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WO2015060458A1 - Composition polymérisable contenant du perfluoropolyéther ayant un groupe hydroxyle - Google Patents

Composition polymérisable contenant du perfluoropolyéther ayant un groupe hydroxyle Download PDF

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Publication number
WO2015060458A1
WO2015060458A1 PCT/JP2014/078499 JP2014078499W WO2015060458A1 WO 2015060458 A1 WO2015060458 A1 WO 2015060458A1 JP 2014078499 W JP2014078499 W JP 2014078499W WO 2015060458 A1 WO2015060458 A1 WO 2015060458A1
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group
poly
hard coat
meth
film
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English (en)
Japanese (ja)
Inventor
将幸 原口
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present invention relates to a polymerizable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as a touch panel display and a liquid crystal display.
  • a large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized.
  • a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM.
  • smartphones and tablet PCs the number of capacitive touch panels having a multi-touch function is rapidly increasing.
  • Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface.
  • a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
  • polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator.
  • the acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity.
  • a means for forming a hard coat layer on the surface of the plastic film for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, and the organic solvent is dried and then cured by ultraviolet rays. Then, a means for forming a hard coat layer is employed.
  • the thickness of the hard coat layer is usually 5 to 10 ⁇ m.
  • the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired.
  • the fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
  • the touch panel display of many smartphones employs a multi-touch function, which allows you to use multiple fingers to expand (pinch out) or reduce (pinch in) the screen, or to flick a finger in a certain direction on the screen. And swipe operation.
  • Patent Document 2 A technique using a compound having a (meth) acryloyl group as a surface modifier via a urethane bond having a hexamethylene skeleton at the other end is disclosed (Patent Document 2).
  • a compound having (meth) acryloyl groups at both ends of a poly (oxyperfluoroalkylene) chain is used as a surface modifier.
  • the compound has a problem that the poly (oxyperfluoroalkylene) chain is immobilized at both ends, so that the compound loses flexibility and is inferior in slipperiness.
  • the above compounds have a structure having (meth) acryloyl groups at both ends via a urethane bond having an isophorone skeleton or a tolylene skeleton, etc., but these rigid skeletons work to increase the friction coefficient. Further, there was a risk of lowering the slipperiness.
  • Patent Document 1 a compound having a fluoroalkyl group at one end of a poly (oxyperfluoroalkylene) chain and a silicone chain in one end of a poly (oxyperfluoroalkylene) chain in Patent Document 2 are used together. Since groups and silicone chains are concentrated on the outermost surface of the hard coat layer, it is effective for expressing slipperiness, but on the other hand, it is not fixed to the matrix resin, so it is inferior in scratch resistance. There was a problem. Furthermore, the hard coat layer described in any of the literature has excellent scratch resistance. The thickness of the hard coat layer is as thick as 10 ⁇ m, and the scratch resistance in the thin film region of 1 to 5 ⁇ m is as follows. There is no mention. That is, there has been a demand for a hard coat layer that is excellent in scratch resistance even in a thin film region and that exhibits high slipperiness.
  • a hydroxyl group is bonded to one end of a molecular chain containing a poly (oxyperfluoroalkylene) structure via a poly (oxyalkylene) group at one end.
  • a polymerizable composition using a compound having an active energy ray polymerizable group via a poly (oxyalkylene) group at the other end as a fluorine-based surface modifier has a thickness of 1 to 5 ⁇ m.
  • the inventors have found that a hard coat layer having excellent scratch resistance and high slipperiness can be formed even in a thin film, and completed the present invention.
  • the present invention provides, as a first aspect, (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (B) having an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and via a poly (oxyalkylene) group at the other end
  • the present invention relates to a polymerizable composition comprising 0.1 to 10 parts by mass of a perfluoropolyether having a hydroxy group and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
  • the polymerizable composition according to the first aspect wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units.
  • the present invention relates to the polymerizable composition according to the first aspect or the second aspect, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
  • the component (a) the polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
  • the present invention relates to the polymerizable composition according to any one of the above.
  • the present invention relates to the polymerizable composition according to any one of the first aspect to the fourth aspect, in which the component (c) polymerization initiator is a mixture of alkylphenones and thioxanthones.
  • the present invention relates to the polymerizable composition according to any one of the first aspect to the fifth aspect, further including (d) a solvent.
  • the present invention relates to a cured film obtained from the polymerizable composition according to any one of the first aspect to the sixth aspect.
  • a hard coat film comprising a hard coat layer on at least one surface of the film substrate, wherein the hard coat layer is polymerizable according to any one of the first to sixth aspects.
