JP6536571B2 - Molded body and method for producing the same - Google Patents

Description

  The present invention relates to a molded article, more particularly, to 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 imprinting mold formed from such a molded body.

  Nanoimprint technology is known as a technology for obtaining a pattern of microstructures. In the nanoimprint technology, a mold (mold) having a fine pattern surface with asperities is pressed against the curable resin layer on the substrate to transfer the microstructure, and UV light is applied to cure the curable resin layer. Is a technique for immobilizing the transferred microstructure.

  A mold used in such a nanoimprint technique is required to have high releasability in order to reliably maintain the transferred microstructure when releasing from a curable resin.

  On the other hand, although a mold made of quartz can generally be used as a mold used in the nanoimprint technology, this is very expensive. Therefore, there is known a technique of using such a quartz mold as an original plate (also referred to as "master mold" or "mother mold") to produce a resin replica mold and using this replica mold for nanoimprint technology. .

  However, such a resin replica mold has a problem that the releasability is low, and the fine structure transferred at the time of mold release is likely to be missing. In order to solve such a problem, Patent Document 1 proposes a mold on the surface of which a silicone-based mold release agent or a fluorine-based coupling agent is applied. Further, Patent Document 2 proposes a mold in which a part having mold release performance is unevenly distributed in the vicinity of the surface of the mold by using a specific macromonomer. Further, Patent Document 3 proposes a mold in which a release agent is contained on the surface of a resin mold to form a layer bonded to the surface of the resin mold.

JP, 2008-178984, A International Publication No. 2012/018043 International Publication No. 2012/018045

  However, in the field of imprinting, the demand for mold release durability, ie, the ability to maintain mold release property for a long time, is increasing day by day, and the molds described in Patent Documents 1 to 3 meet this demand. It can not be said that it is enough.

  Therefore, an object of the present invention is to provide an imprinting mold having high mold release durability. Another object of the present invention is to provide a molded body that can be processed into such an imprint mold, and a method of manufacturing the same.

  As a result of intensive investigations, the present inventors introduced a graft chain containing a perfluoropolyether group or a perfluoroalkyl group into a resin substrate, thereby providing good releasability and release durability to the resin substrate. It has been found that it is possible to give a sex, and the present invention has been completed.

That is, the present invention is:
The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is present from the surface of the resin substrate to at least a depth of 0.2 μm and a depth of at most 200 μm And a molded body characterized in that the depth does not exceed 95% of the thickness of the resin base material;
The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain contains the remaining compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. A formed body characterized by being a base;
The surface of the resin substrate is irradiated with ionizing radiation to generate radicals, and graft polymerization is performed on the generated radicals and a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with the radicals. Molded body;
The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is present from the surface of the resin substrate to at least a depth of 0.2 μm and a depth of at most 40 μm An imprinting mold characterized in that it does not exist over a depth of 95% of the thickness of the resin substrate;
The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain contains the remaining compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. And an imprinting mold characterized by being a group; and the surface of the resin substrate is irradiated with ionizing radiation to generate radicals, and the generated radicals react with the perfluoropolyether group or the perfluoroalkyl group and the radicals. Provided is an imprinting mold obtained by graft polymerization with a compound containing a functional group.

  According to the present invention, by introducing a graft chain containing a perfluoropolyether group or a perfluoroalkyl group into a resin substrate, a molded body having a small surface free energy and capable of maintaining this state over a long period of time It becomes possible to offer. Further, according to the present invention, it is possible to provide an imprint mold having excellent releasability and excellent releasability.

FIG. 1 shows the results of release durability tests for the resin films of Example 1 and Comparative Examples 2 and 3. FIG. 2 is a SEM image of the imprinting mold obtained in Example 2. FIG. 3 is a drawing for explaining the manufacturing process of the third embodiment.

  In the molded article of the present invention, the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and this graft chain is at least 0.2 μm deep from the surface of the resin substrate, at most. It is characterized by existing to a depth of 200 μm and not exceeding a depth of 95% of the thickness of the resin substrate.

  The molded article of the present invention comprises the steps of: irradiating the surface of a resin substrate with ionizing radiation to generate radicals; and producing the generated radicals, a compound containing a perfluoropolyether group or a perfluoroalkyl group, and a group reactive with the radicals Can be produced by graft polymerization. Specifically, it is manufactured as follows.

  First, a resin base material is prepared.

  The material forming the resin base material is a resin capable of generating radicals upon irradiation with ionizing radiation, for example, a compound from which a radiation chemical reaction is caused by irradiation with ionizing radiation and hydrogen atoms or fluorine atoms are eliminated, or ionizing radiation The resin is not particularly limited as long as it is a resin formed of a compound whose main chain / side chain is cleaved by irradiation, and, for example, a fluorine resin and a non-fluorine resin can be used. It is preferable to use a fluorine resin, because it has higher transparency to UV light, higher releasability, and higher resistance to light, heat, chemicals and the like. In addition, the molecular weight of the resin base material may be any molecular weight that can maintain the material properties according to the application, and may be reduced in molecular weight by ionizing radiation irradiation for introducing a graft chain onto the surface. .

  Examples of the fluorine resin include ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), perfluoroalkoxy copolymer (PFA), ethylene -Chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-hexafluoropropylene copolymer (VdF-HFP) Other than vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer (VdF-TFE-HFP), other fluorocarbon resins, fluororubbers, etc., and blend resins and polymer alloys thereof It may be. Among them, ethylene-tetrafluoroethylene copolymer is preferable.

  Examples of the non-fluorinated resin include polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyolefins such as cycloolefin resin, modified polyolefin and polyvinyl chloride. Acrylic resin such as vinyl chloride resin, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamide imide, polycarbonate, poly- (4-methylpentene-1), ionomer, polymethyl methacrylate (PMMA), acrylic-styrene copolymer Combined (AS resin), ethylene-tetrafluoroethylene copolymer (ETFE), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyesters such as polycyclohexane terephthalate (PCT), polyethers, polyetherketones (PEK), polyetheretherketones (PEEK), polyetherimides, polyacetals (POM), polyphenylene oxides, modified polyphenylene oxides, Polyarylate, aromatic polyester (liquid crystal polymer), styrene resin, polyurethane resin, chlorinated polyethylene resin, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polydimethyl silicone (PDMS) And polyurethanes, or copolymers, blends and polymer alloys containing these. Among them, cycloolefin resins, acrylic resins such as polymethyl methacrylate (PMMA), and polyolefin resins are preferable.

  The shape of the resin substrate 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 have to be completely flat, and may partially or entirely have a curved surface, for example, a dome shape, a cylindrical shape, or the like. Preferably, the resin substrate is in the form of a sheet or a film, more preferably in the form of a film.

  The thickness of the resin substrate is not particularly limited, and may be, for example, 5 μm to 20 mm, preferably 10 μm to 10 mm, and more preferably 10 μm to 1 mm.

  When the resin substrate is a film, the thickness of the resin substrate is not particularly limited, but is preferably 10 to 200 μm, more preferably 30 to 125 μm, and still more preferably 30 to 60 μm.

  Next, the resin base material is irradiated with ionizing radiation. By irradiating the resin base material with ionizing radiation, for example, hydrogen atoms or fluorine atoms are detached from the compound forming the resin base material in the resin base material, or the main chain of the compound forming the resin base material Radicals are generated by cleavage of the side chain by radiation chemical reaction. These radicals undergo surface graft polymerization with the grafting monomer described later.

  The ionizing radiation is not particularly limited as long as it can generate radicals when the resin base material is irradiated. For example, an electron beam, an X-ray, a γ-ray, a neutron beam, an ion or the like can be used. The electron beam is preferable because it is easy to control the penetration depth (range) of ionizing radiation and easily generate radicals in the resin.

  The absorbed dose of ionizing radiation to be irradiated is 1 to 1000 kGy, preferably 10 to 500 kGy, more preferably 50 to 300 kGy. By setting the absorbed dose to 1000 kGy or less, the deterioration of the resin substrate in the surface layer can be minimized. Also, by setting the absorbed dose to 1 kGy or more, it is possible to generate a sufficient amount of radicals for surface graft polymerization. The amount of energy absorbed by the resin substrate can be measured by a scintillation detector or a semiconductor detector, but is more preferably measured by, for example, a cellulose triacetate film (CTA: Cellulose triacetate) dosimeter or a radiochromic film dosimeter can do.

  When an electron beam is used, the energy of the electrons of the electron beam irradiated to 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 still more preferably using an electron accelerator. Preferably, they are 40 keV to 70 keV. By setting the energy of electrons on the sample surface to 100 keV or less, the electron beam is absorbed substantially only in the vicinity of the surface of the resin base material, and the electron beam penetrating to the inside of the base material is reduced. Deterioration of the resin base material can be suppressed. Furthermore, since the absorption of the electron beam inside the resin which is not involved in the surface graft polymerization is small and the number of the electron beams transmitting through the resin base is small, the energy absorption efficiency can also be enhanced. On the other hand, by setting the energy of electrons on the sample surface to 5 keV or more, radicals on the surface of the substrate can be generated to a degree sufficient for surface graft polymerization.

