Classifications

• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • 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
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • 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
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

• the present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display devices such as a touch panel display and a liquid crystal display, and is particularly excellent in scratch resistance and antiglare property (antiglare function).
• the present invention relates to a curable composition capable of forming a hard coat layer having excellent initial water repellency.
• An antiglare hard coat film having a hard coat layer of about several ⁇ m with irregularities formed on the surface is attached to the surface of these touch panel displays in order to prevent a reduction in visibility due to the reflection of external light on the screen.
• Method is used.
• a method of forming irregularities on the surface a method of containing fine particles having a particle diameter of about several ⁇ m in the hard coat layer is generally used.
• the capacitive touch panel is operated by touching it with a human finger. Therefore, there is a possibility that fingerprints may be attached to the surface of the touch panel every time the operation is performed, the visibility of the image on the display may be significantly impaired, or the appearance of the display may be impaired. Fingerprints contain 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 any of these from adhering. ing.
• the capacitive touch panel is touched by a person's finger every day, even if the initial antifouling property has reached a considerable level, it may be damaged during use and the visibility of the display image and the antifouling property may be reduced. Often, sexual function declines. In particular, the hard-coating antiglare layer has irregularities on its surface, so that it tends to be caught and scratched. Therefore, durability of antifouling property in the use process has been a problem.
• a perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group through a urethane bond is used as a surface modifier and a hard coat layer with an antiglare property.
• a technique using polymethylmethacrylate particles as a component for imparting the property is disclosed (Patent Document 2).
• Patent Document 2 provides scratch resistance and sufficient antiglare property, but has a problem that the initial water contact angle is not sufficient and the water repellency is low. That is, there has been a demand for a hard coat layer that has excellent antiglare properties and scratch resistance, and that exhibits high initial water repellency.
• the present inventors have conducted extensive studies in order to achieve the above-mentioned object, and as a result, a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, wherein poly(oxyalkylene) is present at both ends of its molecular chain.
• a perfluoropolyether having an active energy ray-polymerizable group as a fluorine-based surface modifier through a urethane bond instead of a group and further adopting a curable composition containing fine particles, excellent
• the present invention has been completed by finding that a hard coat layer having antiglare property and high scratch resistance and exhibiting high initial water repellency can be formed.
• the present invention as a first aspect, (A) 100 parts by mass of active energy ray-curable polyfunctional monomer, (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (however, 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.
• Curable including (c) 5 parts by mass to 40 parts by mass of fine particles having an average particle size of 0.2 ⁇ m to 15 ⁇ m, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. It relates to a composition.
• the curable composition according to the first aspect wherein the (b) perfluoropolyether has at least two active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain.
• the curable composition according to the second aspect wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups through urethane bonds at both ends of its molecular chain.
• the poly(oxyperfluoroalkylene) group has both a repeating unit —[OCF 2 ]— and a repeating unit —[OCF 2 CF 2 ]—, and these repeating units are block-bonded or random-bonded.
• the curable composition according to any one of the first to third aspects which is a group formed by a block bond and a random bond.
• the curable composition according to the fourth aspect wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].
• n is the total number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, and represents an integer of 5 to 30,
• the repeating unit —[OCF 2 CF 2 ]— and the repeating unit —[OCF 2 ]— are bonded by a block bond, a random bond, or a block bond and a random bond.
• a sixth aspect relates to the curable composition according to any one of the first to fifth aspects, wherein the fine particles of component (c) are organic fine particles.
• a seventh aspect relates to the curable composition according to the sixth aspect, wherein the organic fine particles of component (c) are polymethyl methacrylate fine particles.
• An eighth aspect relates to the curable composition according to any one of the first to seventh aspects, which further contains (e) a solvent.
• a ninth aspect relates to a cured film obtained from the curable composition according to any one of the first to eighth aspects.
• a tenth aspect relates to a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to the ninth aspect.
• An eleventh aspect relates to the hard coat film according to the tenth aspect, wherein the hard coat layer has a layer thickness of 1 ⁇ m to 20 ⁇ m.
• a twelfth aspect relates to the hard coat film according to the eleventh aspect, wherein the hard coat layer has a layer thickness of 3 ⁇ m to 15 ⁇ m.
