WO2006059702A1 - 組成物、硬化物および物品 - Google Patents

組成物、硬化物および物品 Download PDF

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Publication number
WO2006059702A1
WO2006059702A1 PCT/JP2005/022150 JP2005022150W WO2006059702A1 WO 2006059702 A1 WO2006059702 A1 WO 2006059702A1 JP 2005022150 W JP2005022150 W JP 2005022150W WO 2006059702 A1 WO2006059702 A1 WO 2006059702A1
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group
composition
film
meth
mass
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PCT/JP2005/022150
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English (en)
French (fr)
Japanese (ja)
Inventor
Makoto Terauchi
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Mitsubishi Chemical Corporation
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Priority to CN2005800411741A priority Critical patent/CN101068845B/zh
Priority to US11/720,809 priority patent/US8017211B2/en
Priority to JP2006546628A priority patent/JP4872670B2/ja
Publication of WO2006059702A1 publication Critical patent/WO2006059702A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • compositions Compositions, cured products and articles
  • the present invention relates to a novel organic polymer, a composition containing the organic polymer, which can be used as a stain resistance imparting agent having excellent hardness and scratch resistance, a cured product using the composition, and It relates to goods.
  • the present invention relates to a composition or the like that provides a coating film having sufficient performance for a thin film.
  • Plastic products are used for containers, automotive instrument panels and outer panels, window materials, roofing materials, packaging materials, various housing materials, optical disk substrates, etc. because of their light weight, easy processability, and impact resistance. It is used in various applications such as plastic lenses, liquid crystal displays, plasma displays, and substrates of display devices such as projection TVs.
  • polycarbonate polymethylol methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methylmethacrylate monostyrene copolymer (MS resin), acrylonitrile styrene copolymer (AS resin)
  • ABS acrylonitrile butadiene styrene copolymer
  • MS resin methylmethacrylate monostyrene copolymer
  • AS resin acrylonitrile styrene copolymer
  • styrene-based resins such as styrene-based resins, salt-based resin-based resins, and cellulose acetates such as triacetyl cellulose are particularly excellent in light weight, easy processability and impact resistance, and are suitable for the above-mentioned applications.
  • Japanese Patent Application Laid-Open No. 2000-52472 describes that a coating film having high hardness can be obtained by increasing the elastic modulus of the second layer coating agent to be greater than that of the first layer coating agent.
  • the hardness of the first layer coating agent is set to be larger than that of the second layer coating agent. It is described that a high coat film can be obtained.
  • the total thickness of the coating film becomes 10 m or more, and the productivity is poor because two or more layers are applied.
  • a first layer is coated with a methacrylic polymer
  • the second layer is made of an organopolyester composed of a hydrolyzed condensate of colloidal silica and a specific silicate. It is described that by laminating a coating layer obtained by curing siloxane resin, the total thickness of the coating film can be made 10 m or less and excellent wear resistance can be realized. However, there is no change in the point of applying two or more layers.
  • JP-A-10-316864 a method using a polymerized UV curable resin has been proposed in order to achieve low shrinkage.
  • curing shrinkage is greatly reduced, there is a limit to applications for applications that require lower shrinkage and applications that require higher hardness and scratch resistance.
  • a thin film for example, a film thickness of 2 m or less
  • a method using a cation-polymerizable resin as a (polymerized) UV-curable resin for example, Japanese Patent Application Laid-Open No. 2001-40205) Etc.
  • a method using colloidal silica combined with a low molecular weight organic component capable of cationic polymerization for example, JP-A-2002-53659, etc.
  • these components are usually used as radically polymerizable UV curable resin (organic, (Including both organic and inorganic hybrids) (for example, JP-A-9-278935, JP-A-2002-128887, JP-A-2002-322430, US Pat. No.
  • the inventor of the present application has an acrylic group and a polysiloxane on the side chain.
  • active energy ray-curable compositions containing, as an essential component, a copolymer containing a sun group and, if necessary, a fluorine-containing alkyl group (see, for example, JP-A-2000-80169, JP 2001-98188, JP 2002-194084, etc.)
  • JP 2003-335984 A discloses an active energy including a copolymer having fluorine and polysiloxane groups and simultaneously containing an acrylic group. It is described that the wire curable resin composition forms a cured film having a good balance of contamination resistance, high hardness and scratch resistance.
  • optical recording media such as optical discs and optical articles such as touch panels!
  • contamination by contaminants such as dust affects not only the appearance but also performance.
  • this may cause recording Z playback failure and increased errors during recording Z playback.
  • the recording Z playback beam diameter has been reduced by shortening the recording Z playback wavelength to about 400 nm, or by increasing the aperture (NZA) of the objective lens.
  • An optical disc with a higher recording density than DVD is proposed. For example, Blu-Ray Disc or HD DVD.
  • JP-A-10-110118 proposes blending a non-crosslinked fluorosurfactant with a hard coat coating on the surface of a disk substrate.
  • Japanese Patent Application Laid-Open No. 11-293159 proposes that a cross-linking type and a non-cross-linking type fluorosurfactant are blended simultaneously.
  • Japanese Patent Application Laid-Open No. 11-293159 proposes that a cross-linking type and a non-cross-linking type fluorosurfactant are blended simultaneously.
  • an organic-inorganic hybrid containing a slip agent such as an acrylic resin modified with an organopolysiloxane skeleton is disclosed. It is described that an optical disk on which a hard coat film having a resin composition strength is formed has excellent slip properties. However, these were mainly aimed at protecting the media contained in the cartridge, and attention was not paid to fingerprint smudges. Slip properties and fingerprint resistance (so-called stain resistance) are fundamentally different, and in general, the majority of slip agents have insufficient fingerprint resistance (so-called stain resistance).
  • the present invention is intended to solve the above-described problems, and it is possible to increase the hardness and impart wear resistance even with a thin film, and to provide excellent contamination resistance and contamination resistance.
  • a composition capable of imparting durability is provided.
  • composition or the like that can impart weather resistance while maintaining these performances as required, or can impart more excellent thin film 'surface curability as required.
  • a composition containing a structure corresponding to a specific copolymer (copolymer) containing a photopolymerizable group, or a structure obtained by reacting the light-powered thione polymerizable group with (meth) acrylic acid is a stain-proofing agent. And found to be extremely effective. Specifically, it was achieved by the following means.
  • radically polymerizable monomer 5 to 30 mass 0/0 having an alkyl group, a, omega over dimercapto polysiloxane 0.01 to 5 wt%, radicals having optical power thione polymerizable epoxy groups 5 to 40% by mass of the polymerizable monomer, and 25 to 75% by mass of other radical polymerizable monomer copolymerizable therewith, and the molar ratio of the mercapto group to the epoxy group is 0.0001 to 0.005.
  • An organic polymer having a structure corresponding to a radically polymerizable copolymer of a monomer mixture of 025 and a structure in which (meth) acrylic acid is reacted with an epoxy group of the radically polymerizable copolymer.
  • a composition comprising the organic polymer according to (1) or (2), and further comprising a cationically polymerizable photoinitiator and a soot or radically polymerizable photoinitiator.
  • inorganic oxide fine particles mainly composed of colloidal silica, and — ⁇ —Si—R— bond (R is a linear or branched alkylene group having 2 to 10 carbon atoms).
  • R is a linear or branched alkylene group having 2 to 10 carbon atoms.
  • An organic-inorganic composite having a (meth) attarylloyl group bonded via a Z, or a polyfunctional (meth) atalyl containing three or more (meth) atalyloyl groups in one molecule
  • the composition according to (3) comprising
  • radically polymerizable organic (meth) atalytoi compounds and Z or radically polymerizable organic (meth) acrylamide compounds polymers having radically polymerizable groups, organic epoxy compounds, and
  • linear alkyl (meth) acrylate and photopower thione polymerization with 12 or more carbon atoms An organic polymer having a structure corresponding to a copolymer of a mixture containing a (meth) acrylate having a possible epoxy group, and Z or a structure obtained by reacting an epoxy group of the copolymer with (meth) acrylic acid (3 The composition according to any one of -6.
  • a 5 m thick film formed by irradiation and polymerization has a pencil hardness of HB or more and a contact angle with water of 80 degrees or more.
  • a film having a thickness of 5 m formed by irradiation and polymerization has a pencil hardness of HB or more, a contact angle with water of 90 degrees or more, and a contact angle with hexadecane of 20 degrees or less. object.
  • a film having a thickness of 5 m formed by polymerization is usually a composition having a wear resistance of 25.0 or less and a warpage of 1 mm or less after being cured in an oxygen concentration atmosphere.
  • composition according to any one of (3) to (11), wherein the composition is applied onto a 100 m-thick easy-adhesive polyethylene terephthalate substrate and irradiated with active energy rays.
  • a laminate for an optical display comprising a transparent resin base material, wherein a cured film is provided on at least one outermost surface of the laminate for an optical display, and the cured film comprises (3) to ( 13)
  • a laminate for an optical display which is a film obtained by polymerizing the composition according to item 1 by irradiation with active energy rays.
  • the organic polymer of the present invention has a photopower thionic group, and the composition containing the organic polymer undergoes cationic polymerization at the time of curing. For this reason, it was clarified that oxygen inhibition was less likely due to the difference in the polymerization termination reaction than in the case of radical polymerization. This made it possible to form a thin film with a hard coat film. In addition, since the shrinkage is lower than the addition polymerization of unsaturated bonds, it is possible to increase the thickness of the hard coat film.
  • a composition containing a polymer obtained by adding (meth) acrylic acid to a photo-thionic group and converting it to a photo-radical polymerizable group unexpectedly is relatively oxygenated at the time of curing, although it is radical polymerization. It is difficult to be inhibited and has low shrinkage, and it is still thin and thick. Has suitability suitable for both. Therefore, this composition can be applied to applications where a light-power thione polymerization initiator can be used.
  • a photothion polymerization initiator generally generates an acid, but is easily attacked by an acid. ⁇ It is easily deteriorated by an acid such as an optical recording medium having a recording layer. ⁇
  • the composition is applied to an article and cured. There is also an advantage that does not adversely affect.
  • the composition of the present invention has excellent curability, scratch resistance, transparency, and stain resistance even if it is a thin film that is thinly applied to the surface of the article and cured. Furthermore, it has become possible to enhance the durability of these performances. Therefore, there is an advantage that the optical article having such a cured film on the surface has high hardness and wear resistance, and also has excellent stain resistance and stain resistance durability.
  • optical discs DVD, Blu-Ray Disc, HD DVD, etc.
  • read-only optical discs dye-type optical discs
  • phase-change optical discs phase-change optical discs
  • magneto-optical discs or transparent displays for optical displays such as touch panels are hard. Since the demand for the thin film of the coating film is high, it is suitable for use in the present invention.
  • composition of the present invention when the composition of the present invention is thickly applied to the surface of an article or the like and cured, it is possible to combine excellent hardness. As a result, it can be suitably used in a wide range of applications requiring both hardness and stain resistance.
  • composition of the present invention can be applied to a specific polyolefin base material, acrylic base material, or fluororesin base material, which is hard to adhere to a normal hard coat agent (particularly, a stain resistance imparting hard coat agent). Has the advantage of having excellent adhesion.
  • the polymerization referred to in the present invention includes so-called copolymerization unless otherwise specified. Accordingly, the polymer (polymer) includes a copolymer (copolymer).
  • the room temperature in the present invention refers to the temperature of the place where the experiment is conducted, for example, 15 It means a temperature of -30 ° C, more preferably 20-25 ° C.
  • the normal oxygen concentration means 18 to 22%, more preferably 19 to 21%.
  • the organic polymer of the present invention comprises a radically polymerizable monomer having a perfluoroalkyl group, 5 to 30% by mass, ⁇ , ⁇ -dimercaptopolysiloxane 0.01 to 5% by mass, photopower thione polymerizable epoxy group And 5 to 40% by mass of a radically polymerizable monomer having 25 to 75% by mass, and 25 to 75% by mass of other radically polymerizable monomer copolymerizable therewith, and the molar ratio of the mercapto group to the epoxy group is from 0.0001 to It has a structure corresponding to a radical copolymer of a monomer mixture which is 0.025. Alternatively, it has a structure in which (meth) acrylic acid is reacted with the epoxy group of this copolymer. May have both structures.