  When using an electron beam from an electron accelerator, if the space from the electron gun to the sample is in a vacuum environment, the energy of the electrons corresponds to the acceleration voltage, and 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.

  For example, when the accelerating voltage of the electron beam is 60 kV, the penetration depth of the electron beam may be about 20 μm.

  On the other hand, in the case of an electron accelerator in which there is an irradiation window for taking out to the atmosphere from the electron gun to the sample, the energy of the electrons is attenuated when passing through the irradiation window even if the irradiation is in vacuum. So the accelerating voltage needs to be higher according to the decay of the energy of the electrons. Of course, when passing through a nitrogen stream, it is also necessary to increase in consideration of the energy to be attenuated according to the density and the distance in the stream to the sample.

When using an electron beam, irradiation dose of the electron irradiating the ^{sample, 10μC / cm 2 ~10mC / cm} 2, ^{preferably, 50μC / cm 2 ~1mC / cm} 2, more preferably 100μC ^/ cm 2 ~300μC ^/ cm ² , for example 200 μC / cm ² . By setting the irradiation dose in such a range, radicals can be generated efficiently.

The irradiation of ionizing radiation to the resin base material is preferably performed in an atmosphere substantially free of oxygen, for example, with an oxygen concentration of 1000 ppm or less, more preferably 500 ppm, from the viewpoint of suppressing pair annihilation of the generated radicals. Still more preferably, it is carried out under an atmosphere of 100 ppm or less. For example, the irradiation of ionizing radiation is performed under vacuum or under an inert gas atmosphere, for example under a nitrogen or argon atmosphere. The vacuum does not have to be a complete vacuum, but may be a substantially vacuum, for example, a low vacuum of about 10 ³ Pa or a high vacuum of about 10 ^-2 Pa. Also, in another embodiment, the irradiation of ionizing radiation may be performed under the atmosphere to obtain peroxide radicals, or oxygen may be supplied after radical formation. Moreover, in order to prevent the deactivation of the radicals generated in the resin base material of the present invention, the resin base material after irradiation is preferably stored at a low temperature equal to or less than the glass transition temperature of the polymer constituting the resin. Storage under vacuum or inert atmosphere is more preferred.

  The penetration depth of ionizing radiation is preferably 0.001 to 95%, for example 0.01 to 95%, 0.1 to 95% or 0.2 to 95%, more preferably 5 to 80% of the thickness of the substrate. %, More preferably 10 to 60%, even more preferably 20 to 60%. For example, the penetration depth of ionizing radiation is from the surface of the substrate to a depth of 0.1 to 200 μm, preferably 1 to 40 μm, more preferably 2 to 30 μm, still more preferably 3 to 20 μm, for example The depth may be 5 to 20 μm or 10 to 20 μm.

  The penetration depth of ionizing radiation means the depth at which the resin substrate absorbs the energy of ionizing radiation. The penetration depth of ionizing radiation is substantially the same as the area where surface graft polymerization takes place, but because the surface of the sample slightly swells due to the surface grafting reaction, graft chains are present in the molded body after the grafting reaction The depth may be deeper than the penetration depth of ionizing radiation. The depth at which the graft chains are present is, for example, a scanning electron microscope (SEM) analysis of energy dispersive X-ray (EDX) analysis of a cross section of a molded product after surface graft polymerization, an EPMA (Electron Probe Microanalyser) analysis, etc. It can be measured by The depth at which the graft chain exists can also be measured by microscopic FT-IR, a Raman microscope, or the like.

  In addition, the depth at which the graft chain exists in the molded article after the grafting reaction can also be measured by positron lifetime measurement. Since the positron lifetime obtained by measuring the time from positron generation to electron pair annihilation is correlated with the amorphous free volume of the polymer and the size of atomic vacancies in the crystal, the graft chain is As grafting occurs, the free volume of amorphous in the substrate decreases and the positron lifetime also decreases. From this, it is possible to measure the depth at which the graft chain exists by positron lifetime measurement. Positron lifetime measurement generally detects gamma rays emitted during β + decay and annihilation gamma rays with different scintillation detectors, and counts the frequency of positrons annihilated at a certain time from their difference in incident time. The positron lifetime can be determined by analyzing the decay curve obtained in this way. For example, in the "Free volume study of the functionalized fluorinated polymer" by T. Oka published in The 2nd Japan-China Joint Workshop on Positron Science (JWPS 2013), an example in which styrene is grafted onto a fluorine resin is introduced. Also in the present invention, the presence of graft chains can be measured by this method.

  Next, the radical in the resin base material produced | generated by irradiation with ionizing radiation and the compound as a monomer (henceforth a "graft monomer") are graft-polymerized.

  The graft polymerization is carried out by bringing a graft monomer into contact with a radical in a resin substrate generated by irradiation with ionizing radiation. The contact between the radical in the resin substrate and the grafting monomer is carried out, for example, by immersing the resin substrate in a solution of the grafting monomer, dropping or applying the grafting monomer onto the resin substrate, or in the presence of a gaseous monomer. It is carried out by placing a resin substrate. Even if the wettability of the surface of the resin substrate and the grafting monomer is low, a method of immersing the resinous substrate in a solution of the grafting monomer is preferable because uniform and reliable contact can be achieved.

  Although the reaction temperature of the said graft polymerization is not specifically limited, For example, room temperature-100 degreeC, Preferably it is 30-80 degreeC, More preferably, it is 30-60 degreeC.

  Although the reaction time of the said graft polymerization is not specifically limited, For example, 30 minutes-32 hours, Preferably it is 1 to 12 hours, More preferably, it is 2 to 6 hours.

  The graft polymerization can be carried out by bringing the resin base and the graft monomer into contact with each other after irradiation with ionizing radiation as described above, but the invention is not limited thereto. The grafting monomers may be contacted. For example, ionizing radiation may be applied while the resin substrate is immersed in a solution of a graft monomer, or in an atmosphere in which a gaseous graft monomer is present. Alternatively, the resin base material and the grafting monomer may be brought into contact in advance, and ionizing radiation may be irradiated in this state. For example, the grafting monomer may be dropped or coated on the resin substrate and the ionizing radiation may be irradiated.

  The graft polymerization can proceed not only to the surface of the resin substrate but also to a certain depth, for example, a depth of 200 μm from the surface, preferably 40 μm, more preferably 20 μm.

  The grafting monomer has a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. Preferably, the grafting monomer has a perfluoropolyether group and a group reactive with a radical.

The above 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, and the sum of a, b, c and d is at least 1 and each repeating unit enclosed in parentheses The order of existence of is arbitrary in the formula. ]
Means a group represented by

  In the above formulae, a, b, c and d are each independently an integer of 0 or 1 and there is no particular limitation as long as the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 or more and 200 or less, more preferably each independently an integer of 0 or more and 100 or less, for example 1 It is an integer greater than or equal to 100. 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. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c or d is present is arbitrary in the formula.

Of the above recurring _{units, - (OC 4 F 8)} - _{is, - (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)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - ( It may be any of OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-, but is preferably is _{- (OCF 2 CF 2 CF 2} CF 2) - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. _{Also, - (OC 2 F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but it may be any of, preferably - _{(OCF 2} CF 2) - in is there.

In one aspect, PFPE is — (OC ₃ F ₆ ) _b — (wherein b is an integer of 1 or more and 200 or less, preferably 10 or more and 100 or less), preferably — (OCF ₂ CF ₂ CF ₂ ) _b- (wherein b is as defined above).

In another embodiment, the PFPE is — (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 c and d each independently represents 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 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less The order of existence of the respective repeating units enclosed in parentheses with the subscripts a, b, c or d Is optionally 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. For example, PFPE _{is, - (OCF 2 CF 2)} c - (OCF 2) d - ( wherein, c and d is as defined above) may be used.

In yet another embodiment, PFPE ^{_{is, - (OC 2 F 4 -R}} 11) n - is a group represented by. Wherein 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. For example, -OC ₂ F ₄ OC ₃ F _6- , -OC ₂ F ₄ OC ₄ F ₈ −, −OC ₃ F ₆ OC ₂ F ₄ −, −OC ₃ F ₆ OC ₃ F ₆ −, −OC ₃ F ₆ OC ₄ F ₈ −, −OC ₄ F ₈ OC ₄ F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC ₄ F ₈ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ −, −OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ −, −OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ −, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 _{F 4 OC 3 F 6 -,} - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _{-OC 4 F 8 OC 2 F 4} OC 2 F 4 - , and the like. The above n is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be linear or branched, preferably linear. In this embodiment, PFPE is _{preferably, - (OC 2 F 4 -OC} 3 F 6) n - or _{- (OC 2 F 4 -OC 4} F 8) n - is.

