WO2014171431A1 - Composition de résine durcissable destinée à former un microcanal, et microcanal correspondant - Google Patents

Composition de résine durcissable destinée à former un microcanal, et microcanal correspondant Download PDF

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WO2014171431A1
WO2014171431A1 PCT/JP2014/060658 JP2014060658W WO2014171431A1 WO 2014171431 A1 WO2014171431 A1 WO 2014171431A1 JP 2014060658 W JP2014060658 W JP 2014060658W WO 2014171431 A1 WO2014171431 A1 WO 2014171431A1
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group
substrate
meth
microchannel
composition
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PCT/JP2014/060658
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English (en)
Japanese (ja)
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宙志 山口
孝彦 黒澤
稗田　克彦
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Jsr株式会社
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Priority claimed from JP2013088241A external-priority patent/JP2014210865A/ja
Priority claimed from JP2013115327A external-priority patent/JP2014234411A/ja
Application filed by Jsr株式会社 filed Critical Jsr株式会社
Publication of WO2014171431A1 publication Critical patent/WO2014171431A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00833—Plastic

Definitions

  • the present invention relates to a radiation curable resin composition for forming a microchannel, an anaerobic curable resin composition for forming a microchannel, a microchannel, and a method for manufacturing the microchannel.
  • a micro-channel which is a small device with a micro-fluidic channel, valve, fluid inlet, outlet, etc. formed of a liquid or gas in the chip substrate (depending on the application, micro-channel chip, microreactor Etc.) have been developed and applied to various uses such as separation analysis of various substances, sensors, chemical reactions and the like. Recently, micro-channels have been attracting attention for high-throughput screening of pharmaceuticals and agricultural chemicals by performing separation analysis and synthesis of biologically related substances such as proteins, nucleic acids such as DNA and RNA, and sugar chains. ing.
  • the microchannel has a structure in which a channel having a width and depth of about 10 to 100 ⁇ m is formed in a substrate made of glass, polysiloxane, synthetic resin, or the like (Non-patent Document 1, Patent Document). 1).
  • a channel is a channel whose upper part is closed by forming a groove with an open upper part such as a rectangular or U-shaped cross section on a substrate and providing a lid using another substrate as necessary. It is formed by forming.
  • the substrate on which the groove is formed and the substrate serving as a lid are bonded with an adhesive or welded by heat or the like.
  • the channel can be formed by a method such as injection molding. Can be formed.
  • the substrate on which the groove is formed and the substrate or substrate film to be a lid are bonded by a method such as hot pressing, ultrasonic welding, or adhesive.
  • MEMS micro electro mechanical systems
  • a flow path is formed on a silicon substrate using a photocurable material such as a photoresist.
  • the biological substance when a biological substance is allowed to flow through a microchannel, the biological substance may be adsorbed nonspecifically to an adhesive or the like exposed on the surface of the channel or a part of the channel.
  • the detection sensitivity and the reaction yield are lowered when performing separation analysis and synthesis reaction of related substances.
  • the present invention has been made paying attention to such problems, and provides a material for forming a microchannel with a small amount of non-specific adsorption of a biological substance.
  • ultraviolet curable adhesive when used in the production of the microchannel, in the case of a microchannel having a channel sandwiched between substrates that do not transmit ultraviolet rays, such as a silicon substrate, ultraviolet rays are used as an adhesive. It is difficult to reach the layer, and there are structural limitations such as making at least one substrate a transparent substrate that transmits ultraviolet rays.
  • the present invention has been made paying attention to such a problem, and provides a material for forming a microchannel that hardly deteriorates a biological substance such as a protein.
  • the inventor of the present application (A) a copolymer having a radiation reactive group and a fluorine atom and having a number average molecular weight of 1,000 to 500,000, It has been found that the above object can be achieved by a radiation curable resin composition containing (B) a compound other than (A) having a radiation reactive group and a fluorine atom, and (C) a radiation polymerization initiator.
  • the inventor of the present application contains an ethylenically unsaturated group and a fluorine atom, a specific molecular weight copolymer, a compound having an ethylenically unsaturated group and a fluorine atom, an organic peroxide, and a polymerization accelerator. It has been found that an anaerobic curable resin composition capable of achieving the above-mentioned purpose.
  • the present invention includes (A) a copolymer having an ethylenically unsaturated group and a fluorine atom and a number average molecular weight of 1,000 to 500,000, (B) a compound other than (A) having an ethylenically unsaturated group, (The present invention provides an anaerobic curable resin composition for forming a microchannel containing an organic peroxide and (D) a polymerization accelerator. Further, the present invention is a micro flow path in which a substrate serving as a lid is bonded to a substrate having a flow path pattern, and the substrate having the flow path pattern and the substrate serving as a lid are formed using the composition. In addition, the present invention provides a micro flow channel bonded through an adhesive layer.
  • the present invention is a microchannel in which a substrate serving as a lid is integrally formed on a substrate having a channel pattern, and the substrate having the channel pattern and the substrate serving as a lid are formed using the composition.
  • the present invention provides a microchannel bonded through an adhesive layer that is formed.
  • the present invention also relates to a method of manufacturing a microchannel, in which a substrate serving as a lid is bonded to a substrate having a channel pattern, wherein the composition is disposed between the substrate having the channel pattern and the substrate serving as a lid.
  • the present invention provides a method for producing a microchannel having a step of forming an adhesive layer using a material, and a step of bonding a substrate having the channel pattern and a substrate to be the lid.
  • the present invention is a method of manufacturing a micro flow path in which a substrate serving as a lid is integrally formed on a substrate having a flow path pattern, wherein the substrate having a flow path pattern and the substrate serving as a lid
  • the present invention provides a method for producing a microchannel having a step of forming an adhesive layer using a composition and a step of bonding a substrate having the channel pattern and a substrate to be the lid.
  • the radiation curable resin composition of the present invention does not substantially contain an organic solvent, a volatile substance is not generated, the environmental load is small, and the viscosity is easy to handle at room temperature, so that the flow path pattern has a thickness of up to about 200 ⁇ m.
  • the micro-channel formed by using the radiation curable resin composition of the present invention as an adhesive has a refractive index of the adhesive layer of glass. Since it is approximate, it has high transparency, and since it has high adhesion to the glass substrate, there can be obtained a microchannel excellent in durability without liquid leakage or the like.
  • the channel pattern is a channel groove whose upper surface is open. By providing a lid on the upper surface of the channel pattern, a channel whose upper surface is closed is formed.
  • a microchannel means a chip or device having a channel.
  • the anaerobic curable resin composition of the present invention does not substantially contain an organic solvent, it does not generate volatile substances, has a low environmental burden, has a viscosity that is easy to handle at room temperature, and does not contain proteins such as antibodies. Curing is possible even at a low temperature of about 40 ° C. or less which is not activated.
  • the microchannel formed using the anaerobic curable resin composition of the present invention as an adhesive has a high adhesion to the substrate, so there is no liquid leakage and the like, and a microchannel with excellent durability can be obtained. it can.
  • the microsensors are bonded to each other at a low temperature of about 40 ° C. without degrading the protein.
  • a flow path can be obtained.
  • the channel pattern is a channel groove whose upper surface is open. By providing a lid on the upper surface of the channel pattern, a channel whose upper surface is closed is formed.
  • a microchannel means a chip or device having a channel.
  • FIG. 1 is a diagram showing a first embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 2 is a diagram showing a second embodiment of a method for forming a microchannel that can be used as a biosensor using the composition of the present invention.
  • FIG. 3 is a diagram showing a third embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 4 is a diagram showing a fourth embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 5 is a diagram showing a fifth embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 6 is a diagram showing a sixth embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 7 is a diagram showing a seventh embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 8 is a diagram showing an eighth embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 9 is a diagram showing a ninth embodiment of a method for forming a microchannel using the composition of the present invention.
  • FIG. 10 is a diagram showing a first embodiment of a method for forming a microchannel that can also be used as a biosensor using the composition of the present invention.
  • FIG. 11 is a diagram showing a second embodiment of a method for forming a microchannel that can also be used as a biosensor using the composition of the present invention.
  • the radiation curable resin composition of the present invention comprises (A) a copolymer having a radiation reactive group and a fluorine atom as essential components and a number average molecular weight of 1,000 to 500,000, and (B) a radiation reactive group and fluorine. It contains a compound other than (A) having an atom, and (C) a radiation polymerization initiator.
  • a copolymer having a radiation-reactive group and a fluorine atom and having a number average molecular weight of 1,000 to 500,000 (hereinafter referred to as “radiation-reactive group-containing fluorine-containing copolymer”) used in the composition of the present invention. It preferably has one or more structures selected from the group consisting of a polyvinyl structure, a poly (meth) acrylic structure, a polyurethane structure, a polyether structure, a polyester structure, a polyepoxy structure, a polyamide structure, and a polyimide structure.
  • the radiation-reactive group is not particularly limited as long as it is a functional group that undergoes a polymerization reaction directly by radiation or via an initiator.
  • (meth) acryloyl group, N-vinyl group, vinyl ether group, vinyl group , Epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group, cyclic thioether group, cyclic siloxane group, and the like and the (meth) acryloyl group can be cured more easily. More preferred are compounds having
  • the component (A) used in the composition of the present invention is a copolymer having a radiation-reactive group and a fluorine atom and having a number average molecular weight of 1,000 to 500,000 (hereinafter referred to as “radiation-reactive group-containing fluorine-containing copolymer). It is also called “union”.)
  • the molecular weight of component (A) is preferably 1,000 to 500,000 as a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • GPC gel permeation chromatography
  • the number average molecular weight of component (A) is more preferably from 5,000 to 200,000, and even more preferably from 10,000 to 100,000.
  • the number average molecular weight of the component (A) is a polystyrene equivalent number average molecular weight measured by a gel permeation chromatography method. Specifically, a number average molecular weight in terms of polystyrene measured using a composite column connected to an HPLC system (HLC-8220GPC: manufactured by Tosoh Corporation) in the following order, using tetrahydrofuran (THF) as a developing solvent at a flow rate of 1 ml / min. It is.
  • TSKgel G4000H XL TSKgel G3000H XL, TSKgel G2000H XL, TSKgel G2000H XL, TSKgel G4000H XL, TSKgel G3000H XL.
  • the (A) radiation-reactive group-containing fluorine-containing copolymer having a polyvinyl structure is not particularly limited as long as it is a vinyl polymer having a radiation-reactive group and a fluorine atom.
  • the vinyl polymer having a radiation reactive group and a fluorine atom contains, for example, a fluorinated vinyl polymer having an active hydrogen group and a group that forms a covalent bond with the radiation reactive group and the active hydrogen group in one molecule. It is obtained by reacting with the compound to be obtained.
  • a hydroxyl group, an amino group, a thiol group, a carboxyl group, etc. are mention
  • the group that forms a covalent bond with the active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, a carbonyl halide group, an epoxy group, and a glycidyl group.
  • a compound containing a radiation-reactive group and a group that forms a covalent bond with an active hydrogen group examples include a group that forms a covalent bond with at least one radiation-reactive group and at least one active hydrogen group in the molecule. If it is a compound containing this, it will not restrict
  • Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- (Bisacryloyloxymethyl) ethyl isocyanate may be used alone or in combination of two or more.
  • the Showa Denko Co., Ltd. make, brand name Karenz MOI, AOI, BEI etc. are mentioned, for example.
  • Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferable.
  • hydroxyl group-containing (meth) acrylate 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferable.
  • examples of commercially available hydroxyl group-containing polyfunctional (meth) acrylates include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA; Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30; Toagosei Co., Ltd., trade name. Available as Aronix M-215, M-233, M-305, M-400, etc.
  • Fluorinated vinyl polymer having active hydrogen groups preferably comprises the following structural units (a), (b) and (c ′).
  • A A structural unit represented by the following formula (1).
  • B A structural unit represented by the following formula (2).
  • C ′ A structural unit represented by the following formula (7).
  • R 1 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group, a group represented by — (CH 2 ) x —OR 5 or —OCOR 5 (R 5 represents an alkyl group, glycidyl A group or an aminoalkyl group, and x represents a number of 0 or 1), a carboxyl group, an alkoxycarbonyl group or a hydroxythioalkoxy group]
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a hydrogen atom or a hydroxyalkyl group
  • v represents a number of 0 or 1
  • examples of the fluoroalkyl group represented by R 1 and R 2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. Examples thereof include a fluoroalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group represented by R2 include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl and cyclohexyl groups.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom.
  • fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluorovinyl ethers; Perfluoro (alkyl vinyl ethers) such as fluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl) such as perfluoro (propoxypropyl vinyl ether) Vinyl ethers) may be used singly or in combination of two or more. Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more prefer
  • the content of the structural unit (a) is 20 to 70 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorinated vinyl polymer is 100 mol%. More preferably, it is 25 to 65 mol%, more preferably 30 to 60 mol%.
  • examples of the alkyl group represented by R4 include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and lauryl group. , A methoxycarbonyl group, an ethoxycarbonyl group, and the like.
  • examples of the hydroxythioalkoxy group include a hydroxythiomethoxy group, a hydroxythioethoxy group, and the like.
  • the structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component.
  • vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid
  • the content of the structural unit (b) is 10 to 70 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorinated vinyl polymer is 100 mol%. It is more preferably 20 to 60% by mole, and further preferably 30 to 60% by mole.
  • the structural unit (c ′) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples thereof include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and polypropylene. Glycol (meth) acrylate or the like can be used.
  • the content of the structural unit (c ′) is 5 to 70 mol when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorinated vinyl polymer is 100 mol%. %, More preferably 5 to 40 mol%, still more preferably 5 to 30 mol%.
  • the active hydrogen group-containing fluorinated vinyl polymer may further comprise the following structural unit (d).
  • R 9 and R 10 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
  • the alkyl group of R 9 and R 10 is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group.
  • C1-C4 fluoroalkyl groups such as ethyl, perfluoropropyl, and perfluorobutyl groups
  • aryl groups include phenyl, benzyl, and naphthyl groups.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (6).
  • An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).
  • R 13 to R 16 may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group; R 17 to R 20 may be the same or different; Or an alkyl group, p and q are numbers from 1 to 6, r and s are numbers from 0 to 6, t is a number from 1 to 200, and u is a number from 1 to 20]
  • the structural unit (d) is included in the fluorinated vinyl polymer containing an active hydrogen group as a part of the structural unit (e).
  • examples of the alkyl group represented by R 13 to R 16 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group.
  • examples of the alkyl group of 17 to R 20 include alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).
  • the content of the structural unit (d) is 0 to 10 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorinated vinyl polymer is 100 mol%.
  • the content is 0.1 to 5 mol%, more preferably 0.1 to 3 mol%.
  • the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.
  • the active hydrogen group-containing fluorinated vinyl polymer preferably further comprises the following structural unit (C).
  • R 21 represents a group represented by the following formula (12).
  • n a number from 1 to 20
  • m a number from 0 to 4
  • k a number from 3 to 50
  • Structural unit (C) can be introduced by using a reactive emulsifier as a polymerization component.
  • reactive emulsifiers include compounds represented by the following formula (13).
  • the content of the structural unit (C) is from 0.1 to 5 mol when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluoropolymer is 100 mol%. % Is preferable. The reason for this is that when the content is 0.1 mol% or more, the solubility of the active hydrogen group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol%, the curable resin This is because the adhesiveness of the composition does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used for a coating material or the like. For these reasons, the content of the structural unit (C) is more preferably 0.1 to 3 mol% with respect to the total amount of the active hydrogen group-containing fluorinated vinyl polymer. More preferably, it is 2 to 3 mol%.
  • a radiation-reactive group-containing fluorinated vinyl polymer is a compound containing an active hydrogen group possessed by a fluorinated vinyl polymer having an active hydrogen group, and a group that forms a covalent bond with the radiation-reactive group and the active hydrogen group. It is obtained by a reaction between an active hydrogen possessed by and a group that forms a covalent bond.
  • the group that forms a covalent bond with the active hydrogen group is preferably 0.5 to 1.0 equivalent with respect to 1.0 equivalent of the active hydrogen group.
  • the compound containing a radiation-reactive group and a group that forms a covalent bond with an active hydrogen group is a compound containing a radiation-reactive group and a group that forms a covalent bond with an active hydrogen group used in the production of a polyvinyl compound.
  • the (A) radiation-reactive group-containing fluorine-containing copolymer having a poly (meth) acrylic structure (hereinafter referred to as “poly (meth) acrylic compound”) has a radiation-reactive group and a fluorine atom (meth). If it is an acrylic polymer, it will not specifically limit.
  • the (meth) acrylic polymer having a radiation reactive group and a fluorine atom includes, for example, a fluorinated (meth) acrylic polymer having an active hydrogen group, a group that forms a covalent bond with the radiation reactive group and the active hydrogen group, and It is obtained by reacting with a compound containing Although it does not specifically limit as an active hydrogen group, A hydroxyl group, an amino group, a thiol group, a carboxyl group, etc. are mention
  • the group that forms a covalent bond with the active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, a carbonyl halide group, an epoxy group, and a glycidyl group.
  • the compound containing a radiation-reactive group and a group that forms a covalent bond with an active hydrogen group is a compound containing a radiation-reactive group and a group that forms a covalent bond with an active hydrogen group used in the method for producing a polyvinyl compound. Is the same.
  • the active hydrogen group-containing fluorinated (meth) acrylic polymer is not particularly limited as long as it is a (meth) acrylic polymer containing an active hydrogen group and a fluorine atom.
  • the following structural units (a), (b) and A hydroxyl group-containing fluorinated (meth) acrylic polymer comprising (c ′) is preferred.
  • (C ′) A structural unit represented by the following formula (26).
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a monovalent organic group having no active hydrogen group
  • R 7 represents a hydrogen atom or a methyl group
  • v represents a number of 1 to 20
  • Structural unit (a) In the above formula (21), m is 1 to 8, preferably 1 to 4, and more preferably 2. n is 1 to 20, preferably 3 to 12, more preferably 4 to 8, and most preferably 6.
  • the structural unit (a) can be introduced by using a compound represented by the following formula (27) as a polymerization component.
  • a typical example of such a compound is perfluorohexylethyl (meth) acrylate.
  • R 1, m and n are each identical to R 1, m and n in formula (21)]
  • the content of the structural unit (a) in the hydroxyl group-containing fluorinated (meth) acrylic polymer is 20 to 70 mol%, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. Preferably, it is 30 to 60 mol%, and more preferably 35 to 60 mol%.
  • R 3 in the above formula (22) is a monovalent organic group having no active hydrogen group.
  • R 3 is not particularly limited as long as R 3 is a monovalent organic group having no active hydrogen, but particularly because the balance between Young's modulus and refractive index of a cured product obtained by curing the composition of the present invention is suitable.
  • a monovalent organic group having an alicyclic structure is preferred.
  • the alicyclic structure includes a heterocyclic structure.
  • Structural unit (b) can be introduced by using a compound represented by the following formula (28) as a polymerization component.
  • Particularly suitable compounds include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like.
  • the content of the structural unit (b) in the hydroxyl group-containing fluorinated (meth) acrylic polymer is 10 to 70 mol%, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. Preferably, it is 20 to 60 mol%, and more preferably 20 to 55 mol%.
  • the content of the structural unit (b) exceeds 70 mol%, there is a side effect of increasing the refractive index of the hydroxyl group-containing fluorinated (meth) acrylic polymer.
  • it is less than 20 mol% there is a side effect of reducing the solubility of the hydroxyl group-containing fluorinated (meth) acrylic polymer.
  • the structural unit (c ′) can be introduced by using a compound represented by the following formula (29) as a polymerization component.
  • a compound represented by the following formula (29) include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol ( A (meth) acrylate etc. can be used.
  • R 7 and v are each identical to R 7 and v in the formula (26).
  • the content of the structural unit (c ′) in the hydroxyl group-containing fluorinated (meth) acrylic polymer is 5 to 70 mol, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. %, Preferably 10 to 40 mol%, more preferably 10 to 20 mol%.
  • the content of the structural unit (c ′) exceeds 70 mol%, there is a side effect of increasing the refractive index of the fluoropolymer. On the other hand, if it is less than 5 mol%, there is a side effect that the radiation reactive group may not be sufficiently introduced.
  • the radiation-reactive group-containing fluorinated (meth) acrylic polymer is a group that forms a covalent bond with the active hydrogen group in the active hydrogen group-containing fluorinated (meth) acrylic polymer, the radiation-reactive group, and the active hydrogen group. It is obtained by reacting a group that forms a covalent bond with an active hydrogen group in a compound containing.
  • the number of moles of the group that forms a covalent bond with the active hydrogen group in the compound containing the radiation-reactive group and the group that forms a covalent bond with the active hydrogen group is the active hydrogen group-containing fluorination (metathesis). It is preferably 0.5 to 1.0 times the number of moles of active hydrogen groups in the acrylic polymer.
  • the (A) radiation-reactive group-containing fluorine-containing copolymer having a polyurethane structure is not particularly limited as long as it is a polyurethane compound having a radiation-reactive group and a fluorine atom.
  • a polyurethane compound having a radioactive reactive group and a fluorine atom that is, a radiation reactive group-containing fluorinated polyurethane, reacts, for example, a fluorinated polyol, a diisocyanate, and a compound having a hydroxyl group and a radiation reactive group in one molecule. Is obtained. In particular, those obtained by reacting a fluorinated polyol, a diisocyanate, and a hydroxyl group-containing (meth) acrylate are preferred.
  • the radiation-reactive group-containing fluorinated polyurethane is basically formed by reacting a polyol, a diisocyanate, and a compound having a hydroxyl group and a radiation-reactive group. That is, it is formed by reacting the isocyanate group of diisocyanate with the hydroxyl group of the polyol and the hydroxyl group in the compound having a hydroxyl group and a radiation reactive group.
  • reaction for example, a method in which polyol, diisocyanate and hydroxyl group-containing (meth) acrylate are charged together and reacted; a method in which polyol and diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; A method of reacting acrylate and then reacting polyol; reacting diisocyanate and hydroxyl group-containing (meth) acrylate, then reacting polyol, and finally reacting hydroxyl group-containing (meth) acrylate again.
  • fluorine-containing polyol examples include perfluoropolyether represented by the following formula (31).
  • Z is the same or different and represents —CH 2 (OCH 2 CH 2 ) n OH (n is 0 to 10, preferably 1 to 7), and p is 1 to 40 A number, q represents a number from 1 to 70)
  • the molecular weight of the perfluoropolyether represented by the formula (31) is preferably 1000 to 5000, particularly preferably 1000 to 3000.
  • Fluorolink E made by Solvay Solexis
  • diisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p.
  • the compound having a hydroxyl group and a radiation reactive group is not particularly limited as long as it is a compound having at least one hydroxyl group and at least one radioactive reactive group in the molecule, but a hydroxyl group-containing (meth) acrylate is preferable.
  • the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl (meth) acrylate.
  • 1,4-butanediol mono (meth) acrylate 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) a Relate the following chemical formula (32) or (33)
  • R 2 represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15)
  • (Meth) acrylate represented by the following.
  • the compound obtained by addition reaction with glycidyl group containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can also be used.
  • glycidyl group containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid
  • hydroxyl group-containing (meth) acrylates 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable.
  • the use ratio of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate is such that the isocyanate group contained in the diisocyanate is 1 to 3 equivalents and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.2 to 1 equivalent to 1 equivalent of the hydroxyl group contained in the polyol.
  • the equivalent of the hydroxyl group in the polyol and acrylate is preferably substantially equal to the equivalent of the isocyanate group in the diisocyanate.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, titanium tetraalkoxide, zirconium tetraalkoxide, zirconium acetylacetonate, etc. It is preferable to use 0.01 to 1 part by mass with respect to 100 parts by mass in total.
  • the reaction temperature is usually 10 to 90 ° C., preferably 30 to 80 ° C.
  • the (A) radiation-reactive group-containing fluorine-containing copolymer having a polyether structure (hereinafter referred to as “polyether compound”) is not particularly limited as long as it is a polyether compound having a radiation-reactive group and a fluorine atom.
  • the radiation-reactive group-containing fluorinated polyether is obtained, for example, by reacting a fluorinated polyether polyol with a compound having a radiation-reactive group and a group that forms an ether bond with a hydroxyl group in one molecule. .
  • Examples of the group that forms an ether bond with a hydroxyl group include a halogenated alkyl group, an epoxy group, and a halogenated carbonyl group. That is, by reacting a hydroxyl group in a fluorinated polyether polyol with a group that forms an ether bond with a hydroxyl group in a compound having a radiation-reactive group and a group that forms an ether bond with a hydroxyl group in one molecule, A radiation-reactive group-containing fluorinated polyether can be formed.
  • a fluorine-containing polyol used here it is the same as the fluorine-containing polyol used for manufacture of the polyurethane compound which is a component (A).
  • the compound having a radiation-reactive group and a group that forms an ether bond with a hydroxyl group is a compound having at least one radioactive-reactive group and at least one group that forms an ether bond with a hydroxyl group in one molecule.
