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
  • 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
  • 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols

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 elements, and capable of forming a hard coat layer excellent in slipperiness, scratch resistance, abrasion resistance and water repellency. , relates to homogeneous curable compositions free of suspensions and sediments.
• perfluoropolyether used in the present invention refers to one having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group.
• the "poly(oxyperfluoroalkylene) group A compound having an active energy ray-polymerizable group at the end of a molecular chain containing a fluoroalkylene) group is referred to as a “perfluoropolyether”.
• touch panels have been introduced into various devices such as portable information terminal devices such as mobile phones and tablet computers, laptop computers, home appliances, and automobile interior and exterior parts. is often operated by touching with a finger or a pen.
• the surface of the touch panel is required to be water and oil repellent in order to facilitate the removal of fingerprints, and the water and oil repellency is maintained even after repeated finger rubbing.
• Abrasion resistance is required.
• the surface of the touch panel is operated with a finger or a pen, the surface is required to have smoothness from the viewpoint of the touch feeling of the finger or the pen.
• the surface of the touch panel is required to have scratch resistance in order to prevent scratches.
• a surface coat layer such as a hard coat layer is provided.
• Fluorine-containing compounds exhibit high lubricity and water and oil repellency, and are therefore used as materials for forming hard coat layers. method is used. Fluorine-based surface modifiers are known to segregate on the surface of the hard coat layer due to the low surface energy of fluorine atoms.
• a method in which a high-density crosslinked structure is formed to increase the surface hardness of the hard coat layer and provide resistance to external force.
• a material for forming such a hard coat layer at present, polyfunctional acrylate materials that are three-dimensionally crosslinked by radicals generated by irradiation with active energy rays are most used.
• the fluorine-based surface modifier added to the coating liquid for forming the hard coat layer is generally a material having an active energy ray-polymerizable group in order to impart scratch resistance and wear resistance to the hard coat layer.
• Patent Document 1 From the viewpoint of scratch resistance and wear resistance, a low-molecular-weight material capable of forming a high-density crosslinked structure and having many active energy ray-polymerizable groups and having a so-called small acrylic equivalent is preferred.
• Patent Document 2 in order to obtain durability properties such as scratch resistance and wear resistance in the hard coat layer, for example, when a fluorine-based surface modifier having a crosslinkable group is used, fluorine atoms are added. The molecular chains contained therein are immobilized, and the slipperiness of the hard coat layer is reduced. In other words, there is a trade-off relationship between durability properties such as scratch resistance and wear resistance, and slipperiness, and it is difficult to achieve both high levels of properties.
• Patent Document 3 discloses a fluorine-containing polyether that becomes aggregates when obtaining a hard coating agent composition and causes cloudiness of the composition, and the composition. have reported the combined use of a fluorine-containing block copolymer with excellent compatibility with
• Patent Document 4 a linear polymer having a fluoropolyether in the main chain and having an acrylic group at one or both ends of the molecular chain and having a fluorine content of 48% by mass to 62% by mass, and a fluoropolyether as the main chain
• a linear polymer having a siloxane skeleton with a fluorine content of 25% by mass or more and less than 45% by mass having a plurality of acrylic groups at both ends of the molecular chain the fluorine content is 48% by mass. % to 62% by mass of the straight-chain polymer improves the solubility in the composition, resulting in a hard coat layer with excellent water repellency and slipperiness.
• paragraph [0006] of Patent Document 4 describes "wear resistance typified by slipperiness", and wear resistance is indirectly evaluated by slipperiness. Therefore, there are no specific examples regarding scratch resistance and abrasion resistance.
• An object of the present invention is to provide a homogeneous curable composition free of suspended solids and sediments, capable of forming a hard coat layer having both durability and lubricity, which are in a trade-off relationship, at a high level of properties. do. In addition to these, it is necessary for the hard coat layer to have high liquid repellency in consideration of actual use.
• the present invention provides (a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, (b) a perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 (however, (c) perfluoropolyether described later) excluding fluoropolyethers), (c) a perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and (d) active A curable composition containing a polymerization initiator that generates radicals by energy rays.
• the (c) perfluoropolyether has the active energy ray-polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.
• the (c) perfluoropolyether has an active energy ray-polymerizable group via a urethane bond.
• the (c) perfluoropolyether has a fluorine atom content of 35% by mass to 65% by mass.
• the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has repeating units -(CF 2 O)- and/or repeating units -(CF 2 CF 2 O)-, and both repeating units is a group formed by combining these repeating units by block bonding, random bonding, or block bonding and random bonding.
• the molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a structure represented by the following formula [1].
• m is the number of repeating units -(CF 2 CF 2 O)-
• n is the number of repeating units -(CF 2 O)-
• m and n each independently represent an integer of 0 or more
• q is the number of oxyethylene groups and represents an integer of 0 to 20.
• n each independently represent an integer of 1 or more.
• the (c) perfluoropolyether is a compound represented by the following formula [2].
• m, n and q have the same definitions as in the above formula [1]
• A represents the terminal group having the active energy ray-polymerizable group.
• the terminal group A is a group represented by the following formula [A1] or [A2].
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• * is a bond with the urethane bond of the compound represented by the above formula [2] represents.
• the (b) perfluoropolyether has the active energy ray-polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
• the molecular chain containing the poly(oxyperfluoroalkylene) group of the (b) perfluoropolyether has a structure represented by the following formula [3].