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.

  Examples of the “group reactive with a radical” include, but are not limited to, for example, a group having an ethylenic double bond and an oxygen-containing cyclic group (eg, glycidyl group, oxetanyl group), and derivatives thereof.

［式中、Ｒ^ｂは、結合または−ＯＣ（Ｏ）−であり、
Ｒ^ｃは、水素原子、フッ素原子、あるいはフッ素原子により置換されていてもよい炭素数１〜１０のアルキル基（好ましくは、炭素数１〜３のアルキル基、より好ましくはメチル基）またはフェニル基を表し、好ましくは、メチル基または水素原子であり、
Ｒ^ｄは、それぞれ独立して、水素原子、フッ素原子、あるいはフッ素原子により置換されていてもよい炭素数１〜１０のアルキル基（好ましくは、炭素数１〜３のアルキル基、より好ましくはメチル基）またはフェニル基を表し、好ましくはメチル基または水素原子であり、より好ましくは水素原子であり、
ｎは、１〜５の整数であり、好ましくは１または２であり、より好ましくは１である。］
で表される基である。Preferred radicals and groups reactive are those of the following formula:

[Wherein, R ^b represents a bond or -OC (O)-,
R ^c is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group) or a phenyl group And preferably a methyl group or a hydrogen atom,
Each R ^d independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by 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. ]
Is a group represented by

［式中、Ｒ^ｃおよびＲ^ｄは、上記と同意義である。］
で表される基である。More preferred radical and reactive groups have the following formula:

[Wherein, R ^c and R ^d are as defined above. ]
Is a group represented by

［式中、Ｒｆは、それぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し、
ＰＦＰＥは、上記と同意義であり、
Ｒ^１は、それぞれ独立して、ラジカルと反応性の基を表し、
Ｘは、２価の有機基を表し、
Ｒ^２は、下記式：
−（Ｑ）_ｅ−（ＣＦＺ）_ｆ−（ＣＨ_２）_ｇ−
（式中、Ｑは、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、−ＮＲ^ａ−（式中、Ｒ^ａは、水素原子または有機基を表す）または２価の極性基を表し、Ｚは、各出現においてそれぞれ独立して、水素原子、フッ素原子または低級フルオロアルキル基を表し、ｅ、ｆおよびｇは、それぞれ独立して、０以上５０以下の整数であって、ｅ、ｆおよびｇの和は少なくとも１であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり、
Ｒ^３は、それぞれ独立して、２価の有機基を表し、
Ｒ^４は、各出現においてそれぞれ独立して、Ｒ^４ａまたはＲ^４ｂを表し：ただし、少なくとも１つのＲ^４はＲ^４ａであり、
Ｒ^４ａは、各出現においてそれぞれ独立して、ラジカルと反応性の基を有する２価の有機基を表し、
Ｒ^４ｂは、各出現においてそれぞれ独立して、ラジカルと反応性の基を有しない２価の有機基を表し、
ｎ１は、それぞれ独立して、１以上５０以下の整数であり、
Ｒ^５は、それぞれ独立して、−Ｏ−、−Ｓ−、−ＮＨ−または単結合を表し、
Ｒ^６は、それぞれ独立して、１価の有機基または水素原子を表し、
Ｒ^７は、環構造、ヘテロ原子および／または官能基を有してもよい（ｎ２＋ｎ３）価または（ｎ５＋ｎ６＋ｎ７）価の有機基を表し、
Ｒ^８は、２価の有機基を表し、
ｎ２は、１以上３以下の整数であり、
ｎ３は、１以上３以下の整数であり、
Ｒ^９は、３〜８価の有機基を表し、
ｎ４は、２以上７以下の整数であり、
Ｒ^１１は、−Ｒ^８−Ｒ^１または−Ｒ^９（Ｒ^１）_ｎ４であり、
Ｒ^１２は、Ｓｉを含む基であり、
ｎ５は、１以上３以下の整数であり、
ｎ６は、１以上３以下の整数であり、
ｎ７は、１以上３以下の整数である。］
で表される少なくとも１つの化合物が挙げられる。Examples of the grafting monomer include, but are not limited to, for example, any of the following formulas (A1), (A2), (B1), (B2) and (C1):

[Wherein, each Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms,
PFPE is as defined above,
Each R ¹ independently represents a group reactive with a radical,
X represents a divalent organic group,
R ² has the following formula:
_{- (Q) e - (CFZ} ) f - (CH 2) g -
(Wherein, Q is each independently at each occurrence thereof, an oxygen atom, phenylene, carbazolylene, -NR ^a- (wherein, R ^a represents a hydrogen atom or an organic group) or a divalent polar group. And Z each independently represent a hydrogen atom, a fluorine atom or a lower fluoroalkyl group at each occurrence, e, f and g each independently represent an integer of 0 or more and 50 or less, and e, f And the sum of g is at least 1, and the order of existence of each repeating unit in parentheses is arbitrary in the formula.)
Is a group represented by
Each R ³ independently represents a divalent organic group,
R ⁴ independently at each occurrence represents R ^4a or R ^4b , provided that at least one R ⁴ is R ^4a ,
R ^4a each independently represents a divalent organic group having a group reactive to a radical, at each occurrence;
R ^4b independently represents a divalent organic group having no radical reactive group at each occurrence;
n1 is each independently an integer of 1 or more and 50 or less,
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 (n 2 + n 3) -valent or (n 5 + n 6 + n 7) -valent organic group which may have a ring structure, a heteroatom and / or a functional group,
R ⁸ represents a divalent organic group,
n2 is an integer of 1 or more and 3 or less,
n3 is an integer of 1 or more and 3 or less,
R ⁹ represents a trivalent to octavalent organic group,
n4 is an integer of 2 or more and 7 or less,
R ¹¹ is —R ⁸ —R ¹ or —R ⁹ (R ¹ ) _n4 ;
R ¹² is a group containing Si,
n5 is an integer of 1 or more and 3 or less,
n6 is an integer of 1 or more and 3 or less,
n7 is an integer of 1 or more and 3 or less. ]
And at least one compound represented by

  As used herein, "monovalent organic group" and "divalent organic group" mean carbon-containing monovalent and divalent groups, respectively.

In the above formulas (A1) and (A2), each R ¹ independently represents a group reactive with a radical.

［式中、Ｒ^ｃおよびＲ^ｄは、上記と同意義である。］
で表される基であり、より好ましくは、下記式：

［式中、Ｒ^ｃ’は、水素原子またはメチル基である。］
で表される基である。R ¹ is preferably of the following formula:

[Wherein, R ^c and R ^d are as defined above. ]
Is more preferably a group represented by the following formula:

[Wherein, R ^{c ′} is a hydrogen atom or a methyl group. ]
Is a group represented by

  In the above formulas (A1), (B1) and (C1), Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.

  The "C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by one or more fluorine atoms is a branched chain even if it is linear or It is preferably 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.

Further, Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted by one or more fluorine atoms, more preferably a CF ₂ H-C _1-15 perfluoroalkylene group, More preferably, it is a perfluoroalkyl group having 1 to 16 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, in particular, 1 to 3 carbon atoms.

In the formulas (A1) and (A2), X each independently represents a divalent organic group. The X group is understood to be a linker linking PFPE and R ¹ . Accordingly, the X group may be any divalent organic group as long as the compounds represented by the above (A1) and (A2) can be stably present.

Although it does not specifically limit as an example of said X, For example, following formula:
-(CFZ) _x- (CH ₂ ) _y- (Y) _z-
[Wherein, Z represents a fluorine atom or a C 1 to C 3 perfluoroalkyl group or a derivative 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 in which each repeating unit in parentheses is attached with x, y or z is arbitrary in the formula. ]
The group represented by is preferable.

As a specific example of the above X, 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.

In the above formula (B1) and (B2), ^{R 2} has the formula _:-( Q) e - is a group represented by _{- (CFZ) f - (CH} 2) g. Here, 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 existence of the respective repeating units enclosed in parentheses is It is optional in the formula.

In the above formulas, 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 a divalent Is a polar group, more preferably an oxygen atom.

The “divalent polar group” in Q above is not particularly limited, and —C (O) —, —C (= NR ^e ) —, and —C (O) NR ^e — (wherein ^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, such as methyl, ethyl and n-propyl, which may be substituted by one or more fluorine atoms.

  In the above formula, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.

  The above “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, It is preferably 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, bracketed) The order in which each repeating unit is present is arbitrary in the formula).

Examples of the group represented by the above formula:-(O) _e- (CF ₂ ) _f- (CH ₂ ) _g- include, for example,-(O) _{e '} -(CF ₂ ) _f' -(CH ₂ ) _{g '} -O-[(CH ₂ ) _{g ′ ′} -O-] _{g ′ ′ ′} (wherein, e ′ is 0 or 1, and f ′, g ′ and g ′ ′ are each independently 1 to 10) And g ′ ′ ′ is 0 or 1).