  • the organic polymer of the present invention is obtained by applying an organic polymer satisfying the above requirements (hereinafter sometimes referred to as ( ⁇ )) onto a 100 ⁇ m-thick easy-adhesive polyethylene terephthalate (PET) substrate, and applying active energy rays.
  • a film with a thickness of 5 m formed by irradiation and polymerization is an organic polymer with a lead brush hardness of HB or more, a contact angle with water of 100 degrees or more, and a contact angle force with hexadecane of 0 degrees or more. Preferred.
  • examples of preferable active energy rays include ultraviolet rays, electron beams, ⁇ rays, j8 rays, and ⁇ rays. Therefore, as the “polymerization by irradiation with active energy rays” in the present invention, photoradical polymerization or photopower thione polymerization is preferred, and examples thereof are given.
  • the organic polymer (i) of the present invention comprises a radically polymerizable monomer having a perfluoroalkyl group (hereinafter sometimes referred to as (AF)), ⁇ , ⁇ -dimercaptopolyester.
  • Siloxane hereinafter sometimes referred to as (A-Si)
  • A-2 a radically polymerizable monomer having an epoxy group capable of photopower thione polymerization
  • A-3 Polymers obtained by radical polymerization of these monomers and radically polymerizable monomers that can be radically copolymerized, and structures corresponding thereto
  • a polymer having the above can be preferably employed.
  • (A) organic polymers radically polymerizable monomers having (AF) perfluoroalkyl groups are greatly involved in the development of stain resistance against oily soils such as fingerprints. These groups are considered to have excellent oil repellency.
  • (A- Si) a ⁇ -dimercaptopoly Siloxane is greatly involved in the development of overall stain resistance. Since this group has high water repellency, it is considered that the stain resistance against hydrophilic soil can be particularly improved.
  • the organic polymer has a cationic polymerizable group derived from (A-2) a radically polymerizable monomer component having an epoxy group capable of photopower thione polymerization, so that the composition containing the (A) organic polymer The product will undergo cationic polymerization during curing.
  • cationic polymerization is less susceptible to oxygen inhibition, and
  • a coating film (hereinafter sometimes simply referred to as “coating film”) coated with a composition containing an organic polymer is a thin film. Even if it exists, it can be cured sufficiently.
  • ring-opening polymerization of epoxy groups has lower shrinkage than addition polymerization of unsaturated bonds, so that even if the coating film is thick, warping and distortion hardly occur, so that it is possible to increase the film thickness.
  • a composition comprising an organic polymer (having a structure in which (meth) acrylic acid is reacted with an epoxy group), wherein (meth) acrylic acid is added to a photopower thione group and converted to a radical photopolymerizable group
  • a composition comprising an organic polymer (having a structure in which (meth) acrylic acid is reacted with an epoxy group), wherein (meth) acrylic acid is added to a photopower thione group and converted to a radical photopolymerizable group
  • it is relatively resistant to oxygen inhibition during curing and has low shrinkage, and still has suitable properties for both thinning and thickening.
  • the perfluoroalkyl group is a concept including a perfluoroalkylene group.
  • a perfluoroalkyl (alkylene) group it may be referred to as a perfluoroalkyl (alkylene) group.
  • a monomer is a (meth) acrylate having a perfluoroalkyl (alkylene) group. Further, it may have an arbitrary substituent as long as the effects of the present invention are not significantly impaired.
  • Such monomers include perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, perfluorohexyl acrylate, and pentafluoromethacrylate. And methoxyethyl perfluoroethyleneethyl acrylate. Of course, it is not limited to these.
  • the number of carbon atoms of the perfluoroalkyl (alkylene) group is preferably 3 or more, and more preferably 5 or more. By setting it to 3 or more, it becomes possible to further improve the stain resistance.
  • the upper limit of the number of carbon atoms of the perfluoroalkyl (alkylene) group is not particularly defined, but examples For example, it can be 15 or less. By setting it to 15 or less, the hardness can be further increased.
  • the perfluoroalkyl (alkylene) group is preferably contained in the side chain in the polymer.
  • (A-F) may be used alone or in combination of two or more.
  • (AF) is contained in the organic polymer (A) in an amount of 5% by mass or more, preferably 10% by mass or more. If it is less than 5% by mass, the stain resistance derived from the perfluoroalkyl (alkylene) group will be insufficient.
  • (AF) is contained in the organic polymer (A) in an amount of 30% by mass or less, and preferably 25% by mass or less. If it exceeds 30% by mass, the hardness of the polymer decreases, and the scratch resistance and pencil hardness of the surface decrease.
  • (A-Si) ⁇ , ⁇ -dimercaptopolysiloxane preferably has a polysiloxane structure in which two or more of the following repeating structural units are linked.
  • each of R 1 and R 2 represents an optionally substituted alkyl group or a phenyl group.
  • R 1 and R 2 are preferably each an alkyl group which may be substituted with a hydroxyl group or an alkoxyl group.
  • R 1 and R 2 are more preferably each substituted with a hydroxy group or an alkoxyl group, and may be an alkyl group having 1 to 3 carbon atoms.
  • R 1 and R 2 are more preferably an alkyl group having 1 to 3 carbon atoms having no substituent, and most preferably a methyl group.
  • (A—Si) may have an arbitrary substituent without departing from the gist of the present invention.
  • (A—Si) preferably has a number average molecular weight of about 1000 to 5000. By adopting such a range, it is possible to achieve a better balance between contamination resistance and hardness.
  • (A-Si) may be used alone or in combination of two or more.
  • (A—Si) is contained in 0.01% by mass or more in (A) the organic polymer. If it is less than 0.01% by mass, the stain resistance will not be sufficiently exhibited.
  • (A-Si) is contained in the (A) organic polymer in a range of 5% by mass or less. If it exceeds 5% by mass, the oleophilicity will increase and the anti-fingerprint stain resistance will decrease, or the slip property will become too high, resulting in poor wiping.
  • Examples of (A-2) include acrylic acid esters, methacrylic acid esters, acrylamides and methacrylamides having an epoxy group or oxetane group in the side chain.
  • Typical examples include glycidinoreatalylate, glycidinoremetatalylate, 3, 4 epoxy cyclohexyl acrylate, 3, 4 epoxycyclohexenoremetatalylate, 3, 4 epoxycyclohexyl methyl acrylate. 3, 4 Epoxycyclohexylmethyl methacrylate, 1-methyloxata-loxymethyl acrylate, 1-methyloxeta-loxymethyl methacrylamide, and the like are not limited thereto.
  • glycidyl methacrylate, (3) and 4 (epoxycyclohexane), which are preferred for (meth) acrylate having an epoxy group capable of photothion polymerization, are preferred due to the modification property with (meth) acrylic acid and the availability.
  • Particularly preferred are hexyl acrylate, 3, 4 epoxycyclohexyl methacrylate, 3, 4 epoxycyclohexyl methyl acrylate, 3, 4 epoxycyclohexyl methyl methacrylate.
  • (A-2) may be used alone or in combination of two or more.
  • (A-2) is contained in an organic polymer in an amount of 5% by mass or more, preferably 10% by mass or more. If it is less than 5% by mass, high curability due to photothion polymerization (or photo-radical polymerization by (meth) acrylic acid modification), high hardness and surface curability cannot be expressed.
  • (A-2) is contained in the organic polymer in an amount of 40% by mass or less, and preferably 35% by mass or less. If it exceeds 40% by mass, the viscosity of the polymer solution may be lowered or the liquid stability may be lowered, and further improvement in high curability and high hardness can be seen.
  • the ratio is between 0.0001 and 0.025. That is, it is necessary to radically polymerize the mercapto group in the range of 0.0001 to 0.025 mol with respect to 1 mol of the epoxy group.
  • the viscosity is controlled so as not to cause substantial increase in viscosity or solubility due to crosslinking or branching (branching) due to the reaction between the mercapto group and the epoxy group. is doing.
  • the molar ratio of the mercapto group to the epoxy group is less than 0.0001, the polymerization termination effect due to the chain transfer of the mercapto group may not be exhibited.
  • the mercapto group with respect to 1 mol of the epoxy group is preferably 0.0005 or more. Further, the mercapto group with respect to 1 mol of the epoxy group is preferably not more than 0.020.
  • (A-3) is not particularly limited as long as it is a radically polymerizable monomer capable of radical copolymerization with (A-F), (A-Si), and (A-2).
  • Preferred are monomers that have low reactivity with epoxy groups and do not reduce the stability of the resulting polymer, or monomers that have a rigid skeleton and do not lower the hardness.
  • styrene or a substituted derivative of a lower alkyl group of styrene for example, an alkyl group having 1 to 4 carbon atoms
  • a lower alkenyl group for example, an alkenyl group having 2 to 4 carbon atoms
  • alkyl (meth) acrylates having 8 alkyls alkyl (meth) acrylamides, cycloalkyl (meth) acrylates having (poly) cycloalkyl side chains having 5 to 20 carbon atoms, and (meth) acrylamides.
  • alkyl (meth) acrylates having 1 to 8 carbon atoms are preferred.
  • (A-3) may be used alone or in combination of two or more.
  • a solvent may be added in order to improve uniformity.
  • solvents include ketone solvents such as acetone and methyl ethyl ketone (MEK), ethanol, methanol, isopropyl alcohol (IP A), alcohol solvents such as isobutanol, etc., ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxy cetyl acetate Preferred examples include system solvents, aromatic hydrocarbon solvents such as toluene, and water.
  • ketone solvents such as acetone and methyl ethyl ketone (MEK), ethanol, methanol, isopropyl alcohol (IP A), alcohol solvents such as isobutanol, etc.
  • ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether
  • esters such as ethy
  • the method for mixing and dissolving the polymerization component and the solvent is not particularly limited.
  • radical polymerization initiators known radical polymerization initiators can be used, such as organic peroxides such as benzoyl peroxide and di-tert-butyl peroxide, 2,2, -azobisbutyrate.
  • Azo radical polymerization initiators such as rhonitrile, 2,2, -azobis (2,4-dimethylvaleronitrile), 2,2,1azobis (4-methoxy-1,2,4-dimethylvaleritol-tolyl) Preferred is given as an example.
  • the total concentration of the monomer components in the mixture is preferably 10 to 60% by mass.
  • the radical polymerization initiator is preferably used in an amount of 0.1 to 10% by mass, more preferably 0.1 to 4% by mass, and still more preferably 0.2 to 2% by mass, based on the monomer component.
  • the preferred polymerization temperature and polymerization time vary depending on the radical polymerization initiator used. Generally, the polymerization temperature is 20 ° C to 150 ° C, and the polymerization time is 1 hour to 72 hours.
  • composition containing the organic polymer (A) a part of (A) may be the following organic polymer (Ai) (hereinafter sometimes abbreviated as (Ai)).
  • the organic polymer (Ai) is a radically polymerizable monomer (A-2) (preferably a linear alkyl (meth) acrylate (A-L) having 12 or more carbon atoms and an epoxy group capable of photothion polymerization. Or an organic polymer having a structure corresponding to a copolymer of a mixture containing (meth) acrylate and a structure in which (meth) acrylic acid is reacted with an epoxy group of Z or the copolymer.
  • This organic polymer (Ai) increases the lipophilicity, but also has the effect of making oily stains noticeable.For example, for specific touch panels and display applications, even when the fingerprint is attached, the stain is removed. Good for applications that require less visibility Is suitable.
  • the organic polymer (Ai) is preferably a radically polymerizable monomer (A-2) having 5 to 35% by mass of a linear alkyl (meth) acrylate (AL) having 12 or more carbon atoms and an epoxy group capable of photopower thione polymerization. ) 5 to 40% by mass, and other radically polymerizable monomers copolymerizable therewith (A-3) having a structure corresponding to a radical copolymer of a monomer mixture containing 25 to 75% by mass. Alternatively, it has a structure in which (meth) acrylic acid is reacted with the epoxy group of this copolymer. You may have both structures.