• a thirteenth aspect is a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is described in any one of the first to eighth aspects. It relates to a method for producing a hard coat film, which comprises the steps of forming a coating film by applying the curable composition of (1) on a film substrate and irradiating the coating film with an active energy ray to cure the coating film.
• a fourteenth aspect relates to a display provided with the hard coat film according to any one of the tenth to twelfth aspects.
• a fifteenth aspect relates to a polarizing plate including the hard coat film according to any one of the tenth to twelfth aspects.
• a cured film and a hard coat exhibiting excellent scratch resistance and high anti-glare property even in a thin film having a thickness of about 1 ⁇ m to 20 ⁇ m and excellent appearance as well as exhibiting high initial water repellency.
• a curable composition useful for forming layers can be provided. Further, according to the present invention, it is possible to provide a hard coat film having on its surface a hardened film obtained from the curable composition or a hard coat layer formed from the hardened film, and antiglare property, scratch resistance and It is possible to provide a hard coat film having excellent appearance and excellent initial water repellency.
• the curable composition of the present invention specifically comprises (A) 100 parts by mass of active energy ray-curable polyfunctional monomer, (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of its molecular chain via urethane bonds (however, 0.05 parts by mass to 10 parts by mass, excluding perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.
• Curable including (c) 5 parts by mass to 40 parts by mass of fine particles having an average particle size of 0.2 ⁇ m to 15 ⁇ m, and (d) 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. It relates to a composition.
• a polymerization initiator that generates radicals by active energy rays.
• the active energy ray-curable polyfunctional monomer refers to a monomer that undergoes a polymerization reaction and is cured by being irradiated with an active energy ray such as ultraviolet rays.
• the preferable (a) active energy ray-curable polyfunctional monomer in the curable composition of the present invention includes a monomer selected from the group consisting of polyfunctional (meth)acrylate compounds.
• a (meth)acrylate compound means 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, pentaerythritol tetraacrylate.
• preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• a polyfunctional urethane (meth)acrylate compound can be mentioned as a polyfunctional (meth)acrylate compound.
• 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 bond (—NHCOO—).
• Examples of the polyfunctional urethane (meth)acrylate compound include those obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group, a polyfunctional isocyanate, a (meth)acrylate having a hydroxy group, and a polyol. Examples thereof include those obtained by the reaction, but the polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.
• 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, dipentaerythritol penta(meth)acrylate. Examples thereof include acrylate and tripentaerythritol hepta(meth)acrylate.
• polystyrene resin examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; these diols and succinic acid, maleic acid.
• diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; these diols and succinic acid, maleic acid.
• polyester polyols, polyether polyols, and polycarbonate diols which are reaction products of aliphatic dicarboxylic acids such as acid and adipic acid or dicarboxylic acid anhydrides.
• the (a) active energy ray-curable polyfunctional monomer one selected from the group consisting of the polyfunctional (meth)acrylate compound (compound containing no urethane bond) and the polyfunctional urethane (meth)acrylate compound. Can be used alone or in combination of two or more. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth)acrylate compound (compound containing no urethane bond) and a polyfunctional urethane (meth)acrylate compound in combination.
• polyfunctional (meth)acrylate compound it is preferable to use a polyfunctional (meth)acrylate compound having 5 or more functional groups and a polyfunctional (meth)acrylate compound having 4 or less functional groups (in this case, a urethane bond is contained). It does not matter whether or not it is the same below).
• a polyfunctional (meth)acrylate compound compound containing no urethane bond
• a polyfunctional (meth)acrylate compound compound containing no urethane bond
• a polyfunctional urethane (meth)acrylate compound It is preferable to use 20 parts by mass to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound, and more preferably 30 parts by mass to 70 parts by mass, relative to 100 parts by mass. Further, in the above polyfunctional (meth)acrylate compound, when the polyfunctional (meth)acrylate compound having 5 or more functional groups and the polyfunctional (meth)acrylate compound having 4 or less functional groups are used in combination, a polyfunctional compound having 5 or more functional groups is used. With respect to 100 parts by mass of the functional (meth)acrylate compound, it is preferable to use 10 parts by mass to 100 parts by mass of a polyfunctional (meth)acrylate compound having a functionality of 4 or less, and more preferably 20 parts by mass to 60 parts by mass.