In the above formulas (B1) and (B2), R ³ represents a divalent organic group.

The R ³ group is preferably —C (R ^3a ) (R ^3b ) —. Here, R ^3a and R ^3b each independently represent a hydrogen atom or an alkyl group, preferably, one of R ^3a and R ^3b is an alkyl group.

In formulas (B1) and (B2) above, R ⁴ is independently at each occurrence R ^4a or R ^4b . However, at least one R ⁴ is R ^4a .

The aforementioned R ^4a each independently represents a divalent organic group having a group reactive with a radical.

で表される基である。R ^4a is preferably of the following formula:

Is a group represented by

In the above formulas, each occurrence of R ³¹ independently represents a hydrogen atom or an alkyl group. The R ³¹ is preferably a hydrogen atom.

In the above formulas, R ³² each independently represents a hydrogen atom or an alkyl group at each occurrence. The R ³² is preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom

In the above formulas, each occurrence of R ³³ independently represents an organic group having a group reactive with a radical.

As the group reactive with such a radical, the same groups as those described above may be mentioned, and CH ₂ CXCX ¹ —C (O) — (wherein, X ¹ represents a hydrogen atom, a halogen atom such as chlorine atom, or fluorine) An atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine is preferable, and specifically, CH ₂ CC (CH ₃ ) —C (O) — or CH ₂ CHCH—C O)-is mentioned.

In the above formulae, Y ¹ represents -O-, -N (R ^f )-, phenylene or carbazolylene. Here, R ^f represents an organic group, preferably an alkyl group.

Y ¹ is preferably -O-, phenylene or carbazolylene, more preferably -O- or phenylene, still more preferably -O-.

In the above formulae, Y ² represents a linker in which the number of atoms in the main chain is 1 to 16 (more preferably 2 to 12, more preferably 2 to 10). The Y ² is not particularly limited, and for example,-(CH ₂ -CH ₂ -O) _p1- (p1 represents an integer of 1 to 10, for example, an integer of 2 to 10),- (CHR ^g ) _{p 2} -O- (where p 2 is an integer of 1 to 40 and R ^g is hydrogen or a methyl group),-(CH ₂ -CH ₂ -O) _{p 3} -CO-NH-CH (the p3, 1 to 10 integer, an integer of example _{2~10) 2 -CH 2 -O-, -} CH 2 -CH 2 -O-CH 2 -CH 2 -, - (CH 2) p4 - (p4 represents an integer of _{1~6), - (CH 2)} p5 -O-CONH- (CH 2) p6 - (p5 is an integer of 1 to 8, preferably represents 2 or 4, p6 1 And an integer of -6, preferably 3, or -O- (wherein Y ¹ is not -O-). . Preferred as Y ² is — (CH ₂ —CH ₂ —O) _p 1 — (p 1 is an integer of 1 to 10, for example, an integer of 2 to 10) or — (CHR ^d ) _{p 2} —O— (p 2 is is an integer of 1 to 40, ^{R d} represents hydrogen or a methyl group), _{specifically, - (CH 2 -CH 2 -O} ) 2 - or _-CH 2 _-CH 2 -O- is It can be mentioned. In these groups, the left end is bonded to the molecular main chain side (Y ¹ side), and the right end is bonded to a radical-reactive group side (R ³³ side).

で表される基である。More preferably, R ^4a has the following formula:

Is a group represented by

In the above formula, X ¹ represents a hydrogen atom, a halogen atom such as chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, preferably a hydrogen atom or 1 to 10 carbon atoms Is an alkyl group such as a methyl group. In the above formula, 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 reactive group independently at each occurrence.

R ^4b is preferably-(CHR ^4c -CR ^4d R ^4e ) _s- . Here, R ^4c and R ^4d each independently represent a hydrogen atom or an alkyl group, s is an integer of 0 to 50, and the R ^4e group is -Q'-R ^4f . Here, Q 'is the same as the above Q, R ^4f is an organic group having no group reactive with a radical, and a group R ^4g described below is bonded to Q' directly via a linker or 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)-( ^CHR4h ) _s2- O- (s2 represents a repeating number which is an integer of 1 to 40. ^R4h represents hydrogen or a methyl group),
_{(C) - (CH 2 -CH} 2 -O) s1 -CO-NH-CH 2 -CH 2 -O-, (s1 are as defined above.)
_{(D) -CH 2 -CH 2 -O} -CH 2 -CH 2 -,
_{(E) - (CH 2)} s3 - (. S3 is an integer from 1 to 6), or _{(f) - (CH 2)} s4 -O-CONH- (CH 2) s5 - (s4 is 1-8 And preferably represents 2 or 4. s5 represents an integer of 1 to 6, preferably 3. or (g) -O- (provided that Q 'is not -O-).
It is.

R ^4g is preferably the following group:
(I) Alkyl group Example: methyl, ethyl

(Ii) a chain group containing a fluorine-substituted alkyl group;

(Iii) A group containing one or more cyclic moieties selected from the group consisting of monocyclic carbon rings, bicyclic carbon rings, tricyclic carbon rings, and tetracyclic carbon rings.

(Iv) a group containing a hydrocarbon group substituted with one or more (preferably 1 or 2) carboxy groups;

(V) a group containing one or more (preferably one) amino group (vi) hydrogen (vii) a group containing an imidazolium salt

R ^4g is more preferably a hydrogen atom or an alkyl group which may be fluorinated and may be bonded via an ethylene chain, and 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), more preferably 3- (perfluoroethyl) propoxyethyl group [representative formula: CF _3- (CF ₂ )-(CH ₂ ) ₃ -O- (CH ₂ ) ) _2- ].

In the above R ⁴ , the structural unit R ^{4 a} and the structural unit R ^{4 b} may each form a block or may be randomly bonded.

  In the above formulas (B1) and (B2), n1 is an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 50 or less, more preferably an integer of 2 or more and 30 or less.

R < ⁵ > represents -O-, -S-, -NH- or a single bond in said Formula (B1) and (B2), Preferably it is -O-.

In formulas (B1) and (B2), 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 by fluorine More preferably, it is a C1-C6 alkyl group, More preferably, it is methyl.

In the above formula (C1), R ⁷ represents a (n 2 + n 3) -valent organic group which may have a ring structure, a hetero atom and / or a functional group.

  In said formula (C1), n2 is an integer of 1 or more and 3 or less.

  In said formula (C1), n3 is an integer of 1 or more and 3 or less.

  Preferably, n2 + n3 is 3, for example n2 is 1 and n3 is 2 or n2 is 2 and n3 is 1.

Examples of the “ring structure, hetero atom and / or (n 2 + n 3) valent organic group which may have a functional group” in R ⁷ above include (n 2 + n 3 −1) hydrogen atoms from the monovalent organic group, for example Included are groups derived by removal.

で表される基である。R ⁷ preferably has the following formula:

Is a group represented by

で表される基である。More preferably, R ⁷ has the following formula:

Is a group represented by

In the above formula (C1), R ⁸ represents a divalent organic group. The R ⁸ is preferably —O— (CH ₂ ) _r — (wherein r is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 3 or less), —NH— (CH ₂ ) _r -(Wherein, r is as defined above), more preferably -O- (CH ₂ ) _r- (wherein, r is an integer of 1 or more and 3 or less).

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^３、Ｒ^６、Ｘ^１、Ｚ、およびｎ１は、上記と同意義であり、
ｇは０または１であり、
ｈは１または２であり、
ｑ１は１以上５以下の整数である。］
で表される少なくとも１種の化合物であってもよい。In one aspect, the compounds represented by the above formulas (B1) and (B2) are each represented by the following general formulas (B1a) and (B2a):

[Wherein, Rf, PFPE, R ³ , R ⁶ , X ¹ , Z and n 1 are as defined above,
g is 0 or 1,
h is 1 or 2 and
q1 is an integer of 1 or more and 5 or less. ]
Or at least one compound represented by

［式中、Ｒｆ、ＰＦＰＥ、Ｚ、ｇおよびｈは、上記と同意義である。］
で表される少なくとも１種の活性水素含有化合物、および、下記式（ａ３）：

［式中、Ｘ^１は、上記と同意義であり、
Ｒ^３０は、２価の有機基を表す。］
で表される少なくとも１種の活性水素含有化合物の活性水素を反応させることにより得られる少なくとも１種の化合物である。In another embodiment, the compound represented by the above formula (C1) is:
(A) NCO groups present in triisocyanate obtained by trimerizing diisocyanate
(B) Formula (a1) or Formulas (a1) and (a2):

[Wherein, R f, PFPE, Z, g and h are as defined above. ]
And at least one active hydrogen-containing compound represented by the following formula (a3):

[Wherein, X ¹ is as defined above,
R ³⁰ represents a divalent organic group. ]
Or at least one compound obtained by reacting the active hydrogen of at least one active hydrogen-containing compound represented by

R ³⁰ in the formula (a3) is preferably — (CH ₂ ) _{r ′} — (wherein r ′ is an integer of 1 to 10, preferably an integer of 1 to 3), —CH (CH 2) _{3) -, - CH (CH} 2 CH 3) -, - CH (CH 2 OC 6 H 5) - , more preferably _{an, - (CH 2) r '} - ( wherein, r' is 1 or more 3 Is an integer below).