  • Examples of the radically polymerizable monomer (AL) having a linear alkyl group having 12 or more carbon atoms include (meth) acrylates having a linear alkyl group having 12 or more carbon atoms.
  • (meth) acrylates having a linear alkyl group having 12 or more carbon atoms For example, lauryl acrylate, lauryl methacrylate, myristyl acrylate, myristyl methacrylate, stearyl acrylate, stearyl methacrylate, beryl acrylate, benzyl methacrylate, etc.
  • the straight-chain alkyl group usually has 30 or less carbon atoms.
  • (AL) can be used alone or in combination of two or more.
  • (A-2) and (A-3) may be the same as those described in the organic polymer (A).
  • the polymerization method and polymerization conditions are the same as described for the organic polymer (A).
  • the composition of the present invention contains at least an organic polymer (A), and further contains at least one of a cationic polymerizable photoinitiator (C) and a radical polymerizable photoinitiator (D). Both may be included.
  • a cationic polymerizable photoinitiator (C) When the organic polymer (A) or the organic polymer (Ai) has an epoxy group, at least the cationic polymerizable photoinitiator (C) is included.
  • Organic polymer (A) or organic polymer (Ai) force When it has a structure in which (meth) atallylic acid is reacted with an epoxy group, it contains at least a radically polymerizable photoinitiator (D). This is to obtain a cured film with sufficient hardness.
  • composition of the present invention preferably comprises the following component (B).
  • Component (B) includes inorganic oxide fine particles mainly composed of colloidal silica, and —O—Si—R— bonds (where R is a straight chain of 2 to Represents an branched alkylene group, and is an organic-inorganic composite having a (meth) atalyloyl group bonded via Body (Bi), polyfunctional (meth) atalylate containing 3 or more (meth) atalyloyl groups in one molecule (
  • the organic-inorganic composite that can be used in the present invention is one having inorganic oxide fine particles and (meth) atallyloyl groups bonded to the inorganic oxide fine particles through —O—Si—R— bonds.
  • R represents a linear or branched alkylene group having 2 to 10 carbon atoms.
  • the alkylene group may or may not have a substituent.
  • an organic-inorganic composite that can be used in the present invention (hereinafter sometimes referred to as (Bi))
  • a silane coupling agent (B-1) having a (meth) atallyloyl group (Bi)
  • B-1 silane coupling agent having a (meth) atallyloyl group.
  • —O—Si—R—bond (wherein R represents a linear or branched alkylene group having 2 to 10 carbon atoms) (more preferably —O—Si—R—S—bond) on the surface of the inorganic oxide fine particles It is preferable to use a silane coupling agent (hereinafter sometimes referred to as (B-1)) having a (meth) atalyloyl group in order to bond a group having a (meth) atalyloyl group via ,.
  • B-1 silane coupling agent having a (meth) atalyloyl group in order to bond a group having a (meth) atalyloyl group via ,.
  • a silane coupling agent having a molecular weight of 300 or more and containing at least one taliloyl group or methacryloyl group as a radical polymerizable functional group can be mentioned.
  • the number of attalyloyl groups or methacryloyl groups is not particularly limited, it is preferable to have 1 to 5 polymerizable functional groups per molecule. Further, the position is not particularly limited, but is preferably at the end of the molecule.
  • (B-1) is more preferably an organic compound having a functional group represented by the following formula (1).
  • X and ⁇ each independently represent an oxygen atom, a sulfur atom or an imino group).
  • the functional group represented by the formula (1) increases the mechanical strength by generating moderate cohesive force due to hydrogen bonds between the molecules, and improves the adhesion to the substrate and heat resistance. And also acts as a spacer between the surface of the inorganic oxide fine particles and the radical polymerizable functional group.
  • Specific examples include OCONH, 1 SCONH, 1 SCSNH, 1 OC SNH—, —NHCONH and —NHCSNH— (hereinafter, these may be collectively referred to as Formula (2)). Of these groups, OCONH— and —SCONH are particularly preferred from the viewpoint of thermal stability and ease of synthesis.
  • (B-1) may be an organic compound having a thioether group at the same time.
  • the thioether group is also preferred because it acts as a spacer between the silica surface and the radical polymerizable functional group or a specific polar functional group, and has the effect of suppressing excessive aggregation.
  • an alkoxysilyl group that is a group capable of forming a silanol group is particularly preferred.
  • the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, and among them, a trialkoxysilyl group of a lower alcohol such as a trimethoxysilyl group or a triethoxysilyl group. Is particularly preferable in view of reactivity.
  • the position of these groups in the molecule is preferably at the end of the molecule opposite the (meth) atalyloyl group.
  • the number of groups in one molecule is preferably 1 to 3, and more preferably 1.
  • a silanol group or a silanol group-forming unit is a generated unit that binds to inorganic oxide fine particles by a condensation reaction that occurs following a condensation reaction or hydrolysis. Examples of the preference of such compounds!
  • a compound containing two or more (meth) attalyloyl groups in the molecule, and a tri group having an SH group A compound in which an alkoxysilane is bonded to a thioether formed by Michael addition reaction to an unsaturated group of a SH group (a (meth) atalyloyl group), and
  • Examples of (meth) atalylate having a pendant group include mono (meth) atalylate (such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate), and di (meth) acrylate.
  • (Meth) acrylate such as glycerin di (meth) acrylate and trimethylolpropane di (meth) acrylate), tri-poly (meth) acrylate (pentaerythritol tritalate, dipentaerythritol tri-pentaacrylate and Ditrimethylolpropane triatrate, etc.) is preferred!
  • Trialkoxysilane compounds having an NCO group include, for example, triethoxysilyl propylene isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd., etc., 9007), trimethoxysilylpropyl isocyanate, and trimethoxysilylpropyl.
  • Trialkoxysilyl alkyl mercaptans such as mercaptans (Shin-Etsu Chemical Co., Ltd., ⁇ 803, and Toray Dow Co., Ltd., SH6062) and diisocyanates (isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate) Examples thereof include compounds in which one NCO group of a nate (MDI) and toluene diisocyanate (TDI) is bonded via a thiourethane bond.
  • MDI nate
  • TDI toluene diisocyanate
  • OCONH can be generated by reaction of ⁇ group and NCO group by mixing each compound NCO group ⁇ 11 group ⁇ 1 and mixing and stirring at 60 ⁇ : L00 ° C for 1 hour to 20 hours. can get.
  • a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol, and phenothiazine to prevent polymerization due to acrylic groups during the reaction.
  • the amount of the polymerization initiator is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the reaction mixture.
  • a known reaction catalyst such as di-n-butyltin dilaurate and diazabicyclooctane (DABCO) may be added.
  • this reaction can be carried out, for example, with methyl ethyl ketone and Ketone solvents such as methyl isobutyl ketone, ether solvents such as ethylene glycol jetyl ether and diethylene glycol dimethyl ether, carboxylic acid ester solvents such as ethyl acetate and butyl acetate, and aromatic hydrocarbons such as xylene and toluene
  • the reaction can be carried out in the presence of a polyfunctional acrylate having three or more (meth) atallyloyl groups in the molecule without containing a group capable of reacting with an isocyanate group such as a solvent, or at the same time.
  • the (meth) atalytotoy compound having an NCO group j8-isocyanate ethyl (meth) acrylate (made by Showa Denko, power lens MOI or power lens AOI), or OH group
  • j8-isocyanate ethyl (meth) acrylate made by Showa Denko, power lens MOI or power lens AOI
  • OH group One NCO group of (meth) acrylates (made by Showa Denko, Power Lens MOI or Power Lens AOI) and diisocyanates (such as isophorone diisocyanate, hexamethylene diisocyanate, MDI and TDI) And the like, and the like can be exemplified.
  • trialkoxysilane compound having an SH group examples include trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Co., Ltd., SH6062 etc.).
  • NHCOS can be generated by the reaction of NCO group and SH group in the same way as NHCOO generation by reaction of NCO group and OH group.
  • a, ⁇ -hydroxy-terminated polyalkylene glycol mono (meth) acrylate ester compounds include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate Examples thereof include poly (ethylene-propylene) glycol mono (meth) acrylate and poly (ethylene-tetramethylene) glycol mono (meth) acrylate.
  • Reaction of mono (meth) acrylic acid ester compound of a, ⁇ -hydroxy-terminated polyalkylene glycol and trialkoxysilyl compound having NCO group is similar to NHCOO formation by reaction of NCO group and ⁇ group Can be done by the method.
  • the inorganic oxide fine particles are not particularly limited as long as they do not depart from the spirit of the present invention, but silicon, aluminum, zirconium, titanium, Specifically, oxides of lead, lead, germanium, indium, tin, antimony, cerium, lithium, or complex oxides thereof are preferred. Examples of silicon oxides (silica) and aluminum oxides are preferred. Ceramics (alumina), silicon-aluminum complex oxides, zirconium oxides (zircoua), titanium oxides (titanium), acid bismuth, tin oxide, antimony doped acid Examples thereof include tin oxide, indium-tin composite oxide (ITO), cerium oxide, and silica-lithium oxide composite oxide. Of these, silica (colloidal silica) as the main component is particularly preferred.
  • colloidal silica as a main component
  • the shape of the inorganic oxide fine particles is more preferably spherical, hollow, porous, rod-like, fiber-like or plate-like, or spherical with an indefinite shape being preferred.
  • the term “spherical” as used in the present invention is intended to include a substantially spherical shape in addition to a strict sphere.
  • the primary particle diameter of the inorganic oxide fine particles is preferably 1 to: LOOnm.
  • the inorganic oxide fine particles of the present invention can be obtained in a dry powder state or dissolved or dispersed in water or an organic solvent.
  • a sol dissolved or dispersed in water or an organic solvent (hereinafter sometimes referred to as an inorganic oxide fine particle sol) is preferable because it exhibits excellent dispersibility.
  • an aqueous silica sol dissolved or dispersed in water an organic silica sol dissolved or dispersed in an organic solvent having an OH group or a polar organic solvent having an ester group or a ketone group is preferably used as a main component. ,.
  • aqueous silica sol As the aqueous silica sol, basic aqueous silica sol (manufactured by Nissan Chemical Industries, ST-20), acidic aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., ST-0), weakly acidic aqueous silica sollumina sol (Nissan Chemical Industry Co., Ltd., ST-AK) and basic silica / lithium oxide (Nissan Chemical Industry Co., Ltd., lithium silicate) are preferred and can be mentioned as examples.
  • Organosilica sols include IPA-dispersed organosilica sol (Nissan Chemical Industries, IPA-ST, IPA-ST-ZL), MEK-dispersed organosilica sol (Nissan Chemical Industries, MEK-ST, MEK- ST-MS), MIBK-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MIBK-ST), PMA-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST), and other materials.
  • a sol for example, PGM-dispersed organosilica sol substituted with an organic solvent having an OH group is preferred as an example.
  • organic solvent used herein examples include methanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethinoreserosonole, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl ethyl ketone, Examples include til isobutyl ketone, dimethylacetamide and xylene, and mixed solvents thereof.
  • the solid content in the dispersion is preferably 5 to 50% by mass and more preferably 10 to 40% by mass from the viewpoint of easy handling and availability.
  • Bonding of inorganic oxide fine particles (B-2) and silane coupling agents (B1) having (meth) attalyloyl groups can be achieved by various methods commonly used in this type of compound formation. Is possible. Basically, there is a method in which the alkoxysilyl group of (B-1) is hydrolyzed to form a silane group, and a condensation reaction is carried out with an alkoxy group and a hydroxy group on the surface of the inorganic oxide fine particles. It is common.
  • the water used is used as long as the performance of the membrane and the stability of the coating solution are not impaired.
