[go: up one dir, main page]

WO2015152310A1 - Article moulé et son procédé de fabrication - Google Patents

Article moulé et son procédé de fabrication Download PDF

Info

Publication number
WO2015152310A1
WO2015152310A1 PCT/JP2015/060282 JP2015060282W WO2015152310A1 WO 2015152310 A1 WO2015152310 A1 WO 2015152310A1 JP 2015060282 W JP2015060282 W JP 2015060282W WO 2015152310 A1 WO2015152310 A1 WO 2015152310A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
depth
graft
integer
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/060282
Other languages
English (en)
Japanese (ja)
Inventor
数行 佐藤
大島　明博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
University of Osaka NUC
Original Assignee
Daikin Industries Ltd
Osaka University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Osaka University NUC filed Critical Daikin Industries Ltd
Priority to JP2016511971A priority Critical patent/JP6536571B2/ja
Publication of WO2015152310A1 publication Critical patent/WO2015152310A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a molded article, more specifically, a molded article having a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and a method for producing the same.
  • the present invention also relates to an imprint mold formed from such a molded body.
  • Nanoimprint technology is known as a technology for obtaining fine structure patterns.
  • the nanoimprint technology is a method in which a mold having a concavo-convex fine pattern surface is pressed against a curable resin layer on a substrate to transfer the fine structure, and the curable resin layer is cured by irradiating UV light or the like. This is a technique for fixing the transferred microstructure.
  • the mold used in such a nanoimprint technology is required to have high releasability in order to reliably maintain the transferred microstructure when it is released from the curable resin.
  • a quartz mold can be generally used, but this is very expensive. Therefore, a technique is known in which such a quartz mold is used as an original plate (also referred to as “master mold” or “mother mold”) to produce a resin replica mold, and this replica mold is used in the nanoimprint technique. .
  • Patent Document 1 proposes a mold having a surface coated with a silicone-based mold release agent or a fluorine-based coupling agent. Further, Patent Document 2 proposes a mold in which a specific macromonomer is used so that a part having mold release performance is unevenly distributed near the surface of the mold. Further, Patent Document 3 proposes a mold in which a layer containing a release agent and bonded to the surface of the resin mold is formed on the surface of the resin mold.
  • JP 2008-178984 A International Publication No. 2012/018043 International Publication No. 2012/018045
  • an object of the present invention is to provide an imprint mold having high release durability. Moreover, an object of this invention is to provide the molded object which can be processed into such an imprint mold, and its manufacturing method.
  • the present inventors have introduced a graft chain containing a perfluoropolyether group or a perfluoroalkyl group into the resin base material, so that the resin base material has good release properties and release durability. As a result, the present invention has been completed.
  • the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain exists from the surface of the resin substrate to a depth of at least 0.2 ⁇ m and a depth of up to 200 ⁇ m. And a molded body characterized by not exceeding a depth of 95% of the thickness of the resin substrate;
  • the resin base material has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is a residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group.
  • Molded body characterized in that it is a base; Radiation is generated by irradiating the surface of a resin substrate with ionizing radiation, and the resulting radical is graft polymerized with a compound containing a perfluoropolyether group or perfluoroalkyl group and a radical and a reactive group. Molded body;
  • the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain exists from the surface of the resin substrate to a depth of at least 0.2 ⁇ m and a depth of up to 40 ⁇ m.
  • the resin base material has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is a residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group.
  • Imprint mold characterized by being a group; and the surface of a resin substrate is irradiated with ionizing radiation to generate radicals, and the generated radicals react with perfluoropolyether groups or perfluoroalkyl groups and radicals.
  • an imprint mold obtained by graft polymerization with a compound containing a functional group.
  • a graft chain containing a perfluoropolyether group or a perfluoroalkyl group into a resin base material, a molded body that has a small surface free energy and can maintain this state for a long time. It becomes possible to provide. Further, according to the present invention, it is possible to provide an imprint mold having excellent release properties and excellent release durability.
  • FIG. 1 shows the results of a release durability test for the resin films of Example 1 and Comparative Examples 2 and 3.
  • FIG. 2 is an SEM image of the imprint mold obtained in Example 2.
  • FIG. 3 is a diagram for explaining a manufacturing process according to the third embodiment.
  • the resin base material has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain has a depth of at least 0.2 ⁇ m from the surface of the resin base material. It has a depth of 200 ⁇ m and does not exceed a depth of 95% of the thickness of the resin substrate.
  • the molded body of the present invention is a method in which a surface of a resin base material is irradiated with ionizing radiation to generate radicals, and the generated radicals and a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group Can be produced by graft polymerization. Specifically, it is manufactured as follows.
  • a resin base material is prepared.
  • the material that forms the resin substrate is a resin that can generate radicals upon irradiation with ionizing radiation, for example, a compound that undergoes a radiation chemical reaction upon irradiation with ionizing radiation and a hydrogen atom or fluorine atom is eliminated, or ionizing radiation.
  • the resin is not particularly limited as long as it is a resin formed from a compound whose main chain / side chain is cleaved by irradiation.
  • a fluororesin and a non-fluorine resin can be used. It is preferable to use a fluororesin because it has higher transparency to UV light, higher releasability, and higher resistance to light, heat, chemicals, and the like.
  • the molecular weight of the resin substrate may be any molecular weight that can maintain the material properties according to the application, and may be reduced by irradiation with ionizing radiation for introducing a graft chain onto the surface. .
  • fluororesin examples include, for example, ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), perfluoroalkoxy copolymer (PFA), ethylene.
  • ETFE ethylene-tetrafluoroethylene copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA perfluoroalkoxy copolymer
  • ECTFE -Chlorotrifluoroethylene copolymer
  • PVDF polyvinyl fluoride
  • PCTFE polychlorotrifluoroethylene
  • VdF-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • VdF-TFE-HFP Vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer
  • other fluororesins fluororubber, etc. It may be.
  • an ethylene-tetrafluoroethylene copolymer is preferable.
  • non-fluorine resin examples include polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyolefin such as cycloolefin resin, modified polyolefin, and polyvinyl chloride.
  • polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyolefin such as cycloolefin resin, modified polyolefin, and polyvinyl chloride.
  • Acrylic resins such as vinyl chloride resin, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, polymethyl methacrylate (PMMA), acrylic-styrene copolymer Polymer (AS resin), ethylene-tetrafluoroethylene copolymer (ETFE), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene tele Polyester such as tarate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, Polyarylate, aromatic polyester (liquid crystal polymer), styrene resin, polyurethane resin, chlorinated
  • the shape of the resin base material is not particularly limited, and may be any shape such as a block shape, a plate shape, a sheet shape, and a film shape. These surfaces do not need to be completely flat, and some or all of them may have a curved surface, for example, a dome shape, a cylindrical shape, or the like.
  • the resin substrate is in the form of a sheet or film, more preferably in the form of a film.
  • the thickness of the resin substrate is not particularly limited, but may be, for example, 5 ⁇ m to 20 mm, preferably 10 ⁇ m to 10 mm, and more preferably 10 ⁇ m to 1 mm.
  • the thickness of the resin substrate is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 30 to 125 ⁇ m, and still more preferably 30 to 60 ⁇ m.