• a polyfunctional (meth)acrylate compound having 4 or less functional groups 30 parts by mass to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound and 100 parts by mass of a polyfunctional (meth)acrylate compound having 5 or more functional groups with respect to 100 parts by mass of a polyfunctional (meth)acrylate compound (compound containing no urethane bond).
• a polyfunctional (meth)acrylate compound having a functionality of 4 or less To 10 parts by mass to 100 parts by mass of a polyfunctional (meth)acrylate compound having a functionality of 4 or less, 30 parts by mass to 70 parts by mass of a polyfunctional urethane (meth)acrylate compound and 100 parts by mass of a polyfunctional (meth)acrylate compound having 5 or more functional groups with respect to 100 parts by mass of a polyfunctional (meth)acrylate compound (compound containing no urethane bond).
• (B) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has active energy ray-polymerizable groups at both ends of its molecular chain via urethane bonds (provided that , Except perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond.)]
• the component (b) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, and a urethane bond is introduced at both ends of the molecular chain thereof without interposing the poly(oxyalkylene) group.
• a perfluoropolyether having an active energy ray-polymerizable group (hereinafter, also simply referred to as “(b) perfluoropolyether having a polymerizable group at both ends of a molecular chain”) is used.
• the component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied. Further, the component (b) has excellent compatibility with the component (a), thereby suppressing the clouding of the hard coat layer and enabling the formation of a hard coat layer having a transparent appearance.
• the above poly(oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
• the number of carbon atoms of the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but it is 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 an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
• examples thereof include groups such as -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, and in that case, the bonds of plural kinds of oxyperfluoroalkylene groups are block bonds and random bonds. It may be any combination.
• poly(oxyperfluoroalkylene) groups -[OCF 2 ]-(oxyperfluoromethylene group) and -[OCF 2 CF 2 ] are used. It is preferable to use a group having both —(oxyperfluoroethylene group) as a repeating unit.
• repeating units: -[OCF 2 ]- and -[OCF 2 CF 2 ]- are in a molar ratio of [repeating unit: -[OCF 2 ]-]:
• [repeat Unit: —[OCF 2 CF 2 ]—] is preferably a group containing at a ratio of 2:1 to 1:2, and more preferably a group containing at a ratio of about 1:1.
• the bond of these repeating units may be either a block bond or a random bond.
• the total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
• the weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured by gel permeation chromatography in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3,000. ..
• Examples of the active energy ray-polymerizable group include (meth)acryloyl group and vinyl group.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is not limited to one having one active energy ray-polymerizable group such as a (meth)acryloyl group at both ends of the molecular chain. It may have one or more active energy ray-polymerizable groups at both ends of the molecular chain.
• the terminal structure containing the active energy ray-polymerizable group may be represented by the following formulas [A1] to [A1]. A5] and the structures in which the acryloyl group in these structures is substituted with a methacryloyl group.
• Examples of such a perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2].
• A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group
• PFPE represents Represents a poly(oxyperfluoroalkylene) group (provided that the side directly bonded to L 1 is an oxy terminal and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and L 1 is 1 to 3 fluorine atoms.
• alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms examples include, for example, —CH 2 CHF—, —CH 2 CF 2 —, —CHFCF 2 —, —CH 2 CH 2 CHF. —, —CH 2 CH 2 CF 2 —, —CH 2 CHFCF 2 —, and —CH 2 CF 2 — is preferable.
• Examples of the partial structure (A-NHC( ⁇ O)O) m L 2 — in the compound represented by the above formula [2] include structures represented by the following formulas [B1] to [B12]. Can be mentioned. (In the formulas [B1] to [B12], A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which the acryloyl group in these structures is substituted with a methacryloyl group.
• the structure represented by the formula [B3] is preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.
• n represents the total number of repeating units -[OCF 2 CF 2 ]- and repeating units -[OCF 2 ]-, preferably an integer in the range of 5 to 30, An integer in the range of 21 to 21 is more preferable.
• the ratio of the number of repeating units -[OCF 2 CF 2 ]- to the number of repeating units -[OCF 2 ]- is preferably in the range of 2:1 to 1:2, and is approximately 1:1. It is more preferable to set the range to.