  • the amount of water added is not less than the amount that (B-1) can be hydrolyzed to 100% as the theoretical amount, preferably 100-300% equivalent, more preferably 100-200% equivalent .
  • Examples of water used include distilled water, ion exchange water, industrial water and soft water.
  • an acid or alkali, or other suitable compound may be added as a catalyst in order to promote this hydrolysis condensation reaction. Any of these can be used as long as the performance of the film is not impaired and the performance of the coating solution is not impaired.
  • the acid catalyst includes an inorganic acid such as a hydrogen chloride solution, a phosphoric acid solution, and boric acid, an organic acid such as citrate, maleic acid, acetic acid, and paratoluene sulfonic acid, and an alcoholic hydroxide as an alkaline catalyst.
  • examples include potassium, ammonia, trialkylamines and heterocyclic amines such as dimethylaminopyridine.
  • metal acetylacetylacetone complexes such as aluminum triacetylacetonate are also effective.
  • the amount of these used is preferably 0.1-5 parts by mass, more preferably 0.5-5 parts by mass with respect to 100 parts by mass of the silanic compound.
  • the reaction is preferably 20-100 ° C, 1 hour to 100 hours (more preferably 20 ° C-25 ° C, 4 hours or more) after the reaction, heated at 40-70 ° C for 1-: LO hours. Let the reaction proceed.
  • the reaction system may be diluted with a solvent.
  • the solvent used is preferably one that is compatible with the water or catalyst used, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • ethers such as tetrahydrofuran and dioxane, and hydroxyl-containing ethers such as propylene glycol monomethyl ether.
  • the mass ratio of the inorganic oxide fine particles (solid content) and the silane compound is preferably 100ZO.1 to 100Z10, more preferably 100Zl to 100Z5. By setting it within such a range, it is preferable that an appropriate amount of functional groups can be introduced into the inorganic oxide fine particles ( ⁇ -2).
  • an alkoxysilyl compound having a functional group capable of generating a linking group represented by formula (1) or formula (2) is first described. After reacting with the inorganic oxide fine particle sol, another compound is reacted, and a polymerizable unsaturated group and a bonding group represented by the formula (1) or formula (2) are introduced into the compound. be able to.
  • silane compounds capable of introducing a linking group of the formula (1) as a compound having an alkoxysilyl group, a trialkoxysilane compound having an SH group is prepared in advance with inorganic oxide fine particles ( ⁇ -2). ).
  • a trialkoxysilane having an SH group is reacted with ( ⁇ -2), then the SH group is reacted with a diisocyanate compound, and one NCO group is used to connect with an NHCOS bond. Then, a structure similar to the previous method can be obtained by a method in which the remaining NCO group is made to act by a (meth) atalyte toy compound having an OH group and connected by NHCOO bonds.
  • a trialkoxysilane having an SH group is reacted with (B-2), and then reacted with a (meth) atalytoi compound having an NCO group and a Z or (meth) acrylamide compound.
  • B-2 a trialkoxysilane having an SH group
  • a (meth) atalytoi compound having an NCO group and a Z or (meth) acrylamide compound A structure similar to the previous method can be obtained.
  • the reaction ratio of the trialkoxysilane having an SH group and (B-2) is generally 0.1 / 99.9 to 95Z5, preferably 2Z98 to 90Z10, more preferably 10Z90 to 808020 in mass ratio. It is. By setting it in such a range, the surface of the inorganic oxide can be more sufficiently protected, and further, the dispersion state due to polymerization and crosslinking of the alkoxysilane itself can be further stabilized, and an increase in viscosity can be prevented. More preferred.
  • the molecular weight of trialkoxysilane having an SH group is preferably 150 or more, more preferably 300 or more. By setting it to 150 or more, the effect of producing a protective colloid is further enhanced, and aggregation and gelling due to condensation and crosslinking of the trialkoxysilane itself having an SH group can be more effectively suppressed.
  • the reaction is preferably carried out at room temperature to 100 ° C for 1 hour to 100 hours, more preferably at room temperature for 4 hours or more, followed by heating at room temperature to 70 ° C for 1 to L0 hours.
  • the reaction system may be diluted with a solvent.
  • This solvent is preferably a hydrolyzate silane alkoxide, water or a catalyst compatible, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • ketones such as tetrahydrofuran, ethers such as tetrahydrofuran and dioxane, and hydroxyl group-containing ethers such as propylene glycol monomethyl ether.
  • a part of (B-1) may be replaced with another silane coupling agent.
  • silane coupling agents in addition to various well-known commercial silane coupling agents, a silane coupling agent having a polyalkylene glycol structure without a radical polymerizable functional group, a COOH group or a COOR ′ group (R ′ Is a silane coupling agent having an alicyclic structure, and a silane obtained by the reaction of a bulky alcohol having a branched structure and an alkoxysilyl group having an NCO group A coupling agent etc. are illustrated.
  • R is an alkylene group which may have a branch having 2 to 10 carbon atoms
  • P is a polymer unit having at least one (meth) atalyloyl group.
  • the inorganic oxide fine particles (B-2) are hydrolyzed and condensed (first step), and at least one monomer having at least one epoxy group and at least one radical polymerizable group is added thereto. It can be obtained by radical polymerization of one species (second step), and adding a compound having a carboxyl group and a (meth) taroloyl group (third step).
  • the inorganic oxide fine particles are hydrolytically condensed.
  • the reaction and bonding of the mercaptosilane and the inorganic oxide fine particle sol can be achieved by various methods commonly used in the production of this type of compound. Basically, the alkoxysilyl group of mercaptosilane is hydrolyzed to form a silanol group, which is then subjected to a hydrolytic condensation reaction with the alkoxy group and Z or hydroxy group of the inorganic oxide surface to bond them together. It is.
  • the water used is used as long as the performance of the membrane and the stability of the coating solution are not impaired.
  • the amount of water added is preferably an amount equivalent to 100% -300%, more preferably an amount equivalent to 100-200%, as long as the amount of mercaptosilane can be hydrolyzed 100% in theory. .
  • Examples of water used include distilled water, ion exchange water, industrial water and soft water.
  • the acid catalyst includes an inorganic acid such as a hydrogen chloride solution, a phosphoric acid solution and boric acid, an organic acid such as citrate, maleic acid, acetic acid and paratoluenesulfonic acid, and an alkaline catalyst such as alcoholic potassium hydroxide.
  • examples include ammonia, trialkylamines, and heterocyclic-containing amines such as dimethylaminoviridine.
  • metal acetylacetylacetone complexes such as aluminum-muth triacetylacetonate are also effective.
  • the amount of these used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of mercaptosilane.
  • the reaction is preferably 20 to 100 ° C., 1 hour to 100 hours (more preferably 20 ° C. to 25 ° C., 4 hours or more). After the reaction, the mixture is heated at 40 to 70 ° C. for 1 to L0 hours. Let the reaction proceed.
  • the reaction system may be diluted with a solvent.
  • the solvent used is preferably one that is compatible with the water or catalyst used, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • ethers such as tetrahydrofuran and dioxane, and hydroxyl-containing ethers such as propylene glycol monomethyl ether.
  • the mass ratio of mercaptosilane and inorganic oxide fine particles is preferably 0.1 / 99.9 to 95/5, more preferably 2/98 to 90/10. This is preferable to S. By setting it within such a range, an appropriate amount of mercapto groups can be introduced into the inorganic oxide fine particles.
  • At least one monomer having at least one epoxy group and at least one radical polymerizable group is radically polymerized.
  • radical polymerization of monomers in the presence of inorganic oxide fine particles having mercapto groups the chain transfer reaction between the radicals of the monomers in the growth reaction and the mercapto groups bonded to the inorganic oxide fine particles occurs during the polymerization process. Occurs, and the polymer and inorganic oxide fine particles are bonded through a sulfid bond. At this time, the epoxy group in the monomer remains as it is. Maintained.
  • Monomers having an epoxy group and one radical polymerizable group used in the second step include glycidyl (meth) acrylate, 3 1, 4 Epoxycyclohexyl (meth) acrylate, 3, 4 Epoxy cyclohexyl methyl (meth) acrylate, etc. are preferred and can be mentioned as examples.
  • the monomer having an epoxy group can be radically copolymerized with other monomers.
  • Other monomers are not particularly limited as long as they do not react with epoxy groups.
  • the monomer epoxy group-containing monomer and other monomers used together if desired
  • inorganic oxide fine particles solid content
  • Polymerization at 50Z50 to 90ZlO It is more preferable to react.
  • This radical polymerization reaction is performed in a solvent using a normal radical polymerization initiator.
  • Solvents include alcohols (ethanol, isopropanol, isobutanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols having an alkoxy group (methoxy ethanol, ethylene glycol monoethyl ether).
  • ethers ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.
  • ether esters propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, etc.
  • aromatic hydrocarbons Toluene, xylene, etc.
  • esters ethyl acetate, propyl acetate, etc. and the like can be mentioned as preferred examples, and these can be used in combination.
  • radical polymerization initiators used in the polymerization reaction include peroxides such as benzoyl peroxide, di tert butyl peroxide and tamen hydroperoxide, 2, 2'-azosobutyronitrile, 2, 2'-azobis. Mono (2,4 dimethylvaleronitrile), 2,2'-azobis (4-methoxy-1,2,4 dimethylvale-tolyl), etc. are preferably used.
  • the monomer concentration in the reaction system is preferably Is 10 to 60% by mass, and is a polymerization initiator Is usually 0.1 to 10% by mass relative to the total mass of the monomers.
  • Examples of the compound having a carboxyl group and a (meth) atalyloyl group used in the third step include (meth) acrylic acid, 2- (meth) atalyloyloxetyl succinic acid, 2- (meta) Ataliloyloxetyl hexahydrophthalic acid, pentaerythritol tri (meth) acrylate and acid anhydride adducts such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dipentaerythritol penta (meta ) Examples include adducts of acrylate and acid anhydrides such as succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride.
  • the epoxy group possessed by the polymer reacts with the carboxyl group possessed by the (meth) atalyloyl group introduction reagent. It is more preferable to mix the polymer and the (meth) atallyloyl group-introducing reagent at a ratio of 1 to 10, which is preferably mixed at a ratio of epoxy group Z carboxyl group of 1 or more.
  • the reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours.
  • known catalysts such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride and triphenylphosphine are used to accelerate the reaction.
  • the amount used is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the reaction mixture. Further, in this reaction, it depends on the (meth) atalyloyl group.
  • polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butyl catechol and phenothiazine, for example.
  • the amount of the polymerization inhibitor used is preferably from 0.01 to 1% by mass, more preferably from 0.05 to 5% by mass, based on the reaction mixture.
  • component (Bi) when such a component is used as the component (Bi), it may be desired to further add a solvent for the purpose of improving the coating property.
  • Solvents used are various reaction materials used in the respective production steps of the inorganic oxide fine particles.
  • it may be a dispersion medium of inorganic oxide fine particles used in the first step or a solvent used in the reaction of the second step.
  • it may be a solvent used for viscosity adjustment after the inorganic oxide fine particles are produced.
  • the following method may be preferable because the purity of the product is further improved.
  • At least one monomer having at least one epoxy group and at least one radical polymerizable group is radical polymerized to obtain a polymer having an alkoxysilyl group at one end.
  • First step To this is added a compound having a carboxyl group and a (meth) atalyloyl group (second step). Further, in this presence, the inorganic oxide fine particles (B-2) are hydrolyzed and condensed (third step).
  • Other various conditions (detailed conditions for polymerization, addition and hydrolysis condensation) can be carried out as described in the above-mentioned (B-4) specific production method (2).
  • polyfunctional (meth) ataretoy compounds having three or more (meth) atalyloyl groups in one molecule include pentaerythritol triatalylate, pentaerythritol tetraacrylate, dipentaerythritol pentaatalylate. , Dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, polyester acrylate, multifunctional urethane acrylate, polyepoxy acrylate, polyethoxy acrylate, isocyanurate ring (produced by Toagosei Co., Aronix M315, Such as M313), but is not limited thereto.