• r is the number of repeating units -(CF 2 CF 2 O)-
• s is the number of repeating units -(CF 2 O)-
• r and s each independently represent an integer of 0 or more, and when both repeating units are present, these repeating units are block-bonded, random-bonded, or block-bonded and random-bonded. .
• r and s each independently represent an integer of 1 or more.
• the (b) perfluoropolyether is a compound represented by the following formula [4].
• r and s have the same definitions as in the above formula [3]
• A represents the terminal group having the active energy ray-polymerizable group.
• the terminal group A is a group represented by the following formula [A1] or [A2].
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• * is a bond with the urethane bond of the compound represented by the above formula [4] represents.
• the curable composition of the present invention further comprises (e) a solvent.
• a cured film obtained from the curable composition is a cured film obtained from the curable composition.
• a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film.
• the film substrate has a lower layer of the hard coat layer between the surface of the film substrate and the hard coat layer, and the film substrate is a resin film.
• the hard coat layer has a thickness of 1 ⁇ m to 20 ⁇ m.
• a method for producing a hard coat film comprising the steps of coating the curable composition on a film substrate to form a coating film, and irradiating the coating film with an active energy ray to cure it to form a hard coat layer.
• a step of applying the curable composition on a film substrate to form a coating film, a step of removing the solvent from the coating film by heating, and a hard coating by irradiating the coating film with an active energy ray and curing it A method for producing a hard coat film, comprising a step of forming layers.
• Forming a hard coat film further comprising the step of forming a lower layer of the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film and a coating film is formed on the lower layer of the hard coat layer. Production method.
• a surface modifier comprising a perfluoropolyether (B) which is a reaction product of a compound having a functional group and the active energy ray-polymerizable group.
• the perfluoropolyether (B) has the active energy ray-polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1,550 to 3,500.
• the perfluoropolyether (B) has a fluorine atom content of 35% by mass to 65% by mass.
• the perfluoropolyether (A) has the active energy ray-polymerizable group at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
• the molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether (A) has a structure represented by the following formula [3]
• the poly(oxyperfluoroalkylene) of the perfluoropolyether (B) alkylene) group has a structure represented by the following formula [1].
• m is the number of repeating units -(CF 2 CF 2 O)-
• n is the number of repeating units -(CF 2 O)-
• m and n each independently represent an integer of 0 or more
• q represents the number of oxyethylene groups and represents an integer of 0 to 20
• r represents a repeating unit -(CF 2 CF 2 O)- number and s are the number of repeating units -(CF 2 O)-, satisfying 5 ⁇ (r+s) ⁇ 40
• r and s each independently represent an integer of 0 or more
• the repeating unit -(CF 2 CF 2 O)- and repeating unit -(CF 2 O)-, these repeating units are combined by block bond, random bond, or block bond and random bond .
• n and n each independently represent an integer of 1 or more
• r and s each independently represent an integer of 1 or more.
• the perfluoropolyether (A) is a compound represented by the following formula [4]
• the perfluoropolyether (B) is a compound represented by the following formula [2].
• m, n and q have the same definitions as in the above formula [1]
• r and s have the same definitions as in the above formula [3]
• A is the above represents a terminal group having an active energy ray-polymerizable group
• the terminal group A is a group represented by the following formula [A1] or [A2].
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• * is the urethane of the compound represented by the above formula [2] or formula [4] Represents a bond with a bond.
• a curable composition useful for forming a cured film and a hard coat layer having both excellent scratch resistance/wear resistance and excellent slipperiness even in a thin film having a thickness of 1 ⁇ m to 20 ⁇ m. can provide.
• a curable composition useful for forming a cured film and a hard coat layer imparting high water repellency in addition to achieving both of the above properties, and a hard coat layer excellent in these properties are provided.
• a hard coat film can be provided.
• the active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule is an active It refers to a monomer that undergoes a polymerization reaction and cures when irradiated with energy rays.
• Preferred (a) polyfunctional monomers in the curable composition of the present invention are selected from the group consisting of monomers selected from the group consisting of polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds described later. Monomers selected from the group consisting of monomers and lactone-modified polyfunctional (meth)acrylate compounds can be mentioned.
• the polyfunctional monomer (a) one of the above polyfunctional (meth)acrylate compounds can be used alone, or two or more of them can be used in combination.
• the (meth)acrylate compound includes both an acrylate compound and a methacrylate compound.
• (meth)acrylic acid includes acrylic acid and methacrylic acid.
• the (a) polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene-modified monomer include oxymethylene-modified, oxyethylene-modified, and oxypropylene-modified.
• examples of the oxyalkylene-modified polyfunctional monomer include oxyalkylene-modified compounds of the polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound.
• the oxyalkylene-modified polyfunctional monomers may also be used singly or in combination of two or more.
• polyfunctional monomers preferable in the present invention include polyfunctional monomers having at least 3 (meth)acryloyl groups per molecule, for example, at least 4 per molecule.
• polyfunctional monomers include monomers selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups in one molecule. .
• Examples of the polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth) Acrylates, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin
• preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. can be mentioned.
• Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound include oxyalkylene-modified polyol (meth)acrylate compounds.