  • the acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, methacrylic acid bromide, and the like are particularly preferable.
  • the use ratio of the compound having a fluorinated polyether polyol, a group that forms an ether bond with a hydroxyl group, and a radiation reactive group is such that the radiation reactive group and the hydroxyl group with respect to 1 equivalent of the hydroxyl group in the fluorinated polyether polyol.
  • the group that forms an ether bond with the hydroxyl group in the compound having a group that forms an ether bond is adjusted to 0.5 to 1.0 equivalent.
  • the radiation-reactive group-containing fluorine-containing copolymer as component (A) is usually blended in an amount of 10 to 80% by mass, preferably 20 to 60% by mass, particularly preferably based on the total amount of the composition. 30 to 60% by mass is blended.
  • Component (B) used in the composition of the present invention is a compound other than (A) having a radiation-reactive group.
  • the radiation-reactive group is not particularly limited as long as it is a functional group that undergoes a polymerization reaction directly by radiation or via an initiator.
  • the component (B) preferably has a fluorine atom. When the component (B) has a fluorine atom, the refractive index of the composition of the present invention can be further reduced, and a microchannel excellent in light transmittance can be formed.
  • component (B1) having a fluorine atom
  • component (B1) include compounds represented by the following formulas (41) to (45).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a fluorine atom
  • m represents 1 to 2
  • n represents 2 to 8.
  • CR 3 2 CR 3- (CF 2 ) p F (42)
  • each R 3 independently represents a hydrogen atom or a fluorine atom, and p represents 2 to 8.
  • CR 4 2 CR 4 —O— (CF 2 ) q F (43)
  • R 4 each independently represents a hydrogen atom or a fluorine atom, and q represents 2 to 8.
  • R 5 independently represents a hydrogen atom or a fluorine atom
  • R 6 represents an oxygen atom or a sulfur atom
  • r represents 2 to 8.
  • R 7 represents an oxygen atom or a sulfur atom, and s represents 2 to 8.
  • a compound having a (meth) acryloyl group represented by the above formula (41) is particularly preferred because the curable resin composition described later can be more easily cured.
  • Specific examples of the formula (41) are not particularly limited as long as they are compounds corresponding to the formula (41), but 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, Examples include 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, and the like.
  • Examples of these commercially available products include biscoat 13F, 17F, 4F, 8F and the like (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
  • 2-perfluorohexylethyl (meth) acrylate is preferable because it is suitable for dissolving the component (A) and is easily available.
  • the component (B1) is usually blended in an amount of 15 to 50% by mass with respect to the total amount of the composition, preferably 20 to 45% by mass, particularly preferably 30 to 45% by mass.
  • (B) having no fluorine atom (B2) a compound having no aromatic structure and a polar group and having two or more ethylenically unsaturated groups, (B3) having no aromatic structure and a polar group , Compounds having one ethylenically unsaturated group, and compounds having an ethylenically unsaturated group other than the components (B4), (B2) and (B3).
  • blended with the composition of this invention is a compound which does not have an aromatic structure and a polar group, and has two or more ethylenically unsaturated groups. Since the component (B2) does not have a polar group, when used in combination with the component (B1), the solubility of the component (A) is increased to give a uniform composition. Moreover, the hardened
  • the polar group includes polar groups such as a carbonyl group and an alkylene oxide group having 3 or less carbon atoms in addition to a dissociable group such as a carboxyl group and an amino group, but a hydroxyl group is excluded.
  • the component (B2) is not particularly limited as long as it has a structure that satisfies the above requirements.
  • component (B2) include, for example, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc. And (meth) acrylates containing aliphatic structure.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the component (B2) is usually blended in an amount of 0 to 40% by mass with respect to the total amount of the composition, preferably 0 to 35% by mass, particularly preferably 0 to 20% by mass.
  • Specific examples of compounds having no aromatic structure and no polar group and having one ethylenically unsaturated group include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam; hydroxybutyl vinyl ether, Vinyl ethers such as lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether; diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide acrylamides such as t-octyl (meth) acrylamide; isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, -Alicyclic structure-containing (meth) acrylates
  • the component (B3) is usually added in an amount of 0 to 30% by mass, preferably 0 to 25% by mass, particularly preferably 0 to 20% by mass, based on the total amount of the composition.
  • (B4) Specific examples of compounds having an ethylenically unsaturated group other than the components (B2) and (B3) include polar groups such as aromatic structure-containing (meth) acrylates, carboxyl groups and alkylene oxide structures ( And (meth) acrylate.
  • the component (B4) tends to increase the refractive index of the cured product like the aromatic structure-containing (meth) acrylate, and reduces the solubility of the component (A) like the polar group-containing (meth) acrylate. Since there exists a tendency, it is preferable that the compounding quantity of (B4) component shall be 5 mass% or less by making the composition whole quantity into 100 mass%.
  • components (B) are usually blended in an amount of 20 to 70% by mass with respect to the total amount of the composition, preferably 25 to 65% by mass, particularly preferably 30 to 65% by mass.
  • the blending amount of the component (B1) having a fluorine atom is preferably 30 to 100% by mass and more preferably 50 to 100% by mass with respect to the total amount of the component (B).
  • ⁇ Ingredient (C)> When the composition of the present invention is cured by irradiation with radiation such as ultraviolet rays, it is desirable to blend (C) a radiation polymerization initiator.
  • a radiation polymerization initiator As a radiation polymerization initiator, a radiation radical polymerization initiator and a radiation acid generator are mentioned.
  • a radiation radical polymerization initiator When the radiation reactive group which component (A) and component (B) have is a radical polymerizable group such as a (meth) acryloyl group, a radiation radical polymerization initiator is used.
  • a radiation reactive group which component (A) and component (B) have is a cationically polymerizable group such as an epoxy group, for example, a radiation acid generator is used as component (C).
  • the radiation radical polymerization initiator (C) include, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-y Propylthioxanthone, 2-chlorothioxan
  • a photosensitizer can be used in combination.
  • the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Isoamyl; Ubekryl P102, 103, 104, 105 (above, manufactured by UCB) and the like.
  • the thermal polymerization initiator and the radiation polymerization initiator can be used in combination.
  • the radiation radical polymerization initiator is preferably blended in an amount of 0.1 to 10% by mass, particularly 0.3 to 7% by mass, based on the total amount of the composition.
  • the component (C) is a radiation cationic polymerization initiator.
  • the radiation cationic polymerization initiator is a compound capable of releasing a substance that initiates the cationic polymerization of the components (A) and (B) by receiving energy rays such as light.
  • energy rays such as light mean visible light, ultraviolet light, infrared light, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • a particularly preferred compound (C) is an onium salt having a structure represented by the following formula (51).
  • the onium salt represented by the formula (51) is a compound that releases a Lewis acid by receiving light.
  • Specific examples of the anion [MX n + m ] in the formula (51) include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoroarsenate ( AsF 6 ⁇ ), hexachloroantimonate (SbCl 6 ⁇ ) and the like.
  • An onium salt having an anion represented by the formula [MX n (OH) ⁇ ] can be used. Further, perchlorate ion (ClO 4 ⁇ ), trifluoromethane sulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3 ⁇ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate Onium salts having other anions such as anions can also be used.
  • aromatic onium salts are particularly effective as the component (C).
  • Group VIA aromatic onium salts described in JP-A-55420, JP-A-55-125105, etc. Group VA aromatic onium salts described in JP-A-50-158698, etc.
  • JP-A-56-8428 Oxosulfoxonium salts described in JP-A-56-149402 and JP-A-57-192429
  • an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned.
  • UVI-6950, UVI-6970, UVI-6974, UVI-6990 manufactured by Union Carbide
  • Adekaoptomer SP-150, SP-151, SP -170, SP-172 above, manufactured by Asahi Denka Kogyo Co., Ltd.
  • Irgacure 261 above, made by Ciba Specialty Chemicals
  • CI-2481, CI-2624, CI-2639, CI-2064 aboveve, made by Nippon Soda Co., Ltd.
  • CD-1010, CD-1011, CD-1012 aboveve, manufactured by Sartomer
  • UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-172, CD-1012, and MPI-103 exhibit high photocuring sensitivity in the resin composition containing them. It is particularly preferable because Said radiation cationic polymerization initiator can comprise (C) component individually by 1 type or in combination of 2 or more types.
  • component (C) for example, a salt of diphenyl (phenylthiophenyl) sulfonium including a structure represented by the following formula (52) is also preferable.
  • component (C) include more specifically salts containing antimony atoms such as diphenyl (phenylthiophenyl) sulfonium hexafluoroantimonate, diphenyl (phenylthiophenyl) sulfonium hexafluorophosphate, diphenyl ( And salts containing no antimony atom, such as phenylthiophenyl) sulfonium tris (pentafluoroethyl) trifluorophosphate.
  • a salt containing no antimony atom is preferable from the viewpoint of safety.
  • Examples of commercially available products of the component (C) represented by the above formula (52) include CPI-100A, CPI-101A, CPI-110A, CPI-200K (manufactured by San Apro).
  • the blending ratio of (C) the radiation cationic polymerization initiator is usually 0.1 to 10% by mass, preferably 0.5 to 100% by mass of the total composition. It is ⁇ 10% by mass, more preferably 1 to 10% by mass.
  • (D) (Meth) acrylic acid or a dimer thereof can be further blended in the composition of the present invention.
  • adhesion to glass, quartz, and siloxane-based material can be improved.
  • the component (D) is usually added in an amount of 0 to 10% by mass, preferably 1 to 7% by mass, based on the total amount of the composition. If it exceeds 10% by mass, the storage stability of the composition may be impaired.
  • composition of the present invention various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, and a thermal polymerization, as long as they do not impair the characteristics of the present invention.
  • Inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, coating surface improvers and the like can be blended.
  • the viscosity of the composition of the present invention is preferably 0.5 to 10 Pa ⁇ s, particularly preferably 1 to 6 Pa ⁇ s at 25 ° C.
  • composition of this invention is hardened
  • the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • the microchannel can be formed by using the composition of the present invention, for example, by the following method.
  • a microchannel having a function of a biosensor or the like can be formed using the composition of the present invention as an adhesive.
  • the composition material [4] of the present invention is thickened by, for example, a coating method on a transparent substrate [3] such as a glass substrate having a through hole that is a liquid inlet [1] and a discharge port [2] having a diameter of 1 mm. It is applied at a thickness of 30 to 100 ⁇ m (step 2).
  • ultraviolet rays such as i-line having a wavelength of 365 nm, for example, are irradiated through a photomask [5] so as to be about 500 mJ / cm 2 to 1000 mJ / cm 2, and only a desired area is exposed to be exposed / cured (step 3). ).
  • a glass substrate with a flow path pattern [10] is obtained by removing uncured regions by immersing in a desired organic solvent (step 4). In this way, a coating film that has entered each hole of a glass substrate having a plurality of relatively large mm-sized holes can be removed as an uncured region at the time of development, such as an inlet [1] and an outlet [2].
  • the flow path pattern can be formed without blocking the through hole.
  • the composition of the present invention is applied on the silicon substrate [6] having good flatness by, for example, spin coating or the like so that the thickness becomes, for example, about 5 ⁇ m to 10 ⁇ m, and the coating film [7] of the composition is formed. It forms and obtains base material [11] with an adhesive coating film (process 5).
  • the flow path pattern upper plane part of the glass substrate with a flow path pattern obtained in step 4 and the coating film surface of the composition of the substrate with an adhesive coating film obtained in step 5 are brought into close contact (step 7).
  • a part of the coating film of the composition is transferred onto the upper plane of the flow path pattern by separating the substrate with the adhesive coating film from the glass substrate with the flow path pattern again (step 8).
  • a silicon substrate on which a coating film of the composition formed on the upper plane of the flow path pattern formed on the glass substrate obtained in step 8 and a biosensor region using an antibody or the like is formed [ 12].
  • the entire surface of the transparent glass substrate side is irradiated with ultraviolet rays such as i-line having a wavelength of 365 nm, for example, at about 1000 mJ / cm 2 from the transparent substrate [3] side, whereby the glass substrate with flow path pattern [10] and silicon
  • the substrate [12] is bonded to obtain the microchannel [100] (step 9).
  • proteins such as antibodies may be immobilized on the silicon substrate [12].
  • an affinity column structure in which the antibody is immobilized on the inner surface of the microchannel can be formed.
  • a biosensor using an antibody or the like a biosensor using an electrode or the like can be formed on the silicon substrate.