  • the present invention relates to a hard coat film formed by a step of applying a composition on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays and curing.
  • the hard coat film according to the eighth aspect wherein the hard coat layer has a thickness of 0.1 to 10 ⁇ m.
  • the hard coat film according to the ninth aspect wherein the hard coat layer has a thickness of 1 to 5 ⁇ m.
  • an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and a poly (oxyalkylene) group at the other end.
  • the present invention relates to a perfluoropolyether compound having a hydroxy group via
  • the present invention relates to a surface modifier comprising the perfluoropolyether compound described in the eleventh aspect.
  • a thirteenth aspect relates to the use of the perfluoropolyether compound described in the eleventh aspect as a surface modifier.
  • the present invention relates to a polymerizable composition comprising a perfluoropolyether having a hydroxy group.
  • A 100 parts by mass of an active energy ray-curable polyfunctional monomer,
  • B having an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and via a poly (oxyalkylene) group at the other end
  • the present invention relates to a polymerizable composition comprising 0.1 to 10 parts by mass of a perfluoropolyether having a hydroxy group and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
  • the components (a) to (c) will be described first.
  • the active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
  • the preferable (a) active energy ray-curable polyfunctional monomer in the polymerizable composition of the present invention is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
  • the polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
  • the polyfunctional urethane (meth) acrylate is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol.
  • the polyfunctional urethane (meth) acrylate compound which can be used by this invention is not limited only to this illustration.
  • Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
  • Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth).
  • An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
  • polyols examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.
  • the (a) active energy ray-curable polyfunctional monomer one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination.
  • the component (b) has an active energy ray-polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and poly (oxy) at the other end.
  • a perfluoropolyether having a hydroxy group via an (oxyalkylene) group (hereinafter, also simply referred to as “(b) a perfluoropolyether having a hydroxy group”) is used.
  • the component (b) serves as a surface modifier in the hard coat layer to which the polymerizable composition of the present invention is applied.
  • the number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
  • — [OCF 2 ] (oxyperfluoromethylene group), — [OCF 2 CF 2 ] — (oxyperfluoroethylene group), — [OCF 2 CF 2 CF 2 ] — (oxyperfluoropropane) -1,3-diyl group) and-[OCF 2 C (CF 3 ) F]-(oxyperfluoropropane-1,2-diyl group).
  • the above oxyperfluoroalkylene groups may be used alone or in combination of two or more. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.
  • the poly (oxyperfluoroalkylene) group — [OCF 2 ] — (oxyperfluoromethylene group) and — [OCF 2 CF 2 ] — It is preferable to use a group having both (oxyperfluoroethylene group) as a repeating unit.
  • the bond of these repeating units may be either a block bond or a random bond.
  • the number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
  • the weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. .
  • the number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked.
  • the oxyalkylene groups may be used singly or in combination of two or more. In that case, the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
  • the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
  • the number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is more preferably in the range of 1 to 10.
  • Examples of the active energy ray polymerizable group bonded through the poly (oxyalkylene group) include a (meth) acryloyl group, a urethane (meth) acryloyl group, and a vinyl group.
  • Examples of the urethane moiety constituting the urethane (meth) acryloyl group include the structures U1 to U28 shown below.
  • the (meth) acryloyl moiety constituting the urethane (meth) acryloyl group includes, for example, the following structures A1 to A5 and structures obtained by substituting the acryloyl group in these structures with methacryloyl groups.
  • A1 to A5 represent structures represented by the formulas [A1] to [A5]
  • PFPE represents the poly (oxyperfluoroalkylene) group
  • n represents a repeating unit of an oxyethylene group. Represents a number, preferably a number from 1 to 10.
  • the perfluoropolyether having a hydroxy group is 0.1 to 10 parts by mass, preferably 0.2 to It is desirable to use at a ratio of 5 parts by mass.
  • the (b) perfluoropolyether having a hydroxy group is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group,
  • a method of urethanizing 2- (meth) acryloyloxyethyl isocyanate to a group a method of dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, itaconic anhydride It can be obtained by a method of esterifying an acid.
  • the (b) poly (oxyperfluoroalkylene) group has an active energy ray polymerizable group at one end of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group, and the other end has a poly (oxyalkylene) group.
  • a perfluoropolyether compound having a hydroxy group via the above is also an object of the present invention, and a surface modifier comprising the perfluoropolyether compound, and use of the perfluoropolyether compound as a surface modifier. Is also an object of the present invention.