  • the resin substrate is irradiated with ionizing radiation.
  • ionizing radiation By irradiating the resin base material with ionizing radiation, in the resin base material, for example, a hydrogen atom or a fluorine atom is eliminated from the compound forming the resin base material, or the main chain of the compound forming the resin base material And / or a side chain is cut
  • the ionizing radiation is not particularly limited as long as it can generate radicals when irradiated onto a resin substrate, and for example, an electron beam, X-ray, ⁇ -ray, neutron beam, ion, or the like can be used.
  • An electron beam is preferable because the penetration depth (range) of ionizing radiation is easy and radicals are easily generated in the resin.
  • the absorbed dose of the ionizing radiation irradiated is 1 to 1000 kGy, preferably 10 to 500 kGy, more preferably 50 to 300 kGy.
  • the energy absorption amount of the resin base material can be measured with a scintillation detector or a semiconductor detector, but more preferably, for example, measured with a cellulose triacetate film (CTA: Cellulose triacetate) dosimeter or a radiochromic film dosimeter can do.
  • CTA Cellulose triacetate
  • the electron energy of the electron beam irradiated onto the sample is preferably 5 keV to 100 keV, more preferably 10 keV to 80 keV, still more preferably 30 keV to 70 keV, and even more preferably, on the sample surface using an electron accelerator. Preferably, it is 40 keV to 70 keV.
  • the energy absorption efficiency can be improved.
  • the electron energy on the sample surface to 5 keV or more, radicals sufficient for surface graft polymerization can be generated on the substrate surface.
  • the electron energy corresponds to the acceleration voltage
  • the acceleration voltage is preferably 5 to 100 kV, more preferably 10 to 80 kV. More preferably, it may be 30 to 70 kV, and still more preferably 40 to 70 kV.
  • the arrival depth of the electron beam can be about 20 ⁇ m.
  • the irradiation dose of electrons irradiated on the sample is 10 ⁇ C / cm 2 to 10 mC / cm 2 , preferably 50 ⁇ C / cm 2 to 1 mC / cm 2 , more preferably 100 ⁇ C / cm 2 to 300 ⁇ C / cm 2.
  • cm 2 for example 200 ⁇ C / cm 2 .
  • Irradiation of ionizing radiation to the resin substrate is preferably performed in an atmosphere substantially free of oxygen from the viewpoint of suppressing the pair annihilation of the generated radical, for example, an oxygen concentration of 1000 ppm or less, more preferably 500 ppm, Even more preferably, it is performed under an atmosphere of 100 ppm or less.
  • the irradiation with ionizing radiation is performed in a vacuum or in an inert gas atmosphere, for example, in a nitrogen or argon atmosphere.
  • the vacuum need not be a complete vacuum, but may be substantially a vacuum, for example, a low vacuum of about 10 3 Pa or a high vacuum of about 10 ⁇ 2 Pa.
  • the irradiation with ionizing radiation may be performed in the atmosphere in order to obtain peroxide radicals, and oxygen may be supplied after radical generation.
  • the resin base material after irradiation is preferably stored at a low temperature below the glass transition temperature of the polymer constituting the resin, Storage in a vacuum or inert atmosphere is more preferred.
  • the penetration depth of the ionizing radiation is preferably 0.001 to 95% of the thickness of the substrate, for example 0.01 to 95%, 0.1 to 95% or 0.2 to 95%, more preferably 5 to 80. %, More preferably 10 to 60%, still more preferably 20 to 60%.
  • the penetration depth of ionizing radiation is 0.1 to 200 ⁇ m, preferably 1 to 40 ⁇ m, more preferably 2 to 30 ⁇ m, and even more preferably 3 to 20 ⁇ m from the surface of the substrate, for example, The depth may be 5-20 ⁇ m or 10-20 ⁇ m.
  • the penetration depth of ionizing radiation means the depth at which the resin base material absorbs the energy of ionizing radiation.
  • the penetration depth of the ionizing radiation is substantially the same as the region where surface graft polymerization occurs, but the surface of the sample slightly swells due to the surface graft reaction, so there are graft chains in the molded product after the graft reaction.
  • the depth can be deeper than the penetration depth of the ionizing radiation.
  • the depth at which the graft chain exists is the cross section of the molded product after surface graft polymerization, such as EDX (Energy Dispersive X-ray) analysis by Scanning Electron Microscope (SEM), EPMA (Electron Probe Probe Microanalyser) analysis, etc. Can be measured.
  • the depth at which the graft chain exists can also be measured with a microscopic FT-IR, a Raman microscope, or the like.
  • the depth at which the graft chain is present in the molded product after the graft reaction can also be measured by positron lifetime measurement.
  • the positron lifetime obtained by measuring the time from the generation of a positron to the pair annihilation with the electron is correlated with the amorphous free volume of the polymer and the size of the vacancies in the crystal. As the grafting, the amorphous free volume in the substrate decreases, and the positron lifetime also decreases. From this, the depth at which the graft chain exists can be measured by positron lifetime measurement.
  • positron lifetime measurement In the positron lifetime measurement, generally, gamma rays and annihilation gamma rays emitted at the time of ⁇ + decay are detected by different scintillation detectors, and the frequency of positrons annihilated at a certain time is counted from the difference in incident time.
  • the positron lifetime can be determined by analyzing the attenuation curve thus obtained. For example, "Free volume, study, functional, fluorinated polymer,” published by T. Oka, published at The 2nd Japan-China Joint Workshop, on Positron Science (JWPS2013), introduces an example of styrene grafted on a fluororesin. Also in the present invention, the presence of graft chains can be measured by this method.
  • graft monomer a radical in the resin substrate generated by irradiation with ionizing radiation and a compound as a monomer (hereinafter also referred to as “graft monomer”) are graft-polymerized.
  • the graft polymerization is carried out by bringing the radicals in the resin substrate generated by irradiating with ionizing radiation into contact with the graft monomer.
  • the contact between the radical in the resin substrate and the graft monomer may be performed by, for example, immersing the resin substrate in a solution of the graft monomer, dropping or coating the graft monomer on the resin substrate, or in the presence of a gaseous monomer. This is done by placing a resin substrate. Even when the wettability between the surface of the resin substrate and the graft monomer is low, a method of immersing the resin substrate in a solution of the graft monomer is preferable because the resin substrate can be contacted uniformly and reliably.
  • the reaction temperature of the graft polymerization is not particularly limited, but is, for example, room temperature to 100 ° C., preferably 30 to 80 ° C., more preferably 30 to 60 ° C.
  • the reaction time of the graft polymerization is not particularly limited, but is, for example, 30 minutes to 32 hours, preferably 1 to 12 hours, more preferably 2 to 6 hours.
  • the graft polymerization can be performed by bringing the resin base material and the graft monomer into contact with each other after irradiation with ionizing radiation, but is not limited thereto, and the resin base material and the resin base material simultaneously with the ionizing radiation irradiation.
  • a graft monomer may be contacted.
  • ionizing radiation may be irradiated in a state where the resin substrate is immersed in a solution of the graft monomer or in an atmosphere in which a gaseous graft monomer is present.
  • the resin base material and the graft monomer may be brought into contact with each other in advance and irradiated with ionizing radiation.
  • a graft monomer may be present on the resin substrate by dropping or coating, and irradiation with ionizing radiation may be performed.
  • the graft polymerization can proceed not only to the surface of the resin substrate, but also to a certain depth, for example, within a range of 200 ⁇ m from the surface, preferably 40 ⁇ m, more preferably 20 ⁇ m.
  • the graft monomer has a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group.
  • the graft monomer has a perfluoropolyether group and a radical reactive group.
  • the perfluoropolyether group (hereinafter also referred to as “PFPE”) has the following formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- [Wherein, a, b, c and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and d is at least 1, and each repeating unit enclosed in parentheses The order of presence of is arbitrary in the formula. ] Means a group represented by
  • a, b, c and d are each independently an integer of 0 or 1 and are not particularly limited as long as the sum of a, b, c and d is at least 1.