In the formula (D1), ^{R 9} represents a 3-8 valent organic group. As is clear from the formula (D1), the R ⁹ is (n 4 + 1) valent.

Specific examples of R ⁹ above include:
_{-O-CH 2 -C (CH 2} -) 3; or _{-O-CH 2 -C (CH 2} -) 2 -CH 2 OCH 2 -C (CH 2 -) 3
Can be mentioned.

In a preferred embodiment, R ⁹ (R ¹ ) _n4 is
_{-O-CH 2 -C (CH 2} -OC (O) -CR 2 = CH 2) 3; or ^{_{-O-CH 2 -C (CH 2}} -OC (O) -CR 2 = CH 2) 2 -CH ₂ OCH ₂ -C (CH ₂ -OC (O) -CR ² = CH ₂ ) ₃
Can be mentioned.

  In the above formula (D1), n2 is an integer of 1 or more and 3 or less.

  In the above formula (D1), n3 is an integer of 1 or more and 3 or less.

  In the above formula (D1), n4 is an integer of 2 or more and 7 or less, preferably 3 or more and 6 or less.

In the above formula (E1), R ⁷ is as defined above (C1). However, in Formula (E1), the valence of R ⁷ is (n5 + n6 + n7).

In the above formula ^{(E1), R 11} is, ^-R 8 -R ¹ or ^-R 9 ^(R ₁₎ is _n4. These ^-R 8 -R ¹ and ^-R 9 ^(R _{1) n4} radicals are each as defined the formula (C1) and the formula (D1).

In formula (E1), R ¹² is a group containing Si.

で表される少なくとも１種の化合物であり得る。The group containing Si is preferably represented by the following formula:

And at least one compound represented by

In the above formulae, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently an alkyl group or an aryl group.

The above alkyl group is not particularly limited, and includes 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. Specifically, preferred is n-butyl group for R ²¹ and methyl group for R ^{22 to} R ²⁵ .

  Although it does not specifically limit as said aryl group, A C6-C20 aryl group is mentioned. The aryl group may contain two or more rings. The preferred aryl group is a phenyl group.

  The alkyl group and the aryl group may optionally contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in the molecular chain or ring thereof.

Furthermore, the above-mentioned alkyl group and aryl group are optionally halogen; C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group which may be substituted by one or more halogens , C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5 to 10 membered heterocyclyl group, 5 to 10 membered unsaturated heterocyclyl group, C _{6 to 10} aryl group, 5 to 10 membered hetero It may be substituted by one or more substituents selected from aryl groups.

In the above formulae, R ²⁶ represents a divalent organic group. Preferably, R ²⁶ is — (CH ₂ ) _r — (wherein, r is an integer of 1 to 20, preferably an integer of 1 to 10).

  In the above formula, 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 The integer is from 20 to 20, for example, from 1 to 20, and p is 0 or 1.

As a specific group shown by the said Formula, the following group is mentioned, for example.

  In said Formula (E1), n5 is an integer of 1 or more and 3 or less.

  In the above formula (E1), n6 is an integer of 1 or more and 3 or less.

  In said formula (E1), n7 is an integer of 1 or more and 3 or less.

  In the molded article produced as described above, at least the surface molecule of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and this graft chain is from the substrate surface, At least 0.2 μm deep, up to 200 μm deep, preferably at least 1 μm deep, up to 40 μm deep, more preferably at least 3 μm deep, up to 20 μm deep, eg 10-20 μm deep Exists. The greater the thickness at which the graft chains are present, the better the mold release durability. In addition, the smaller the thickness at which the graft chain is present, the higher the strength of the resin equipment.

  Confirming that the surface of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group by elemental analysis of the surface (for example, to a depth of 0.1 μm) of the resin substrate Can. As a method of elemental analysis, for example, X-ray Photoelectron Spectroscopy (XPS) or Attenuated Total Reflection (ATR) can be used.

  Therefore, according to the present invention, the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is at least 0.2 μm deep and at most deep from the substrate surface. Molded bodies characterized by being present up to 200 μm, preferably at least 1 μm deep and up to 40 μm deep, more preferably at least 3 μm deep and up to 20 μm deep, eg 10 to 20 μm deep provide. Preferably, the graft chains do not exceed 95% of the thickness of the resin substrate.

  The term "grafted chain" means a side chain which is branched to the main chain of the polymer constituting the resin substrate, and is not limited by the production method. That is, in addition to the graft chains formed by, for example, the above-mentioned graft polymerization, the graft chains also include chains introduced into the main chain of the polymer constituting the resin substrate by other methods.

  In a preferred embodiment, the "grafted chain" may be a branched chain branched to the polymer backbone of the resin substrate, wherein a grafting monomer is covalently bonded to the polymer backbone by irradiation with ionizing radiation. .

  Preferably, the depth at which the graft chains are present is from the surface of the substrate to a depth of from 0.001 to 95% of the thickness of the resin substrate, for example, from 0.01 to 95% or from 0.1 to 0.1%. It can be up to 95% deep. The depth at which the graft chains are present may more preferably be 5 to 80% deep, more preferably 10 to 60% deep, even more preferably 20 to 60% deep . For example, the graft chain is from the surface of the resin substrate to a depth of 0.2 to 200 μm, preferably 1 to 40 μm, more preferably 2 to 30 μm, still more preferably 3 to 20 μm, for example 5 to 20 μm or 10 to 20 μm. It may exist. In other words, the graft chain is at least 0.2 μm deep and at most 200 μm deep, more preferably at least 1 μm deep and at most 40 μm deep, more preferably at least depth from the surface of the resin substrate. 2 μm, maximum depth 30 μm, more preferably at least 3 μm depth, maximum 20 μm depth, eg at least 5 μm depth, maximum 20 μm depth, or at least 10 μm depth, 20 μm maximum You may

  The lower limit of the thickness of the graft chain is preferably 0.001%, more preferably 0.01%, still more preferably 0.1%, still more preferably 0.5%, for example, 1%, 5%, 10 %, 20% or 30% are preferred. The upper limit of the thickness is preferably 90%, more preferably 80%, still more preferably 70%, still more preferably 60%, for example 50% or 45%.

  The lower limit of the depth at which the graft chain exists is preferably 0.2 μm, more preferably 0.3 μm, still more preferably 0.5 μm, still more preferably 1.0 μm, for example 2.0 μm, 5.0 μm, 10 μm Or 15 μm is preferred. The upper limit of the depth is preferably 150 μm, more preferably 100 μm, still more preferably 70 μm, still more preferably 50 μm, for example, 40 μm or 30 μm.

  The depth at which the graft chains exist in the shaped body can be measured, for example, by observing the cross section of the film by means of a scanning electron microscope. In more detail, it can measure by performing elemental analysis or positron lifetime measurement by EPMA or EDX mentioned above.

  Moreover, the molded object manufactured as mentioned above may have a graft ratio of 0.1 to 1,500%.

  Therefore, according to the present invention, the molecular chain present in 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%. It also provides a shaped body characterized by a certain feature.

The "grafting ratio" means the proportion of graft chains introduced to the resin substrate. Specifically, the grafting ratio (Dg) can be calculated by measuring the weight change of the resin substrate before and after the graft polymerization reaction and using the following equation.
Graft _{ratio: Dg [%] = (W} 1 -W 0) / W 0 × 100
[Wherein, W ₀ is the weight of the resin substrate before graft polymerization, and W ₁ is the weight of the resin substrate after graft polymerization. ]
The grafting ratio Dg is calculated by assigning the total weight of the base material, so when the graft layer is extremely thin, it has a small value with respect to the film thickness and may show a value of 0.1% or less. However, the area of the graft chain in the depth direction can also be proved by elemental analysis by SEM-EDX or EPMA. For example, when a graft chain containing 5 μm of perfluoropolyether group is introduced to a resin with a specific gravity of 2 and a thickness of 5 mm and a weight of 30 g, it is 0.1% of the thickness of the resin substrate, The grafting rate shows a value of less than approximately 0.1%.

  Moreover, the said graft ratio can also be calculated by thermogravimetry (TG: thermogravimetric analysis). Specifically, the change in weight of the molded product is measured by changing the temperature of the molded product according to a certain program (heating or cooling) according to a fixed program, and calculating from the change in weight. Can. Thermogravimetry can be performed, for example, using a Rigaku Corporation or Shimadzu TGA measuring device.