  • a polymerization initiator that generates radicals by a preferable active energy ray is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
  • polymerization initiator (c) examples include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones.
  • the present invention it is preferable to use a mixture of alkylphenones and thioxanthones as the polymerization initiator (c) from the viewpoint of transparency, surface curability, and thin film curability.
  • a mixture of alkylphenones and thioxanthones it is possible to obtain a cured film that is more excellent in slipperiness and further improved in scratch resistance.
  • thioxanthones examples include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone and the like.
  • the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
  • a) active energy ray-curable polyfunctional monomer is desirable.
  • thioxanthones 100: 1 to 1: 100, and 100: 5 to 1: 1. It is more preferable to use in the ratio.
  • the polymerizable composition of the present invention may further contain (d) a solvent, that is, may be in the form of a varnish (film forming material).
  • the solvent is appropriately selected in consideration of the workability at the time of coating and the drying before and after curing for dissolving the components (a) to (c) and forming a cured film (hard coat layer) described later.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, Halides such as methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene S such as glycol monomethyl ether acetate Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl
  • the amount of the solvent (d) used is not particularly limited.
  • the solvent is used at a concentration such that the solid content in the polymerizable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass.
  • the solid content concentration (also referred to as non-volatile content concentration) refers to the solid content (excluding solvent components from all components) relative to the total mass (total mass) of the components (a) to (d) of the polymerizable composition of the present invention. Content).
  • additives generally added as necessary, for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a surface activity, unless the effects of the present invention are impaired.
  • An agent, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended.
  • the polymerizable composition of the present invention can form a cured film by coating (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray for polymerization (curing).
  • the cured film is also an object of the present invention.
  • the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like.
  • the shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
  • the coating method on the base material is a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate).
  • Lithographic printing, screen printing, etc. can be selected as appropriate, and in particular, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the polymerizable composition is filtered in advance using a filter having a pore diameter of about 0.2 ⁇ m and then applied.
  • the coating film is preliminarily dried with a hot plate or an oven as necessary to remove the solvent.
  • the heat drying conditions at this time are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
  • the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable.
  • a light source used for ultraviolet irradiation sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used. Furthermore, after that, polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
  • the thickness of the formed cured film is usually 0.01 to 50 ⁇ m, preferably 0.05 to 20 ⁇ m after drying and curing.
  • a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced.
  • the hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
  • the hard coat layer in the hard coat film of the present invention is formed by a step of coating the above-described polymerization of the present invention on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays to cure the coating film. Can be formed.
  • various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned ⁇ cured film> are used.
  • a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • polycarbonate polymethacrylate
  • polystyrene polyolefin
  • polyamide polyamide
  • polyimide polyimide
  • triacetyl cellulose triacetyl cellulose
  • the method quoted in the above-mentioned ⁇ cured film> can be used for the coating method (coating film formation process) of the polymeric composition on the said film base material, and the ultraviolet irradiation method (curing process) to a coating film.
  • the solvent is contained in the polymerization composition of this invention (varnish form)
  • the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process.
  • the drying method (solvent removal process) of the coating film quoted to the above-mentioned ⁇ cured film> can be used.
  • the thickness of the hard coat layer thus obtained is preferably 0.1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • Bar coat application device PM-9050MC manufactured by SMT Co., Ltd.
  • Bar OSG Systems Products A-Bar OSP-25, maximum film thickness 25 ⁇ m (corresponding to wire bar # 10)
  • Application speed 4 m / min
  • Oven Equipment Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
  • UV irradiation device Device H02-L41 manufactured by Eye Graphics Co., Ltd.
  • Film thickness measurement device Filmetrics F20 film thickness measurement system
  • Contact angle measurement device Kyowa Interface Science Co., Ltd.
  • Dynamic friction coefficient measurement apparatus Shinto Kagaku Co., Ltd.
  • Pencil hardness measurement apparatus Electric pencil scratch hardness tester No. 1 manufactured by Yasuda Seiki Seisakusho Co., Ltd. 553M Load: 750g Pencil: Uni (registered trademark) series manufactured by Mitsubishi Pencil Co., Ltd.