  • a, b, c and d are each independently an integer of 0 to 200, for example, an integer of 1 to 200, more preferably an integer of 0 to 100, for example, 1 An integer of 100 or less. More preferably, the sum of a, b, c and d is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less.
  • the order of presence of each repeating unit with a, b, c or d in parentheses is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF ( CF 3 ) CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 )) —, — (OCF 2 C (CF 3 ) 2 ) —, — ( OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-are preferred, but Is — (OCF 2 CF 2 CF 2 CF 2 ) —.
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • PFPE is — (OC 3 F 6 ) b — (wherein b is an integer of 1 to 200, preferably 10 to 100), preferably — (OCF 2 CF 2 CF 2 ) b — (wherein b is as defined above).
  • PFPE has the following structure:-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (wherein a and b are each independently And are integers of 0 or more and 1 or more and 30 or less, preferably 0 or more and 10 or less, and c and d are each independently an integer of 1 or more and 200 or less, preferably 10 or more and 100 or less. The sum of c and d is not less than 10, preferably not less than 20, and not more than 200, preferably not more than 100.
  • Presence order of each repeating unit in parentheses with the suffix a, b, c or d Is optional in the formula), preferably — (OCF 2 CF 2 CF 2 CF 2 ) a — (OCF 2 CF 2 CF 2 ) b — (OCF 2 CF 2 ) c — (OCF 2 ) d -(Wherein a, b, And d is a is) as defined above.
  • PFPE may be — (OCF 2 CF 2 ) c — (OCF 2 ) d — (wherein c and d are as defined above).
  • PFPE is a group represented by — (OC 2 F 4 —R 11 ) n —.
  • R 11 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • N is an integer of 2 to 100, preferably an integer of 2 to 50.
  • OC 2 F 4 , OC 3 F 6 and OC 4 F 8 may be either linear or branched, preferably linear.
  • the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) n — or — (OC 2 F 4 —OC 4 F 8 ) n —.
  • the perfluoroalkyl group is a group represented by C n F 2n + 1 (n is an integer of 1 to 30, preferably an integer of 3 to 20, for example, an integer of 5 to 10).
  • the perfluoroalkyl group may be linear or branched, but is preferably linear.
  • the “radical-reactive group” is not particularly limited, and examples thereof include a group having an ethylenic double bond and an oxygen-containing cyclic group (for example, glycidyl group, oxetanyl group), and derivatives thereof.
  • R b is a bond or —OC (O) —
  • R c represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group) which may be substituted by a fluorine atom or a phenyl group
  • R d is independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom (preferably an alkyl group having 1 to 3 carbon atoms, more preferably methyl Group) or a phenyl group, preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom
  • n is an integer of 1 to 5, preferably 1 or 2, and more preferably 1. ] It is group represented by these.
  • radicals and groups reactive with radicals are: [Wherein, R c and R d are as defined above. ] It is group represented by these.
  • graft monomers include, but are not limited to, any of the following formulas (A1), (A2), (B1), (B2) and (C1):
  • Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, PFPE has the same meaning as above,
  • Each R 1 independently represents a radical and a reactive group;
  • X represents a divalent organic group,
  • R 2 represents the following formula: - (Q) e - (CFZ ) f - (CH 2) g -
  • each Q independently represents an oxygen atom, phenylene, carbazolylene, —NR a — (wherein R a represents a hydrogen atom or an organic group) or a divalent polar group.
  • Z each independently represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, and e, f and g each independently represent an integer of 0 to 50, And the sum of g is at least 1, and the order of presence of each repeating unit in parentheses is arbitrary in the formula.
  • a group represented by Each R 3 independently represents a divalent organic group;
  • R 4 represents, independently at each occurrence, R 4a or R 4b : provided that at least one R 4 is R 4a R 4a independently represents a divalent organic group having a radical and a reactive group at each occurrence;
  • R 4b independently represents a divalent organic group having no radical and a reactive group at each occurrence;
  • n1 is each independently an integer of 1 to 50,
  • Each R 5 independently represents —O—, —S—, —NH— or a single bond;
  • Each R 6 independently represents a monovalent organic group or a hydrogen atom;
  • R 7 represents a (n2 +
  • monovalent organic group and “divalent organic group” mean a monovalent and divalent group containing carbon, respectively.
  • R 1 each independently represents a radical and a reactive group.
  • R 1 is preferably represented by the following formula: [Wherein, R c and R d are as defined above. ] And more preferably the following formula: [Wherein R c ′ represents a hydrogen atom or a methyl group. ] It is group represented by these.
  • Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted by one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group, More preferred is a perfluoroalkyl group having 1 to 16 carbon atoms, and even more preferred is a perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms.
  • X each independently represents a divalent organic group.
  • the X group is understood as a linker connecting the PFPE and R 1. Therefore, the X group may be any divalent organic group as long as the compounds represented by the above (A1) and (A2) can exist stably.
  • Examples of X are not particularly limited.
  • Z represents a fluorine atom, a perfluoroalkyl group having 1 to 3 carbon atoms or a derivative group thereof
  • Y represents —OCO—, —OCONH— or —CONH—, or an organic group containing one of these
  • x, y and z are each independently an integer of 0 to 3
  • the order of presence of each repeating unit attached with x, y or z and enclosed in parentheses is arbitrary in the formula.
  • the group represented by these is preferable.
  • X include, for example: —CF 2 CF 2 CH 2 — —CF 2 CF 2 CH 2 —OCO— —CF 2 CF 2 CH 2 —CONH— —CF 2 CF 2 CH 2 —OCONH— Etc.
  • R 2 is a group represented by the formula: — (Q) e — (CFZ) f — (CH 2 ) g —.
  • e, f and g are each independently an integer of 0 or more and 50 or less, the sum of e, f and g is at least 1, and the order of presence of each repeating unit enclosed in parentheses is It is arbitrary in the formula.
  • Q represents an oxygen atom, phenylene, carbazolylene, —NR a — (wherein R a represents a hydrogen atom or an organic group) or a divalent polar group, preferably an oxygen atom or divalent And more preferably an oxygen atom.
  • the “divalent polar group” in Q is not particularly limited, but —C (O) —, —C ( ⁇ NR e ) —, and —C (O) NR e — (in these formulas, R e represents a hydrogen atom or a lower alkyl group).
  • the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.
  • Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
  • the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
  • R 2 is preferably of the formula: — (O) e — (CF 2 ) f — (CH 2 ) g — (wherein e, f and g are as defined above and bracketed).
  • the order in which each repeating unit is present is arbitrary in the formula).
  • R 3 represents a divalent organic group.
  • the R 3 group is preferably —C (R 3a ) (R 3b ) —.
  • R 3a and R 3b each independently represent a hydrogen atom or an alkyl group, and preferably one of R 3a and R 3b is an alkyl group.
  • R 4 is independently R 4a or R 4b at each occurrence. However, at least one R 4 is R 4a .
  • R 4a represents a divalent organic group having a radical and a reactive group independently at each occurrence.
  • R 4a is preferably represented by the following formula: It is group represented by these.
  • each occurrence of R 31 independently represents a hydrogen atom or an alkyl group.
  • R 31 is preferably a hydrogen atom.
  • each occurrence of R 32 independently represents a hydrogen atom or an alkyl group.
  • R 32 is preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom.
  • R 33 independently represents an organic group having a radical and a reactive group at each occurrence.
  • Examples of the group reactive with the radical include those similar to the above, but CH 2 ⁇ CX 1 —C (O) — (wherein X 1 is a halogen atom such as a hydrogen atom or a chlorine atom, fluorine (Representing an alkyl group having 1 to 10 carbon atoms which may be substituted with an atom or fluorine), specifically, CH 2 ⁇ C (CH 3 ) —C (O) — or CH 2 ⁇ CH—C ( O)-.
  • X 1 is a halogen atom such as a hydrogen atom or a chlorine atom, fluorine (Representing an alkyl group having 1 to 10 carbon atoms which may be substituted with an atom or fluorine)
  • CH 2 ⁇ C (CH 3 ) —C (O) — or CH 2 ⁇ CH—C ( O)- specifically, CH 2 ⁇ C (CH 3 ) —C (O) — or CH 2 ⁇ CH—C ( O)-.
  • Y 1 represents —O—, —N (R f ) —, phenylene or carbazolylene.
  • R f represents an organic group, preferably an alkyl group.