• Examples of the polyols include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
• polyfunctional urethane (meth)acrylate compound for example, a compound obtained by reacting a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group, and a compound obtained by reacting a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group with a polyol
• examples include compounds obtained by reaction, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.
• polyfunctional isocyanates examples include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
• (meth)acrylates having a hydroxy group examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)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 and maleic acid.
• polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as adipic acid; polyether polyols; and polycarbonate diols.
• the polyfunctional monomer may be a lactone-modified polyfunctional (meth)acrylate compound, and the lactone to be modified is preferably ⁇ -caprolactone.
• the lactone-modified polyfunctional (meth)acrylate compound include ⁇ -caprolactone-modified pentaerythritol tri(meth)acrylate, ⁇ -caprolactone-modified pentaerythritol tetra(meth)acrylate, and ⁇ -caprolactone-modified dipentaerythritol penta(meth)acrylate. , and ⁇ -caprolactone-modified dipentaerythritol hexa(meth)acrylate.
• (b) Perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1,400 to 3,500 The perfluoropolyether having an active energy ray-polymerizable group at the end of the molecular chain containing the (b) component poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 is hereinafter simply referred to as "(b ) perfluoropolyether”.
• (b) Perfluoropolyether excludes (c) perfluoropolyether described later.
• the (b) perfluoropolyether which is preferable in the curable composition of the present invention, has an active energy ray-polymerizable group via a urethane bond at the end of the molecular chain containing the poly(oxyperfluoroalkylene) group.
• the ends of the molecular chain containing the poly(oxyperfluoroalkylene) group may be all or part of the ends of the molecular chain.
• all terminals and part of the molecular chain are both terminals and one terminal of the linear molecular chain, respectively.
• linking group between the poly(oxyperfluoroalkylene) group and the urethane bond examples include a hydrocarbon group having an ether bond, and in the hydrocarbon group, at least one hydrogen atom is substituted with a fluorine atom. may have been Also, preferred (b) perfluoropolyethers do not have silicon atoms in their chemical structure.
• (b) Perfluoropolyether serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
• component (c) described below serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
• the (b) perfluoropolyether has excellent compatibility with the (a) polyfunctional monomer, clouding is suppressed and it is possible to form a hard coat layer exhibiting a transparent appearance.
• poly(oxyperfluoroalkylene) group -[CF 2 O]-(oxyperfluoromethylene group) and -[CF 2 CF 2 O]- from the viewpoint of obtaining a cured film having good scratch resistance.
• a group having both (oxyperfluoroethylene groups) as repeating units is preferred. In that case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.
• Perfluoropolyether is not limited to those having one active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and two or more active energy ray-polymerizable groups may have Examples of the active energy ray-polymerizable group include (meth)acryloyl groups and vinyl groups. group. Among these terminal groups, a group having two active energy ray-polymerizable groups and represented by the formula [A2] is preferable.
• the perfluoropolyether has active energy ray-polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film with good scratch resistance. More preferably, the number of the active energy ray-polymerizable groups in one molecule is large. The number of the polymerizable groups is preferably 2 or more, more preferably 3 or more, at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.
• Perfluoropolyether having a weight average molecular weight of 1,400 to 3,500 can provide a hard coat layer with excellent scratch resistance, abrasion resistance, and slipperiness.
• the content of (b) perfluoropolyether in the curable composition of the present invention is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer parts to 5 parts by mass, or 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass.
• the perfluoropolyether content is 0.05 parts by mass or more, so that the hard coat layer can be provided with sufficient scratch resistance, and (b) the perfluoropolyether content is When it is 3 parts by mass or less, it is sufficiently compatible with (a) the polyfunctional monomer, and a hard coat layer with little cloudiness can be obtained.
• Perfluoropolyethers can be used singly or in combination of two or more. When two or more types are combined, one end (one end) of the molecular chain containing the poly(oxyperfluoroalkylene) group has an active energy ray-polymerizable group via a urethane bond, and other than the molecular chain A perfluoropolyether having a hydroxy group at one end (the other end) may be included.
• Perfluoropolyether is, for example, a raw material perfluoropolyether having a hydroxy group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and the hydroxy It is obtained by reacting a group-reactive functional group and a compound having the active energy ray-polymerizable group.
• the functional group that reacts with the hydroxy group include a hydroxy group, a carboxy group and an isocyanate group.
• a fluorine atom-containing group more preferably a trifluoromethoxy group, at one end opposite to the one end having a hydroxyl group of the raw material perfluoropolyether.
• the active energy ray polymerization The (c) perfluoropolyether having a fluorine atom-containing group at one end opposite to the one end having a functional group can sufficiently migrate to the surface of the hard coat layer, and exhibits excellent water repellency and It can express slipperiness.”
• Perfluoropolyether is not limited to those having one active energy ray-polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and two or more active energy ray-polymerized It may have a sexual group.
• the active energy ray-polymerizable group include (meth)acryloyl groups and vinyl groups. group.
• these terminal groups a group having two active energy ray-polymerizable groups and represented by the formula [A2] is preferable.
• the (c) perfluoropolyether together with the (b) perfluoropolyether, functions as a surface modifier in the hard coat layer formed from the curable composition of the present invention.
• (c) perfluoropolyether has excellent compatibility with (b) perfluoropolyether, it is possible to form a hard coat layer that suppresses white turbidity and presents a transparent appearance.