  The grafting ratio is preferably 0.1 to 500%, more preferably 0.5% to 300%, and still more preferably 5 to 200%, for example 10 to 150%, when the resin base material is composed of a non-fluororesin. Or it may be 20 to 100%. On the other hand, the graft ratio is preferably 0.1 to 250%, more preferably 0.2% to 150%, still more preferably 5 to 120%, for example 10 to 100, when the resin base material is composed of a fluorine resin. % Or 20-80%.

  The molded article of the present invention has small surface free energy because a perfluoropolyether group or a perfluoroalkyl group is present on the surface of the resin substrate. Specifically, the surface free energy of the molded article of the present invention may be 20 mN / m or less. Thus, the molded article of the present invention having a low surface free energy, particularly a film, can exhibit high releasability particularly when molded into an imprint mold.

  Furthermore, in the molded article of the present invention, the graft chain containing the perfluoropolyether group or the perfluoroalkyl group is strongly bonded to the compound constituting the resin substrate, and therefore has high durability. The surface free energy of the molded article of the present invention may be 20 mN / m or less even after ultrasonic cleaning for 3 minutes with hydrofluoroether (HFC 7200 (manufactured by 3M)) Such a molded article of the present invention In particular, when molded into an imprint mold, high mold release durability can be exhibited.

  Therefore, according to the present invention, the molecular chains present in at least the surface portion of the resin substrate have a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the surface free energy after washing with a hydrofluoroether is , 20 mN / m or less.

  In one embodiment, the graft chain in the molded article of the present invention is a residue of the graft monomer, preferably a residue of a compound comprising a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. It is.

  Therefore, in the present invention, the molecular chain present in at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and this graft chain is a perfluoropolyether group or per Also provided is a molded article characterized in that it is a residue of a compound comprising a fluoroalkyl group and a group reactive with a radical.

であり得る。Here, "the residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical" includes a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. It means a moiety derived from a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical after the compound and the resin base are bonded. For example, a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical is, for example, R-OC (O) -CH = CH ₂ (R is a perfluoropolyether group or a perfluoroalkyl group And the residue of the compound containing a group reactive with a perfluoropolyether group or a perfluoroalkyl group and a radical is

It can be.

  The molded article 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 μm, more preferably 30 to 125 μm, and still more preferably 30 to 60 μm.

  In a preferred embodiment, the shaped body of the present invention can have high light transmission in the ultraviolet region. Specifically, the light transmittance at 365 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. By having such a high light transmittance, the molded article of the present invention can be molded and used as an imprint mold using an ultraviolet-curable resin.

  As described above, the molded body of the present invention has a small surface free energy and can maintain this low surface energy for a long time, so that it has an excellent mold release property and mold release durability. In particular, it can be molded into a mold for nanoimprinting.

  Accordingly, the present invention also provides the above-mentioned molded article used for producing an imprinting mold.

  In addition, the mold for nanoimprinting of the present invention can further harden the surface of the mold by the irradiation crosslinking reaction by ionizing radiation such as electron beam and γ ray.

  Further, according to the present invention, the molecular chain present in at least the surface portion of the resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and this graft chain has a thickness of 0% of the thickness of the resin substrate. Provided is an imprinting mold characterized by existing to a depth of 1 to 95%.

  The imprinting mold of the present invention can be obtained by molding the above-described molded article of the present invention. That is, the imprinting mold of the present invention can have the same characteristics as the above-described molded article of the present invention.

Therefore, according to the present invention, the molecular chains present in at least the surface portion of the resin substrate have a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the surface free energy after washing with a hydrofluoroether is And an imprinting mold characterized by having 20 mN / m or less;
The molecular chain present in at least the surface portion of the resin substrate is characterized by having a graft chain containing a perfluoropolyether group or a perfluoroalkyl group and having 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 per-part There is also provided an imprinting mold characterized in that it is a residue of a compound comprising a fluoroalkyl group and a group reactive with a radical.

  The molding of the imprinting mold of the present invention from the above-described molding of the present invention is carried out, for example, by pressing a master mold having a predetermined pattern onto the surface of the molded article on which the graft chains are present. Such molding can be performed by any of the batch manufacturing method and the continuous manufacturing method described below.

(1) Batch Production Method Using a nanoimprint apparatus, a master mold made of silicon, nickel metal or quartz is formed on a surface of a resin substrate having a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, Forming an imprint mold having a pattern shape in which the master mold is accurately inverted by pressing it at a predetermined temperature and pressure conditions, for example, at a pressure of 250 ° C. and a pressure of 5 MPa for a predetermined time, for example 3 minutes it can.

(2) Continuous manufacturing method Silicon, nickel using an imprint apparatus while continuously extruding a film having a graft chain containing a perfluoropolyether group or a perfluoroalkyl group on the surface of a resin substrate from a film roll A metal or quartz master mold is brought into contact with the film at a predetermined temperature and pressure conditions, for example, at 100 ° C. and a pressure of 40 MPa to transfer the pattern onto the film to form a continuous imprint mold be able to.

  In the production of the imprint mold, preferably, the master mold is preferably subjected to a release agent treatment. The release agent is not particularly limited, but a perfluoro-type release agent is preferable.

  The temperature at the time of the above 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, it is carried out at 80 to 300 ° C. .

  Alternatively, the imprinting mold of the present invention may be manufactured by molding the resin substrate into an imprinting 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, and the generated radicals are reactive with the perfluoropolyether group or the perfluoroalkyl group and the radicals. It can manufacture by graft-polymerizing with the compound containing this group.

  The irradiation of ionizing radiation and graft polymerization can be carried out by substantially the same method as the method for the molded article of the present invention described above.

  The mold for imprinting of the present invention has excellent releasability because a perfluoropolyether group or a perfluoroalkyl group is present on the surface of the resin substrate, and the perfluoropolyether group or perfluoroalkyl group is also excellent. Since the graft chain containing is firmly bonded to the molecule that constitutes the resin substrate, it has excellent release durability.

  The mold for imprinting of the present invention has excellent releasability, so that breakage of the pattern at the time of mold release is unlikely to occur, and very fine and complex patterning, for example, fine patterning on the order of nanometers, becomes possible. For example, the imprinting mold of the present invention may have a pattern with a pitch width of 50 nm to 2,000 nm.

  The imprinting mold of the present invention can be used to manufacture devices for a wide range of applications such as electronic, optical, medical and chemical analysis. For example, electronic devices include integrated circuits such as transistors, memories, light emitting diodes (ELs), lasers, solar cells, and the like. Examples of optical devices include color filters for liquid crystal displays, display pixels such as organic EL, light memories, light modulation elements, light shutters, second harmonic (SHG) elements, polarization elements, photonic crystals, lens arrays, etc. Be Examples of magnetic devices include next-generation hard disk drives (discrete tracks), next-generation hard disk drives (patterned media), and next-generation semiconductors. Examples of the medical device include DNA arrays, protein arrays, biochips such as sheet arrays for cell culture, and the like. As a chemical analysis device, it can be used for microchemical chips such as microchemical plants and microchemical analysis systems. In particular, the mold for imprinting of the present invention includes a substrate of an LED element (particularly a high brightness LED element), a moth-eye structure antireflective film, a solar light condensing film, a film having a regular uneven structure such as a liquid crystal polarizing plate It can be used suitably for manufacture.

Example 1
Reaction product of acrylic acid and perfluoropolyether group-containing alcohol (F (CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ CH ₂ -OH: average molecular weight about 2300) reacted with sulfuric acid catalyst ( Perfluoropolyether group and acryloyl group containing 2000 mg / l of sodium acrylate by neutralizing residual acrylic acid (3.1%) to pH 11 with 10% aqueous sodium hydroxide solution, separating the aqueous layer and removing the acid component The compound containing the group was obtained. Next, 10% by weight of water was mixed with a static mixer with respect to the obtained compound, and the mixture was left to stand for 20 minutes. After separation, the highly purified compound was obtained with a water content of 1.6% and a sodium acrylate content of 80 mg / l. Incidentally, the problem did not occur in the purification process for removing the _{F (CF 2 CF 2 CF 2} O) n -CF 2 CF 2 CH 2 -OH and byproducts unreacted.

  Next, using an ultra-low energy electron beam on one surface of a film made of ethylene-tetrafluoroethylene copolymer (trade name: NEOFLON ETFE, manufactured by Daikin Industries, Ltd., film thickness 50 μm) under a nitrogen atmosphere The electron beam was irradiated at 160 kGy (irradiation conditions: acceleration voltage 60 kV). Then, the film was taken out to the atmosphere for 5 minutes to convert the radicals formed on the surface of the ethylene-tetrafluoroethylene copolymer into peroxide radicals. After conversion, the dissolved oxygen in the compound solution obtained above was removed under nitrogen contamination, and then immersed in the solution at 40 ° C. for 2 hours. After immersion, the film was washed with hydrofluoroether HFE 7200 (manufactured by 3M) and dried to obtain a film having a graft chain containing a perfluoropolyether group.