  • Y 1 is preferably —O—, phenylene, or carbazolylene, more preferably —O— or phenylene, and still more preferably —O—.
  • Y 2 represents a linker having 1 to 16 atoms (more preferably 2 to 12, more preferably 2 to 10) in the main chain.
  • the Y 2 is not particularly limited.
  • — (CH 2 —CH 2 —O) p1 — (p1 represents an integer of 1 to 10, for example, an integer of 2 to 10), — (CHR g ) p2 —O— (p2 is an integer of 1 to 40, R g represents hydrogen or a methyl group), — (CH 2 —CH 2 —O) p3 —CO—NH—CH (the p3, an integer from 1 to 10, an integer, for example 2 ⁇ 10) 2 -CH 2 -O- , - CH 2 -CH 2 -O-CH 2 -CH 2 -, - (CH 2) p4 - (P4 represents an integer of 1 to 6), — (CH 2 ) p5 —O—CONH— (CH 2 ) p6 — (p5
  • Y 2 is — (CH 2 —CH 2 —O) p1 — (p1 represents an integer of 1 to 10, for example, an integer of 2 to 10) or — (CHR d ) p2 —O— (p2 is 1 to 40, R d represents hydrogen or a methyl group), specifically, — (CH 2 —CH 2 —O) 2 — or —CH 2 —CH 2 —O— Can be mentioned.
  • the left end is bonded to the molecular main chain side (Y 1 side), and the right end is bonded to the radical reactive side (R 33 side).
  • R 4a is more preferably represented by the following formula: It is group represented by these.
  • X 1 represents a hydrogen atom, a halogen atom such as a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, preferably a hydrogen atom or 1 to 10 carbon atoms.
  • q1 is an integer of 1 to 10, preferably an integer of 1 to 5, for example 1 or 2.
  • q2 is an integer of 1 to 10, preferably an integer of 1 to 5, for example 2.
  • R 4b is a divalent organic group having no radical and a reactive group independently at each occurrence.
  • R 4b is preferably — (CHR 4c —CR 4d R 4e ) s —.
  • R 4c and R 4d each independently represents a hydrogen atom or an alkyl group
  • s is an integer of 0 to 50
  • the R 4e group is —Q′—R 4f .
  • Q ′ has the same meaning as Q above
  • R 4f is an organic group having no radical-reactive group
  • the group R 4g described below is bonded to Q ′ via a linker or directly. It is a group.
  • the linker is preferably (A) — (CH 2 —CH 2 —O) s1 — (s1 represents an integer of 1 to 10, for example, an integer of 2 to 10), (B) — (CHR 4h ) s2 —O— (s2 represents a repeating number which is an integer of 1 to 40.
  • R 4h represents hydrogen or a methyl group), (C) — (CH 2 —CH 2 —O) s1 —CO—NH—CH 2 —CH 2 —O— (s1 is as defined above), (D) —CH 2 —CH 2 —O—CH 2 —CH 2 —, (E) — (CH 2 ) s3 — (s3 represents an integer of 1 to 6), or (f) — (CH 2 ) s4 —O—CONH— (CH 2 ) s5 — (s4 is 1 to 8 , Preferably 2 or 4. s5 represents an integer of 1 to 6, preferably 3.), or (g) —O— (where Q ′ is not —O—) It is.
  • R 4g is preferably the following group.
  • (I) Alkyl group Example: methyl, ethyl
  • R 4g is more preferably a hydrogen atom or an alkyl group which may be fluorinated and may be bonded via an ethylene chain, more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group, or R 3i -CF 2 - (CF 2 ) s6 - (CH 2) s7 -O- (CH 2) 2 - (R x is a fluorine atom or a hydrogen atom, s6 is an integer from 0 to 6, and s7 is an integer of 1 to 6, and more preferably a 3- (perfluoroethyl) propoxyethyl group [shown by the formula: CF 3- (CF 2 )-(CH 2 ) 3 -O- (CH 2 2 ⁇ ].
  • each of the structural unit R 4a and the structural unit R 4b may form a block or may be bonded at random.
  • n1 is an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 2 to 30.
  • R 5 represents —O—, —S—, —NH— or a single bond, and preferably —O—.
  • R 6 represents a monovalent organic group or a hydrogen atom.
  • R 6 is preferably Rf-PFPE-R 2 (wherein Rf, PFPE and R 2 are as defined above), or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine More preferably, it is an alkyl group having 1 to 6 carbon atoms, and more preferably methyl.
  • R 7 represents a (n2 + n3) -valent organic group that may have a ring structure, a hetero atom, and / or a functional group.
  • n2 is an integer of 1 to 3.
  • n3 is an integer of 1 to 3.
  • n2 + n3 is 3, for example, n2 is 1 and n3 is 2, or n2 is 2 and n3 is 1.
  • Examples of the “(n2 + n3) -valent organic group optionally having a ring structure, heteroatom and / or functional group” in R 7 include (n2 + n3-1) hydrogen atoms from a monovalent organic group. And groups derived by removal.
  • R 7 is preferably represented by the following formula: It is group represented by these.
  • R 7 has the following formula: It is group represented by these.
  • R 8 represents a divalent organic group.
  • R 8 is preferably —O— (CH 2 ) r — (wherein, r is an integer of 1 to 10, preferably 1 to 3), —NH— (CH 2 ) r — (Wherein r is as defined above), and more preferably —O— (CH 2 ) r — (wherein r is an integer of 1 or more and 3 or less).
  • the compounds represented by the above formulas (B1) and (B2) are represented by the following general formulas (B1a) and (B2a): [Wherein, Rf, PFPE, R 3 , R 6 , X 1 , Z, and n1 are as defined above, g is 0 or 1, h is 1 or 2, q1 is an integer of 1 to 5. ] It may be at least one compound represented by:
  • the compound represented by the above formula (C1) is: (A) an NCO group present in a triisocyanate obtained by trimerizing diisocyanate; (B) The following formula (a1) or formulas (a1) and (a2): [Wherein, Rf, PFPE, Z, g and h are as defined above. ] And at least one active hydrogen-containing compound represented by formula (a3): [Wherein X 1 is as defined above, R 30 represents a divalent organic group. ] At least one compound obtained by reacting active hydrogen of at least one active hydrogen-containing compound represented by the formula:
  • R 30 in formula (a3) is preferably — (CH 2 ) r ′ — (wherein, r ′ is an integer of 1 to 10, preferably 1 to 3), —CH (CH 3 )-, —CH (CH 2 CH 3 ) —, —CH (CH 2 OC 6 H 5 ) —, more preferably — (CH 2 ) r ′ — (wherein r ′ is 1 or more and 3 It is the following integer).
  • R 9 represents a tri to octavalent organic group. As is clear from the formula (D1), R 9 has an (n4 + 1) valence.
  • R 9 include, for example: —O—CH 2 —C (CH 2 —) 3 ; or —O—CH 2 —C (CH 2 —) 2 —CH 2 OCH 2 —C (CH 2 —) 3 Is mentioned.
  • n2 is an integer of 1 to 3.
  • n3 is an integer of 1 to 3.
  • n4 is an integer of 2 to 7, preferably 3 to 6.
  • R 7 has the same meaning as the above (C1). However, in formula (E1), the valence of R 7 is (n5 + n6 + n7).
  • R 11 is —R 8 —R 1 or —R 9 (R 1 ) n4 .
  • These -R 8 -R 1 and -R 9 (R 1 ) n4 groups have the same meanings as those of formula (C1) and formula (D1), respectively.
  • R 12 is a group containing Si.
  • the group containing Si is preferably represented by the following formula: It may be at least one compound represented by:
  • R 21 , R 22 , R 23 , R 24 and R 25 are each independently an alkyl group or an aryl group.
  • the alkyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. .
  • the alkyl group may be linear or branched, but is preferably linear.
  • Preferable specific examples include an n-butyl group for R 21 and a methyl group for R 22 to R 25 .
  • the aryl group is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms.
  • the aryl group may contain two or more rings.
  • a preferred aryl group is a phenyl group.
  • the alkyl group and aryl group may contain a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom, in the molecular chain or ring, if desired.
  • alkyl group and aryl group are optionally halogen; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, which may be substituted with one or more halogens.
  • R 26 represents a divalent organic group.
  • R 26 is — (CH 2 ) r — (wherein r is an integer of 1 to 20, preferably 1 to 10).
  • l and n are each independently 0 or 1; m is an integer of 1 to 500, preferably 1 to 200, more preferably 5 to 150; o is 0 An integer of ⁇ 20, for example, an integer of 1 to 20, and p is 0 or 1.
  • n5 is an integer of 1 to 3.
  • n6 is an integer of 1 to 3.
  • n7 is an integer of 1 to 3.
  • the molded body produced as described above has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group at least on the surface of the resin substrate, and the graft chain is formed from the surface of the substrate. At least 0.2 ⁇ m deep, up to 200 ⁇ m deep, preferably at least 1 ⁇ m deep, up to 40 ⁇ m deep, more preferably at least 3 ⁇ m deep, up to 20 ⁇ m deep, for example, 10-20 ⁇ m deep Exists. The greater the thickness at which the graft chain is present, the better the mold release durability. Moreover, the strength of the resin equipment is improved as the thickness where the graft chain is present is smaller.
  • the surface of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group by elemental analysis of the surface of the resin substrate (for example, to a depth of 0.1 ⁇ m).
  • elemental analysis for example, X-ray photoelectron spectroscopy (XPS) or total reflection measurement (ATR) can be used.
  • XPS X-ray photoelectron spectroscopy
  • ATR total reflection measurement
  • the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain has a depth of at least 0.2 ⁇ m and a maximum depth from the substrate surface.
  • a molded body characterized in that it is present up to 200 ⁇ m, preferably at least 1 ⁇ m deep, at most up to 40 ⁇ m deep, more preferably at least 3 ⁇ m deep, up to 20 ⁇ m deep, for example 10 to 20 ⁇ m deep. provide.