• (c) perfluoropolyether preferably has a poly(oxyalkylene) group from the viewpoint of compatibility with (a) the polyfunctional monomer.
• a poly(oxyethylene) group is preferred as the poly(oxyalkylene) group.
• the (c) perfluoropolyether preferable in the curable composition of the present invention has an active energy ray-polymerizable group via a urethane bond only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group.
• the poly(oxyperfluoroalkylene) group -[CF 2 O]-(oxyperfluoromethylene group) and -[CF 2 CF 2 O]- from the viewpoint of obtaining a cured film having good scratch resistance.
• a group having both (oxyperfluoroethylene groups) as repeating units is preferred. In that case, the bonding of these oxyperfluoroalkylene groups may be either block bonding or random bonding.
• Perfluoropolyether has a fluorine atom content of, for example, 35% by mass or more and 65% by mass or less, preferably 40% by mass or more and 65% by mass, more preferably 45% by mass or more and 65% by mass. is.
• a hard coat layer having excellent water repellency and slipperiness can be obtained. There is a possibility that sufficient characteristics cannot be obtained.
• the perfluoropolyether has a weight average molecular weight of 1,550 to 3,500, preferably 1,600 to 3,500, and more preferably 1,700 to 3,500.
• (c) perfluoropolyether tends to stay on the surface of the hard coat layer obtained from the curable composition of the present invention, and the layer surface Since the shear stress is sufficiently reduced, a hard coat layer with excellent slipperiness can be obtained.
• the weight-average molecular weight of (c) the perfluoropolyether is within the above range, the hardness of the layer surface is appropriately adjusted, and a hard coat layer having excellent durability such as scratch resistance can be obtained. . That is, when the weight-average molecular weight of (c) the perfluoropolyether is within the above range, both lubricity and durability can be achieved.
• the content of (c) perfluoropolyether in the curable composition of the present invention is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer parts to 5 parts by mass, or 0.05 parts to 3 parts by mass.
• the content of (c) perfluoropolyether is 0.05 parts by mass or more, (c) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention. Therefore, a hard coat layer having excellent lubricity can be obtained.
• the content of (c) perfluoropolyether is 3 parts by mass or less, it is sufficiently compatible with (b) perfluoropolyether, and a hard coat layer with little cloudiness can be obtained.
• the content of (c) perfluoropolyether is, for example, 10 to 800 parts by mass, more preferably 10 to 500 parts by mass with respect to 100 parts by mass of (b) perfluoropolyether, More preferably, it is 10 to 400 parts by mass.
• Perfluoropolyethers can be used singly or in combination of two or more.
• the (d) polymerization initiator that is preferable in the curable composition of the present invention is a polymerization initiator that generates radicals upon exposure to active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly ultraviolet irradiation.
• polymerization initiators such as benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones , biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts.
• polymerization initiators may be used alone or in combination of two or more.
• alkylphenones As the polymerization initiator (d), it is preferable to use alkylphenones as the polymerization initiator (d). By using alkylphenones, a cured film with improved scratch resistance can be obtained.
• alkylphenones examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)- ⁇ -hydroxyalkyl such as 2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one Phenones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. 2,2-dimethoxy-1,2-diphenylethan-1-one; and methyl phenylglyoxylate.
• the content of the polymerization initiator (d) in the curable composition of the present invention is, for example, 0.5 parts by mass to 20 parts by mass, preferably 1 part by mass to 100 parts by mass of the polyfunctional monomer (a). 20 parts by mass, more preferably 2 to 10 parts by mass.
• the curable composition of the present invention may contain (e) a solvent as an optional component, ie, it may be in the form of a varnish.
• a solvent As the solvent, the solubility and dispersibility of the components (a) to (d), and the workability during coating of the curable composition for forming a cured film (hard coat layer) described later, It may be appropriately selected in consideration of the drying properties before and after curing.
• the (e) solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; Halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve Esters or ester ethers such as acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4
• amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethylsulfoxide (DMSO), and solvents obtained by mixing two or more of these solvents.
• DMF N,N-dimethylformamide
• DMAc N,N-dimethylacetamide
• NMP N-methyl-2-pyrrolidone
• sulfoxides such as dimethylsulfoxide (DMSO), and solvents obtained by mixing two or more of these solvents.
• the content of (e) the solvent in the curable composition of the present invention is not particularly limited. It is the concentration that becomes mass %.
• the solid content concentration also referred to as non-volatile content concentration refers to the solid content ( excluding the solvent component from all components) content.
• the curable composition of the present invention may generally contain additives, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, which are generally added as necessary, as long as they do not impair the effects of the present invention.
• additives such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, which are generally added as necessary, as long as they do not impair the effects of the present invention.
• Agents, adhesion imparting agents, plasticizers, ultraviolet absorbers, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc. may be used singly or in combination of two or more thereof.
• the curable composition of the present invention can form a cured film by coating (coating) a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (cure) it,
• the cured film is also an object of the present invention.
• the hard coat layer in the hard coat film to be described later the cured film can be used.
• the base material examples include various resins (polyesters such as polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polyolefins, polyamides, polyimides, epoxy resins, , melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin), metal, wood, paper, glass, slate can be done.
• the shape of these substrates may be plate-like, film-like or three-dimensional molded body.
• a primer layer an ultraviolet absorbing layer, an infrared absorbing layer, a near-infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, and an antistatic layer may be added to the surface of the base material.