  • the content of (B) in the composition of the present invention (the total content of (Bi) and (Bii)) is not particularly defined unless it departs from the gist of the present invention, but requires particularly high hardness.
  • the mass ratio of (B) Z (A) is preferably 99.5 / 0.5 to 80Z20.
  • (B-1) may be blended untreated.
  • the blending amount is 0. 01-20% by mass is preferred!
  • the cationically polymerizable photoinitiator (C) is not particularly limited, but is preferably an aromatic iodine salt compound or an aromatic sulfo salt compound.
  • (C) is a dialyrhodonium salt type or a triarylsulfo salt type, and examples of ions include PF, SbF, AsF, BPh, CF OSO, etc. Is preferred.
  • the content of (C) can be appropriately determined depending on the type, but (A) is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass.
  • amines such as triethanolamine
  • phosphines such as tributylphosphine
  • thixanthones may be used in combination.
  • these compounds are preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of (A).
  • radical polymerizable photopolymerization initiator known ones can be widely used.
  • alkylphenone type compounds ⁇ -hydroxyacetophenone, at-aminoacetophenone, benzyl ketal, etc.
  • acyl phosphine oxide type compounds oxime ester type compounds, oxyphenyl acetates, benzoin ethers, ketones and amine compounds.
  • benzoin methyl ether benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methoxyacetophenone, benzyldimethyl ketal, 2-hydroxy 2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone 2, 4, 6 Trimethyl benzoin diphosphine phosphoxide, 2 methyl [4 (methylthio) phenol] 2 morpholino 1-propanone, 2 benzyl 1 2 dimethylamino 1 1 (4 morpholino phenol) 1 Preferred are butane-1-one, Michler's ketone, ⁇ , ⁇ ⁇ isoamyl dimethylaminobenzoate, 2-chlorothioxanthone, 2,4 jetylthioxanthone, and the like. Two or more of these photopolymerization initiators can be used in combination as appropriate.
  • the content of the radically polymerizable photoinitiator (D) can be appropriately determined depending on the type of the radically polymerizable photoinitiator (1). Better Good.
  • radical polymerization photoinitiator (D) is used in an amount of 20% by mass or more of component (D), polymerization inhibition due to oxygen is further reduced, and surface curability and thin film curability are improved. May be seen and may be particularly preferred.
  • a aminoacetophenone initiator for example, 2-methyl [4 (methylthio) phenol] 2 morpholino 1 prono ⁇ non, 2-benzyl-1-2-dimethylamino-1- (4 -Morpholinol) 1-butane 1-on, etc.
  • Oxime ester initiators eg, Irgacure OXE-01, manufactured by Ciba Specialty Chemicals
  • the composition of the present invention may further comprise (E) a radical polymerizable organic (meth) acrylate compound and Z or a radical polymerizable organic (meth) acrylamide compound, (F) It can contain at least one member of a group having a radically polymerizable group, (G) an organic epoxy compound, and (H) an organic oxetane compound.
  • organic (meth) ataretoy compounds and Z or (meth) acrylamide compounds include organic (meth) acrylate compounds having 1 to 2 (meth) acryl groups in one molecule and organic (meta) ) Prefer acrylamide compound.
  • Organic (meth) acrylate compounds and organic (meth) acrylamide compounds with 1 to 2 (meth) acrylic groups per molecule are preferred for adjusting viscosity and other physical properties.
  • Examples of (meth) atalytotoyl compounds having one (meth) acrylic group in one molecule include alkyl (meth) acrylates such as butyl methacrylate and stearyl acrylate, cyclohexyl acrylate and isobolites.
  • -Cycloaliphatic (meth) acrylates such as rumetatalylate, (meth) acrylate with aromatic ring, (meth) acrylate with hydroxy group, (meth) acrylate with polyalkylene glycol chain are preferred.
  • Butyl methacrylate is more preferred to alkyl (meth) acrylates such as stearyl aryl acrylate, and alicyclic (meth) acrylates such as cyclohexyl acrylate and isoborn methacrylate. Of course, this is not to exclude other things.
  • (meth) atareto toy compound having two (meth) acrylic groups in one molecule Preference is given to di (meth) acrylates of aliphatic or cycloaliphatic diols such as sundiol diatalylate, and polyalkylene glycol di (meth) acrylates such as polyethylene glycol diatalate. Of course, this is not to exclude other things.
  • Examples of (meth) acrylamide compounds having 1 to 2 (meth) acrylic groups in one molecule include alkyl (meth) acrylamides such as ethyl acrylamide and N, N dimethylaminopropyl acrylamide. Amaminoalkyl (meth) acrylamide is preferred. Of course, this is not to exclude other things.
  • the content of (E) can be appropriately determined according to the type thereof. 90% by mass or less of the sum of the polymerizable components (A) and (B) is preferred, and 10 to 80% by mass is more preferred.
  • the polymer having a radically polymerizable group is preferably a (meth) acrylate polymer other than (A) having a radically polymerizable group such as an attalyloyl group or a methacryloyl group in the side chain, such as It is a copolymer of a polymer and another radical polymer monomer such as styrene.
  • glycidinoaretalylate glycidinoremethacrylate, 3, 4 epoxy cyclohexyl acrylate, 3, 4 epoxy cyclohexyl methacrylate, 3, 4-epoxycyclohexyl methyl acrylate, 3 , 4
  • a polymer obtained by adding (meth) acrylic acid to a polymer obtained by polymerizing epoxycyclohexylmethyl metatalylate as a main component, and having a (meth) acryloyl group in the side chain is preferred. Of course, nothing other than these is excluded.
  • the content of (F) is preferably a force that can be appropriately determined according to the type thereof, and is preferably 60% by mass or less of the sum of the polymerizable components of (A) and (B), more preferably 0 to 40% by mass.
  • Organic epoxy compounds include compounds having two or more epoxy groups in one molecule, compounds having one epoxy group in one molecule, and compounds having both an epoxy group and a (meth) atalyloyl group in one molecule. preferable.
  • the compound power having two or more epoxy groups in one molecule.
  • a compound having one epoxy group in one molecule is preferred.
  • the compound having two or more epoxy groups in one molecule include bisphenol epoxide hydrates and their respective hydrides, novolac type epoxy hydrates and their respective hydrides, aromatic amine amine di-polyepoxy compounds, Other bifunctional to polyfunctional epoxy compounds are listed as preferred examples, but are not limited thereto.
  • the compound having one epoxy group in one molecule for example, phenyl glycidyl ether, butyl daricidyl ether, etc. are preferred, and the power that can be mentioned as an example is not limited thereto.
  • Polymers having two or more epoxy groups in one molecule include glycidyl atylate, glycidinoremethalate, 3,4-epoxycyclohexenorea taleate, 3,4 epoxycyclohexylmethalate, 3, 4 Epoxy cyclohexyl methyl acrylate, 3, 4—Epoxy cyclohexyl methyl methacrylate
  • the polymer that has been polymerized as a main component Power that can be cited as a preferred example It is not limited to these .
  • Examples of compounds having an epoxy group and a (meth) atalyloyl group in one molecule include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3, 4 Epoxy cyclohexyl methyl acrylate, 3, 4 Epoxy cyclohexyl methyl methacrylate, or partial (meth) acrylic acid adducts of polymers polymerized with these as main components U, for example It can be mentioned, but is not limited to these.
  • the content of (G) can be appropriately determined according to the type thereof.
  • the content of (A) and (B) is preferably 30% by mass or less of the sum of the polymerizable components, and more preferably 0 to 20% by mass.
  • organic oxetane compounds include a series of oxetane compounds (for example, EXOA and derivatives thereof, XDO) that are available from Toagosei Co., Ltd., and those described in JP 2001-40205 A!
  • EXOA and derivatives thereof, XDO oxetane compounds
  • XDO XDO
  • a polymer having a side chain is preferred, and examples thereof include, but are not limited to.
  • (H) is a force that can be appropriately determined depending on the type thereof.
  • (A) 30% by mass or less of the sum of the polymerizable components of (B) is preferred, and 0 to 20% by mass is more preferred.
  • composition of the present invention includes Sarako, UV absorber (I), hindered amine light stabilizer C, Antistatic agent (K), slipperiness imparting agent (L), antifogging imparting agent (M) and peelability imparting agent (N) At least one of the following groups can be contained.
  • UV absorber (I) is hindered amine light stabilizer CF
  • the weather resistance is remarkably improved, which may be preferable.
  • Preferred examples of the ultraviolet absorber (I) include benzotriazole, benzophenone, salicylic acid, cyanoacrylate, and triazine ultraviolet absorbers.
  • hindered amine light stabilizer (J) for example, ⁇ ⁇ ⁇ -methyl isomers such as Sanol LS765 are preferable, but ordinary ⁇ - isomers such as LS-770 may be used.
  • the compounding amount varies depending on the desired weathering resistance level. In many cases, 0.5 to 30 parts by mass is preferable with respect to 100 parts by mass of the sum of ( ⁇ ) to ( ⁇ ). 10 parts by mass is more preferable.
  • the composition of the present invention includes an antioxidant (for example, a hindered phenol-based, sulfur-based, phosphorus-based anti-oxidation agent, etc.), an anti-blocking agent, and a slip agent for the purpose of improving the physical properties of the coating film.
  • an antioxidant for example, a hindered phenol-based, sulfur-based, phosphorus-based anti-oxidation agent, etc.
  • an anti-blocking agent for the purpose of improving the physical properties of the coating film.
  • Various additives that are blended in this type of stain resistance imparting agent such as a leveling agent may be blended.
  • the amount of this case is preferably 0.01 to 2 mass 0/0.
  • the total amount of (Bi) and (Bii) above is usually 0 to 20000 parts by mass with respect to 100 parts by mass of the organic polymer ( ⁇ ).
  • the total amount of (Bi) and (Bii) is 500 parts by mass or more with respect to (A) 100 parts by mass.
  • the amount is 500 parts by mass or more, the hardness can be further increased, and the curing shrinkage can be reduced and the warpage can be further suppressed.
  • the total amount of (Bi) and (Bii) is 10000 parts by mass or less with respect to (A) 100 parts by mass. It is preferable that In general, (Bi) is preferably 30% by mass or more, more preferably 50% by mass or more based on the total amount of (Bi) and (Bii)! /.
  • a part of (A) may be replaced with (Ai).
  • the total amount of (A) and (Ai) It is preferable to set the amount to 80% by mass or more, and more preferably 90% by mass or more.
  • the composition of (Ai) is large. For example, 80 masses of (Ai) with respect to the total amount of (A) and (Ai). It is more preferable to set it to 90% by mass or more.
  • the total amount of the cationic polymerizable photoinitiator (C) and the radical polymerizable photoinitiator (D) is The amount is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. By setting the content to 0.5 parts by mass or more, higher hardness can be obtained.
  • the upper limit is not particularly defined, but is usually 20 parts by mass or less, preferably 10 parts by mass or less.
  • the total amount of the compound (E), the radically polymerizable polymer (F), the organic epoxy compound (G) and the organic oxetane compound (H) is preferably 70 parts by mass or less, and preferably 30 parts by mass or less. More preferred.
  • UV absorber (1) hindered amine light stabilizer CO, antistatic agent ( ⁇ ), slipperiness for 100 parts by mass of total amount of (A), (Ai), (Bi), (Bii)
  • the total amount of the agent (L), the antifogging agent ( ⁇ ) and the release agent ( ⁇ ) is preferably 30 parts by mass or less, more preferably 10 parts by mass or less.
  • part of ( ⁇ ) and (Ai) can be replaced with (F) or (G).
  • (Bi) and (Bii) can be replaced by (E).
  • the total amount of (E), (F), and (G) is 30 parts by mass with respect to 100 parts by mass of the total amount of (A), (Ai) ⁇ (Bi) 100 (Bii). Preferred to be below.
  • a cured product obtained by polymerizing the composition of the present invention by irradiation with active energy rays is excellent in properties such as stain resistance and hardness.