Test Example 1
(Thermogravimetric measurement)
The graft ratio of the obtained film was measured by thermogravimetry using a differential thermal balance (TG-DTA). As a result of the measurement, it was confirmed that 3.5% by mass of the film was a surface graft chain.

  The surface fluorine concentration of the obtained film of 50 μm thickness was measured by elemental analysis of the film cross section using an electron beam microanalyzer (EPMA), and it was confirmed that the graft chain exists from the surface to a depth of 20 μm ( The thickness of the graft is 40% of the thickness of the film).

(X-ray photoelectron spectroscopy)
The film obtained above and the untreated film were subjected to elemental analysis of the surface by X-ray photoelectron spectroscopy (XPS) using an X-ray photoelectron spectrometer. The intensity ratio (F1s / C1s) of the spectra of F1s and C1s was as follows.

  From the above results, it was confirmed that in the film obtained in Example 1, the grafting reaction was progressing on the surface irradiated with the electron beam.

(Contact angle)
The initial contact angles of water and n-hexadecane were measured for the film obtained above and the untreated film. Specifically, the initial static contact angle was carried out with 1 μL each of water and n-hexadecane using a contact angle measurement device. Moreover, the surface free energy of each was calculated from these results according to the "Owens-Wendt method" described in DK Owens and RC Wendt, J. Appl. Polym. Sci., 13, 1741 (1969). The results are shown below.

  From the above results, it was confirmed that the surface free energy of the electron beam irradiated surface of the film obtained in Example 1 is smaller than the surface not irradiated with the untreated film and the electron beam irradiated surface. .

Test example 2
Mold Release Durability Test Using a Film Having a Surface Graft Chain Containing Perfluoropolyether Group The film obtained in Example 1 was irradiated with an electron beam and a photocured resin (trade name) on the surface on which the surface graft chain was introduced. 0.2 ml of PAK-02 manufactured by Toyo Gosei Co., Ltd. is dropped, a polycarbonate film is covered thereon, and it is pressed at 1.0 MPa using a continuous light nanoimprint apparatus consisting of Step & Repeat method and simultaneously irradiated with ultraviolet light (10 mW / cm ² ) Was performed for 20 seconds, and the releasability test with the above-mentioned film by the photocurable resin was conducted. This releasability test was continuously performed, and the contact angle (water) of the film surface was measured every 225 times. The contact angle was measured with 1 μL of water using a contact angle measurement 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 μm) is subjected to atmospheric pressure plasma treatment, and peroxide radical groups are formed on the surface. after introduction, perfluoropolyethers having primary amino groups useful in the molecular end to a ring-opening reaction of the epoxy ring _{((F (CF 2 CF 2} CF 2 O) n-CF 2 CF 2 CH 2 -NHCH 2 A hydrofluoroether solution (HFE 7200) containing CH ₃ ) is spin-coated (grafting treatment) Excessive physisorbed perfluoropolyether chains are washed with hydrofluoroether (HFE 7200: 3M) and dried Example 1 except that a plasma film having surface graft chains containing perfluoropolyether groups was obtained. It was carried out in the same manner. The results are shown in Figure 1.
In addition, when the surface fluorine concentration of the obtained film of 50 μm thickness is measured by elemental analysis of the film cross section using an electron beam microanalyzer (EPMA), it is possible that graft chains exist from the surface to a depth of 0.1 μm. confirmed.

Comparative example 2
(1) Production of resin In a flask equipped with a stirrer, a nitrogen gas introduction pipe, 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 macromer 20 parts by weight of (manufactured by the method described in Example 1 of Japanese Patent Application Publication No. 11-503183, molecular weight 8000) and 100 parts by weight of toluene were added. Thereafter, the contents of the flask are heated to 80 ° C. while introducing nitrogen gas at a rate of 0.3 liter / minute into the flask, and dimethyl-2,2′-azobis (2-methylpropionate) as an initiator. 0.5 parts by weight (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was kept at 80 ° C. for 8.0 hours.
After 8 hours, the introduction of nitrogen gas was stopped, 100 parts by weight of toluene was added, and the temperature of the contents was lowered to terminate the reaction to obtain a resin mold resin. The weight average molecular weight (MW) of the obtained resin measured by gel permeation chromatography was 83,000.

(2) Formation of resin thin film layer The resin produced in the above step (1) is diluted 10 times with toluene, and a PET film as a substrate (trade name: LumilarTM, manufactured by Toray Industries, Inc., thickness; The spin coating was performed on 0.125 mm), and the coating was dried at 130 ° C. for 15 minutes using a hot plate to prepare a resin thin film layer having a thickness of 1.2 μm. The results are shown in FIG.

Comparative example 3
A film (film thickness 50 μm) made of a commercially available ethylene-tetrafluoroethylene copolymer not irradiated with an electron beam was treated with a release modifier (F (CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ CH _2- After immersion in Si (OCH ₃ ) ₃ : average molecular weight about 2300) for 1 minute, it was pulled up and heat treated at 80 ° C. for 1 hour. Then, it wash | cleaned and dried similarly to Example 1, and obtained the film made from an ethylene- tetrafluoroethylene copolymer. However, the film surface was not modified with a release modifier because there was no reactive group.

  As apparent from FIG. 1, the film having the surface graft chains of Example 1 was able to maintain a contact angle close to 100 ° even if the number of times of mold release exceeded 3,000. On the other hand, in the film surface-grafted with plasma of Comparative Example 1 and the PET film modified with the fluorine resin thin film layer of Comparative Example 2, the contact angle decreases according to the number of times of mold release, and the contact angle becomes too large It decreased to less than 80 °.

Example 2: Batch production of mold for imprinting The 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 to obtain the above master mold. C. for 3 minutes at a pressure of 5 MPa at 250.degree. C. to form an imprinting mold having a pattern shape in which the pattern of the master mold is correctly inverted.
In addition, the following processes were performed as a mold release agent process to the master mold which consists of silicon | silicone. The master mold was dipped in a perfluoropolyether-based mold release agent solution (trade name Optool HD-1100, manufactured by Daikin Industries, Ltd.) for 1 minute, and then pulled up and heat-treated at 80 ° C. for 1 hour. Thereafter, 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.

  The surface of the obtained imprinting mold was observed by 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 As shown in FIG. 3, the ETFE film 130 obtained in Example 1 is 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 460 nm and a depth of 200 nm). Thereafter, processing such as cooling is performed by a plurality of rolls 134, and cut into a desired size using a cutting machine 135 to continuously form an imprint mold.
In addition, as a mold release agent treatment to a mother roll mold made of nickel metal, after being immersed in trade name OPTOOL HD-2100Z (manufactured by Daikin Industries, Ltd.) for 1 minute, the pulling treatment is not carried out for 1 hour under 80 ° C. environment. The same process as Comparative Example 3 was performed.

  As a result of observing the surface of the obtained mold for imprinting with a scanning electron microscope, it was confirmed that a pattern having a diameter of 230 nm, a pitch of 460 nm, and a depth of 200 nm was favorably formed.

Example 4
Photo nanoimprinting 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.) was added onto the imprinting mold obtained in Example 2 as 0. 2 ml of the solution was dropped, a polycarbonate film was covered thereon, and pressing was performed using a continuous light nanoimprint apparatus made of Step & Repeat method, and ultraviolet irradiation was performed at the same time.

  Thereafter, the pattern surface of the resin mold was observed to confirm that the mold had no transfer defect. Further, with respect to the transferred resin, when the pattern surface 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). In addition, it was confirmed that even when 200-shot continuous photo nanoimprinting was performed using this resin mold, imprinting could be satisfactorily performed without a transfer defect.

Example 5
A film having surface graft chains was obtained in the same manner as in Example 1 except that electron beam irradiation was performed under a vacuum of 1 × 10 ³ Pa. Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Example 6
A film having a surface graft chain is obtained in the same manner as in Example 1 except that C ₆ F ₁₃ CH ₂ CH ₂ OCOCHCHCH ₂ is used instead of the compound containing a perfluoropolyether group and an acryloyl group as a grafting monomer. The Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Example 7
The electron beam irradiation conditions are irradiated under a vacuum of 1 × 10 ³ Pa, and C ₆ F ₁₃ CH ₂ CH ₂ OCOCHCHCH ₂ is used as a grafting monomer instead of a compound containing a perfluoropolyether group and an acryloyl group. A film having surface graft chains was obtained in the same manner as in Example 1 except that the film had a surface graft chain. Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Example 8
Instead of a film made of ethylene-tetrafluoroethylene copolymer (trade name: NEOFLON ETFE, manufactured by Daikin Industries, Ltd., film thickness 50 μm), using a 10 cc syringe made of polypropylene molded by injection molding as a molded body A molded product having a surface graft chain was obtained in the same manner as in Example 1 except that the inner surface of the injection cylinder was irradiated with an ultra low energy electron beam.