• a layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, etc. may be formed as a lower layer of the hard coat layer, and a plurality of lower layers of the hard coat layer may be laminated.
• the layer formed on the surface of the substrate is not particularly limited as long as it does not impair the effects of the present invention.
• the coating method on the substrate includes 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 (letterpress printing method , Intaglio printing method, lithographic printing method, screen printing method, etc.) can be appropriately selected, among which roll-to-roll method can be used, and from the viewpoint of thin film coating, letterpress printing method In particular, it is desirable to use the gravure coating method. It is preferable that the curable composition of the present invention is filtered in advance using a filter having a pore size of about 0.2 ⁇ m, and then applied. When applying, a solvent may be added to the curable composition, if necessary. Examples of the solvent in this case include various solvents listed in the above [(e) solvent].
• the coating film is pre-dried with a heating means such as a hot plate or an oven to remove the solvent (solvent removal step).
• a heating means such as a hot plate or an oven to remove the solvent (solvent removal step).
• the heat drying conditions are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
• the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Active energy rays include, for example, ultraviolet rays, electron beams and X-rays, and ultraviolet rays are particularly preferred.
• the polymerization may be completed by performing post-baking, specifically by heating using a heating means such as a hot plate or an oven.
• the thickness of the cured film formed is usually 0.1 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m after drying and curing.
• a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced using the curable composition of the present invention.
• 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 touch panels and liquid crystal displays.
• the hard coat layer in the hard coat film of the present invention comprises the steps of applying the curable composition of the present invention onto a film substrate to form a coating film, optionally removing the solvent by heating, and It can be formed by a method including a step of irradiating the film with an active energy ray such as ultraviolet rays to cure the coating film.
• the present invention also includes a method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, including these steps.
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polyurethanes, thermoplastic polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrenes, polyolefins, Films such as polyamide, polyimide, and triacetyl cellulose (TAC) can be used.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene naphthalate
• TPU thermoplastic polyurethanes
• TPU thermoplastic polyurethanes
• Films such as polyamide, polyimide, and triacetyl cellulose (TAC) can be used.
• the film substrate may be formed by laminating a plurality of layers.
• a primer layer an ultraviolet absorption layer, an infrared absorption layer, a near-infrared absorption layer, an electromagnetic wave absorption layer, a color correction layer, a refractive index adjustment layer, a weather resistant layer, an antireflection layer, and an antistatic layer may be added to the surface of the resin film.
• a discoloration prevention layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and the like, which are different from the resin film may be laminated as a lower layer of the hard coat layer, and the hard coat layer may be under the A plurality of layers may be laminated.
• the layer laminated on the surface of the resin film is not particularly limited as long as it does not impair the effects of the present invention.
• the method of applying the curable composition of the present invention on the film substrate (coating film forming step) and the method of irradiating the active energy ray to the coating film (curing step) are listed in the above-mentioned ⁇ cured film>.
• method can be used.
• the curable composition of the present invention contains a solvent (in the form of a varnish)
• a step of drying the coating film to remove the solvent can be included after the coating film forming step, if necessary.
• the method of drying the coating film (solvent removal step) mentioned in the above ⁇ Cured film> can be used.
• the layer thickness (film thickness) of the hard coat layer thus obtained is, for example, 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 10 ⁇ m.
• the present invention also includes a surface modifier containing a perfluoropolyether (B) which is a reaction product with a compound having a reactive functional group and an active energy ray-polymerizable group.
• perfluoropolyether (A) is the same as the above-mentioned (b) perfluoropolyether
• perfluoropolyether (B) is the same as the above-mentioned (c) perfluoropolyether.
• Coating device by bar coater PM-9050MC manufactured by SMT Co., Ltd.
• Bar A-Bar OSP-15 manufactured by OSG System Products Co., Ltd.
• Film thickness measurement device F20 film thickness measurement system manufactured by Filmetrics Co., Ltd.
• Oven device Two-layer clean oven (upper and lower type) PO- manufactured by Sanki Keiso Co., Ltd. 250-45-D
• UV curing device CV-110QC-G manufactured by Heraeus Co., Ltd.
• Lamp Electrodeless lamp H-bulb manufactured by Heraeus Co., Ltd.
• Scratch resistance test and abrasion resistance test Apparatus Reciprocating abrasion tester TRIBOGEAR TYPE: 30S manufactured by Shinto Kagaku Co., Ltd. Scanning speed: 3200 mm/min Scanning distance: 50 mm (6)
• Contact angle measurement device DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measurement temperature: 23°C (7)
• Probe 0.6mmR sapphire pin Load: 200g Scanning speed: 2 mm/sec Scanning distance: 10 mm (8) Total light transmittance, haze measurement device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
• Polyfunctional acrylate PA1 dipentaerythritol pentaacrylate/hexaacrylate mixture [Aronix (registered trademark) M-403 manufactured by Toagosei Co., Ltd.]
• Multifunctional acrylate PA2 Oxyethylene-modified multifunctional acrylate [Daiichi Kogyo Seiyaku Co., Ltd.
• PFPE2 A perfluoropolyether of the following structure having one hydroxy group at one end without a poly(oxyalkylene) group [manufactured by Solvay Specialty Polymers, Inc., calculated from the analysis results by X 19 F-NMR and 1 H-NMR.