  • An article having on its surface a film obtained by polymerizing the composition of the present invention by irradiation with active energy rays is excellent in properties such as stain resistance and hardness.
  • the composition After the composition is applied to the surface of the article, it may be polymerized by irradiating with active energy rays, or a polymerized film by irradiating with active energy rays may be separately produced and then laminated on the article.
  • the application method is not particularly limited, but preferred examples include dip coating, flow coating, spin coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, and the like. Can be mentioned.
  • composition on the substrate After coating the composition on the substrate, it is dried to remove the solvent to form a coating film, and then polymerized by irradiation with an active energy line to obtain a cured film.
  • the type, source, and irradiation method of the active energy ray are not particularly limited, but ultraviolet rays that can emit light such as xenon lamp, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp, etc.
  • An electron beam, ⁇ -ray, j8-ray, ⁇ -ray, etc. extracted from a 20 to 2000 kV particle accelerator can be used.
  • Ultraviolet rays are preferably used because they are easy to handle and do not require complicated equipment.
  • the cured film has an excellent balance between productivity and physical properties.
  • curing refers to curing by irradiating active energy rays. Unless otherwise specified, curing is usually performed in an oxygen concentration atmosphere.
  • the thickness of a film obtained by coating, polymerization and curing is not particularly limited as long as it is appropriately selected according to the purpose.
  • the composition of the present invention is excellent in that both thinning and thickening are possible.
  • the composition may be 5 ⁇ m or more, or 2 ⁇ m or less.
  • the film thickness after curing is 0.01 m or more. This is to obtain sufficient contamination resistance and hardness. More preferably, it is 0.04 / z m or more, and still more preferably 0.0. Particularly when hardness is important, 0.5 m or more is preferable, and 1 m or more is more preferable.
  • the film thickness is preferably 200 m or less. This is because the hardness of the film tends to decrease even if it is too thick, and warpage and distortion due to curing shrinkage are suppressed. More preferably, it is 100 micrometers or less, More preferably, it is 50 micrometers or less.
  • a cured product (including a film formed on an article) obtained by polymerizing and curing the composition of the present invention with active energy rays preferably satisfies the following physical properties.
  • the composition of the present invention is applied to a 100 ⁇ m thick PET film so that the film thickness after curing is 5 ⁇ m, and the pencil hardness of the cured film is preferably HB or more. More preferably, it is F or more. Pencil hardness is 6 ⁇ , 5 ⁇ , HB, F, ⁇ 2H, 3H, ... 9 ⁇ .
  • an easily adhesive film (ultraviolet curable resin easily adhesive film) is used as the PET film.
  • the pencil hardness of a cured film that has been applied to a 100 / zm-thick PET film at a film thickness of 10 m after curing is 3H or more. It is preferable that
  • the composition of the present invention was applied to a 100 ⁇ m thick PET film so that the film thickness after curing was 5 ⁇ m, and the cured film imparted stain resistance at a position where the surface force of the film was 3 nm.
  • the group content is preferably at least 3 times the average content of the stain resistance-imparting group in the entire membrane. That is, it is preferable that the stain resistance-imparting group is present at a high concentration specifically on the surface of the film.
  • One of the characteristics of the composition of the present invention is that such a constitution can be obtained. As a result, even if the content of the stain resistance imparting group in the composition is low, the amount of the stain resistance imparting group on the coating film surface is low. As a result, the contamination resistance of the film becomes excellent. More preferably, it is 3.2 times or more, more preferably 3.5 times or more. However, it is usually 100 times or less.
  • the stain resistance imparting group means a group capable of imparting stain resistance, such as a perfluoroalkyl group, a polysiloxane group, and a long chain alkyl group having 12 or more carbon atoms.
  • the average content of the antifouling group in the entire film can be calculated, for example, as the average composition specific power of the composition.
  • the content of the stain resistance-imparting group in the film can be determined, for example, by measurement with an X-ray photoelectron spectrometer (hereinafter referred to as ESCA). In other words, the number ratio of atoms in the range of 3 nm from the surface can be obtained using ESCA.
  • compositions of the present invention 100 / zm when irradiated with ultraviolet rays was applied using cured thickness after 0. 5 / zm thick PET film, cured until complete tack-free ultraviolet irradiation amount of 300MiZcm 2 Preferably proceeds.
  • the curing proceeds until tack-free with an ultraviolet irradiation amount of 150 mjZcm 2 .
  • the amount of warpage of a cured film obtained by applying the composition of the present invention to a PET film having a thickness of 5 ⁇ m after being cured on a 100 ⁇ m-thick PET film and curing in a normal oxygen concentration atmosphere is preferably 10 mm or less. . More preferably, it is 2 mm or less, and more preferably 1 mm or less.
  • the cured film obtained by applying the composition of the present invention to a PET film having a thickness of 5 ⁇ m after curing on a PET film having a thickness of 100 ⁇ m and curing in a normal oxygen concentration atmosphere should have an abrasion resistance of 25.0 or less. I like it.
  • the haze value of a cured film obtained by applying the composition of the present invention to a 100 ⁇ m thick PET film at a film thickness of 5 ⁇ m after curing is preferably 1.5% or less.
  • the fingerprint can be completely removed by a wiping operation within 3 reciprocations. Is preferred. More preferably, it is within 2 round trips. It is also one of the characteristics of the composition of the present invention that it has surface characteristics with excellent fingerprint removability.
  • Fingerprint resistance and durability it is preferable that fingerprint removability does not deteriorate even if fingerprints or artificial fingerprint liquid is adhered, and the 200 g load is repeated 3 times with tissue paper and the wiping operation is repeated 20 times.
  • the composition of the present invention has a high hardness after curing and prevents the stain resistance-imparting group from being fixed in the polymer and removed from the film surface. For this reason, even if the wiping operation is repeated several tens of times, it is possible to prevent fine stains on the surface !, scratches and dirt, and the loss of surface resistance of the stain resistance imparting agent can be prevented. High durability. More preferably, even if the above operation is repeated 40 times, the fingerprint removability is not lowered.
  • Conventional anti-fingerprinting agents for optical recording media and optical displays generally have, for example, a small amount of dirt and a small adhesion diameter, and excellent anti-adhesion properties. Due to lack of hardness, dirt tends to spread on the surface, and there was a tendency for dirt to be removed unless the number of wipes was increased. According to the composition of the present invention, since the hardness after curing is high and there is no excessive slip, there is an advantage that it can be wiped off with a small number of times of wiping.
  • the cured film of the present invention can be applied to various articles.
  • optical recording media optical displays, transparent films for agricultural greenhouses (contamination resistance is necessary because sunlight needs to be taken in effectively)
  • Surface protection transparent film for solar cells contamination resistance is required to prevent battery efficiency degradation
  • transparent film for retroreflective sign surface protection headlamp lights and even relatively dark light from outside light
  • transparency and anti-contamination function are required
  • optical lenses optical prisms, prism sheets, automobile window materials, building window materials, eyeglass lenses, etc.
  • the composition of the present invention is coated, dried and cured on various substrates to form a hard coat layer.
  • the type of base material is not particularly limited, but a base material made of resin is also preferred because of its high adhesiveness.
  • the resin base material may be any of a plate shape, a sheet shape, and a film shape, and may be a molded product having an arbitrary shape. Further, another layer may be interposed between the substrate and the cured film, which may be a part of the laminate.
  • the resin base material may be a thermoplastic resin, or a hard resin cured by heat or active energy rays. It may be a coconut oil.
  • thermoplastic resin examples include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), methyl methacrylate (MMA) -containing copolymers (methyl methacrylate-styrene copolymer resin (MS resin)), polycarbonate (PC), triacetyl cellulose, acrylonitrile butadiene styrene copolymer (ABS resin), modified polyolefin resin, fluorine resin (for example, vinylidene fluoride resin (PVDF), fluorine Hydrogenated polystyrene resin, cycloolefin-based resin (for example, Arton manufactured by SR, ZEONEX manufactured by ZEON, ZEONOR, Abel manufactured by Mitsui Chemicals, Inc.), and the like.
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • cured resin examples include epoxy resins, urethane resins, cured products of thermosetting and photocurable acrylic resins, and cured products such as thermosetting and photocurable organic-inorganic hybrid resins. Is mentioned.
  • These base materials may be, for example, films formed by coating themselves or molded products obtained by various molding methods.
  • the cured film of the present invention is excellent in transparency, stain resistance and hardness, it is highly effective when applied to optical articles that require high transparency.
  • the substrate needs to be transparent, it is desirable that the substrate is formed by any of the coating method, the melt extrusion method, and the solvent cast method.
  • the substrate contains a functional group that can be cured by active energy ray light or heat, it may be more preferable to cure by irradiation with active energy ray or heating.
  • the term “transparent” generally means that the transmittance of light having a target wavelength is 80% or more.
  • the cured film of the present invention can also be suitably used as a stain-proof layer or a coated layer of an optical recording medium.
  • a typical optical recording medium is an optical disk, but the type may be any of a phase change type, a dye type, a magneto-optical type, a read-only type, and the like. Above all, it is an optical disc for high density recording such as DVD, HD DVD, Blu-Ray Disc. In order to increase the recording density, the recording mark and the recording Z playback laser beam diameter are both small, so it is sensitive to dirt and scratches and jitter. There is a need for a hard coat layer with excellent anti-contamination and hardness that makes it easy to increase the height and record Z playback errors.
  • a preferred configuration is an optical recording medium having a multilayer film having at least a recording layer or a reflective layer on a substrate, and a configuration having at least the outermost surface on the light incident side of the optical recording medium. It is. If there is dirt or scratches on the outermost surface on the light incident side, the recording Z reproduction beam is blocked and an error occurs. Therefore, it is preferable to provide the cured film of the present invention on the outermost surface on the light incident side as a stain-resistant node coat layer. .
  • the hard coat layer needs to be light transmissive.
  • the light transmissive property generally means a state where the transmittance is 80% or more with respect to the light having the wavelength of the recording Z reproduction light.
  • the cured film of the present invention may be provided on the outermost surface opposite to the light incident side.
  • a preferable layer structure of such an optical recording medium has a (reflection layer) recording layer and a hard coat layer (cured film) in this order on a substrate. More preferably, a light transmission layer is provided between the recording layer and the hard coat layer. Providing a light transmission layer is preferable because the distance between the outermost surface on the light incident side of the optical recording medium and the recording layer (reflective layer) is increased, and the recording Z reproduction beam is affected by dirt and scratches on the medium surface. .
  • the thickness of the light transmission layer is preferably 30 m or more, more preferably.
  • the thickness of the light transmission layer is preferably 200 m or less, and more preferably 150 m or less.
  • Arbitrary layers may be provided between the respective layers according to the purpose.
  • an inorganic protective layer such as a dielectric may be provided above and below the recording layer.
  • a plurality of recording layers and reflection layers may be provided through a single light transmission spacer.
  • the light transmissive spacer layer is provided to prevent mixing of signals between a plurality of recording layers, and the film thickness is preferably the same as that of the light transmissive layer.
  • Examples of particularly preferred layer configurations include: substrate Z reflective layer Z inorganic protective layer Z recording layer Z inorganic protective layer Z light transmissive layer Z hard coat layer, substrate Z reflective layer Z light transmissive layer Z hard coat layer Substrate configuration, substrate Z reflective layer Z inorganic protective layer Z recording layer Z inorganic protective layer Z light transmissive spacer layer Z reflective layer Z inorganic protective layer Z recording layer Z inorganic protective layer Z light transmissive layer Z hard coat layer
  • the substrate Z inorganic protective layer Z recording layer Z inorganic protective layer Z light transmitting layer Z hard coat layer, and the like are preferred. The force is not limited to these.
  • the materials of the substrate, recording layer, reflective layer, and inorganic protective layer are not particularly limited, and known and / or misaligned materials can be used for optical recording media.
  • the substrate it is possible to use polycarbonate, polyacrylate, polyolefin, or the like, or glass.
  • the substrate When recording / reproducing light is incident from the substrate side, the substrate must be transparent to the recording Z reproducing light.