  • the graft chain does not exceed 95% of the thickness of the resin substrate.
  • “Graft chain” means a side chain bonded in a branched manner to the main chain of the polymer constituting the resin substrate, and is not limited by the production method. That is, the graft chain includes, for example, a chain introduced into the main chain of the polymer constituting the resin substrate by other methods in addition to the graft chain formed by the above graft polymerization.
  • the “graft chain” is a branched chain that is branched with respect to the polymer main chain of the resin base material, and can be obtained by covalently bonding the graft monomer to the polymer main chain by irradiation with ionizing radiation. .
  • the depth at which the graft chain is present is from the surface of the substrate to a depth of 0.001 to 95% of the thickness of the resin substrate, for example, a depth of 0.01 to 95% or 0.1 to It can be up to 95% deep.
  • the depth at which the graft chain is present may more preferably be 5 to 80% deep, more preferably 10 to 60% deep, and even more preferably 20 to 60% deep.
  • the graft chain has a depth of 0.2 to 200 ⁇ m, preferably 1 to 40 ⁇ m, more preferably 2 to 30 ⁇ m, still more preferably 3 to 20 ⁇ m, such as 5 to 20 ⁇ m or 10 to 20 ⁇ m, from the surface of the resin substrate. May be present.
  • the graft chain is at least 0.2 ⁇ m deep and at most 200 ⁇ m deep, more preferably at least 1 ⁇ m deep, and at most 40 ⁇ m deep, more preferably at least depth from the surface of the resin substrate. 2 ⁇ m, up to a depth of 30 ⁇ m, more preferably at least 3 ⁇ m in depth, up to a depth of 20 ⁇ m, for example at least 5 ⁇ m in depth, up to a depth of 20 ⁇ m, or at least 10 ⁇ m in depth, up to a depth of 20 ⁇ m May be.
  • 0.001% is preferred, 0.01% is more preferred, 0.1% is still more preferred, 0.5% is still more preferred, for example, 1%, 5%, 10% %, 20% or 30% is preferred.
  • 90% is preferable, 80% is more preferable, 70% is further more preferable, 60% is still more preferable, for example, 50% or 45% is preferable.
  • the lower limit of the depth at which the graft chain is present is preferably 0.2 ⁇ m, more preferably 0.3 ⁇ m, still more preferably 0.5 ⁇ m, still more preferably 1.0 ⁇ m, for example 2.0 ⁇ m, 5.0 ⁇ m, 10 ⁇ m. Or 15 micrometers is preferable.
  • the upper limit of the depth is preferably 150 ⁇ m, more preferably 100 ⁇ m, still more preferably 70 ⁇ m, still more preferably 50 ⁇ m, for example 40 ⁇ m or 30 ⁇ m.
  • the depth at which the graft chain is present in the molded product can be measured, for example, by observing the cross section of the film with a scanning electron microscope. More specifically, it can be measured by performing elemental analysis or positron lifetime measurement by EPMA or EDX described above.
  • the molded body produced as described above can have a graft ratio of 0.1 to 1,500%.
  • the molecular chain present on at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft ratio is 0.1 to 1,500%.
  • a molded body characterized in that it is.
  • “Graft ratio” means the ratio of graft chains introduced to the resin substrate.
  • the graft ratio Dg is calculated by allocating by the total weight of the base material, when the graft layer is extremely thin with respect to the film thickness, it becomes a small value and may show a value of 0.1% or less.
  • the region of the graft chain in the depth direction can be verified by elemental analysis using SEM-EDX or EPMA.
  • SEM-EDX a graft chain containing a perfluoropolyether group of 5 ⁇ m is introduced into a resin having a specific gravity of 2 and a weight of 30 g in a sheet of 5 mm in thickness, it is 0.1% of the thickness of the resin substrate, The graft ratio is approximately less than 0.1%.
  • the graft ratio can also be calculated by thermogravimetry (TG). Specifically, for a molded body having a graft chain, change the temperature of the molded body according to a certain program (heat or cool), measure the change in the weight of the molded body, and calculate from this weight change. Can do.
  • the thermogravimetric measurement can be performed, for example, using a TGA measuring instrument manufactured by Rigaku or Shimadzu Corporation.
  • the graft ratio is preferably 0.1 to 500%, more preferably 0.5% to 300%, still more preferably 5 to 200%, for example, 10 to 150% when the resin substrate is composed of a non-fluorine resin. Or it may be 20-100%.
  • the graft ratio is preferably from 0.1 to 250%, more preferably from 0.2% to 150%, still more preferably from 5 to 120%, for example from 10 to 100 when the resin substrate is made of a fluororesin. % Or 20-80%.
  • the molded product of the present invention has a small surface free energy because a perfluoropolyether group or a perfluoroalkyl group is present on the surface of the resin substrate.
  • the surface free energy of the molded body of the present invention may be 20 mN / m or less.
  • the molded article of the present invention having a low surface free energy, particularly a film can exhibit high releasability particularly when it is molded into an imprint mold.
  • the graft chain containing a perfluoropolyether group or a perfluoroalkyl group is strongly bonded to the compound constituting the resin substrate, and thus has high durability.
  • the surface free energy of the molded product of the present invention can be 20 mN / m or less even after ultrasonic cleaning with hydrofluoroether (HFC7200 (manufactured by 3M) for 3 minutes.
  • HFC7200 hydrofluoroether
  • the molecular chain present on at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the surface free energy after washing with the hydrofluoroether is low. , 20 mN / m or less is also provided.
  • the graft chain in the molded article of the present invention is a residue of the graft monomer, preferably a residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group. It is.
  • the molecular chain present on at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is a perfluoropolyether group or a perfluoropolyether group.
  • a molded article characterized by being a residue of a compound containing a fluoroalkyl group and a radical-reactive group.
  • the residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group includes a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group. It means a portion derived from a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical and a reactive group after the compound and the resin substrate are bonded.
  • a compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical-reactive group is R—OC (O) —CH ⁇ CH 2, where R contains a perfluoropolyether group or a perfluoroalkyl group.
  • R contains a perfluoropolyether group or a perfluoroalkyl group.
  • Group of the compound containing a perfluoropolyether group or a perfluoroalkyl group and a radical reactive group It can be.
  • the molded body of the present invention is preferably in the form of a film, and the thickness thereof is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 30 to 125 ⁇ m, and further preferably 30 to 60 ⁇ m.
  • the molded article of the present invention can have high light transmittance in the ultraviolet region.
  • the light transmittance at 365 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the molded body of the present invention can be molded and used as an imprint mold using an ultraviolet curable resin.
  • the molded article of the present invention has a small surface free energy and can maintain this low surface energy over a long period of time, so that the mold for imprinting has excellent release properties and release durability. In particular, it can be formed into a nanoimprint mold.
  • the present invention also provides the above-mentioned molded body used for manufacturing an imprint mold.
  • the mold for nanoimprinting of the present invention can further harden the mold surface by irradiation cross-linking reaction with ionizing radiation such as electron beam and ⁇ -ray.
  • the molecular chain present on at least the surface portion of the resin base material has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain has a thickness of 0 of the resin base material.
  • the imprint mold of the present invention can be obtained by molding the above-described molded product of the present invention. That is, the imprint mold of the present invention may have the same characteristics as the above-described molded body of the present invention.
  • the molecular chain present on at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the surface free energy after washing with the hydrofluoroether is low. , 20 mN / m or less imprint mold,
  • the molecular chain present on at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and has a graft ratio of 0.1 to 1,500%.
  • a mold for imprinting; and a molecular chain present on at least a surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is a perfluoropolyether group or a perfluoropolyether group.