• PFPE3 A perfluoropolyether of the following structure having one hydroxy group via a poly(oxyethylene) group only at one end [Fomblin (registered trademark) 4102X 19 F-NMR and 1 H-NMR manufactured by Solvay Specialty Polymers Co., Ltd.
• PFPE4 A perfluoropolyether having the following structure having one hydroxy group only at one end without a poly(oxyalkylene) group [FO2 manufactured by Apollo Scientific, molecular weight 978.15]
• PFPE5 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly(oxyalkylene) group (1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol ) [C10GOL manufactured by Exfluor Research, molecular weight 548.1]
• PFPE6 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly(oxyalkylene) group (1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol ) [C10GOL manufactured by Exfluor Research, molecular weight 548.1]
• PFPE6 A perfluoropolyether having the following structure having one hydroxy group at only one end without a poly
• N1 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Kalenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.]
• N2 2-acryloyloxyethyl isocyanate [Karenzu (registered trademark) AOI manufactured by Showa Denko K.K.]
• SMA6 Perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group [Optool (registered trademark) DAC
• Neostan (registered trademark) U-830]
• MEK methyl ethyl ketone
• PGME propylene glycol monomethyl ether
• PGMEA propylene glycol monomethyl ether acetate
• MeOH methanol
• O2959 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one
• IGM Resins OMNIRAD registered trademark 2959
• AN1 PEDOT-PSS aqueous dispersion [Sigma-Aldrich PEDOT-PSS 3.0% by mass to 4.0% by mass aqueous dispersion high conductive grade product number 655201]
• the weight average molecular weight Mw of the obtained SMA3 measured in terms of polystyrene by GPC was 1908, and the degree of dispersion Mw/Mn was 1.0. Further, the content of fluorine atoms in SMA3 calculated by combustion ion chromatography was 47% by mass.
• the weight average molecular weight Mw of the obtained SMA4 measured in terms of polystyrene by GPC was 1299, and the degree of dispersion Mw/Mn was 1.0.
• the fluorine atom content in SMA4 calculated by combustion ion chromatography is 51% by mass, which is about the same as the fluorine atom content of 51% by mass theoretically calculated from the structure of SMA4. rice field.
• the weight average molecular weight Mw of the obtained SMA5 measured in terms of polystyrene by GPC was 1029, and the degree of dispersion Mw/Mn was 1.0.
• the fluorine atom content in SMA5 calculated by combustion ion chromatography is 46% by mass, which is about the same as the fluorine atom content of 47% by mass theoretically calculated from the structure of SMA5. rice field.
• the weight average molecular weight Mw of the obtained SMA8 measured in terms of polystyrene by GPC was 1609, and the degree of dispersion Mw/Mn was 1.0. Further, the content of fluorine atoms in SMA8 calculated by combustion ion chromatography was 54% by mass.
• Examples 1 to 9, Comparative Examples 1 to 13 Each component shown in Table 1 was mixed to prepare a curable composition having a solid concentration shown in Table 1.
• the solid content refers to components other than the solvent.
• [parts] represents [parts by mass]
• [%] represents [% by mass].
• the polyfunctional acrylate and the surface modifier in Table 1 each represent the solid content.
• curable compositions are applied to an A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 ⁇ m] having a primer layer formed on both sides by a bar coater. to obtain a coating film.
• the coating film was dried in an oven at 60° C. for 8 minutes to remove the solvent.
• a hard coat film having a hard coat layer (cured film) was produced by exposing the obtained film to UV light at an exposure dose of 300 mJ/cm 2 in a nitrogen atmosphere.
• Examples 10 to 11, Comparative Examples 14 to 15 Each component shown in Table 2 was mixed to prepare a curable composition having a solid concentration shown in Table 2.
• the solid content refers to components other than the solvent.
• [parts] represents [parts by mass]
• [%] represents [% by mass].
• the polyfunctional acrylate and the surface modifier in Table 2 each represent the solid content.
• curable compositions are applied to an A4 size PET film [Lumirror (registered trademark) U403 (also known as U40) manufactured by Toray Industries, Inc., thickness 100 ⁇ m] having a primer layer formed on both sides by a bar coater. to obtain a coating film.
• the coating was dried in an oven at 65°C for 3 minutes to remove the solvent.
• a hard coat film having a hard coat layer (cured film) was produced by exposing the obtained film to UV light at an exposure dose of 300 mJ/cm 2 in a nitrogen atmosphere.
• the surface of the hard coat layer of the obtained hard coat film was subjected to 5,000 reciprocations at a stroke of 50 mm with a steel wool [BONSTAR (registered trademark) #0000 (ultrafine)] attached to a reciprocating abrasion tester under a load of 1 kg. rubbed. After that, visually check the degree of scratches in the area excluding the range of 5 mm width at both ends of the stroke of 50 mm, and confirm that the scratches are on the surface of the hard coat layer with a microscope (Keyence Corporation). Evaluated according to Criteria A, B and C.
• A No scratches (0 scratches)
• B Scratches (1 to 4 scratches with a length of 1 mm to 9 mm)
• C Scratches (5 or more scratches with a length of 1 mm to 9 mm, or 1 or more scratches with a length of 1 cm or more) [Water repellency] 1 ⁇ L of water was applied to the surface of the hard coat layer, and after 5 seconds, the contact angle ⁇ was measured 5 times, and the average value was evaluated according to the following criteria.