• the bond of these repeating units may be either a block bond or a random bond.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain is 0.05 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is used in a proportion of, for example, 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. (B) By using the perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hard coat layer.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain in a proportion of 10 parts by mass or less, it is sufficiently compatible with (a) the active energy ray-curable polyfunctional monomer.
• a hard coat layer with less white turbidity can be obtained.
• the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) is, for example, a compound represented by the following formula [3].
• PFPE, L 1 , L 2 and m have the same meanings as those in the formula [2].
• a polymerizable group for the hydroxy group present at both terminals of the compound represented by the formula [2].
• An isocyanate compound having, that is, a compound having an isocyanato group bonded to a bond in a structure represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group for example, It can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate) to form a urethane bond.
• the curable composition of the present invention comprises (b) a poly(oxyperfluoroalkylene) group-containing perfluoropolyether, which has active energy ray polymerization at both ends of its molecular chain via urethane bonds.
• a perfluoropolyether having a polymerizable group provided that the poly(oxyperfluoroalkylene) group and the urethane bond do not have a poly(oxyalkylene) group.
• a perfluoropolyether having a hydroxy group at the end thereof (provided that the poly(oxyperfluoroalkylene) group is between the urethane bond and the poly(oxyperfluoroalkylene) group is between the hydroxy group.
• Perfluoropolyether having a hydroxy group (provided that a poly(oxyperfluoroalkylene) group is not present between the poly(oxyperfluoroalkylene) group and the hydroxy group.) [Has an active energy ray-polymerizable group Compound not included] may be included.
• the fine particles having an average particle diameter of 0.2 ⁇ m to 15 ⁇ m are the surface of the hard coat layer formed from the curable composition.
• the (c) fine particles organic fine particles, inorganic fine particles, and organic-inorganic composite fine particles can be used. Among these fine particles, it is preferable to use organic fine particles from the viewpoint of transparency.
• the organic fine particles can also play a role of controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition that is the material for forming the hard coat layer.
• the shape of the fine particles (c) is not particularly limited, and may be, for example, a bead-like substantially spherical shape, or an irregular shape such as powder, but a substantially spherical shape is preferable, and more preferable. , Substantially spherical particles having an aspect ratio of 1.5 or less, and most preferably spherical particles.
• organic fine particles examples include polymethylmethacrylate fine particles (PMMA fine particles), silicone fine particles, polystyrene fine particles, polycarbonate fine particles, acrylic styrene fine particles, benzoguanamine fine particles, melamine fine particles, polyolefin fine particles, polyester fine particles, polyamide fine particles, polyimide fine particles, and polyfluorine fine particles. Ethylene oxide fine particles. These organic fine particles may be used alone or in combination of two or more. Among these organic fine particles, polymethylmethacrylate fine particles can be preferably used.
• the average particle size of the fine particles (c) used in the present invention is in the range of 0.2 ⁇ m to 15 ⁇ m, and preferably in the range of 1 ⁇ m to 10 ⁇ m.
• the average particle diameter ( ⁇ m) is a 50% volume diameter (median diameter) obtained by a laser diffraction/scattering method based on Mie theory. If the average particle size of the fine particles (c) is larger than the above numerical range, the image clarity of the display is lowered, and if it is smaller than the above numerical range, sufficient antiglare properties cannot be obtained and glare becomes large. Is likely to occur.
• the particle size distribution of the (c) fine particles is not particularly limited, but monodispersed fine particles having a uniform particle size are preferable.
• the fine particles (c) are preferably fine particles having a refractive index having a refractive index difference of 0 to 0.20 with the cured product of the active energy ray-curable polyfunctional monomer (a).
• the refractive index difference is preferably 0 to 0.10.
• organic fine particles commercially available products can be preferably used, and for example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series [above, Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive ⁇ Performance Materials Japan (same)]; Eposter (registered trademark) series, same MA series, same ST series, same MX series [above, Nippon Shokubai Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Co., Ltd.]; Flow Bead Series [Sumitomo Seika Co., Ltd.]; Trepearl (registered trademark) PPS, PAI, PES, EP [above, Toray Industries, Inc.
• the fine particles (c) are 5 parts by mass to 40 parts by mass, for example, 5 parts by mass to 30 parts by mass, preferably 8 parts by mass, relative to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a). Parts to 25 parts by weight.