  • the thickness of the substrate is usually 0.3 to 1. In many cases, groups (grooves) and pits are formed on the substrate.
  • the recording layer includes a phase change type, a dye type, and a magneto-optical type.
  • the read-only type may not have a recording layer.
  • chalcogen alloys are often used, and examples thereof include GeSbTe alloys, InSbTe alloys, GeSnTe alloys, and AglnSbTe alloys.
  • the thickness of the phase change recording layer is usually 3 ⁇ ! ⁇ 50nm.
  • azo dyes, cyanine dyes, phthalocyanine dyes, porphyrin dyes and the like can be used, but are not limited thereto.
  • the thickness of the dye-type recording layer is usually 50 ⁇ ! ⁇ 10 m.
  • the material of the inorganic protective layer is determined in consideration of the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, and the like, and usually a dielectric is used.
  • a dielectric is used as the material for the inorganic protective layer.
  • oxides, sulfides, oxysulfides, nitrides, and fluorides such as Ca, Mg and Li, which are transparent and have a high melting point.
  • the thickness of the inorganic protective layer is usually about 5 to 200 nm.
  • the reflective layer is preferably made of a material having high reflectance and thermal conductivity.
  • the reflective layer material having high reflectivity and thermal conductivity include metals mainly composed of Ag, Au, Al, Cu and the like. Above all, Ag has higher reflectivity and thermal conductivity than Au, Al, and Cu. These include Cr, Mo, Mg, Zr, V, Ag, In, Ga, Zn, Sn, Si ⁇ Cu, Au, Al, Pd, Pt, Pb, Ta, Ni, Co, 0, Se, V Nb, Ti, 0, N, etc. may be contained up to about 5 atomic%.
  • the thickness of the reflective layer is usually 30 to 200 nm.
  • the reflective layer is a so-called semi-reflective layer. May be.
  • the light transmissive layer and the light transmissive spacer layer are not particularly limited as long as they are light transmissive and have a predetermined thickness.
  • a resin composition is usually used, and is typically as follows. Formed in two ways.
  • the first method is a method in which a curable resin composition is applied by spin coating or the like and then cured by light or heat to form a film.
  • inorganic oxide fine particles such as colloidal silica as long as the light transmittance is not impaired in order to increase the surface hardness and scratch resistance.
  • the second method is a method in which a film produced by solvent casting or melt extrusion molding is applied directly or via an adhesive. At this time, in order to further increase the surface hardness and scratch resistance, it is preferable to contain inorganic oxide fine particles such as colloidal silica as long as the light transmittance is not impaired. In some cases, groups (grooves) or pits are formed in the light transmitting spacer layer.
  • a general method is to form a cured film by applying an active energy ray on a layer as described above and applying it by spin coating.
  • the film side is affixed directly or via an adhesive to the optical recording medium, and the film is peeled off to form a hard coat layer
  • a method is also preferred.
  • a cured film obtained by polymerization by irradiation with active energy rays is applied directly or via an adhesive.
  • a method of forming the light transmission layer and the hard coat layer at the same time by pasting to an optical recording medium is also preferable.
  • optical recording medium having such a layer structure examples include a Blu-Ray Disc.
  • a preferred layer structure of such an optical recording medium has a recording layer (reflection layer) on the substrate in this order, and a hard coat layer on the other surface of the substrate. Recording Z reproduction light enters the recording layer and the reflective layer through the hard coat layer and the substrate.
  • a light transmission layer may be provided between the substrate and the hard coat layer.
  • Arbitrary layers may be provided between the respective layers according to the purpose. For example, an inorganic protective layer such as a dielectric may be provided above and below the recording layer. Further, in order to increase the recording capacity, a plurality of recording layers and reflection layers may be provided through one light transmission spacer.
  • Examples of particularly preferred layer configurations include hard coat layer Z substrate Z inorganic protective layer Z recording layer Z inorganic protective layer Z reflective layer, hard coat layer Z substrate Z reflective layer, and hard coat layer Z substrate Z inorganic protective layer Layer Z recording layer Z inorganic protective layer Z reflective layer Z light transmissive spacer layer Z inorganic protective layer Z recording layer Z inorganic protective layer Z reflective layer, hard coat layer Z light transmissive layer Z substrate Z inorganic protective layer Z recording layer Z Inorganic protective layer Z Reflective layer, etc.
  • the preferred force is not limited to these.
  • each layer is preferably the same as (1).
  • the optical recording medium having such a layer structure there are various DVDs (including a DVD having a plurality of recording layers) such as DVD ⁇ R, DVD player RW, DVD-R AM, and HD DVD.
  • the formation method of the hard coat layer in this configuration is generally a method in which the composition of the present invention is applied onto a substrate or the like by a spin coat method or the like and then polymerized and cured by irradiation with active energy rays to form a film.
  • composition of the present invention can also be suitably used for optical display applications.
  • it is preferable as an agent for imparting stain resistance to the surface of flat panel displays (liquid crystal displays, plasma displays, rear projection displays, front projector screens, inorganic EL displays, organic EL displays, etc.), and in particular car navigation systems.
  • It can be preferably used as a hard coat layer on the surface of a display having a touch panel input function in a system, a mobile phone, a mopile information terminal (such as a PDA), or a PC monitor.
  • composition of the present invention When the composition of the present invention is applied to a laminate used in such a display, a transparent resin base material is used, and this composition is applied to at least one outermost surface of the laminate so that the active energy line is aligned. It is preferable to form a cured film formed by irradiation and polymerization.
  • a cured product obtained by polymerizing the composition of the present invention by irradiation with active energy rays is excellent in properties such as stain resistance and hardness.
  • the article is excellent in properties such as stain resistance and hardness. After the composition is applied to the surface of the article, it may be polymerized by irradiating with active energy rays, or a film that has been polymerized by irradiating with active energy rays may be laminated on the article.
  • part and% in an example mean a mass part and mass%, respectively.
  • Pencil hardness Using a JIS-compliant pencil hardness meter (manufactured by Dazai Equipment Co., Ltd.), measurement was performed based on the conditions of JIS K-5400, and the hardness was indicated by the hardest pencil number without scratches.
  • Coating film adhesion Tested by a grid pattern method described in JIS K-5400. Here, 100 grids were placed at 1 mm intervals and tested with cellophane tape (manufactured by Ciba). For the evaluation method, the same operation was repeated 5 times (cellophane tape was always new and used), and no scratch or peeling occurred at all. Measurements were evaluated by changing the method to ⁇ for the resulting product and X for the others.
  • Fingerprint wiping property (1 1) The nasal oil was used as a substitute for sebum, the nasal oil was placed on the thumb, and the thumb was pressed against the coating film for 3 seconds to attach the fingerprint to the coating film. The surface of the fingerprint was gently wiped with tissue paper (manufacturer: Cressia), and the number of reciprocations until it became visually invisible at a distance of 15 cm was defined as the fingerprint wiping property (11).
  • Fingerprint wiping property (150) The above-described fingerprint wiping property (11) was repeated on the same coating, and the number of repetitions was repeated up to the 50th. In the 50th operation, gently wipe the surface of the fingerprint with tissue paper (manufacturer: Crescia) and visually observe it at a distance of 15 cm. The number of round trips until it disappeared was defined as the fingerprint wiping property (11).
  • the fingerprint wiping property (1 1) and the fingerprint wiping property (1 50) are the same number of reciprocations, the fingerprint wiping repeatability is excellent.
  • Fingerprint wiping property (2) The surface of the coating film was rubbed 100 times with an eraser, and then evaluated in the same manner as the fingerprint wiping property (11).
  • Fingerprint wiping durability under high load The nasal oil was used as a substitute for sebum, the nasal oil was applied to the thumb, and the thumb was pressed against the coating for 3 seconds to attach the fingerprint to the coating.
  • the operation of wiping the fingerprint with a tissue paper (manufacturer: Crescia) with 200g weight was performed 3 times. This operation was repeated up to the 20th. After the 20th operation, it was marked as ⁇ if it was not visible visually at a distance of 15 cm, and X if visible. This is a durability test under a higher load than (6).
  • the artificial fingerprint liquid was spin-coated on a polycarbonate substrate at 3000 rpm and dried at 60 ° C for 3 minutes to produce an artificial fingerprint liquid master.
  • the end face of the silicone rubber plug (No. 1) with the smaller diameter was uniformly roughened with # 240 abrasive paper to obtain a transfer material.
  • the transfer material is pressed onto the master with a constant load of 4.9 N for 10 seconds, and then pressed against the surface of the coating film with a constant load of 4.9 N. This is operation L1.
  • the adhesion diameter of the artificial fingerprint liquid on the surface of the coating film is visually observed with a microscope with a scale of 100 times, and the operation Ln that maximizes ⁇ in the range where the maximum adhesion diameter is 20 ⁇ m or less. Made with artificial fingerprint liquid adhesion resistance.
  • the adhesion resistance of the artificial fingerprint liquid is preferably L3 or L4, more preferably L4.
  • Slip property evaluation The dynamic friction coefficient between the coating film surfaces was determined by a method based on JIS K-7125. If the dynamic friction coefficient obtained by this method is 0.2 or less, the slip property is high, if it is 0.5 or less, the slip property is high, and if it is 1.0 or more, the slip property is low. I prefer that the slip is too high.
  • the wiping feeling evaluation of (13) is ⁇
  • the slipping evaluation of (12) is the dynamic friction between the coated surfaces. It is desirable that the coefficient is 1.0 or more.
  • Synthesis Example 1 Synthesis of organic polymer (a-1) within the scope of the present invention
  • Mercapto group Z epoxy group 0.008 (mol Z mol).
  • Synthesis Example 2 Synthesis of organic polymer (a-2) within the scope of the present invention
  • Mercapto group Z epoxy group 0.012 (mol Z mol).
  • V65 was divided into two portions, a total of 1.5 g was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., and V65 was completely deactivated. Then, the content mixture was returned to room temperature to obtain a reaction product containing the organic polymer (a-2). The solid concentration was about 34%.
  • Synthesis Example 3 Synthesis of organic polymer (a-3) within the scope of the present invention
  • the reaction product containing the organic polymer (a-2) obtained in Synthesis Example 2 was heated to 90 ° C in an air atmosphere, and then 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. added . After 5 minutes, 15.2 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90 to 105 ° C. Thereafter, the liquid temperature was raised to 110 ° C. and maintained at this temperature for 8 hours, and then returned to room temperature to obtain a reaction product containing the organic polymer (a-3). Solid content is 33%.
  • Synthesis Example 4 Synthesis of organic polymer (a-4) within the scope of the present invention
  • Mercapto group Z epoxy group 0.011 (mol Z mol).
  • V65 was divided into two portions, a total of 1.5 g was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated. Then, the content mixture was returned to room temperature to obtain a reaction product containing the organic polymer (a-4). The solid concentration was about 34%.
  • Perfluorooctyl methylate 18g, Methyl methacrylate 50g, ⁇ , ⁇ ⁇ 0.2 g of dimercaptopolydimethylsiloxane (number average molecular weight 1600), 30 g of cyclomer A400 (manufactured by Daicel) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream.
  • Mercapto group Z epoxy group 0.0015 (mol Z mol).
  • V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C. and V65 was completely deactivated. Then, the content mixture was returned to room temperature to obtain a reaction product containing the organic polymer (a-5). The solid concentration was about 34%.
  • Synthesis Example 7 Synthesis of organic polymer (a-7) outside the scope of the present invention
  • Synthesis Example 8 Synthesis of organic polymer (a-8) outside the scope of the present invention
  • Synthesis Example 10 Synthesis of organic polymer (a-10) outside the scope of the present invention
  • Methyl metatalylate 70 g and cyclomer M100 (manufactured by Daicel) 30 g MEK 200 g were added, and the internal temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., and V65 was completely deactivated. Then, the content mixture was returned to room temperature to obtain a reaction product containing the organic polymer (a-10). The solid concentration was about 34%. This product has no perfluoroalkyl groups and no polysiloxane groups.