  • Adhesion is performed by photo-curing type adhesion, whereby the micro-channel channel can be adhered without destroying or degrading the antibody formed on the silicon substrate side. Since the material forming the microchannel and the material to be bonded have the same characteristics, there is no difference between the materials and the same properties can be obtained.
  • the adhesive can be selectively formed on the tip of the convex portion of the microchannel channel structure, it can be bonded to the silicon substrate at a low temperature without blocking the mm-sized hole formed in the glass substrate.
  • the substrate can be bonded and formed at a low temperature.
  • a photosensitive resin material for example, an acrylic resin-based photoresist (for example, manufactured by JSR), a thick film resist (SU-8), for example, by a coating method, Polydimethylsiloxane (PDMS) or the like is applied to a thickness of about 30 ⁇ m to 50 ⁇ m to form a resist layer [22] (step 2).
  • the coating film formed on the edge of the silicon substrate [21] causes contamination of the exposure stage and particles in the subsequent exposure process, so it is desirable to remove it with an organic solvent such as thinner.
  • ultraviolet rays such as i-line having a wavelength of 365 nm, for example, are exposed through a mask [5] having a desired pattern so that the exposure amount is, for example, about 1000 mJ / cm 2 to be exposed / cured (step 3).
  • PEB Post Exposure Bake
  • PEB Post Exposure Bake
  • PEB Post Exposure Bake
  • TMAH 2.38 wt% tetramethylammonium hydroxide
  • a silicon substrate [22] with a flow path pattern is obtained by heat treatment using an oven in a nitrogen atmosphere at 180 ° C. for 2 hours to obtain a flow path pattern silicon substrate [22].
  • an appropriate protein such as an antibody labeled with a fluorescent substance or the like [23] is immobilized in a desired region using, for example, a spotter (step 5).
  • the composition of the present invention is applied on a silicon substrate by spin coating or the like so as to have a thickness of, for example, about 1 ⁇ m to 10 ⁇ m, and a coating film is formed on the surface.
  • a silicon substrate [24] is formed (step 6).
  • the flow path pattern convex surface of the silicon substrate with flow path pattern [22] obtained in step 5 and the coating film surface of the composition of the silicon substrate with adhesive coating film [24] obtained in step 5 are brought into close contact with each other.
  • Step 7 Next, a part of the coating film of the composition is transferred onto the upper plane of the flow path pattern by peeling again the upper surface of the flow path pattern of the substrate with the adhesive coating film and the silicon substrate (step 8).
  • the glass substrate [25] has through holes which are a liquid inlet [1] and a outlet [2] for a liquid having a diameter of about 1 mm.
  • the entire surface of the transparent glass substrate [25] is irradiated with ultraviolet rays such as i-line having a wavelength of 365 nm so as to be 500 mJ / cm 2 to 1000 mJ / cm 2 (step 9). 22] and the glass substrate [25] are bonded to each other to obtain the microchannel [100] covered with the glass substrate (step 10).
  • the sample liquid is injected from the inlet [1] of the obtained microchannel [100]
  • the substance that specifically binds to the antibody or the like immobilized on the channel is separated from the sample liquid and binds to the antibody or the like.
  • the fluorescence intensity of, for example, a fluorescent label such as an antibody changes, and can be used as a biosensor for detecting the substance in a sample.
  • the refractive index of the composition of the present invention used as an adhesive in this embodiment is desirably close to glass.
  • a plurality of microchannels can be manufactured continuously.
  • the glass substrate with a flow path pattern [10] obtained in step 4 shown in FIG. 1 is placed on, for example, a conveyor so as to move in a certain direction, and at the same time, on the cylindrical surface of the rotating roll [31].
  • the composition [32] is formed on the surface of the roll [31] uniformly using a squeegee [33] or the like to a film thickness of about 1 ⁇ m to 10 ⁇ m.
  • the distance between the roll [31] and the glass substrate is adjusted, and the composition of the present invention is selectively transferred to the surface of the channel of the glass substrate with a channel pattern [10] (steps 1 and 2).
  • the hardness of the roll [31] is optimized, the state of the roll [31] surface (hydrophilic level, etc.), the pressing strength, the roll [31] and glass with a flow path pattern.
  • the distance of the substrate [10] is optimized.
  • the flow path pattern surface of the glass substrate with a flow path pattern obtained in step 2 is brought into close contact with a silicon substrate [34] on which proteins such as antibodies are immobilized.
  • the entire surface of the glass substrate with a flow path pattern [10] is irradiated with ultraviolet rays such as i-line having a wavelength of 365 nm at 500 mJ / cm 2 to 1000 mJ / cm 2 , so that the glass substrate with a flow path pattern [10] and silicon
  • the substrate [34] is bonded to obtain the microchannel [100] (step 3).
  • the composition of the present invention can be continuously applied to the convex surface of the glass substrate with a flow path pattern [10] by adjusting the composition to a uniform film thickness. .
  • the flow path part formed on the silicon substrate on which the sensor and the filter are formed using the composition of the present invention as an adhesive and the flow path forming material, and bio A microchannel can be obtained in which a silicon substrate on which a sensor, an antibody or the like is formed is bonded at a low temperature.
  • a photosensitive resin material for example, an acrylic resin-based photoresist (for example, manufactured by JSR), a thick film resist (SU-8), poly, etc.
  • Dimethylsiloxane (PDMS) or the like is applied to a thickness of about 30 to 50 ⁇ m to form a resist layer [42] (step 2).
  • PDMS Dimethylsiloxane
  • an organic solvent such as thinner.
  • ultraviolet rays such as i-line having a wavelength of 365 nm, for example, are exposed through a mask [5] having a desired pattern so that the exposure amount is, for example, about 1000 mJ / cm 2 to be exposed / cured (step 3).
  • PEB Post Exposure Bake
  • a silicon substrate [42] with a flow path pattern having a flow path pattern made of a cured film of the composition of the present application is obtained by heat-treating using an oven at 180 ° C. for 2 hours in a nitrogen atmosphere to obtain a flow path pattern-containing silicon substrate [42] ( Step 4).
  • the composition of the present invention is applied on the silicon substrate [43] having good flatness, for example, by spin coating or the like so as to have a thickness of about 1 ⁇ m to 10 ⁇ m, for example, and the coating film [44] of the composition is formed. It forms and obtains the base material [45] with an adhesive coating film (process 5).
  • the flow path pattern convex portion plane of the silicon substrate with flow path pattern [42] obtained in step 4 and the coating film surface of the composition of the substrate with adhesive coating film [45] obtained in step 5 are brought into close contact ( Step 6).
  • a part of the coating film [44] of the composition is formed on the upper plane of the flow path pattern by peeling again the base material with adhesive coating film [45] and the silicon substrate with flow path pattern [42]. Is transferred (step 7).
  • the film thickness of the transferred composition at this time is about 1 ⁇ m.
  • the cured film of the present composition is used as a waveguide, for example, at a wavelength of 365 nm.
  • Irradiation with ultraviolet rays such as i-rays is carried out to about 2,000 mJ / cm 2 (step 8). It is preferable to irradiate ultraviolet rays from a plurality of peripheral portions of the silicon substrate. By doing in this way, even the opaque silicon substrates which do not transmit ultraviolet rays can be bonded at a low temperature using the adhesive made of the composition of the present invention.
  • the manufacturing method of this embodiment by using such a manufacturing method, it is possible to adhere at a low temperature of about 40 ° C. without destroying proteins such as antibodies immobilized in a desired region of the flow path. You can do it.
  • proteins such as antibodies are formed on the silicon substrate [41] side on which the flow path pattern is formed, and then the silicon substrates are cooled to about 40 ° C. using the composition of the present invention. It can also be glued with. By doing in this way, the silicon substrate which has the antibody with the biomarker comprised from protein on the inner surface of a microchannel and incorporates a biosensor can be adhere
  • the composition of the present invention is used as an adhesive and a flow path forming material, and a flow path portion formed on a silicon substrate, a biosensor, an antibody, and the like are provided.
  • Another embodiment of the micro flow path in which the formed silicon substrate is bonded is obtained.
  • Steps 1 to 5 of this embodiment are the same as those of the fourth embodiment shown in FIG.
  • the substrate with adhesive coating film [45] obtained in step 5 is cut to take out a plurality of silicon chips with adhesive coating film [51].
  • the following steps are the same as those in the fourth embodiment except that the silicon chip with adhesive coating film [51] is used instead of the substrate with adhesive coating film [45].
  • ultraviolet curing can be performed more reliably by carrying out in the form of a silicon chip with an adhesive coating film [51] having a short ultraviolet irradiation distance.
  • the composition of the present invention is used as an adhesive, a flow path forming material, etc., and a layer having an inlet and an outlet is formed by the composition of the present invention. It is possible to manufacture a microchannel composed of the cured product.
  • the flow path pattern and the cover layer serving as the lid can be formed continuously and integrally by a lithography technique.
  • a silicon substrate [61] with a release layer is formed by applying a material acting as a release layer on the surface of a silicon substrate or the like with a film thickness of about 20 ⁇ m (the release layer is not shown).
  • an easily peelable polyimide material film of Lucera S series (manufactured by JSR) can be used.
  • the composition of the present invention is applied to the film thickness of about 100 ⁇ m to 200 ⁇ m by, for example, a slit coater method or a coating method.
  • a coating film is formed.
  • 3000mJ ultraviolet i-line such as for example a wavelength of 365nm through a mask [62] having a desired pattern for forming a through hole serving as the inlet and outlet diameters 1 ⁇ 2 mm from 1000mJ / cm 2 / cm 2 Only a desired area is exposed / cured so as to obtain a moderate exposure amount (step 2).
  • a cover layer cured film [63] made of the composition of the present invention is formed to obtain a silicon substrate [64] with a cured cover layer film (step 3).
  • Step 3 development is performed by immersing the silicon substrate [64] with a cover layer cured film in a developing solution to remove the uncured coating film in the unexposed area to form a patterned silicon substrate [65] having a desired pattern.
  • the composition of the present invention is applied and formed on the pattern surface of the patterned silicon substrate [65] so as to have a film thickness of, for example, 50 ⁇ m to 100 ⁇ m, and a desired mask for forming a flow path pattern is used.
  • Exposed / cured step 4
  • immersed in an organic solvent developer to remove the uncured portion to form a silicon substrate [66] in which the cover layer is integrally formed on the flow path pattern (step 5). .
  • the composition of the present invention is applied on the surface of the silicon substrate [61] with good flatness by spin coating or the like, for example, to a thickness of about 1 ⁇ m to 10 ⁇ m to form a coating film [67] of the composition on the surface.
  • a silicon substrate with an adhesive coating film is formed, and the flow path pattern convex portion plane portion of the silicon substrate with a channel pattern [66] obtained in step 5 and the composition of the substrate with an adhesive coating film are obtained.
  • the coating film surface is brought into close contact (step 6).
  • a part of the coating film of the composition is selectively transferred onto the upper plane of the flow path pattern by peeling the silicon substrate with the adhesive coating film and the silicon substrate with the flow path pattern [66].
  • a silicon substrate [68] formed using a spotter or the like to form a biosensor or the like is bonded (step 8).
  • the coating film of the composition is cured by irradiating ultraviolet rays from a side surface or the like between the silicon substrate with a flow path pattern [66] and the silicon substrate [68].
  • the release layer-attached silicon substrate [61] can be peeled to form the microchannel [600] (step 9).
  • the production method of this embodiment By using the production method of this embodiment, it can be formed at a low temperature of about 40 ° C. without destroying the structure of the antibody or the like.
  • a layer having a through hole that serves as an inlet and an outlet can be formed integrally. Since the refractive index of the composition of this example is close to glass and the transmittance is high, the fluorescence intensity of the fluorescent marker attached to the biomarker is measured by making visible light incident from the cover layer side as in the past. This makes it possible to estimate the type and amount of adhered substances.
  • a microchannel having a multilayer structure By using the manufacturing method of the seventh embodiment shown in FIG. 7, a microchannel having a multilayer structure can be formed.
  • a material having a role as a release layer [72] is applied to the surface of the first support substrate [71] such as a silicon substrate or a glass substrate, for example, to a thickness of about 10 ⁇ m (step 1).
  • the release layer [72] for example, it is desirable to use a polyimide film having the easy-release characteristics of Lucera S series made by JSR, for example.
  • the composition [73] of the present invention having a thickness of about 50 ⁇ m is applied by, for example, a slit coater method or a coating method (step 2).
  • a slit coater method or a coating method step 2
  • the film extending to the edge portion of the silicon substrate causes contamination of the exposure stage and particle increase in the next exposure process, it is desirable to remove the film with an organic solvent such as thinner.