• a polymerization initiator that generates a radical by a preferable active energy ray is, for example, an active energy such as an electron beam, an ultraviolet ray or an X-ray. It is a polymerization initiator that generates radicals by irradiation of rays, especially by irradiation of ultraviolet rays.
• Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, and benzophenone. And biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. You may use these individually by 1 type or in mixture of 2 or more types.
• alkylphenones as the (d) polymerization initiator from the viewpoint of transparency, surface curability, and thin film curability.
• a cured film having further improved scratch resistance can be obtained.
• alkylphenones examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl) ⁇ -hydroxy such as 2-methylpropan-1-one and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one
• Alkylphenones 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one And ⁇ -aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate.
• the proportion of the polymerization initiator (d) is 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Used in.
• the curable composition of the present invention may further contain (e) a solvent, that is, in the form of a varnish (film forming material).
• a solvent that is, in the form of a varnish (film forming material).
• the components (a) to (d) are dissolved/dispersed, and workability at the time of coating for forming a cured film (hard coat layer) described later and drying property before and after curing are taken into consideration. It may be selected as appropriate.
• aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; methyl chloride, methyl bromide, Halides such as methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dio
• a solvent having a high boiling point can be used for the purpose of controlling the dispersibility of the fine particles at the time of drying after coating.
• a solvent include cyclohexyl acetate, propylene glycol diacetate, 1,3-butynylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol monobutyl ether acetate.
• the amount of the solvent (e) to be used is not particularly limited, but for example, it is used at a concentration such that the solid content concentration in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass.
• the solid content concentration also referred to as the non-volatile content concentration
• the solid content concentration means the solid content relative to the total mass (total mass) of the components (a) to (d) (and optionally other additives) of the curable composition of the present invention. It represents the content of the components (all components excluding the solvent component).
• additives generally added as necessary, for example, a polymerization accelerator, a polymerization inhibitor, a photosensitizer, leveling
• An agent, a surfactant, an adhesion promoter, a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment and a dye may be appropriately mixed.
• inorganic fine particles such as titanium oxide may be blended.
• inorganic fine particles such as silicon dioxide (silica) and silicon dioxide (silica) having a reactive group such as an active energy ray-curable group may be added.
• silicon dioxide (silica) and silicon dioxide (silica) having a reactive group such as an active energy ray-curable group may be added.
• nanoparticles having an average particle diameter of less than 0.2 ⁇ m can be used.
• the curable composition of the present invention can form a cured film by applying (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (curing).
• the cured film is also an object of the present invention.
• the hard coat layer in the hard coat film described later can be made of the cured film.
• the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, Polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, etc.), metal, wood, paper, glass , Slate can be mentioned.
• the shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
• Examples of the coating method on the substrate include cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, spray coating method, bar coating method, die coating method, inkjet method, printing method ( (A letterpress printing method, an intaglio printing method, a lithographic printing method, a screen printing method, etc.) can be appropriately selected, and among these methods, a roll-to-roll method can be used and a thin film coating property can be applied. From the viewpoint of, it is desirable to use the letterpress printing method, especially the gravure coating method. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 ⁇ m and then applied to the coating.
• a solvent may be further added to the curable composition, if necessary.
• the various solvents mentioned in the above [(e) solvent] can be used.
• the coating film is preliminarily dried by a heating means such as a hot plate or an oven to remove the solvent, if necessary (solvent removing step).
• the conditions for heat drying at this time are, for example, preferably 40° C. to 120° C. and about 30 seconds to 10 minutes.
• the coating film is cured by irradiating with 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 ray irradiation for example, sunlight, chemical lamp, low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, xenon lamp, UV-LED can be used.
• the polymerization may be completed by performing post-baking, specifically, heating with a heating means such as a hot plate or an oven.
• the thickness of the cured film formed is usually 0.01 ⁇ m to 50 ⁇ m, for example, 0.05 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 20 ⁇ m, and more preferably 3 ⁇ m to 15 ⁇ 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 preferably 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 comprises a step of applying the curable composition of the present invention onto a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. It can be formed by a method including a step of curing the coating film.
• a method for producing a hard coat film having a hard coat layer on at least one surface of a film base, including these steps, is also an object of the present invention.
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide. , Polyimide, triacetyl cellulose (TAC), and the like.
• the method described in the above ⁇ cured film> should be used.