  • PFPE1 Perfluoropolyether having a poly (oxyalkylene) group and a hydroxy group at both ends
  • PFPE2 Perfluoropolyether having hydroxy groups at both ends
  • PFPE3 Perfluoropolyether having acryloyl groups at both ends (Fluorolink (registered trademark) AD1700, Solvay Specialty Polymers, Inc., nonvolatile content: 70% by mass butyl acetate / ethyl acetate solution
  • PFPE4 Perfluoropolyether having methacryloyl groups at both ends [Fluorolink (registered trademark) 5101X, Solvay Specialty Polymers, Inc., 80% by mass MEK solution in nonvola
  • Example 1 Production of perfluoropolyether SM1 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a hydroxy group at the other end 1.05 g of PFPE1 (0. 5 mmol), 0.07 g (0.5 mmol) of AOI, 0.01 g (0.02 mmol) of DBTDL, and 1.12 g of MEK. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50 mass% MEK solution of SM1.
  • Example 2 Production of perfluoropolyether SM2 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a hydroxy group at the other end 1.05 g of PFPE1 (0. 5 mmol), 0.13 g (0.5 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL, and 1.18 g of MEK. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50 mass% MEK solution of SM2.
  • the obtained hard coat layer was evaluated for film thickness, water and oleic acid contact angle, dynamic friction coefficient ⁇ k, slipperiness, scratch resistance and pencil hardness. The procedure for each evaluation is shown below. The results are also shown in Table 1.
  • [Film thickness] The film thickness at three locations on the hard coat layer surface was measured, and the average value was taken as the film thickness value.
  • [Contact angle] 1 ⁇ L of probe liquid (water or oleic acid) was attached to the surface of the hard coat layer, the contact angle after 5 seconds was measured 5 times, and the average value was taken as the contact angle value.
  • [Dynamic friction coefficient] The dynamic friction coefficients at five locations on the surface of the hard coat layer were measured, and the average value was taken as the dynamic friction coefficient value.
  • the dynamic friction coefficient required for a hard coat layer applied to the surface of a display element such as a touch panel is required to be at least 0.1 or less, and preferably 0.05 or less.
  • A The line drawn with the oil-based marker can be wiped clean without scratching
  • B The line drawn with the oil-based marker can be wiped off cleanly, but the ink drawn with the oil-based marker enters the scratch and cannot be wiped off [pencil hardness] The measurement was performed according to JIS K5600-5-4.
  • perfluoropolyethers SM1 and SM2 having poly (oxyalkylene) and acryloyl groups at one end and poly (oxyalkylene) and hydroxy groups at the other end as surface modifiers in the hard coat layer.
  • the hard coat films of Examples 3 and 4 used were excellent in antifouling property, slipperiness, scratch resistance and hardness at a film thickness of 1.4 to 1.6 ⁇ m.
  • Example 5 using an alkylphenone (I127) alone as a polymerization initiator and Example 6 using a thioxanthone (DETXS) alone the film thickness is 1.8 ⁇ m, and the antifouling property and hardness are excellent.
  • the hard coat film of Comparative Example 5 in which a perfluoropolyether having a methacryloyl group and a perfluoropolyether having a methacryloyl group at both ends were inferior in terms of slipperiness, scratch resistance and hardness.
  • a hard coat film of Comparative Example 3 using perfluoropolyether SM5 having an acryloyl group at one end and a hydroxy group at the other end, and a perfluoropolyether having a poly (oxyalkylene) group and a hydroxy group at both ends The hard coat film of Comparative Example 4 used resulted in the hard coat layer becoming cloudy and inferior in slipperiness, scratch resistance and hardness. And the hard coat film of the comparative example 6 and the comparative example 7 which used the perfluoropolyether which has a (meth) acryloyl group at one end brought a result that it was inferior to slipperiness and scratch resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

[Problème] Fournir un matériau pour former une couche de revêtement dur qui montre une résistance à l'abrasion supérieure et un pouvoir lubrifiant élevé même dans les régions de couche mince. [Solution] Une composition polymérisable incluant: (a) 100 parties en masse d'un monomère polyfonctionnel durcissable par un faisceau énergétique actif ; (b) 0,1-10 parties en masse d'un perfluoropolyéther ayant un groupe polymérisable par faisceau énergétique actif qui est lié par le biais d'un groupe poly(oxyalkylène) à une extrémité d'une chaîne moléculaire qui inclut un groupe poly(oxyperfluoroalkylène), et un groupe hydroxyle qui est lié par le biais d'un groupe poly(oxyalkylène) à l'autre extrémité de la chaîne moléculaire; et (c) 1-20 parties en masse d'un initiateur de polymérisation qui génère des radicaux quand il est exposé au faisceau énergétique actif. L'invention concerne un film de revêtement dur comprenant une couche de revêtement dur formée à partir de ladite composition.