  • an organic solvent such as thinner.
  • ultraviolet rays such as i-line having a wavelength of 365 nm are used to expose only a desired region using an exposure amount of, for example, about 1,000 mJ / cm 2 to be exposed and cured.
  • the size of this Via pattern is set to be slightly smaller than the channel width because it serves to connect the upper and lower channel channels. For example, it is often about 50 ⁇ m to 100 ⁇ m.
  • the composition [73] of the present invention is applied and formed again on the entire surface so as to have a film thickness of, for example, about 50 ⁇ m, and then exposed and cured using a desired mask so as to form a flow path pattern.
  • a first channel layer [75] having a channel pattern step 4
  • the release layer [72] is formed on the surface of the second support substrate [76], and then has a desired Via pattern, for example, about 100 ⁇ m to 200 ⁇ m.
  • a structure to be a channel separation layer [74] having a thickness of is formed.
  • the release layer [72] may be formed using a fluorine-based film.
  • An adhesive layer [77] made of the composition of the present invention is selectively applied to the surface of the protrusion (convex portion) of the first flow path pattern formed in step 4 as in steps 5 to 9 in the first embodiment.
  • a method is used to form and adhere to the cover layer [74] on the second support substrate [76] (step 5). Then, the support substrate [71] is peeled off to obtain the structure [78] having the first flow path, the Via layer, and the cover layer (Step 6).
  • a plurality of Via patterns are formed on the cover layer. Since the cover layer eventually becomes the cover layer of the uppermost layer of the micro flow channel, it is necessary to set the film thickness to have an appropriate strength. A film thickness of about 200 ⁇ m is desirable.
  • the via diameter has a plurality of large holes with a diameter of 1-2 mm.
  • a flow channel pattern is formed on the third support substrate [79] in the same manner as in Steps 1 to 5 of the second embodiment, and then proteins such as antibodies are immobilized.
  • the composition [720] of the present invention is applied on the fourth support substrate [710] having good flatness, for example, by spin coating or the like, for example, to a thickness of about 1 ⁇ m to 10 ⁇ m to form a coating film.
  • the second flow path pattern on the support substrate [79] is brought into intimate contact (step 7). Then, by peeling the fourth support substrate [710], a part of the coating film of the composition is transferred onto the upper plane of the second flow path pattern on the third support substrate [79] (step) 8).
  • step 8 the coating film of the composition formed on the upper plane of the flow path pattern formed on the silicon substrate obtained in step 8 is bonded to the structure [78] obtained in step 6 (step) 9).
  • Ultraviolet rays are irradiated through the second support substrate [76] to cure and bond the composition.
  • the second support substrate [76] having the release layer is peeled off to complete the two-layer flow path structure [700] having the first and second flow paths, the Via layer, and the cover layer (Step 10).
  • the antibody which is the protein which forms the structure which has a two-layer microchannel structure which has the antibody which consists of a protein in a desired area
  • a cover layer having a plurality of holes for injecting liquid from the outside can be integrally formed on the uppermost layer at the same time, and two layers for supplying a biosolution (liquid) to a biosensor formed on a silicon substrate.
  • the microchannel structure can be integrally formed continuously. Since the refractive index of the composition of this example is close to that of glass and the transmittance is high, the fluorescence intensity of the fluorescent marker attached to the biomarker is measured by making visible light incident from the cover material side as in the past. This makes it possible to estimate the type and amount of adhered substances.
  • the formation of the two-layer microchannel is described, but a multilayer microchannel structure can be obtained by repeating this method.
  • the point of the present embodiment is that the flow path pattern and the cover material are continuously formed, the low temperature adhesive is selectively formed only on the upper surface portion of the structure, is cured and bonded, and finally is peeled off from the support material.
  • a multilayer microchannel structure is formed.
  • an example using a JSR release layer is shown, but the release layer is not limited to this, and other release layers may be used.
  • other materials can also be used.
  • the composition of the present invention is selectively formed on the upper surface of the protrusion of the flow channel and cured / adhered.
  • Steps 1 and 2 are the same as those in the first embodiment shown in FIG.
  • a dummy silicon substrate [81] with good flatness is placed on the surface of the composition (step 3).
  • the desired transparent glass substrate surface through a mask for example, by ultraviolet irradiation of i-ray having a wavelength of 365nm to consist 500 mJ / cm 2 to about 1000 mJ / cm 2 was exposed only desired regions photosensitive / Curing (step 4).
  • Step 5 the dummy silicon substrate [81] is removed to obtain a glass substrate on which a flow path pattern is formed.
  • Steps 6 to 9 are the same as those in the first embodiment shown in FIG. This peeling is performed by utilizing the difference between the adhesive strength with the glass and the adhesive strength with the silicon substrate. A layer for releasing may be formed on the dummy silicon substrate side. In this way, the coating film that has entered the through hole of the glass substrate can be removed during development, a flow path pattern can be formed without blocking the through hole, and a flow path pattern with a uniform film thickness can be formed by the dummy silicon substrate [81]. Is obtained. Moreover, since the composition is shielded from oxygen, it is possible to avoid the influence of oxygen inhibition caused by the type of photoinitiator.
  • a microchannel using a PDMS substrate can be manufactured.
  • the PDMS substrate with a flow path pattern [91] formed using a mold or the like is adhered to a transparent substrate [92] such as a glass substrate.
  • the composition of the present invention is applied, for example, to a thickness of about 1 ⁇ m to 10 ⁇ m by spin coating or the like on a silicon substrate [93] with good flatness to form a coating film [94] of the composition.
  • the base material with adhesive coating film [95] is brought into close contact with the flow path pattern surface of the PDMS base material with flow path pattern [91] and the coating film surface of the base material with adhesive coating film [95] (step 2). ). Then, a part of the coating film of the composition is transferred onto the convex surface of the flow path pattern by peeling the substrate with adhesive coating film [95] (step 3). Next, the coating film of the composition formed on the upper plane of the flow path pattern is brought into close contact with a silicon substrate [96] on which a biosensor formed by immobilizing proteins such as antibodies is formed.
  • the entire surface of the transparent glass substrate [92] is irradiated with ultraviolet rays such as i-line having a wavelength of 365 nm of about 1000 mJ / cm 2 through the transparent PDMS to thereby provide a PDMS base material with a flow path pattern [91] and a silicon substrate. [96] is adhered (step 4).
  • the transparent substrate [92] can be peeled off to form a microchannel. Note that a microchannel channel formed of a thick film resist material such as SU-8 in place of PDMS can be formed in the same manner.
  • the anaerobic curable composition is a curable composition mainly composed of a compound having an ethylenically unsaturated group such as (meth) acrylic acid ester, and is in a liquid state for a long time while in contact with oxygen. It has the property of being kept stable and rapidly curing at room temperature when oxygen is blocked or eliminated (Japanese Patent Laid-Open Nos. 2003-313206 and 2003-165806).
  • the anaerobic curable resin composition of the present invention comprises, as essential components, (A) a copolymer having an ethylenically unsaturated group and a fluorine atom and having a number average molecular weight of 1,000 to 500,000, and (B) an ethylenically unsaturated group. It contains a compound other than (A) having a group, (C) an organic peroxide, and (D) a polymerization accelerator.
  • Component (A)> A copolymer having an ethylenically unsaturated group and a fluorine atom and having a number average molecular weight of 1,000 to 500,000 (hereinafter referred to as “ethylenically unsaturated group-containing fluorine-containing copolymer”) used in the composition of the present invention. ) May have one or more structures selected from the group consisting of polyvinyl structures, poly (meth) acrylic structures, polyurethane structures, polyether structures, polyester structures, polyepoxy structures, polyamide structures, and polyimide structures. preferable.
  • the copolymer as the component (A) includes an oligomer.
  • Examples of the ethylenically unsaturated group include a vinyl group, a (meth) acryloyl group, a propenyl group (also referred to as an allyl group), and the like, and the curable resin composition of the present invention can be cured more easily. Therefore, a compound having a (meth) acryloyl group is more preferable.
  • the molecular weight of component (A) is preferably 1,000 to 500,000. When the number average molecular weight is less than 1,000, the mechanical strength of the cured product may be reduced and the strength of the microchannel may be reduced. When the number average molecular weight exceeds 500,000, the composition has a high viscosity. It may become difficult to apply.
  • the number average molecular weight of component (A) is more preferably from 5,000 to 200,000, and even more preferably from 10,000 to 100,000.
  • the number average molecular weight of the component (A) is a polystyrene equivalent number average molecular weight measured by a gel permeation chromatography method. Specifically, the number average in terms of polystyrene measured using a composite column connected to an HPLC system (HLC-8220GPC: manufactured by Tosoh Corporation) in the following order, with tetrahydrofuran (THF) as a developing solvent under a flow rate of 1 ml / min. Molecular weight. TSKgel G4000H XL, TSKgel G3000H XL, TSKgel G2000H XL, TSKgel G2000H XL, TSKgel G4000H XL, TSKgel G3000H XL.
  • the (A) ethylenically unsaturated group-containing fluorine-containing copolymer having a polyvinyl structure is not particularly limited as long as it is a vinyl polymer having an ethylenically unsaturated group and a fluorine atom.
  • the vinyl polymer is a polymer of a monomer having a vinyl group.
  • the vinyl polymer having an ethylenically unsaturated group and a fluorine atom is, for example, a compound containing a fluorine-containing vinyl polymer having an active hydrogen group and a group that forms a covalent bond with the ethylenically unsaturated group and the active hydrogen group. Obtained by reacting with.
  • An active hydrogen group is a group having active hydrogen. Although it does not specifically limit as an active hydrogen group, A hydroxyl group, an amino group, a thiol group, a carboxyl group etc. are mention
  • the group that forms a covalent bond with the active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, a carbonyl halide group, an epoxy group, and a glycidyl group.
  • a compound containing an ethylenically unsaturated group and a group that forms a covalent bond with an active hydrogen group forms a covalent bond with at least one ethylenically unsaturated group and at least one active hydrogen group in the molecule.
  • the compound is not particularly limited as long as it is a compound containing a group. Examples of such a compound include one kind or a combination of two or more kinds such as (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, and (meth) acrylate having an isocyanate group.
  • the (meth) acrylate having an isocyanate group examples include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and the like.
  • the Showa Denko Co., Ltd. make, brand name Karenz MOI, AOI, BEI etc. are mentioned, for example.
  • the (meth) acrylate having an isocyanate group can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferable.
  • hydroxyl group-containing (meth) acrylate 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferable.
  • examples of commercially available hydroxyl group-containing polyfunctional (meth) acrylates include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA; Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30; Toagosei Co., Ltd., trade name. Available as Aronix M-215, M-233, M-305, M-400, etc.
  • Fluorine-containing vinyl polymer having an active hydrogen group preferably comprises the following structural units (a), (b) and (c ′).
  • A A structural unit represented by the following formula (1).
  • B A structural unit represented by the following formula (2).
  • C ′ A structural unit represented by the following formula (7).
  • R 1 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group
  • R 5 represents an alkyl group, glycidyl A group or an aminoalkyl group, and x represents a number of 0 or 1), a carboxyl group, an alkoxycarbonyl group or a hydroxythioalkoxy group
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a hydrogen atom or a hydroxyalkyl group
  • v represents a number of 0 or 1
  • examples of the fluoroalkyl group represented by R 1 and R 2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group. Examples thereof include a fluoroalkyl group having 1 to 6 carbon atoms.
  • alkyl group for R 2 examples include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom.
  • fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluorovinyl ethers; Perfluoro (alkyl vinyl ethers) such as fluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl) such as perfluoro (propoxypropyl vinyl ether) Vinyl ethers) may be used singly or in combination of two or more. Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more prefer
  • the content of the structural unit (a) is 20 to 70 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorine-containing vinyl polymer is 100 mol%. It is preferably 25 to 65 mol%, more preferably 30 to 60 mol%.
  • examples of the alkyl group represented by R 4 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. , A methoxycarbonyl group, an ethoxycarbonyl group, and the like.
  • examples of the hydroxythioalkoxy group include a hydroxythiomethoxy group, a hydroxythioethoxy group, and the like.
  • the structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component.
  • vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid
  • the content of the structural unit (b) is 10 to 70 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorine-containing vinyl polymer is 100 mol%. It is preferably 20 to 60 mol%, more preferably 30 to 60 mol%.
  • the hydroxyalkyl group of R 12 includes a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and a 5-hydroxypentyl group. , 6-hydroxyhexyl group and the like.
  • the structural unit (c ′) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether,
  • hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether
  • hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether; allyl alcohol.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and polypropylene. Glycol (meth) acrylate or the like can be used.