• the contact angle was measured 5 seconds after the water was applied, because the contact angle measured immediately after the water was applied was high and unstable.
• the surface of the hard coat layer was rubbed back and forth 2,500 times with a load of 1 kg using a cylindrical eraser [RUBBER STICK manufactured by Minoan, ⁇ 6.0 mm] attached to a reciprocating abrasion tester. 1 ⁇ L of water was applied to the rubbed portion, and the contact angle ⁇ after 5 seconds was measured at 5 points. Assuming actual use as a hard coat layer, at least B is required, and A is desirable.
• the curable compositions of Examples 1 to 8 had polyfunctional acrylates PA1 to PA4 and poly(oxyperfluoroalkylene) groups at both ends of the molecular chain, respectively.
• a molecular chain piece containing a perfluoropolyether SMA1 having a functional group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group A weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 or PFPE3 having a number average molecular weight of 1750 to 1950 having one hydroxy group only at the end with the isocyanate compound N1 having the active energy ray polymerizable group.
• the curable compositions of Examples 1 to 8 exhibited excellent homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions exhibited excellent It exhibited slipperiness, scratch resistance, water repellency and abrasion resistance.
• the curable composition of Example 9 has an active energy ray-polymerizable group at the end of a molecular chain containing a polyfunctional acrylate PA1, a poly(oxyperfluoroalkylene) group, and a weight average It contains a perfluoropolyether SMA6 having a molecular weight of 1521 and a fluorine atom content of 35% by mass, and has one hydroxy group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group.
• the curable composition of Example 9 contains SMA2 having a weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 with the isocyanate compound N1 having the active energy ray polymerizable group. Then, as shown in Table 3, the curable composition of Example 9 exhibited excellent homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition exhibited excellent lubricity and repellency. It showed water resistance and abrasion resistance.
• the hard coat film comprising the hard coat layer obtained from the curable composition of Example 9 has a hard coat layer comprising the hard coat layer obtained from the curable composition of Examples 1 to 8 in terms of scratch resistance.
• the other items shown in Table 2 showed excellent property levels, albeit slightly worse than the films.
• the curable composition of Comparative Example 1 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
• perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and a hydroxy at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group
• the hard coat film provided with the hard coat layer obtained from the curable composition is superior to that of Examples 1 to 3.
• the hard coat film obtained from the curable composition of Example 9 it showed inferior results in slipperiness and scratch resistance. From this result, even if a perfluoropolyether having an active energy ray-polymerizable group only at one end of a molecular chain containing a (oxyperfluoroalkylene) group with a high fluorine atom content is used, slipperiness and scratch resistance can be improved. It was shown that the weight-average molecular weight of the perfluoropolyether is important for slipperiness and scratch resistance.
• the curable composition of Comparative Example 2 has an active energy ray-polymerizable group at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and a hydroxy at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group
• the curable compositions of Comparative Examples 3 and 4 had one hydroxyl group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
• a perfluoropolyether having a number average molecular weight of 1750 to 1950 which contains SMA4 with a weight average molecular weight of 1299 or SMA5 with a weight average molecular weight of 1029, and which has a hydroxy group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. It contains SMA2 having a weight average molecular weight of 1710 obtained by reacting the compound PFPE2 with the isocyanate compound N1 having the active energy ray-polymerizable group.
• the curable compositions of Comparative Examples 3 and 4 were inferior in homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions had slipperiness and resistance. It showed inferior results in scratch resistance and abrasion resistance. It is believed that this is because the weight average molecular weights of SMA4 and SMA5 are too small to destroy the aggregation structure of SMA2, thereby failing to assist the solubility in the coating solution. As a result, SMA2 agglomerated in the coating liquid, and SMA2 was not sufficiently segregated on the surface of the hard coat layer.
• the curable composition of Comparative Example 5 has active energy ray-polymerizable groups at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group.
• the weight average molecular weight is 3973, and the content of fluorine atoms is 29% by mass.
• SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 having one.
• the curable composition of Comparative Example 5 exhibits excellent homogeneity and exhibits excellent lubricity, but a hard coat film comprising a hard coat layer obtained from the curable composition. showed inferior results in scratch resistance and abrasion resistance. This result indicates that good slipperiness does not necessarily lead to good scratch resistance and abrasion resistance.
• the hard coat film comprising the hard coat layer obtained from the curable composition of Comparative Example 5 is more durable than the hard coat film comprising the hard coat layer obtained from the curable compositions of Examples 1 to 9.
• the reason for the inferior scratch resistance and wear resistance is considered to be that the weight average molecular weight of SMA7 is larger than that of SMA1 and SMA6, and the fixing ability in the film is lowered.
• the content of fluorine atoms in SMA7 is smaller than that of SMA1 and SMA6, and the compatibility between SMA2 and SMA7 is poor, resulting in phase separation between SMA2 and SMA7 on the hard coat layer surface. Conceivable.
• the curable composition of Comparative Example 6 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA2 having a weight average molecular weight of 1710 obtained by reacting a perfluoropolyether compound PFPE2 having a molecular weight of 1750 to 1950 with the isocyanate compound N1 having the active energy ray-polymerizable group. Then, as shown in Table 3, the curable composition of Comparative Example 6 was inferior in homogeneity to the curable composition of Example 1, in which SMA1 was added to the curable composition of Comparative Example 6.