  • ⁇ , ⁇ -dimercaptopolydimethylsiloxane (number average molecular weight 1600) 0.3g, polyethylene glycol monoatalylate 9.7g, methylmetatalylate 60g, cyclomer M100 (manufactured by Daicel) 30g, MEK200g,
  • the internal temperature was raised to about 60 ° C under a nitrogen stream. After that, V65 was divided into 2 times, 1.5 g in total was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., and V65 was completely deactivated. Then, the content mixture was returned to room temperature to obtain a reaction product containing an organic polymer (a-11). The solid concentration was about 34%. This product does not have a perfluoroalkyl group.
  • Synthesis Example 12 Synthesis of silane coupling agent having polyfunctional acrylic group by reaction of OH-containing polyfunctional acrylate and NCO-containing silane coupling agent
  • Synthesis Example 13 By reaction of colloidal silica with a silane coupling agent having a polyfunctional acrylic group, the surface of inorganic oxide fine particles was bonded to the surface of (M) talylol group via —O—Si—R— bond. Of inorganic oxide fine particles (b— 1)
  • MEK-dispersed organosilica sol (Nissan Chemical, MEK-ST, 30% MEK solution) 400g, 400g of the above SCI, hydroquinone monomethyl ether 0.4g, acetylylacetone aluminum 4g well stirred and mixed, then pure water 8g And stirring was continued for 3 hours or more at room temperature. After that, the temperature is raised to 50 to 70 ° C. in an air atmosphere, and stirring is continued for 2 hours or more at that temperature, and the surface of the silica sol is reacted with a silane coupling agent to form a protective colloid, and the target inorganic oxide is obtained. Fine particles (b-1) were obtained.
  • Synthesis Example 14 A (meth) attalyloyl group is bonded to the surface of inorganic oxide fine particles through —O—Si—R— bond by reaction between colloidal silica, silane-terminated polymer having acrylic group and colloidal silica. Synthesis of inorganic oxide fine particles (b-2)
  • Synthesis Example 15 The surface of an inorganic oxide fine particle by a reaction between colloidal silica, a silane-terminated polymer having an acrylic group and colloidal silica, via a (O) -Si-R- bond, (meth) attaroyl Synthesis of inorganic oxide fine particles (b-3) with bonded groups
  • Synthesis Example 16 By reaction of colloidal silica with a silane coupling agent having a polyfunctional acrylic group, the surface of inorganic oxide fine particles is bonded to a (meth) attalyl group via an O-Si-R- bond. Of inorganic oxide fine particles (b— 4)
  • PGMAc-dispersed organosilica sol (manufactured by Nissan Chemical Co., Ltd., PMA-ST, 30% PGMAc dispersion) 400 g of the above SCI, 400 g of hydroquinone monomethyl ether, 0.4 g of hydroquinone monoaluminum, and 4 g of acetylylacetonaluminum Stirring was continued at room temperature for 3 hours or more. Thereafter, the temperature is raised to 50 to 70 ° C. in an air atmosphere, and stirring is continued at that temperature for 2 hours or more. The surface of the silica sol is reacted with a silane coupling agent to form a protective colloid. b-4) was obtained.
  • Comparative Example 1 does not contain a ring-opening polymerizable group capable of cationic polymerization.
  • the coatings made of the composition of the present invention as shown in Examples 1 to 5 have high pencil hardness even in the case of single cured films (both F or higher), and the hardness is compared. It was confirmed that it was superior in hardness to the stain resistance imparting agent (polymer) other than the present invention as in Example 1.
  • a coating film was formed and evaluated in the same manner as in Example 1 except that the light power thione polymerization initiator was not added.
  • the composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • the cured film obtained in Comparative Example 2 was inferior in hardness as compared with the film of the present invention.
  • a coating film was formed and evaluated in the same manner as in Example 1 except that (a-1) was replaced with (a-10) and (a-11), respectively.
  • the composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • the cured films obtained in Comparative Examples 3 and 4 were inferior in hardness or contact angle compared to the film of the present invention! /.
  • the solid content of (b-1) was 90 parts, Irgacure 250 1 part, Irgacure 184 2 parts, and PGM to adjust the solids concentration to 40%.
  • a 125 m thick polymethylmethacrylate (PMMA) film (Mitsubishi Rayon, haze value 0.2%) was applied to a thickness of 1.8 m after drying, and then dried at 80 ° C. The solvent was removed to form a dry film. This was cured using a high-pressure mercury lamp with an output density of 120 WZcm, and the coating film was evaluated.
  • the composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • a coating solution having the composition shown in Table 1 was prepared, applied on each substrate so as to have the thickness after drying shown in Table 1, dried and cured in the same manner as in Example 6, and evaluated.
  • composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • Comparative Examples 5 and 6 are examples (Examples 6, 7, 9, 17) in which the same components are used for the other components (components (B), (C), (D)). ) And the like were inferior in hardness and transparency (haze).
  • composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • the antifouling property of this coating film was evaluated by a method in accordance with the type I antifouling material promotion test for civil engineering (however, the composition of the test solution was changed to 95% water and 5% carbon black). .
  • the brightness difference AL * was -0.0, which was excellent in antifouling property.
  • AL * indicates that the larger the value of 1, the more dirty it is, and it is said that the performance standard of the test is usually met at 7.00 or higher.
  • AL * is 0.1 and excellent antifouling property is maintained even after 500 hours, and the antifouling property is also excellent. I was able to confirm.
  • UV9300 epoxy side chain containing silicone, made by Toshiba GE silicone
  • toluene 20 After diluting to a% concentration, a coating film was prepared in the same manner as in Example 1 except that 3 parts of Irgacure 250 was added to 100 parts of the solid content of UV9300.
  • TP Tinubin P: UV absorber, manufactured by Ciba Specialty Chemicals
  • PET Polyethylene terephthalate film, Mitsubishi Chemical Polyester Film T600E
  • PC Polycarbonate film, GE Lexan film, thickness 500 / z m (Haze 0.2%)
  • PMMA Polymethylmethacrylate film, made by Mitsubishi Rayon, thickness 125 m (Haze 0.2%)
  • Example 1 1.0 H 111 53 ⁇
  • Example 2 1.1 F 109 46 ⁇
  • Comparative Example 6 1.1 H 110 61 o
  • the durability of the stain resistance (fingerprint resistance) of the coating films obtained in Examples 1 to 17 and Comparative Examples 1 to 7 was evaluated. Specifically, fingerprint wiping property (1-1), fingerprint wiping property (150), fingerprint wiping property (2), fingerprint wiping durability, and wiping feeling were evaluated. The results are shown in Table 3.
  • the coating films of Examples 1 to 17 were able to substantially wipe off the attached fingerprints with one or two reciprocations of tissue paper and had excellent fingerprint wiping properties.
  • the fingerprint attachment and wiping operation is performed after rubbing 100 times with an eraser, the original wiping feeling (slippery when wiping off, can be wiped off with a slight rubbing) will not be impaired. Excellent durability.
  • the coating films of Comparative Examples 1 to 7 are inferior in both the fingerprint wiping property (1 1) and the fingerprint wiping property (1 50). Most of them needed more than recovery. In addition, the fingerprint wiping property (1 50) was greater than the fingerprint wiping property (1 1), and thus the fingerprint wiping durability was inferior.
  • the FZC (fluorine Z carbon ratio) of the coating film of Example 1 was measured with ESCA (Shimadzu Corporation ESCA1000).
  • Example 18 (1 -1) (1 -50) (2) Durability Example 1 1 1 1.5 oo Example 2 1.5 1.5 1.5 ⁇ o Example 3 1.5 1.5 1.5 oo Example 4 1 1 1 1.5 0 o Example 5 1 1 1.5 o ⁇ Example 6 1.5 1.5 1.5 oo Example 7 2 2 ⁇ ⁇ Example 8 2 2 oo Example 9 2 2 2 ⁇ ⁇ Example 10 2 2 oo Example 1 1 1.5 1.5 1.5 ⁇ o Implementation Example 1 2 2 2 2 oo Example 13 2 2 2 oo Example 14 2 2 2 ⁇ ⁇ Example 1 5 2 2 2 ⁇ ⁇ Example 16 1.5 1.5 1.5 oo Example 17 2 2 2 oo Comparative Example 1 6 8 10 X ⁇ Comparative Example 2 2.5 5 6 X ⁇ Comparative Example 3 8 10 10 XX Comparative Example 4 5 6 6 X 0 Comparative Example 5 4 7 6 X ⁇ Comparative Example 6 4 6 6 X ⁇ Comparative Example 7 4 F 8 XO [0082] Example 18 to Example 21, Comparative Example 8 to Comparative Example 11
  • a radical polymerizable active energy ray curable material having the following composition After applying a radical polymerizable active energy ray curable material having the following composition to the surface of the first dielectric layer by a spin coating method, using a high pressure mercury lamp with an output density of 120 WZcm, irradiating with ultraviolet rays so as to obtain an integrated light quantity lOOOmjZcm 2 Then, a light-transmitting layer having a thickness of 98 m after curing was formed. The pencil hardness of this surface was 4B.
  • urethane acrylate oligomer one produced by reacting hydroxyethyl acrylate with an isocyanate-terminated oligomer obtained by adding isophorone diisocyanate to polytetramethylene glycol having an average molecular weight of 800 was used.
  • Isocyanuric acid EO-modified triatalylate used was Toagosei Co., Ltd. ALONIX M313.
  • This composition is applied onto the light transmission layer of the optical recording medium by a spin coating method to form a film, dried at 80 ° C., and after removing the solvent to produce a dried film, a high-pressure mercury lamp with an output density of 120 WZcm is used.
  • a high-pressure mercury lamp with an output density of 120 WZcm was used.
  • a hard coat layer having a thickness of 2.5 m after curing was produced.
  • transparency visually Evaluation
  • pencil hardness contact angle (water, hexadecane)
  • adhesion stain resistance
  • stain resistance artificial fingerprint liquid adhesion resistance, artificial fingerprint wiping resistance (1 1), artificial fingerprint wiping durability
  • evaluation of slip properties did. The results are shown in Table 5.
  • the node coat layers (Examples 18 to 21) prepared using the composition within the scope of the present invention have a high contact angle, so that they have excellent anti-adhesion properties and high dynamic friction coefficients, As a result of the high slip performance, it was excellent in wiping performance and wiping durability.
  • a node coat layer (Comparative Examples 8 to 11) prepared using a composition outside the scope of the present invention has a low contact angle with hexadecane and is inferior in adhesion resistance among stain resistance. Slip property is too high. For this reason, the fingerprint smear spreads when wiped off, and as a result, the wiping property and wiping durability are poor.
  • X— 22— 164A manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane having methacryloyl groups at both ends
  • KF— 412 Shin-Etsu Chemical, alkyl-modified silicone
  • KF945A Shin-Etsu Chemical, ether-modified silicone
  • Example 18 ⁇ F 109 47 o L4 2 ⁇ > 1.0
  • Example 1 9 ⁇ F 108 49 o and 4 2 ⁇ > 1.0
  • Example 20 ⁇ F 108 50 ⁇ L4 2 ⁇ > 1.0
  • Example 21 ⁇ F 109 51 o L4 2 ⁇ > 1.0
  • Comparative example 8 ⁇ F 102 38 o and 4 3.5 X 0.8
  • Comparative example 1 1 ⁇ F 106 34 o L3 6 X 0.5 Reference example 1-3
  • DVD-R120HC (DVD made by TDK), BD-RE135N (Blu-Ray Disc made by TDK), DVD—R HG (DVD made by Tatetsu Maxell), which are sales optical discs with a contamination-resistant hard coat film on the surface.
  • the contact angle and stain resistance were evaluated as Reference Examples 1 to 3, respectively. The results are shown in Table 6.
  • the contact angle to hexadecane was low, the adhesion resistance of the artificial fingerprint liquid was excellent, the wiping performance of the object exceeded 3 reciprocations, and the wiping durability was also low.

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