the surface of the substrate using the coating film forming composition of the present invention containing at least Component A, Component B and Component D, It can be manufactured by a manufacturing method including a patterning step by photolithography (specifically, a step of irradiating the coating film with light and a step of developing the coating film after exposure).
  • the present invention also provides such a patterned substrate.
  • the substrate with a pattern of the present invention may be a substrate having one type of pattern produced using only one type of composition for forming a coating film of the present invention.
  • the base material which has 2 or more types of patterns manufactured using 2 or more types may be sufficient.
  • the shape of the pattern is not particularly limited, and when observed from the upper side of the substrate, for example, a square shape, a round shape, a linear shape, a line and space, and the like can be mentioned. When two or more patterns having different response temperatures exist, they may be formed adjacent to each other or may be formed apart from each other. There is no particular limitation on the size of the pattern observed from above and the height observed from the pattern cross section.
  • the size of the pattern (that is, the width of one side of the square, the diameter of the circle, the width of the line, the line and space line width and space width, etc.) is, for example, 0.1 to 1000 ⁇ m, and the height of the pattern is, for example, 5 nm to 1000 ⁇ m.
  • the shape of these patterns can be controlled by using a plurality of masks having different shapes of transmitted light during the exposure process.
  • the patterned substrate of the present invention can be produced by a method known per se, for example, the method described below.
  • the composition for forming a coating film of the present invention containing at least Component A, Component B, and Component D is applied to a substrate by a method such as spin coating or slit coating, and the solvent is removed to remove the surface of the substrate.
  • a coating film is formed on at least a part.
  • g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), ultraviolet light, deep ultraviolet light, electron beam, various lasers (eg, KrF excimer laser (wavelength 248 nm), ArF excimer)
  • light such as laser (wavelength 193 nm)
  • excimer laser such as F2 excimer laser (wavelength 157 nm)
  • mercury lamp light, LED light, etc. is irradiated through a mask in order to obtain a desired pattern, the acid is exposed only at the exposed portion. Is generated, thereby causing cross-linking (curing).
  • g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), ultraviolet rays, deep ultraviolet rays, and electron beams are preferably used for the coating film of the present invention.
  • PEB post-exposure baking
  • the coated film after exposure is developed with a developer or the like, and an unexposed portion (uncured portion of the coating film) is removed to produce a substrate with a pattern.
  • the base material which has 2 or more types of patterns can be manufactured by repeating the said operation for every composition for coating film formation from which a composition differs.
  • Examples of the base material used for the base material having a coating film and the base material with a pattern include metals, metalloids, metal-containing compounds, metalloid-containing compounds, and resins.
  • a biocompatible coating film can be formed without eroding the resin substrate, and therefore the present invention is particularly useful when a resin substrate is used.
  • metal or semimetal examples include aluminum, nickel titanium, stainless steel (SUS304, SUS316, SUS316L, etc.), silicon, and the like.
  • metal-containing compound or metalloid-containing compound examples include ceramics, metal oxide or metalloid oxide (glass, silicon oxide, alumina, etc.), metal carbide or metalloid carbide, metal nitride or metalloid nitride (nitriding). Silicon, etc.), metal borides, metalloid borides and the like.
  • the resin may be a natural resin, a modified natural resin, or a synthetic resin.
  • natural resins include cellulose.
  • modified natural resin include cellulose triacetate (CTA), cellulose on which dextran sulfate is immobilized, and the like.
  • Examples of the synthetic resin include polyacrylonitrile (PAN), polyester polymer alloy (PEPA), polystyrene (PS), polysulfone (PSF), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), Examples include polyurethane (PU), ethylene vinyl alcohol (EVAL), polyethylene (PE), polyester (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), polyethersulfone (PES), and poly-N-isopropylacrylamide.
  • PAN polyacrylonitrile
  • PEPA polyester polymer alloy
  • PS polystyrene
  • PSF polysulfone
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • PVA polyvinyl alcohol
  • Examples include polyurethane (PU), ethylene vinyl alcohol (EVAL), polyethylene (PE), polyester (PE), polypropylene (PP), polyvinylidene fluoride (PVDF),
  • the content of the structural unit derived from N-isopropylacrylamide with respect to all the structural units of the organic polymer 1 is 80 mol%, and the structure derived from 2-hydroxyethyl acrylate.
  • the content ratio of the unit is 20 mol%.
  • the weight average molecular weight of the organic polymer 1 was 19,000 in terms of polystyrene.
  • Organic polymer 1 0.5 g, crosslinking agent (1,3,4,6-tetrakis (methoxymethyl) glycoluril) 0.035 g, photoacid generator (6- (n-butylthio) -2- (tri Fluoromethylsulfonyloxy) -2-aza-2H-phenalene-1,3-dione) (0.075 g) and 2-methoxyethanol (50.2 g) were added to obtain a coating film forming composition 1.
  • Coating film-forming compositions 2 to 18 were obtained in the same manner as in Example 1 except that 2-methoxyethanol in Example 1 was changed to the solvents shown in Table 1.
  • the coating film forming composition 1 was applied onto a silicon wafer using a spin coater, and pre-baked on a hot plate at 80 ° C. for 1 minute to form a coating film on the silicon wafer.
  • the coating film was exposed using an i-line aligner PLA-501 (manufactured by Canon Inc.) while changing the exposure amount. It was then post-exposure baked (PEB) in an oven at 80 ° C. for 20 hours. After the exposure, the baked coating film was exposed to isopropyl alcohol for 1 minute, and then rinsed with shaking at 60 ° C. for 3 minutes. Thereafter, the coating film was dried at 60 ° C. for 10 minutes, and the thickness of the coating film in the exposure area was measured. The results are shown in FIG. In addition, the same result as the above was obtained also when it carried out like the above except having changed the time of post-exposure baking (PEB) from 20 hours to 5 hours.
  • PEB post-exposure baking
  • the coating film forming composition 1 was applied onto a Nunc Thermonox cover slip (made of polyester) (Thermo Fisher Scientific, Inc.) using a spin coater, and prebaked on a hot plate at 80 ° C. for 1 minute. A coating film was formed on the wafer.
  • a line pattern mask with an interval of 20 ⁇ m that is, a mask with an opening width of 20 ⁇ m and a mask width of 20 ⁇ m
  • PEB post-exposure baked
  • the baked coating film was exposed to isopropyl alcohol for 1 minute, and then rinsed with shaking at 60 ° C. for 3 minutes. Then, it was made to dry at 60 degreeC for 10 minute (s), and the base material with a pattern was obtained.
  • the surface of the substrate with the pattern is observed using an atomic force microscope (AFM) (“Dimension Icon” manufactured by Bruker AXS Co., Ltd.). The thickness and width of the missing part were measured. The results are shown in FIG.
  • the base material (base material with a pattern) which has a favorable pattern (a line and space pattern with a line width of 20 ⁇ m and a space width of 20 ⁇ m) was obtained from the coating film forming composition 1.
  • composition for forming a biocompatible coating of the present invention is particularly useful when a biocompatible coating film is formed on a resin substrate.