  • an imprint mold characterized by being a residue of a compound containing a fluoroalkyl group and a radical reactive group.
  • Molding of the imprint mold of the present invention from the above-described molded body of the present invention is performed, for example, by pressing a master mold having a predetermined pattern against the surface where the graft chain of the molded body exists.
  • Such molding can be performed by any of the batch production method and the continuous production method described below.
  • a master mold made of silicon, nickel metal or quartz is formed on a molded body having a graft chain containing a perfluoropolyether group or a perfluoroalkyl group on the surface of a resin substrate, using a nanoimprint apparatus,
  • An imprint mold having a pattern shape obtained by accurately reversing the master mold can be formed by pressing at a predetermined temperature and pressure conditions, for example, at a pressure of 250 ° C. and 5 MPa for a predetermined time, for example, 3 minutes. it can.
  • the imprint mold it is preferable to perform a release agent treatment on the master mold.
  • a release agent treatment it does not specifically limit as a mold release agent, A perfluoro-type mold release agent is preferable.
  • the temperature at the time of the molding can be appropriately selected according to the material of the resin substrate to be used and the production method (batch production method or continuous production method). For example, when ETFE is used, the temperature is 80 to 300 ° C. .
  • the imprint mold of the present invention is manufactured by forming the resin substrate into an imprint mold before introducing a graft chain containing a perfluoropolyether group or a perfluoroalkyl group into the resin substrate. You can also. Specifically, a resin substrate is molded into an imprint mold, and the surface is irradiated with ionizing radiation to generate radicals. The generated radicals are reactive with perfluoropolyether groups or perfluoroalkyl groups and radicals. It can manufacture by carrying out graft polymerization of the compound containing these groups.
  • Irradiation with ionizing radiation and graft polymerization can be performed by a method substantially similar to the above-described method related to the molded article of the present invention.
  • the imprint mold of the present invention has an excellent releasability since a perfluoropolyether group or a perfluoroalkyl group is present on the surface of the resin substrate, and the perfluoropolyether group or perfluoroalkyl group. Since the graft chain containing is firmly bonded to the molecules constituting the resin substrate, it has excellent release durability.
  • the imprint mold of the present invention Since the imprint mold of the present invention has an excellent releasability, the pattern is hardly damaged at the time of demolding, and extremely fine and complicated patterning, for example, fine patterning on the order of nanometers becomes possible.
  • the imprint mold of the present invention may have a pattern with a pitch width of 50 nm to 2,000 nm.
  • the imprint mold of the present invention can be used for manufacturing devices for a wide range of applications such as electronic, optical, medical and chemical analysis.
  • the electronic device include integrated circuits such as a transistor, a memory, a light emitting diode (EL), a laser, and a solar battery.
  • optical devices include display pixels such as color filters for liquid crystal displays and organic EL, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, and the like. It is done.
  • Examples of magnetic devices include next-generation hard disk drives (discrete tracks), next-generation hard disk drives (patterned media), and next-generation semiconductors.
  • the imprint mold of the present invention is a substrate of an LED element (particularly a high-brightness LED element), a moth-eye structure antireflection film, a sunlight condensing film, a film having a regular uneven structure such as a liquid crystal polarizing plate, etc. It can use suitably for manufacture.
  • Example 1 A reaction product obtained by reacting acrylic acid with a perfluoropolyether group-containing alcohol (F (CF 2 CF 2 CF 2 O) n —CF 2 CF 2 CH 2 —OH: average molecular weight of about 2300) with a sulfuric acid catalyst ( Residual acrylic acid (3.1%) was neutralized to pH 11 with 10% aqueous sodium hydroxide, the aqueous layer was separated and the acid component was removed, and the perfluoropolyether group and acryloyl containing 2000 mg / l of sodium acrylate A compound containing groups was obtained. Subsequently, 10% by weight of water was mixed with the static compound with the static compound, and then left and separated for 20 minutes.
  • F (CF 2 CF 2 CF 2 O) n —CF 2 CF 2 CH 2 —OH: average molecular weight of about 2300) Residual acrylic acid (3.1%) was neutralized to pH 11 with 10% aqueous sodium hydroxide, the aqueous layer was separated and
  • an ultra-low energy electron beam was used on one surface of an ethylene-tetrafluoroethylene copolymer film (trade name: NEOFLON ETFE, Daikin Industries, Ltd., film thickness 50 ⁇ m) in a nitrogen atmosphere.
  • the electron beam was irradiated at 160 kGy (irradiation conditions: acceleration voltage 60 kV).
  • the film was taken out into the atmosphere for 5 minutes, and radicals generated on the surface of the ethylene-tetrafluoroethylene copolymer were converted into peroxide radicals.
  • dissolved oxygen in the compound solution obtained above was removed under nitrogen mixing, and then immersed in the solution at 40 ° C. for 2 hours. After immersion, the film was washed with hydrofluoroether HFE7200 (manufactured by 3M) and dried to obtain a film having a graft chain containing a perfluoropolyether group.
  • Test example 1 Thermogravimetry
  • the graft ratio of the obtained film was measured by thermogravimetry using a differential thermobalance (TG-DTA). As a result of the measurement, it was confirmed that 3.5% by mass of the film was a surface graft chain.
  • Example 1 had undergone a graft reaction on the surface irradiated with the electron beam.
  • Test example 2 Release durability test using a film having a surface graft chain containing a perfluoropolyether group Photocurable resin (trade name) on the surface where the film obtained in Example 1 was irradiated with an electron beam and the surface graft chain was introduced 0.2 ml of PAK-02 manufactured by Toyo Gosei Co., Ltd. was dropped, covered with a polycarbonate film, and pressed with 1.0 MPa using a continuous optical nanoimprinting apparatus consisting of a Step & Repeat method, and simultaneously irradiated with ultraviolet light (10 mW / cm 2 ) For 20 seconds, a releasability test with the film using a photo-curing resin was performed. This releasability test was continuously performed, and the contact angle (water) on the film surface was measured every 225 times. The contact angle was measured with 1 ⁇ L of water using a contact angle measuring device. The results are shown in FIG.
  • Comparative Example 1 One surface of a commercially available ethylene-tetrafluoroethylene copolymer film (trade name: NEOFLON ETFE, manufactured by Daikin Industries, Ltd., film thickness 50 ⁇ m) is subjected to atmospheric pressure plasma treatment, and peroxide radical groups are formed on the surface. After the introduction, perfluoropolyether ((F (CF 2 CF 2 CF 2 O) n-CF 2 CF 2 CH 2 —NHCH 2 ) having a primary amino group useful for the ring-opening reaction of the epoxy ring at the molecular end.
  • perfluoropolyether ((F (CF 2 CF 2 CF 2 O) n-CF 2 CF 2 CH 2 —NHCH 2 ) having a primary amino group useful for the ring-opening reaction of the epoxy ring at the molecular end.
  • HFE7200 A hydrofluoroether solution (HFE7200) containing CH 3 ) was spin-coated (grafting treatment), and the perfluoropolyether chain that was physically adsorbed excessively was washed with hydrofluoroether (HFE7200: manufactured by 3M) and dried.
  • Example 1 except that a plasma film having a surface graft chain containing a perfluoropolyether group was obtained It was carried out in the same manner. The results are shown in Figure 1. Further, when the surface fluorine concentration of the obtained film having a thickness of 50 ⁇ m was measured by elemental analysis of the film cross section using an electron beam microanalyzer (EPMA), graft chains may exist from the surface to a depth of 0.1 ⁇ m. confirmed.
  • EPMA electron beam microanalyzer
  • Comparative Example 2 (1) Production of resin In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 80 parts by weight of methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Chemical Co., Ltd.), fluorine-based macromer 20 parts by weight (produced by the method described in Example 1 of JP-T-11-503183, molecular weight 8000) and 100 parts by weight of toluene were added. Thereafter, the contents of the flask were heated to 80 ° C.
  • methyl methacrylate trade name: Light Ester M, manufactured by Kyoeisha Chemical Co., Ltd.