  • the content of the structural unit (c ′) is 5 to 70 mol when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorine-containing vinyl polymer is 100 mol%. %, Preferably 5 to 40 mol%, more preferably 5 to 30 mol%.
  • the fluorine-containing vinyl polymer having an active hydrogen group can further comprise the following structural unit (d).
  • R 9 and R 10 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
  • the alkyl group of R 9 and R 10 is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group.
  • C1-C4 fluoroalkyl groups such as ethyl, perfluoropropyl, and perfluorobutyl groups
  • aryl groups include phenyl, benzyl, and naphthyl groups.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (6).
  • An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).
  • R 13 to R 16 may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group; R 17 to R 20 may be the same or different; Or an alkyl group, p and q are numbers from 1 to 6, r and s are numbers from 0 to 6, t is a number from 1 to 200, and u is a number from 1 to 20]
  • the structural unit (d) is included in the fluorinated vinyl polymer containing active hydrogen groups as a part of the structural unit (e).
  • R 13 to R 16 , R 17 to R 20 , p, q, r, s, and t are the same as those in Formula (8) above]
  • examples of the alkyl group represented by R 13 to R 16 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group.
  • examples of the alkyl group of 17 to R 20 include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).
  • the content of the structural unit (d) is 0 to 10 mol% when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluorine-containing vinyl polymer is 100 mol%.
  • the content is 0.1 to 5 mol%, more preferably 0.1 to 3 mol%.
  • the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.
  • the active hydrogen group-containing fluorinated vinyl polymer preferably further comprises the following structural unit (C).
  • R 21 represents a group represented by the following formula (12).
  • n is a number from 1 to 20
  • m is a number from 0 to 4
  • k is a number from 3 to 50]
  • Structural unit (C) can be introduced by using a reactive emulsifier as a polymerization component.
  • reactive emulsifiers include compounds represented by the following formula (13).
  • the content of the structural unit (C) is from 0.1 to 5 mol when the total amount of the structural units (a) to (c ′) in the active hydrogen group-containing fluoropolymer is 100 mol%. % Is preferable. The reason for this is that when the content is 0.1 mol% or more, the solubility of the active hydrogen group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol%, the curable resin This is because the adhesiveness of the composition does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used for a coating material or the like. For this reason, the content of the structural unit (C) is more preferably 0.1 to 3 mol% with respect to the total amount of the active hydrogen group-containing fluorinated vinyl polymer, More preferably, it is 2 to 3 mol%.
  • Ethylenically unsaturated group-containing fluorine-containing vinyl polymer contains an active hydrogen group possessed by the fluorinated vinyl polymer having an active hydrogen group and a group that forms a covalent bond with the ethylenically unsaturated group and the active hydrogen group. It is obtained by a reaction between an active hydrogen possessed by the compound to be formed and a group that forms a covalent bond.
  • the group that forms a covalent bond with the active hydrogen group is preferably 0.5 to 1.0 equivalent with respect to 1.0 equivalent of the active hydrogen group.
  • the (A) ethylenically unsaturated group-containing fluorine-containing copolymer having a poly (meth) acrylic structure is not particularly limited as long as it is a (meth) acrylic polymer having an ethylenically unsaturated group and a fluorine atom.
  • the (meth) acrylic polymer is a polymer of (meth) acrylic acid ester.
  • the (meth) acrylic polymer having an ethylenically unsaturated group and a fluorine atom forms a covalent bond with, for example, a fluorine-containing (meth) acrylic polymer having an active hydrogen group, and the ethylenically unsaturated group and the active hydrogen group. It is obtained by reacting with a compound containing a group.
  • a compound containing a group Although it does not specifically limit as an active hydrogen group, A hydroxyl group, an amino group, a thiol group, a carboxyl group etc. are mention
  • the group that forms a covalent bond with the active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, a carbonyl halide group, an epoxy group, and a glycidyl group.
  • a compound containing an ethylenically unsaturated group and a group that forms a covalent bond with an active hydrogen group is an ethylenically unsaturated group used in a method for producing an ethylenically unsaturated group-containing fluorine-containing copolymer having a polyvinyl structure. Identical to compounds containing saturated and active hydrogen groups and groups that form covalent bonds.
  • Fluorine-containing (meth) acrylic polymer having an active hydrogen group is not particularly limited as long as it is a (meth) acrylic polymer containing an active hydrogen group and a fluorine atom.
  • C ′ A structural unit represented by the following formula (26).
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a monovalent organic group having no active hydrogen group
  • R 7 represents a hydrogen atom or a methyl group
  • v represents a number of 1 to 20
  • Structural unit (a) In the above formula (21), m is 1 to 8, preferably 1 to 4, and more preferably 2. n is 1 to 20, preferably 3 to 12, more preferably 4 to 8, and most preferably 6.
  • the structural unit (a) can be introduced by using a compound represented by the following formula (27) as a polymerization component.
  • a typical example of such a compound is perfluorohexylethyl (meth) acrylate.
  • R 1, m and n are each identical to R 1, m and n in formula (21)]
  • the content of the structural unit (a) in the hydroxyl group-containing fluorine-containing (meth) acrylic polymer is 20 to 70 mol%, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. It is preferably 30 to 60 mol%, more preferably 35 to 60 mol%.
  • R 3 in the above formula (22) is a monovalent organic group having no active hydrogen group.
  • R 3 is not particularly limited as long as it is a monovalent organic group having no active hydrogen, but particularly because the balance between Young's modulus and refractive index of a cured product obtained by curing the composition of the present invention is suitable.
  • a monovalent organic group having an alicyclic structure is preferred.
  • the alicyclic structure includes a heterocyclic structure.
  • Structural unit (b) can be introduced by using a compound represented by the following formula (28) as a polymerization component.
  • Particularly suitable compounds include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like.
  • the content of the structural unit (b) in the hydroxyl group-containing fluorine-containing (meth) acrylic polymer is 10 to 70 mol%, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. It is preferably 20 to 60 mol%, more preferably 20 to 55 mol%.
  • the content of the structural unit (b) exceeds 70 mol%, there is a side effect of increasing the refractive index of the hydroxyl group-containing fluorine-containing (meth) acrylic polymer.
  • it is less than 20 mol% there is a side effect of lowering the solubility of the hydroxyl group-containing fluorine-containing (meth) acrylic polymer.
  • the structural unit (c ′) can be introduced by using a compound represented by the following formula (29) as a polymerization component.
  • a compound represented by the following formula (29) include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol ( A (meth) acrylate etc. can be used.
  • R 7 and v are each identical to R 7 and v in the formula (26).
  • the content of the structural unit (c ′) in the hydroxyl group-containing fluorine-containing (meth) acrylic polymer is 5 to 70 mol, where the total amount of the structural units (a), (b) and (c ′) is 100 mol%. %, Preferably 10 to 40 mol%, more preferably 10 to 20 mol%.
  • the content of the structural unit (c ′) exceeds 70 mol%, there is a side effect of increasing the refractive index of the fluoropolymer.
  • it is less than 5 mol% there is a side effect that the ethylenically unsaturated group may not be sufficiently introduced.
  • Ethylenically unsaturated group-containing fluorine-containing (meth) acrylic polymer The fluorine-containing (meth) acrylic polymer containing an ethylenically unsaturated group forms a covalent bond with the active hydrogen group in the fluorine-containing (meth) acrylic polymer containing an active hydrogen group and the ethylenically unsaturated group and the active hydrogen group. It can be obtained by reacting an active hydrogen group in a compound containing a group to form a covalent bond.
  • the number of moles of the group that forms a covalent bond with the active hydrogen group in the compound containing the ethylenically unsaturated group and the group that forms a covalent bond with the active hydrogen group is the active hydrogen group-containing fluorine-containing ( It is preferably 0.5 to 1.0 times the number of moles of active hydrogen groups in the (meth) acrylic polymer.
  • the (A) ethylenically unsaturated group-containing fluorine-containing copolymer having a polyurethane structure is not particularly limited as long as it is a polyurethane compound having an ethylenically unsaturated group and a fluorine atom.
  • the polyurethane compound is a compound having a plurality of urethane bonds.
  • the polyurethane compound having an ethylenically unsaturated group and a fluorine atom can be obtained, for example, by reacting a fluorine-containing polyol, diisocyanate, a compound having a hydroxyl group and an ethylenically unsaturated group.
  • a fluorine-containing polyol, diisocyanate, and a hydroxyl group-containing (meth) acrylate are preferred.
  • the ethylenically unsaturated group-containing fluorine-containing copolymer having a polyurethane structure is basically formed by reacting a fluorine-containing polyol, diisocyanate, and a compound having a hydroxyl group and an ethylenically unsaturated group. That is, it is formed by reacting the isocyanate group of diisocyanate with the hydroxyl group of the polyol and the hydroxyl group in the compound having a hydroxyl group and an ethylenically unsaturated group, respectively.
  • reaction for example, a method in which polyol, diisocyanate and hydroxyl group-containing (meth) acrylate are charged together and reacted; a method in which polyol and diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; A method of reacting acrylate and then reacting polyol; reacting diisocyanate and hydroxyl group-containing (meth) acrylate, then reacting polyol, and finally reacting hydroxyl group-containing (meth) acrylate again.
  • fluorine-containing polyol examples include perfluoropolyether represented by the following formula (31).
  • Z is the same or different and represents —CH 2 (OCH 2 CH 2 ) n OH (n is 0 to 10, preferably 1 to 7), and p is 1 to 40 A number, q represents a number from 1 to 70)
  • the molecular weight of the perfluoropolyether represented by the formula (31) is preferably 1000 to 5000, particularly preferably 1000 to 3000.
  • Fluorolink E made by Solvay Solexis
  • diisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane Diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate 6-isopropyl-1,3-phenyl di
  • the compound having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having at least one hydroxyl group and at least one ethylenically unsaturated group in the molecule, but a hydroxyl group-containing (meth) acrylate is preferable.
  • a hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl (meth) acrylate.
  • 1,4-butanediol (meth) acrylate 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Serial chemical formulas (32) or (33)
  • R 2 represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15)
  • (Meth) acrylate represented by the following.
  • the compound obtained by addition reaction with glycidyl group containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can also be used.
  • glycidyl group containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid
  • hydroxyl group-containing (meth) acrylates 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable.
  • the use ratio of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate is such that the isocyanate group contained in the diisocyanate is 1 to 3 equivalents and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.2 to 1 equivalent to 1 equivalent of the hydroxyl group contained in the polyol.
  • the equivalent of the hydroxyl group in the polyol and acrylate is preferably substantially equal to the equivalent of the isocyanate group in the diisocyanate.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, titanium tetraalkoxide, zirconium tetraalkoxide, zirconium acetylacetonate, etc. It is preferable to use 0.01 to 1 part by mass with respect to 100 parts by mass in total.
  • the reaction temperature is usually 10 to 90 ° C., preferably 30 to 80 ° C.
  • the (A) ethylenically unsaturated group-containing fluorine-containing copolymer having a polyether structure is not particularly limited as long as it is a polyether compound having an ethylenically unsaturated group and a fluorine atom.
  • the polyether compound is a compound having a plurality of ether bonds.
  • an ethylenically unsaturated group-containing fluorine-containing copolymer having a polyurethane structure and a polyether structure synthesized using a fluorine-containing polyether polyol as a raw material is an ethylenically unsaturated group-containing fluorine-containing copolymer having a polyurethane structure. It shall be classified as a union.
  • the (A) ethylenically unsaturated group-containing fluorine-containing copolymer having a polyether structure reacts, for example, a fluorine-containing polyol with a compound having an ethylenically unsaturated group and a group that forms an ether bond with a hydroxyl group. Can be obtained.
  • Examples of the group that forms an ether bond with a hydroxyl group include a halogen element, a halogenated alkyl group, an epoxy group, and a halogenated carbonyl group. That is, an ethylenically unsaturated group is obtained by reacting a hydroxyl group in a fluorine-containing polyether polyol with an ethylenically unsaturated group and a hydroxyl group in a compound having a hydroxyl group and a group forming an ether bond with a group forming an ether bond.
  • a saturated group-containing fluorine-containing polyether can be formed.
  • the fluorine-containing polyol used here is the same as the fluorine-containing polyol used in the production of the ethylenically unsaturated group-containing fluorine-containing copolymer having a polyurethane structure.
  • the compound having an ethylenically unsaturated group and a group that forms an ether bond with a hydroxyl group may be a compound having at least one ethylenically unsaturated group and at least one group that forms an ether bond with a hydroxyl group.
  • acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, methacrylic acid bromide and the like are preferable.
  • the ratio of the fluorine-containing polyol, the compound having a group forming an ether bond with a hydroxyl group, and the ethylenically unsaturated group is such that the ethylenically unsaturated group and the hydroxyl group with respect to 1 equivalent of the hydroxyl group in the fluorine-containing polyether polyol.
  • the group that forms an ether bond with the hydroxyl group in the compound having a group that forms an ether bond is adjusted to 0.5 to 1.0 equivalent.
  • component ethylenically unsaturated group-containing fluorine-containing copolymer is usually blended in an amount of 10 to 80% by mass, preferably 20 to 60% by mass, particularly preferably based on the total amount of the composition. Is blended in an amount of 30 to 60% by mass.
  • the component (B) used in the composition of the present invention is a compound other than the component (A) having an ethylenically unsaturated group.
  • the ethylenically unsaturated group is not particularly limited as long as it is a functional group that undergoes a polymerization reaction directly or via an initiator under anaerobic conditions.
  • a vinyl group, a (meth) acryloyl group, a propenyl group also referred to as an allyl group.
  • the component (B) preferably has a fluorine atom. When component (B) has a fluorine atom, the refractive index of the composition of the present invention can be further reduced, and a microchannel excellent in light transmittance can be formed.
  • component (B1) having a fluorine atom
  • component (B1) include, for example, compounds represented by the following formulas (41) to (45).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a fluorine atom
  • m represents 1 to 2
  • n represents 2 to 8.
  • CR 3 2 CR 3- (CF 2 ) p F (42)
  • each R 3 independently represents a hydrogen atom or a fluorine atom, and p represents 2 to 8.
  • CR 4 2 CR 4 —O— (CF 2 ) q F (43)
  • R 4 each independently represents a hydrogen atom or a fluorine atom, and q represents 2 to 8.
  • R 5 independently represents a hydrogen atom or a fluorine atom
  • R 6 represents an oxygen atom or a sulfur atom
  • r represents 2 to 8.
  • R 7 represents an oxygen atom or a sulfur atom, and s represents 2 to 8.
  • a compound having a (meth) acryloyl group described in the above formula (41) is particularly preferable because of high reactivity.
  • these commercially available products include biscoat 13F, 17F, 4F, 8F and the like (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
  • 2-perfluorohexylethyl (meth) acrylate is preferable because it is suitable for dissolving the component (A) and is easily available.
  • Component (B1) is usually blended in an amount of 10 to 70% by mass, preferably 25 to 65% by mass, particularly preferably 30 to 65% by mass, based on the total amount of the composition.
  • (B) having no fluorine atom (B2) a compound having no aromatic structure and a polar group and having two or more ethylenically unsaturated groups, (B3) having no aromatic structure and a polar group , Compounds having one ethylenically unsaturated group, and compounds having an ethylenically unsaturated group other than the components (B4), (B2) and (B3).
  • component (B2) Compound having no aromatic structure and no polar group, and having two or more ethylenically unsaturated groups: Since component (B2) does not have a polar group, when used in combination with component (B1), the solubility of component (A) is increased to give a uniform composition. Moreover, the hardened
  • the polar group includes polar groups such as a carbonyl group and an alkylene oxide group having 3 or less carbon atoms in addition to a dissociable group such as a carboxyl group and an amino group, but a hydroxyl group is excluded.
  • the component (B2) is not particularly limited as long as it has a structure that satisfies the above requirements.
  • component (B2) include, for example, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc. And (meth) acrylates containing aliphatic structure.
  • a component (B2) may be used individually by 1 type, and may use 2 or more types together.
  • Component (B2) is usually blended in an amount of 0 to 40% by mass with respect to the total amount of the composition, preferably 0 to 35% by mass, and particularly preferably 0 to 20% by mass.
  • component (B3) Compound having no aromatic structure and polar group and having one ethylenically unsaturated group: Specific examples of component (B3) include: vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam; vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether and 2-ethylhexyl vinyl ether; diacetone (meth) acrylamide Acrylamides such as isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide t-octyl (meth) acrylamide; isobornyl (meth) acrylate, bornyl ( Containing alicyclic structures such as (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acryl
  • Component (B3) is usually blended in an amount of 0 to 30% by mass, preferably 0 to 25% by mass, particularly preferably 0 to 20% by mass, based on the total amount of the composition.
  • component (B4) Compounds having an ethylenically unsaturated group other than components (B2) and (B3): Specific examples of the component (B4) include aromatic structure-containing (meth) acrylates, polar group-containing (meth) acrylates such as carboxyl groups and alkylene oxide structures, and the like. Component (B4) tends to increase the refractive index of the cured product like aromatic structure-containing (meth) acrylate, and reduces solubility of component (A) like polar group-containing (meth) acrylate Therefore, the amount of the component (B4) is preferably 5% by mass or less with the total amount of the composition being 100% by mass.
  • ком ⁇ онент (B4) include, for example, Iupimer UV, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Aronix M-215, M-315, M-325 (above, manufactured by Toagosei Co., Ltd.), Sartomer CN4000 (Sartomer) -Company Ink), Aronix TO-1210 (manufactured by Toagosei Co., Ltd.), and the like.
  • components (B) are usually preferably blended in an amount of 10 to 70% by weight, more preferably 25 to 65% by weight, particularly preferably 30 to 65% by weight, based on the total amount of the composition.
  • the blending amount of the component (B1) having a fluorine atom is preferably 30 to 100% by mass and more preferably 50 to 100% by mass with respect to the total amount of the component (B).
  • the (C) organic peroxide used in the composition of the present invention is a polymerization initiator for anaerobic curing reaction.
  • Specific examples of the component (C) include hydroperoxides such as cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, di-t Diallyl peroxides such as butyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide, methylcyclohexane peroxide, diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, t-butyl Examples thereof include organic peroxides such as peroxyesters such as peroxybenzoate, t-butyl peroxyacetate, and t-butyl
  • the organic peroxide is preferably blended in an amount of 0.1 to 10% by weight, particularly 0.3 to 7% by weight, based on the total amount of the composition. If it is less than 0.1% by mass, it may be insufficient to cause a polymerization reaction, and if it is more than 10% by mass, the stability of the anaerobic curable composition may be lowered.
  • the component (D) polymerization accelerator used in the composition of the present invention is an anaerobic curing reaction accelerator.
  • D As a polymerization accelerator, amines, organic acids, inorganic acids, amides, imides, etc. are mentioned.
  • amines as component (D) include aliphatic amines such as monoethylamine, diethylamine, triethylamine, cyclohexylamine, benzylamine, N, N-dimethylbenzylamine; aniline, N-ethyl-p-toluidine, Aromatic amines such as N, N-dimethyl-p-toluidine, N, N-dimethyl-O-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethylaniline, N, N-diethylaniline; And heterocyclic amines such as 1,2,3,4-tetrahydroquinoline, piperidine, pyridine, N-methylpyrrolidone, piperazine, pyrimidine, pyrroline, pyrrole and pyrrolidine.
  • aliphatic amines such as monoethylamine, diethylamine, triethylamine, cyclohex
  • Examples of organic acids as component (D) include acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, benzoic acid, salicylic acid, orthonitrobenzoic acid, phenol, p-nitrophenol, picric acid, malonic acid, p-toluenesulfonic acid,
  • Examples of the inorganic acid as component (D) include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and the like.
  • Examples of amides as component (D) include benzamide and formamide.
  • Examples of the imides as component (D) include phthalimide, succinimide, o-benzoixsulfimide (or 3-oxo-2,3-dihydro-1,2-benzisothiazole 1,1-dioxide, or saccharin. A compound represented by the following formula :) and the like.
  • components (D) can be used individually by 1 type or in combination of 2 or more types. Of these, imides are preferred, and o-benzoixsulfimide is particularly preferred.
  • the polymerization accelerator is preferably blended in an amount of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.2 to 3% by mass with respect to the total amount of the composition. If it is less than 0.1% by mass, it may be insufficient to cause a polymerization reaction, and if it is more than 10% by mass, the stability of the anaerobic curable composition may be lowered.
  • (E) (Meth) acrylic acid or a dimer thereof can be further blended in the composition of the present invention.
  • adhesion with glass, quartz, and siloxane-based materials can be improved.
  • Component (E) is usually blended in an amount of 0 to 10% by mass, preferably 1 to 7% by mass, based on the total amount of the composition. If it exceeds 10% by mass, the storage stability of the composition may be impaired.
  • composition of the present invention is cured by irradiation with radiation such as ultraviolet rays in addition to the anaerobic curing reaction, it is desirable to blend (F) a radiation polymerization initiator.
  • Radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • the radiation radical polymerization initiator as component (F) include, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine.
  • Carbazole 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-y Propylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentyl pho
  • the radiation radical polymerization initiator is preferably blended in an amount of 0.1 to 10% by weight, particularly 0.3 to 7% by weight, based on the total amount of the composition.
  • composition of the present invention various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, and a thermal polymerization, as long as they do not impair the characteristics of the present invention.
  • Inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, coating surface improvers and the like can be blended.
  • the content of fluorine atoms contained in the composition of the present invention is preferably 20 to 50% by mass, more preferably 25 to 40% by mass, based on the total amount of the composition.
  • the viscosity of the composition of the present invention is preferably 0.5 to 10 Pa ⁇ s at 25 ° C., particularly preferably 1 to 6 Pa ⁇ s.
  • the composition of the present invention is cured under anaerobic conditions.
  • the anaerobic condition is preferably a gas atmosphere in which the oxygen concentration in the composition is 1% by volume or less, more preferably 0.1% by volume or less, and particularly preferably 0.01% by volume or less.
  • the composition of the present invention is anaerobically cured, for example, it is preferably reacted at 0 to 50 ° C. for 1 minute to 24 hours in a nitrogen gas atmosphere.
  • the reaction time is more preferably 5 minutes to 6 hours, particularly preferably 10 minutes to 60 minutes.
  • the microchannel can be formed by using the composition of the present invention, for example, by the following method.
  • a microchannel sandwiched between a pair of substrates that do not transmit ultraviolet rays can be formed using the composition of the present invention as an adhesive.
  • a CMOS sensor and a biosensor can be formed on the first substrate [10] made of, for example, a silicon substrate that does not transmit ultraviolet rays, if necessary (Step 1).
  • a photosensitive resin material such as an acrylic resin-based photosensitive resin material (for example, manufactured by JSR), an epoxy-based thick film resist (SU-8; manufactured by Nippon Kayaku),
  • a radiation curable resin composition for forming a microchannel (hereinafter referred to as “radiation curable resin composition for forming a specific microchannel”) according to a patent application (Japanese Patent Application No. 2013-88241) by the present applicant.
  • a resist layer [20] is formed by applying a thickness of about 30 ⁇ m to 100 ⁇ m (step 2).
  • the resist layer [20] wrapping around the edge and the back surface of the substrate [10] causes contamination of the exposure stage, contamination particles, and the like in the next exposure process, and therefore it is preferably removed with an organic solvent such as thinner. .
  • a desired region is irradiated from the resist layer [20] side with an ultraviolet ray such as i-line having a wavelength of 365 nm through the mask [5] having a desired pattern so as to have an exposure amount of, for example, about 1,000 mJ / cm 2.
  • the resist layer [20] is cured into a desired pattern (step 3).
  • PEB Post Exposure Bake
  • a desired developer for example, 2.38 mass% tetramethylammonium hydroxide. Development is performed with (TMAH) solution. Next, rinse with pure water. After that, as a final curing process, for example, heat treatment is performed in an oven in a nitrogen atmosphere at 200 ° C. for about 60 to 120 minutes to form a flow path pattern, thereby obtaining a substrate with flow path pattern [11].
  • TMAH tetramethylammonium hydroxide
  • heat treatment is performed in an oven in a nitrogen atmosphere at 200 ° C. for about 60 to 120 minutes to form a flow path pattern, thereby obtaining a substrate with flow path pattern [11].
  • the photosensitive resin material is a radiation curable resin composition for forming a specific microchannel
  • development is performed by immersing in a desired organic solvent for 60 seconds, followed by rinsing with pure water, followed by a rinsing step To form a flow path pattern to obtain a substrate with flow path pattern [11] (step 4).
  • protein or the like [6] such as an antibody can be immobilized on a desired region of the substrate with flow path pattern [11] (step 5).
  • the composition of the present invention is applied to a desired surface of a second substrate [20] made of, for example, a silicon substrate that does not transmit ultraviolet rays, thereby forming an adhesive layer [30] (step 6).