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 μm). . Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Example 10
A film having surface graft chains was obtained in the same manner as in Example 1 except that a film made of PET was used instead of the film made of ethylene-tetrafluoroethylene copolymer (film thickness 50 μm). Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Example 11
A film having surface graft chains 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 μm). The Furthermore, using the present film, an imprint mold was formed in the same process as in Example 2.

Comparative example 4
A film having surface graft chains was obtained in the same manner as in Example 1 except that the accelerating voltage in Example 1 was changed to 250 kV. As a result, the graft thickness of the film was 100% in the graft ratio of the film thickness (ie, graft chains were formed on the back of the film). Next, in the same manner as in Example 4, continuous photo nanoimprinting was performed using the step and repeat method in a continuous photo nanoimprint apparatus using a Step & Repeat method, but this film has a graft chain also on the back surface side, and thus a test device It was not possible to adhere and fix to the substrate, and it was not possible to carry out an imprint test.

Example 12
Next, using a low energy electron beam on one surface of a commercially available ethylene-tetrafluoroethylene copolymer film (trade name: NEOFLON ETFE, manufactured by Daikin Industries, Ltd., film thickness 200 μm), under a nitrogen atmosphere A film having surface graft chains was obtained in the same manner as in Example 1 except that the electron beam was irradiated at 160 kGy (irradiation condition: acceleration voltage 250 kV).
The surface fluorine concentration of the obtained film having a thickness of 200 μm was measured by elemental analysis of the cross section of the film using an electron probe microanalyzer (EPMA), and it was confirmed that a graft chain exists 100 μm deep from the surface (grafting Thickness of the film is 50% of the film thickness).

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 μm) was irradiated with 160 kGy of electron beam under a nitrogen atmosphere using a low energy electron beam ( Irradiation conditions: A film having surface graft chains was obtained in the same manner as in Example 10 except that the accelerating voltage was 250 kV.
The surface fluorine concentration of the obtained film with a thickness of 500 μm was measured by elemental analysis of the film cross section using an electron beam microanalyzer (EPMA), and it was confirmed that a graft chain exists from the surface to a depth of 200 μm (grafting Thickness of the film is 40% of the film thickness).

Example 14
Next, an ultra low energy electron beam was used to irradiate 160 kGy of electron beam under a nitrogen atmosphere on one surface of a commercially available PP molded product (trade name: Novatec PP MA3, manufactured by Nippon Polypropylene Corporation, film thickness 5 mm) A film having surface graft chains was obtained in the same manner as in Example 1 except for the irradiation conditions (irradiation conditions: acceleration voltage 5 kV).
The surface fluorine concentration of the obtained molded product with a thickness of 1 mm was measured by elemental analysis of the cross section of the film using an electron probe microanalyzer (EPMA), and it was confirmed that graft chains were present to a depth of 0.5 μm from the surface (The thickness of the graft is 0.01% of the thickness of the film).

  The low surface energy of the films of the present invention allows them to be used in a variety of applications, particularly in the manufacture of imprinting molds. Moreover, since the mold for imprinting of the present invention is excellent not only in mold releasability but also in mold release durability, it can be used for manufacturing of substrates of various device elements such as LED elements. In addition, since the surface energy is low, it can be applied to a side wall or a roof of a building and used as a water repellent film.

Claims (22)

  The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is present from the surface of the resin substrate to at least a depth of 0.2 μm and a depth of at most 200 μm And a molded body characterized in that the depth does not exceed 95% of the thickness of the resin base material.   2. The molded article according to claim 1, wherein the graft chains are present at least 1 μm deep and at most 40 μm deep from the surface of the resin substrate.   The molded article according to claim 1 or 2, wherein the surface free energy after washing with a hydrofluoroether is 20 mN / m or less.   4. A perfluoropolyether group or a group containing a perfluoroalkyl group is a residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. The molded body described. The radical reactive group has the following formula:

[Wherein, R ^b represents a bond or -OC (O)-,
R ^c represents a hydrogen atom, a fluorine atom, or an alkyl or phenyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom,
Each R ^d independently represents a hydrogen atom, a fluorine atom, or an alkyl or phenyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom.
n is an integer of 1 to 5; ]
The molded object of Claim 4 which is group represented by these.   The surface of the resin substrate is irradiated with ionizing radiation to generate radicals, and graft polymerization is performed on the generated radicals and a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with the radicals. Molded body.   After irradiating the surface of the resin substrate with ionizing radiation, a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical is brought into contact with the surface of the resin substrate, whereby the resin substrate is 7. The molded article according to claim 6, which is obtained by graft polymerizing a constituent polymer and the compound.   8. The shaped body according to claim 6, wherein the ionizing radiation is an electron beam.   The molded article according to any one of claims 1 to 8, wherein the resin base material is formed of a resin capable of generating radicals by irradiation of ionizing radiation.   The molded object according to any one of claims 1 to 9, wherein the resin base material is a fluorine resin.   The fluorine resin is ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroalkoxy copolymer, ethylene-chlorotrifluoroethylene copolymer, polyvinyl fluoride, The molded article according to claim 10, characterized in that it comprises a resin selected from the group consisting of polyvinylidene fluoride and polychlorotrifluoroethylene, or a polymer blend or polymer alloy thereof. Compounds containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical are exemplified by the following formulas (A1), (A2), (B1), (B2), (C2), (C1), (D1) and (E1) One of):

[Wherein, each Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms,
PFPE is as defined above,
Each R ¹ independently represents a group reactive with a radical,
X represents a divalent organic group,
R ² has the following formula:
_{- (Q) e - (CFZ} ) f - (CH 2) g -
(Wherein, Q is each independently at each occurrence thereof, an oxygen atom, phenylene, carbazolylene, -NR ^a- (wherein, R ^a represents a hydrogen atom or an organic group) or a divalent polar group. And Z each independently represent a hydrogen atom, a fluorine atom or a lower fluoroalkyl group at each occurrence, e, f and g each independently represent an integer of 0 or more and 50 or less, and e, f And the sum of g is at least 1, and the order of existence of each repeating unit in parentheses is arbitrary in the formula.)
Is a group represented by
Each R ³ independently represents a divalent organic group,
R ⁴ independently at each occurrence represents R ^4a or R ^4b , provided that at least one R ⁴ is R ^4a ,
R ^4a each independently represents a divalent organic group having a group reactive to a radical, at each occurrence;
R ^4b independently represents a divalent organic group having no radical reactive group at each occurrence;
n1 is each independently an integer of 1 or more and 50 or less,
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 (n 2 + n 3) -valent or (n 5 + n 6 + n 7) -valent organic group which may have a ring structure, a heteroatom and / or a functional group,
R ⁸ represents a divalent organic group,
n2 is an integer of 1 or more and 3 or less,
n3 is an integer of 1 or more and 3 or less,
R ⁹ represents a trivalent to octavalent organic group,
n4 is an integer of 2 or more and 7 or less,
R ¹¹ is —R ⁸ —R ¹ or —R ⁹ (R ¹ ) _n4 ;
R ¹² is a group containing Si,
n5 is an integer of 1 or more and 3 or less,
n6 is an integer of 1 or more and 3 or less,
n7 is an integer of 1 or more and 3 or less. ]
The molded object in any one of Claims 4-11 which is at least 1 type of compound represented by these.   The molded object in any one of Claims 1-12 which is a film shape.   The molded article according to any one of claims 1 to 13, wherein the graft chains are present from the surface of the resin substrate to a depth of 0.1 to 95% of the thickness of the resin substrate.   The molded object in any one of Claims 1-14 used for manufacture of the mold for imprints.   The molded object in any one of Claims 1-15 whose light transmittance in 365 nm is 70% or more.   The resin substrate has a graft chain containing a perfluoropolyether group or a perfluoroalkyl group, and the graft chain is present from the surface of the resin substrate to at least a depth of 0.2 μm and a depth of at most 200 μm An imprinting mold characterized in that it does not exist over a depth of 95% of the thickness of the resin substrate.   18. The imprinting mold according to claim 17, wherein the surface graft chains are present at least 1 μm deep and at most 40 μm deep from the surface of the resin substrate.   19. The imprinting mold according to claim 17, wherein surface free energy after cleaning with a hydrofluoroether is 20 mN / m or less.   18. The imprint according to claim 17, wherein the group containing a perfluoropolyether group or a perfluoroalkyl group is a residue of a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical. mold.   The surface of the resin substrate is irradiated with ionizing radiation to generate radicals, and graft polymerization is performed on the generated radicals and a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with the radicals. Mold for imprinting.   After irradiating the surface of the resin substrate with ionizing radiation, a compound containing a perfluoropolyether group or a perfluoroalkyl group and a group reactive with a radical is brought into contact with the surface of the resin substrate, whereby the resin substrate is 22. The imprinting mold according to claim 21, which is obtained by graft polymerizing a constituent polymer and the compound.

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