  • Comparative Example 3 A film made of a commercially available ethylene-tetrafluoroethylene copolymer (film thickness: 50 ⁇ m) that has not been irradiated with an electron beam is applied to a mold release modifier (F (CF 2 CF 2 CF 2 O) n —CF 2 CF 2 CH 2 —). It was immersed in Si (OCH 3 ) 3 : average molecular weight of about 2300 for 1 minute, then pulled up and heat-treated at 80 ° C. for 1 hour. Thereafter, the film was washed and dried in the same manner as in Example 1 to obtain a film made of an ethylene-tetrafluoroethylene copolymer. However, since the film surface has no reactive group, it was not modified with a release modifier.
  • a mold release modifier F (CF 2 CF 2 CF 2 O) n —CF 2 CF 2 CH 2 —
  • the film having the surface graft chain of Example 1 was able to maintain a contact angle close to 100 ° even when the number of mold release exceeded 3000 times.
  • the film surface-grafted with the plasma of Comparative Example 1 and the PET film modified with the fluororesin thin film layer of Comparative Example 2 have a contact angle that decreases with the number of times of mold release. It decreased to less than 80 °.
  • Example 2 Batch production of imprint mold A master mold (diameter: 230 nm, pitch: 460 nm, depth: 200 nm) made of silicon was applied to the ETFE film obtained in Example 1 using the nanoimprint apparatus.
  • the imprint mold having a pattern shape in which the pattern of the master mold was accurately reversed was pressed at 250 ° C. under a pressure of 5 MPa for 3 minutes.
  • the following process was performed as a mold release agent process to the master mold which consists of silicon
  • the master mold was immersed in a perfluoropolyether release agent solution (trade name: OPTOOL HD-1100, manufactured by Daikin Industries, Ltd.) for 1 minute, and then heated and heated in an 80 ° C. environment for 1 hour.
  • a perfluoropolyether release agent solution trade name: OPTOOL HD-1100, manufactured by Daikin Industries, Ltd.
  • the heat-treated master mold was rinsed with a fluorine-based solvent (trade name: OPTOOL HD-TH, manufactured by Daikin Industries, Ltd.) and allowed to stand in an environment of 23 ° C. and 65% RH for 24 hours.
  • a fluorine-based solvent trade name: OPTOOL HD-TH, manufactured by Daikin Industries, Ltd.
  • the surface of the obtained imprint mold was observed with a scanning electron microscope. As a result of observation, the diameter was 230 nm, the pitch was 460 nm, and the depth was 200 nm. The photograph taken is shown in FIG.
  • Example 3 Continuous Production of Imprint Mold
  • the ETFE film 130 obtained in Example 1 was continuously extruded from a film roll 131, and a master mold 132 (diameter 230 nm, pitch) made of nickel metal.
  • the pattern was transferred to the film 130 using an imprint apparatus 133 having a depth of 460 nm and a depth of 200 nm. Thereafter, processing such as cooling was performed with a plurality of rolls 134, and the sheet was cut into a desired size using a cutting machine 135 to continuously form an imprint mold.
  • Example 4 Photo-nanoimprint using a film mold having a surface graft chain containing a perfluoropolyether group
  • a photocurable resin (trade name: PAK-02 manufactured by Toyo Gosei Co., Ltd.) is placed on the imprint mold obtained in Example 2. 2 ml of the solution was dropped, and a polycarbonate film was placed thereon, and the film was pressed using a continuous optical nanoimprint apparatus composed of the Step & Repeat method and simultaneously irradiated with ultraviolet rays.
  • the pattern surface of the resin mold was observed, and it was confirmed that there was no transfer defect in the mold. Further, when the pattern surface of the transferred resin was observed with a scanning electron microscope and an atomic force microscope, it was confirmed that the pattern was well formed (diameter 230 nm, pitch 460 nm, depth 200 nm). Further, it was confirmed that even when 200 shot continuous optical nanoimprinting was performed using this resin mold, imprinting could be performed satisfactorily without any transfer defects.
  • Example 5 A film having a surface graft chain was obtained in the same manner as in Example 1 except that the electron beam irradiation was performed under a vacuum of 1 ⁇ 10 3 Pa. Furthermore, an imprint mold was formed by the same process as in Example 2 using this film.
  • Example 6 A film having a surface graft chain was obtained in the same manner as in Example 1 except that C 6 F 13 CH 2 CH 2 OCOCH ⁇ CH 2 was used instead of the compound containing a perfluoropolyether group and an acryloyl group as the graft monomer. It was. Furthermore, an imprint mold was formed by the same process as in Example 2 using this film.
  • Example 8 Instead of an ethylene-tetrafluoroethylene copolymer film (trade name: NEOFLON ETFE, Daikin Industries, Ltd., film thickness 50 ⁇ m), a polypropylene 10 cc syringe molded by injection molding is used as a molded body. A molded body having a surface graft chain was obtained in the same manner as in Example 1 except that the inner surface of the syringe barrel was irradiated with an ultra-low energy electron beam.
  • ethylene-tetrafluoroethylene copolymer film trade name: NEOFLON ETFE, Daikin Industries, Ltd., film thickness 50 ⁇ m
  • Example 9 A film having a surface graft chain was obtained in the same manner as in Example 1, except that a film made of COP (cycloolefin polymer) was used instead of the film made of ethylene-tetrafluoroethylene copolymer (film thickness 50 ⁇ m). . Furthermore, an imprint mold was formed by the same process as in Example 2 using this film.
  • COP cycloolefin polymer
  • Example 10 A film having a surface graft chain was obtained in the same manner as in Example 1 except that a PET film was used instead of the ethylene-tetrafluoroethylene copolymer film (film thickness 50 ⁇ m). Furthermore, an imprint mold was formed by the same process as in Example 2 using this film.
  • Example 11 A film having a surface graft chain was obtained in the same manner as in Example 1 except that a film made of PDMS (polydimethyl silicone resin) was used instead of the film made of ethylene-tetrafluoroethylene copolymer (film thickness 50 ⁇ m). It was. Furthermore, an imprint mold was formed by the same process as in Example 2 using this film.
  • PDMS polydimethyl silicone resin
  • Comparative Example 4 A film having a surface graft chain was obtained in the same manner as in Example 1 except that the acceleration voltage in Example 1 was changed to 250 kV. As a result, the graft thickness of the film was 100% (that is, the graft chain was formed even on the back surface of the film).
  • continuous optical nanoimprinting was performed with a continuous optical nanoimprinting apparatus using the Step & Repeat method using the same, but this film is also provided with a graft chain on the back side, so that the test apparatus Adhesive fixation to the substrate could not be performed, and the imprint test could not be performed.
  • Example 12 Next, on one surface of a commercially available ethylene-tetrafluoroethylene copolymer film (trade name: NEOFLON ETFE, manufactured by Daikin Industries, Ltd., film thickness 200 ⁇ m), a low-energy electron beam is used in a nitrogen atmosphere. A film having a surface graft chain was obtained in the same manner as in Example 1 except that 160 kGy of the electron beam was irradiated (irradiation condition: acceleration voltage 250 kV).
  • irradiation condition acceleration voltage 250 kV
  • Example 13 Next, one surface of a commercially available PET film (trade name: Toyobo Ester Film E5100, manufactured by Toyobo Co., Ltd., film thickness 500 ⁇ m) was irradiated with an electron beam at 160 kGy in a nitrogen atmosphere using a low-energy electron beam ( Except for irradiation conditions: acceleration voltage 250 kV, a film having a surface graft chain was obtained in the same manner as in Example 10.
  • a commercially available PET film trade name: Toyobo Ester Film E5100, manufactured by Toyobo Co., Ltd., film thickness 500 ⁇ m
  • Example 14 Next, one surface of a commercially available PP molded product (trade name: Novatec PP MA3, manufactured by Nippon Polypro Co., Ltd., film thickness: 5 mm) is irradiated with an electron beam at 160 kGy in a nitrogen atmosphere using an ultra-low energy electron beam.
  • a film having a surface graft chain was obtained in the same manner as in Example 1 except that (irradiation condition: acceleration voltage 5 kV).
  • EMA electron beam microanalyzer
  • the film of the present invention has low surface energy, it can be used for various purposes, particularly for the production of imprint molds. Moreover, since the mold for imprinting of the present invention is not only excellent in releasability but also excellent in releasability, it can be used for production of substrates of various device elements such as LED elements. In addition, since it has a low surface energy, it can be attached to a side wall of a building or a roof and used as a water-repellent coating.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