  • the flow path pattern surface side of the substrate with flow path pattern [11] obtained in step 4 and the adhesive layer [30] formed on the substrate [20] in step 6 are brought into close contact with each other to form a micro flow path laminate [40]. (Step 7).
  • the microchannel laminate [40] obtained in step 7 is placed in an atmosphere in which the oxygen concentration is kept at 1% by volume or less, and is allowed to stand at room temperature for about 10 to 60 minutes. 30] is cured to obtain a microchannel [100].
  • a flow path pattern can be obtained by a molding method using polydimethylsiloxane (PDMS) or the like instead of the photosensitive resin material.
  • PDMS polydimethylsiloxane
  • Step 3 and Step 4 can be omitted.
  • the radiation curable resin composition for specific microchannel formation is a resin composition which contains (A) component of this invention, (B) component, and a well-known radiation polymerization initiator as an essential component.
  • Step 1 to Step 6 are the same as those in the first embodiment, they are not shown in FIG.
  • the flow path pattern side of the substrate with flow path pattern [11] obtained in step 4 and the adhesive layer [30] formed on the substrate [20] in step 6 are brought into close contact (step 7), and the flow path pattern is again formed.
  • step 7 By peeling the attached substrate [11] and the substrate [20], a part of the adhesive layer [30] is selectively transferred onto the flow path pattern (step 8).
  • the film thickness of the transferred adhesive layer [31] is preferably 1 ⁇ m to 5 ⁇ m.
  • the transferred adhesive layer [31] and a third substrate [50] made of, for example, a silicon substrate that does not transmit ultraviolet light are brought into close contact with each other to obtain a microchannel laminate [40].
  • Step 9 Thereafter, the microchannel laminate [40] obtained in step 9 is placed in an atmosphere in which the oxygen concentration is kept at 1% by volume or less, and the transferred adhesive is left to stand at room temperature for about 10 to 60 minutes.
  • the agent layer [31] is cured to obtain the microchannel [100].
  • protein or the like [6] such as an antibody may be immobilized on the third substrate [50] side instead of the substrate [11] side with the flow path pattern.
  • a silicon substrate is used as each substrate (first substrate, second substrate, third substrate), and the steps shown in the first or second embodiment are performed. After forming two or more microchannels on a single silicon substrate, the silicon substrate is cut and each microchannel is cut into a chip shape, so that a plurality of microchannels can be efficiently formed. Can also be manufactured.
  • hydroxyl group-containing fluoropolymer 1 a hydroxyl group-containing fluoropolymer. This is designated as “hydroxyl group-containing fluoropolymer 1”.
  • the obtained hydroxyl group-containing fluoropolymer 1 was measured for a polystyrene-reduced number average molecular weight by GPC, which was about 70000.
  • the ratio of each monomer component constituting the hydroxyl group-containing fluoropolymer 1 based on the measurement result of fluorine content by the alizarin complexone method, both 1 H-NMR and 13 C-NMR NMR analysis results and elemental analysis results The structural unit derived from hexafluoropropylene, the structural unit derived from perfluoro (propyl vinyl ether), the structural unit derived from ethyl vinyl ether, and the structural unit derived from hydroxyethyl vinyl ether represent the total amount of these four types of structural units. As 100 mol%, they were 25: 25: 25: 25 mol%, respectively.
  • Production Example 2 ((A) Synthesis of radiation-reactive group-containing fluorine-containing copolymer 1): In a 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 41.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 1 was used as a polymerization inhibitor and 2,6-di- -0.01 g of t-butylmethylphenol, 41.0 g of 2-perfluorooctylethyl (meth) acrylate as a diluting solvent, and 17.0 g of neopentylglycol di (meth) acrylate were charged, and a hydroxyl group-containing fluorine-containing heavy at 50 ° C Stirring was performed until the coalescence 1 was dissolved and the solution became transparent and uniform.
  • Test example 1 The liquid curable resin compositions obtained in the examples and comparative examples were cured by the following method to prepare test pieces, and the following evaluations were performed. The results are also shown in Table 1.
  • Young's modulus A liquid curable resin composition was applied onto a glass plate using an applicator bar having a thickness of 250 ⁇ m, and this was cured by irradiation with ultraviolet rays having an energy of 1 J / cm 2 under nitrogen to obtain a film for measuring Young's modulus. .
  • a strip-shaped sample was prepared from this film so that the stretched portion had a width of 6 mm and a length of 25 mm, and a tensile test was performed at a temperature of 23 ° C. and a humidity of 50%. The Young's modulus was determined from the tensile strength at a tensile rate of 1 mm / min and a strain of 2.5%.
  • Breaking strength and breaking elongation Using a tensile tester (manufactured by Shimadzu Corporation, AGS-50G), the breaking strength and breaking elongation of the test piece were measured under the following measurement conditions. Tensile speed: 50 mm / distance between marked lines (measurement distance): 25 mm Measurement temperature: 23 ° C Relative humidity: 50% RH
  • Refractive index A resin composition was applied onto a glass plate using an applicator bar so that the film thickness was 200 ⁇ m, and 1.0 J / cm 2 of ultraviolet light was irradiated under nitrogen to prepare a test piece.
  • the refractive index at 25 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd.
  • Transparency The total light transmittance of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The measurement was performed on the cured film immediately after production and the cured film after being left at 120 ° C. for 72 hours.
  • Adhesion Regarding the compositions obtained in Examples and Comparative Examples, the adhesion strength stability of the cured products was measured. The liquid composition was applied onto a slide glass using an applicator with a thickness of 381 ⁇ m, and irradiated with 0.1 J / cm 2 of ultraviolet light in a nitrogen atmosphere to obtain a cured film having a thickness of about 200 ⁇ m. The cured film on the slide glass was allowed to stand for 24 hours at a temperature of 23 ° C. and a humidity of 50%. Thereafter, a strip-shaped sample was prepared from the cured film so that the stretched portion had a width of 10 mm. This sample was subjected to an adhesion test in accordance with JIS Z0237 using a tensile tester. The adhesion force was determined from the tensile strength at a tensile speed of 50 mm / min.
  • microchannels were produced by the production methods of the first to ninth embodiments described above. In these cases, the lower limit value of the numerical value or the range of values described in the description of each embodiment was used for the thickness of the coating film and the irradiation amount of ultraviolet rays. In either case, a microchannel having a desired structure could be formed satisfactorily.
  • hydroxyl group-containing fluoropolymer 1 a hydroxyl group-containing fluoropolymer. This is designated as “hydroxyl group-containing fluoropolymer 1”.
  • the obtained hydroxyl group-containing fluoropolymer 1 was measured for a polystyrene-reduced number average molecular weight by GPC, which was about 70000.
  • the number average molecular weight was measured under the conditions of a flow rate of 1 ml / min using tetrahydrofuran (THF) as a developing solvent using a composite column connected to an HPLC system (HLC-8220 GPC: manufactured by Tosoh Corporation) in the following order.
  • THF tetrahydrofuran
  • TSKgel G4000H XL TSKgel G3000H XL, TSKgel G2000H XL, TSKgel G2000H XL, TSKgel G4000H XL, TSKgel G3000H XL.
  • the ratio of each monomer component constituting the hydroxyl group-containing fluoropolymer 1 The structural unit derived from hexafluoropropylene, the structural unit derived from perfluoro (propyl vinyl ether), the structural unit derived from ethyl vinyl ether, and the structural unit derived from hydroxyethyl vinyl ether represent the total amount of these four types of structural units. As 100 mol%, they were 25: 25: 25: 25 mol%, respectively.
  • Production Example 4 ((A) Synthesis of fluorine-containing copolymer 1 containing an ethylenically unsaturated group): In a 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 41.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 3 was used as a polymerization inhibitor and 2,6-di- -0.01 g of t-butylmethylphenol, 41.0 g of 2-perfluorooctylethyl (meth) acrylate as a diluting solvent, and 17.0 g of neopentylglycol di (meth) acrylate were added, and a hydroxyl group-containing fluorine-containing heavy at 50 ° C.
  • Example 10 and Comparative Example 5 Each component having the composition shown in Table 2 was charged into a reaction vessel equipped with a stirrer and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a resin composition.
  • Test example 2 For the resin compositions obtained in the above examples and comparative examples, the viscosity is measured and cured by the following method to prepare a test piece, and each evaluation of refractive index, copper sandwich test, and glass sandwich test is performed. It was. The results are also shown in Table 2.
  • microchannels Using the composition listed in Example 10, a microchannel was manufactured by the manufacturing method of the first and second embodiments described above. In these cases, the thickness of the coating film was the lower limit of the numerical value or value range described in the description of each embodiment, and the curing conditions were 60 minutes at 25 ° C. in a nitrogen atmosphere. In either case, a microchannel having a desired structure could be formed satisfactorily.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement radioactif, ladite composition ayant d'excellentes propriétés lui permettant d'être utilisée en tant que matériau pour former un microcanal, notamment un indice de réfraction bas, une transparence stable, une bonne aptitude à l'enduction, une très bonne adhérence sur un matériau de base en verre ou similaire, ainsi qu'une résistance et une souplesse excellentes. La composition de résine durcissable par rayonnement radioactif destinée à former un microcanal comprend : (A) un copolymère comportant à la fois un groupe réactif à un rayonnement et un atome de fluor et ayant un poids moléculaire moyen en nombre de 1000 à 500 000 ; (B) un composé comportant un groupe réactif au rayonnement et qui est différent du composant (A) ; et (C) un initiateur de polymérisation par rayonnement.
PCT/JP2014/060658 2013-04-19 2014-04-15 Composition de résine durcissable destinée à former un microcanal, et microcanal correspondant WO2014171431A1 (fr)

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JP2013088241A JP2014210865A (ja) 2013-04-19 2013-04-19 マイクロ流路形成用放射線硬化性樹脂組成物およびマイクロ流路
JP2013-088241 2013-04-19
JP2013-115327 2013-05-31
JP2013115327A JP2014234411A (ja) 2013-05-31 2013-05-31 マイクロ流路形成用嫌気硬化性樹脂組成物およびマイクロ流路

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WO2016125795A1 (fr) * 2015-02-05 2016-08-11 旭硝子株式会社 Composition de résine photosensible, procédé de production de film de résine, procédé de production d'élément semi-conducteur organique, et polymère contenant du fluor
CN113493372A (zh) * 2020-04-03 2021-10-12 常州强力先端电子材料有限公司 光引发剂的制备方法

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JPH05287216A (ja) * 1992-04-08 1993-11-02 Asahi Glass Co Ltd 厚膜型塗料組成物
JP2007527784A (ja) * 2004-02-13 2007-10-04 ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル マイクロ流体デバイスを作製するための官能性材料及び新規方法
JP2008208226A (ja) * 2007-02-27 2008-09-11 Jsr Corp 放射線硬化性樹脂組成物
JP2008233346A (ja) * 2007-03-19 2008-10-02 Jsr Corp 放射線硬化性樹脂組成物
JP2009167295A (ja) * 2008-01-16 2009-07-30 Jsr Corp 硬化性樹脂組成物及び反射防止膜

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JPH05287216A (ja) * 1992-04-08 1993-11-02 Asahi Glass Co Ltd 厚膜型塗料組成物
JP2007527784A (ja) * 2004-02-13 2007-10-04 ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル マイクロ流体デバイスを作製するための官能性材料及び新規方法
JP2008208226A (ja) * 2007-02-27 2008-09-11 Jsr Corp 放射線硬化性樹脂組成物
JP2008233346A (ja) * 2007-03-19 2008-10-02 Jsr Corp 放射線硬化性樹脂組成物
JP2009167295A (ja) * 2008-01-16 2009-07-30 Jsr Corp 硬化性樹脂組成物及び反射防止膜

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Publication number Priority date Publication date Assignee Title
WO2016125795A1 (fr) * 2015-02-05 2016-08-11 旭硝子株式会社 Composition de résine photosensible, procédé de production de film de résine, procédé de production d'élément semi-conducteur organique, et polymère contenant du fluor
JPWO2016125795A1 (ja) * 2015-02-05 2017-11-16 旭硝子株式会社 感光性樹脂組成物、樹脂膜の製造方法、有機半導体素子の製造方法および含フッ素重合体
US10241404B2 (en) 2015-02-05 2019-03-26 AGC Inc. Photosensitive resin composition, production method for resin film, production method for organic semiconductor element, and fluorine-containing polymer
CN113493372A (zh) * 2020-04-03 2021-10-12 常州强力先端电子材料有限公司 光引发剂的制备方法
CN113493372B (zh) * 2020-04-03 2023-08-08 常州强力先端电子材料有限公司 光引发剂的制备方法

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