PCT/JP2014/078499 2013-10-25 2014-10-27 Composition polymérisable contenant du perfluoropolyéther ayant un groupe hydroxyle Ceased WO2015060458A1 (fr)

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WO2018056370A1 (fr) * 2016-09-21 2018-03-29 日産化学工業株式会社 Matériau de revêtement dur résistant aux rayures
WO2018070438A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Matériau de revêtement dur résistant à la lumière
WO2018070446A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Stratifié à revêtement dur de dureté élevée
JP2018124395A (ja) * 2017-01-31 2018-08-09 パナソニックＩｐマネジメント株式会社 ハードコートフィルム
WO2019044481A1 (fr) * 2017-08-28 2019-03-07 Ａｇｃ株式会社 Stratifié et son procédé de fabrication
KR20200049815A (ko) * 2017-09-01 2020-05-08 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. 신규 (퍼)플루오로폴리에테르 중합체 및 이의 용도
CN112368305A (zh) * 2018-07-05 2021-02-12 日产化学株式会社 柔性涂层用固化性组合物
WO2021241087A1 (fr) * 2020-05-26 2021-12-02 日産化学株式会社 Composition durcissable pour former une couche de revêtement dure contenant du (méth)acrylate d'uréthane et des particules de silice à surface modifiée
WO2022034733A1 (fr) * 2020-08-13 2022-02-17 日産化学株式会社 Composition durcissable pour revêtement dur
WO2022190937A1 (fr) * 2021-03-11 2022-09-15 日産化学株式会社 Composition durcissable pour revêtement dur
WO2022203060A1 (fr) * 2021-03-25 2022-09-29 日産化学株式会社 Composition durcissable contenant deux perfluoropolyéthers

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WO2018056370A1 (fr) * 2016-09-21 2018-03-29 日産化学工業株式会社 Matériau de revêtement dur résistant aux rayures
KR102399829B1 (ko) 2016-10-12 2022-05-19 닛산 가가쿠 가부시키가이샤 고경도 하드코트 적층체
WO2018070446A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Stratifié à revêtement dur de dureté élevée
WO2018070438A1 (fr) * 2016-10-12 2018-04-19 日産化学工業株式会社 Matériau de revêtement dur résistant à la lumière
JPWO2018070446A1 (ja) * 2016-10-12 2019-07-25 日産化学株式会社 高硬度ハードコート積層体
KR20190060978A (ko) * 2016-10-12 2019-06-04 닛산 가가쿠 가부시키가이샤 고경도 하드코트 적층체
JPWO2018070438A1 (ja) * 2016-10-12 2019-07-25 日産化学株式会社 耐光性ハードコート材
JP2018124395A (ja) * 2017-01-31 2018-08-09 パナソニックＩｐマネジメント株式会社 ハードコートフィルム
CN111050929A (zh) * 2017-08-28 2020-04-21 Ａｇｃ株式会社 层叠体及其制造方法
JPWO2019044481A1 (ja) * 2017-08-28 2020-10-22 Ａｇｃ株式会社 積層体およびその製造方法
WO2019044481A1 (fr) * 2017-08-28 2019-03-07 Ａｇｃ株式会社 Stratifié et son procédé de fabrication
JP7010294B2 (ja) 2017-08-28 2022-02-10 Ａｇｃ株式会社 積層体およびその製造方法
KR20200049815A (ko) * 2017-09-01 2020-05-08 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. 신규 (퍼)플루오로폴리에테르 중합체 및 이의 용도
KR102542434B1 (ko) 2017-09-01 2023-06-14 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. 신규 (퍼)플루오로폴리에테르 중합체 및 이의 용도
CN112368305A (zh) * 2018-07-05 2021-02-12 日产化学株式会社 柔性涂层用固化性组合物
CN112368305B (zh) * 2018-07-05 2023-03-28 日产化学株式会社 柔性涂层用固化性组合物
WO2021241087A1 (fr) * 2020-05-26 2021-12-02 日産化学株式会社 Composition durcissable pour former une couche de revêtement dure contenant du (méth)acrylate d'uréthane et des particules de silice à surface modifiée
JPWO2021241087A1 (fr) * 2020-05-26 2021-12-02
JP7678408B2 (ja) 2020-05-26 2025-05-16 日産化学株式会社 ウレタン（メタ）アクリレート及び表面修飾されたシリカ粒子を含むハードコート層形成用硬化性組成物
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JP7569021B2 (ja) 2020-08-13 2024-10-17 日産化学株式会社 ハードコート用硬化性組成物
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