　La présente invention concerne un moule d'impression caractérisé en ce qu'il présente une haute durabilité suite au décollement du moule, le matériau de base en résine ayant une chaîne greffée contenant un groupe perfluoropolyéther ou un groupe perfluoroalkyle, et la chaîne greffée étant présente à une profondeur d'au moins 0,2 μm à partir de la surface du matériau de base en résine, étant présente à une profondeur allant jusqu'à 200 μm au maximum, et ne dépassant pas une profondeur de 95% de l'épaisseur du matériau de base en résine.
PCT/JP2015/060282 2014-03-31 2015-03-31 Article moulé et son procédé de fabrication Ceased WO2015152310A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016511971A JP6536571B2 (ja) 2014-03-31 2015-03-31 成形体およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-074457 2014-03-31
JP2014074457 2014-03-31

Publications (1)

Publication Number Publication Date
WO2015152310A1 true WO2015152310A1 (fr) 2015-10-08

Family

ID=54240628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/060282 Ceased WO2015152310A1 (fr) 2014-03-31 2015-03-31 Article moulé et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP6536571B2 (fr)
WO (1) WO2015152310A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018024106A (ja) * 2016-08-08 2018-02-15 旭化成株式会社 インプリント用モールド
JP2018053093A (ja) * 2016-09-28 2018-04-05 株式会社潤工社 吸着制御表面を有する高分子基材及びその製造方法
WO2018139567A1 (fr) 2017-01-27 2018-08-02 国立大学法人大阪大学 Matériau de moulage et procédé de production de corps de résine moulée au moyen dudit matériau
CN109475901A (zh) * 2016-07-12 2019-03-15 夏普株式会社 防污性膜的制造方法
JP2021126896A (ja) * 2019-09-03 2021-09-02 東レ株式会社 印刷物の製造方法
US11225557B2 (en) 2016-03-09 2022-01-18 Daikin Industries, Ltd. Method for producing molded article
CN114402006A (zh) * 2019-09-17 2022-04-26 大金氟化工（中国）有限公司 改性聚合物、组合物、涂膜和层积体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007320072A (ja) * 2006-05-30 2007-12-13 Asahi Glass Co Ltd モールドおよびその製造方法
WO2012018043A1 (fr) * 2010-08-06 2012-02-09 綜研化学株式会社 Moule en résine pour nano-impression
JP2014028951A (ja) * 2012-07-05 2014-02-13 Daikin Ind Ltd 改質含フッ素共重合体、フッ素樹脂成形品、及び、フッ素樹脂成形品の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000263714A (ja) * 1999-03-09 2000-09-26 Minnesota Mining & Mfg Co <3M> フッ素系剥離シートとその製造方法
JP2015189053A (ja) * 2014-03-27 2015-11-02 住友電工ファインポリマー株式会社 樹脂被覆物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007320072A (ja) * 2006-05-30 2007-12-13 Asahi Glass Co Ltd モールドおよびその製造方法
WO2012018043A1 (fr) * 2010-08-06 2012-02-09 綜研化学株式会社 Moule en résine pour nano-impression
JP2014028951A (ja) * 2012-07-05 2014-02-13 Daikin Ind Ltd 改質含フッ素共重合体、フッ素樹脂成形品、及び、フッ素樹脂成形品の製造方法

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11225557B2 (en) 2016-03-09 2022-01-18 Daikin Industries, Ltd. Method for producing molded article
CN109475901A (zh) * 2016-07-12 2019-03-15 夏普株式会社 防污性膜的制造方法
JPWO2018012343A1 (ja) * 2016-07-12 2019-04-25 シャープ株式会社 防汚性フィルムの製造方法
CN109475901B (zh) * 2016-07-12 2021-12-14 夏普株式会社 防污性膜的制造方法
JP2018024106A (ja) * 2016-08-08 2018-02-15 旭化成株式会社 インプリント用モールド
JP2018053093A (ja) * 2016-09-28 2018-04-05 株式会社潤工社 吸着制御表面を有する高分子基材及びその製造方法
WO2018139567A1 (fr) 2017-01-27 2018-08-02 国立大学法人大阪大学 Matériau de moulage et procédé de production de corps de résine moulée au moyen dudit matériau
CN110248973A (zh) * 2017-01-27 2019-09-17 国立大学法人大阪大学 成型用材料和使用该成型用材料的树脂成型体的制造方法
JPWO2018139567A1 (ja) * 2017-01-27 2019-11-07 国立大学法人大阪大学 成形用材料およびそれを用いた樹脂成形体の製造方法
US11623975B2 (en) 2017-01-27 2023-04-11 Osaka University Molding material and method for producing resin molded body using same
JP2021126896A (ja) * 2019-09-03 2021-09-02 東レ株式会社 印刷物の製造方法
JP7501243B2 (ja) 2019-09-03 2024-06-18 東レ株式会社 印刷物の製造方法
CN114402006A (zh) * 2019-09-17 2022-04-26 大金氟化工（中国）有限公司 改性聚合物、组合物、涂膜和层积体
CN114402006B (zh) * 2019-09-17 2024-07-19 大金氟化工（中国）有限公司 改性聚合物、组合物、涂膜和层积体

Also Published As

Publication number Publication date
JPWO2015152310A1 (ja) 2017-04-13
JP6536571B2 (ja) 2019-07-03

Similar Documents

Publication Publication Date Title
JP6536571B2 (ja) 成形体およびその製造方法
JP5934544B2 (ja) ガスバリアフィルム
Tsougeni et al. Mechanisms of oxygen plasma nanotexturing of organic polymer surfaces: from stable super hydrophilic to super hydrophobic surfaces
JP5908214B2 (ja) 樹脂モールド及びその製造方法
JP5749678B2 (ja) ガスバリアフィルム
JP6786820B2 (ja) 成形体の製造方法
TW200911498A (en) Mold, method for production of the mold, and method for production of substrate having replicated fine pattern
TW201305257A (zh) 表面具有微細凹凸結構的物品及具備該物品的視訊顯示裝置
KR102004630B1 (ko) 성형체
JP5658001B2 (ja) 樹脂モールド
JP2011002759A (ja) 反射防止膜
TW201005430A (en) Mold, process for producing the same, and process for producing substrate having transferred fine pattern
JP2007320072A (ja) モールドおよびその製造方法
US12179189B2 (en) Film for microfluidic device, microfluidic device and method for manufacturing same
JP6875687B2 (ja) 成形用材料およびそれを用いた樹脂成形体の製造方法
US20060234062A1 (en) Method for grafting a chemical compound to a support substrate
JP6011852B2 (ja) ポリマー材料の表面処理方法
CN108369293A (zh) 光学部件以及聚合物层
JP2012101483A (ja) 樹脂モールド製造方法
TW200540865A (en) Process for producing an optical recording medium with several stages and medium obtained thereby
JP2020019904A (ja) 成形用材料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15772869

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016511971

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase
122 Ep: pct application non-entry in european phase

Ref document number: 15772869

Country of ref document: EP

Kind code of ref document: A1