• the curable composition of the present invention contains a solvent (in the form of varnish)
• a step of drying the coating film and removing the solvent may be included after the coating film forming step, if necessary.
• the coating film drying method (solvent removing step) described in the above ⁇ cured film> can be used.
• the layer thickness (film thickness) of the hard coat layer thus obtained is preferably set to be 1 to 10 times the average particle diameter of the fine particles (c).
• the thickness of the hard coat layer is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m.
• the above hard coat film of the present invention can be used as a hard coat film of a display or a polarizing plate, and a display and a polarizing plate provided with the above hard coat film are also the subject of the present invention.
• CV-110QC-G Lamp Heraeus High Pressure Mercury Lamp H-bulb (4) Film thickness (layer thickness) Device: Digital measuring machine made by Nikon Corp. Digimicro MH-15M + Counter TC-101 (5) Glossiness measurement device: Konica Minolta Co., Ltd. Glossmeter GM-268Plus Measuring angle: 60 degrees (6) Scratch resistance test device: Shinto Kagaku Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30H Scanning speed: 4,500 mm/min Scanning distance: 50 mm (7) Total light transmittance, haze device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. (8) Contact angle measuring device: Kyowa Interface Science Co., Ltd. DropMaster DM-501 Measurement temperature: 20°C
• PFPE1 Perfluoropolyether having two hydroxy groups at both ends of the molecular chain without interposing a poly(oxyalkylene) group
• PFPE2 Perfluoropolyether having a hydroxy group through poly(oxyalkylene) groups (repeating unit number 8 or 9) at both ends of the molecular chain
• BEI 1,1-bis(acryloyloxymethyl)ethyl isocyanate
• DOTDD Dioctyltin dineodecanoate
• Neostan registered trademark
• U-830 manufactured by Nitto Kasei Co., Ltd.
• DBTDL dibutyltin dilaurate
• NK ester A-TMM-3LM-N] UA 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel Ornex Co., Ltd.]
• FP1 Crosslinked polymethylmethacrylate true spherical particles [Techpolymer (registered trademark) SSX-105 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 5 ⁇ m]
• FP2 Crosslinked polymethylmethacrylate true spherical particles [Techpolymer (registered trademark) SSX-108 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 8 ⁇ m]
• FP3 Crosslinked polymethylmethacrylate true spherical particles [Techpolymer (registered trademark) SSX-110 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 10 ⁇ m]
• FP4 Crosslinked polymethylmethacrylate true spher
• the resulting hard coat film was evaluated for antiglare property, scratch resistance, water contact angle, haze, and total light transmittance.
• the procedures for evaluating the antiglare property, scratch resistance, and water contact angle are shown below.
• the results are also shown in Table 3.
• [Anti-glare property] The obtained hard coat film was placed on a black base having a gloss Gs (60°) of 11.8, and the gloss Gs (60°) of the hard coat layer surface of the hard coat film was measured. Evaluation was performed according to A, B and C. When actually used as the hard coat layer, at least B is required, and A is desirable.
• the water contact angle (initial water repellency) is required to be A (108° or more).
• C Water contact angle value ⁇ 108°
• a peracryloyl group having four acryloyl groups through urethane bonds (not via poly(oxyalkylene) groups) at both ends of the molecular chain is used as a surface modifier in the hard coat layer.
• Each hard coat film provided with the hard coat layer prepared by using the curable compositions of Examples 1 to 9 in which the fluoropolyether SM1 was mixed with the organic fine particles had a layer thickness of 10 ⁇ m to 14 ⁇ m.
• a hard coat film having a hard coat layer having excellent scratch resistance and antiglare property could be obtained.
• the initial water repellency also resulted in 108° or more, which satisfied all the criteria in consideration of actual use, as compared with Comparative Examples described later.
• the hard coat film of Comparative Example 1 having a hard coat layer produced by using a perfluoropolyether SM2 having an acryloyl group through poly(oxyalkylene) groups at both ends of the molecular chain as a surface modifier is The desired initial water repellency was not obtained. Further, in Comparative Examples 2 and 3 containing no organic fine particles, the desired antiglare property was not obtained. Further, Comparative Example 4 containing 50 parts by mass of organic fine particles obtained high anti-glare property, but resulted in poor scratch resistance.

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