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Abstract

La présente invention concerne une composition qui permet de former un film de revêtement biocompatible sur un substrat (par exemple un substrat résineux). La présente invention concerne une composition qui permet de former des films de revêtement biocompatibles qui comporte (A) un polymère organique et (D) un alcool méthoxy C2-5 en tant que solvant. Le polymère organique (A) comprend, de préférence, une unité structurale ayant, dans une chaîne latérale, au moins un groupe organique choisi parmi un groupe hydroxy, un groupe hydroxyméthyle et des groupes alcoxyméthyle C1-5.
PCT/JP2016/054799 2015-02-20 2016-02-19 Composition pour former un film de revêtement biocompatible Ceased WO2016133189A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018101353A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type négatif, et produit durci associé ainsi que procédé de fabrication de celui-ci

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JPH0923876A (ja) * 1995-07-11 1997-01-28 Kao Corp 細胞培養支持体の製造法
WO2005095510A1 (fr) * 2004-03-31 2005-10-13 Toyama Prefecture Composition polymere thermosensible et utilisations de celle-ci
JP2006158961A (ja) * 2004-11-09 2006-06-22 Jsr Corp 生体関連物質用物品およびその製造方法、ならびに生体関連物質吸着防止用コーティング組成物およびその使用方法
JP2013057058A (ja) * 2011-08-15 2013-03-28 Kawamura Institute Of Chemical Research ブロック共重合体
JP2014023508A (ja) * 2012-07-30 2014-02-06 Tokyo Ohka Kogyo Co Ltd 細胞培養用プレートの作製方法、この作製方法で作製された細胞培養用プレート、細胞培養方法、細胞シート作製方法、細胞シート、及び感光性樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0923876A (ja) * 1995-07-11 1997-01-28 Kao Corp 細胞培養支持体の製造法
WO2005095510A1 (fr) * 2004-03-31 2005-10-13 Toyama Prefecture Composition polymere thermosensible et utilisations de celle-ci
JP2006158961A (ja) * 2004-11-09 2006-06-22 Jsr Corp 生体関連物質用物品およびその製造方法、ならびに生体関連物質吸着防止用コーティング組成物およびその使用方法
JP2013057058A (ja) * 2011-08-15 2013-03-28 Kawamura Institute Of Chemical Research ブロック共重合体
JP2014023508A (ja) * 2012-07-30 2014-02-06 Tokyo Ohka Kogyo Co Ltd 細胞培養用プレートの作製方法、この作製方法で作製された細胞培養用プレート、細胞培養方法、細胞シート作製方法、細胞シート、及び感光性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018101353A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type négatif, et produit durci associé ainsi que procédé de fabrication de celui-ci

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