• the hard coat film comprising the hard coat layer obtained from the curable composition of Example 6 has better slipperiness and resistance than the hard coat film comprising the hard coat layer obtained from the curable composition of Example 1. All of the scratch resistance, water repellency and abrasion resistance were inferior.
• This is a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, which acts as a solubilizer for SMA2. This is probably because SMA2 agglomerates in the coating liquid because it does not contain
• the curable composition of Comparative Example 7 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA3 having a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 having a molecular weight of 1900 with the isocyanate compound N1 having the active energy ray-polymerizable group. Then, as shown in Table 3, although the curable composition of Comparative Example 7 is excellent in homogeneity, the hard coat film provided with the hard coat layer obtained from the curable composition has the curability of Comparative Example 7.
• the scratch resistance and water repellency were inferior. This is because the single use of SMA3 has a strong cohesive force and makes it easy to aggregate inside the film, and SMA3 cannot be sufficiently segregated on the surface of the hard coat layer, and SMA3 is active only at one end. This is probably because the immobilization ability in the membrane is low due to the presence of the energy ray-polymerizable group.
• the curable composition of Comparative Example 8 has a molecular weight of 978 having one hydroxy group only at one end of a molecular chain containing a polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group.
• SMA4 having a weight average molecular weight of 1299 obtained by reacting the perfluoropolyether compound PFPE4 of No. 15 with the isocyanate compound N1 having the active energy ray-polymerizable group.
• the curable composition obtained from the curable composition of Comparative Example 8 was inferior in homogeneity compared to the curable composition of Comparative Example 1 in which SMA1 was added to the curable composition of Comparative Example 8.
• the hard coat film provided with the hard coat layer showed inferior results in all of slipperiness, scratch resistance, and wear resistance. This is probably because SMA4 aggregates inside the film and cannot be sufficiently segregated on the surface of the hard coat layer, and the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA4 is short.
• the curable composition of Comparative Example 9 has a molecular weight of 548 having one hydroxy group only at one end of a molecular chain containing a polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It contains SMA5 having a weight average molecular weight of 1029 obtained by reacting the perfluoropolyether compound PFPE5 of No. 1 with the isocyanate compound N1 having the active energy ray-polymerizable group.
• the hard coat film provided with the hard coat layer obtained from the curable composition is poly(oxyperfluoroalkylene ) group is short, it shows inferior results in all of slipperiness, water repellency, scratch resistance, and abrasion resistance.
• the curable composition of Comparative Example 10 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass.
• the curable composition of Comparative Example 10 is excellent in homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition has water repellency, scratch resistance, and Although it has excellent wear resistance, it does not contain SMA2 compared to the hard coat film provided with the hard coat layer obtained from the curable composition of Example 1 in which SMA2 was added to the curable composition of Comparative Example 10. Therefore, it showed inferior results in slipperiness. This is because SMA1 has eight acrylic groups in one molecule, and thus has a high immobilization ability in the film, so that it has excellent scratch resistance and abrasion resistance. It is considered that the mobility is low and the slipperiness is poor.
• the curable composition of Comparative Example 12 has active energy ray-polymerizable groups at both ends of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA7 having a weight average molecular weight of 3973 and a fluorine atom content of 29% by mass.
• the curable composition of Comparative Example 12 is excellent in homogeneity, but the hard coat film provided with the hard coat layer obtained from the curable composition is cured in Comparative Example 12.
• the curable composition of Comparative Example 13 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight-average molecular weight of 2494 and a fluorine atom content of 42% by mass, and further comprising a poly(oxyperfluoroalkylene) group, a hydroxy group at each of both ends of the molecular chain
• a weight average molecular weight of 1609 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE6 having a number average molecular weight of 1550 and having a fluorine atom content is 54% by mass of SMA8.
• the curable composition of Comparative Example 13 exhibited excellent homogeneity, and the hard coat film comprising the hard coat layer obtained from the curable composition had water repellency and scratch resistance.
• the slip properties and wear resistance were inferior. From these results, a hard coat film obtained from a curable composition containing a perfluoropolyether having an active energy ray-polymerizable group only at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier.
• the curable compositions of Examples 10 to 11 had polyfunctional acrylates PA1 or PA2 and poly(oxyperfluoroalkylene) groups at both ends of the molecular chain, respectively.
• a molecular chain piece containing a perfluoropolyether SMA1 having a functional group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group SMA3 having a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 having a number average molecular weight of 1900 having one hydroxy group only at the terminal with the isocyanate compound N1 having the active energy ray polymerizable group.
• the curable compositions of Examples 10 to 11 exhibited excellent homogeneity, and the hard coat films provided with the hard coat layers obtained from the curable compositions exhibited excellent It exhibited slipperiness, scratch resistance, water repellency and abrasion resistance.
• the curable composition of Comparative Example 14 has an active energy ray-polymerizable group at each end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. and a perfluoropolyether SMA1 having a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and an antistatic agent AN1.
• the curable composition of Comparative Example 14 is excellent in homogeneity, and the hard coat film provided with the hard coat layer obtained from the curable composition has water repellency, scratch resistance, and Although it has excellent wear resistance, it does not contain SMA3 compared to the hardcoat film comprising the hardcoat layer obtained from the curable composition of Example 10, which is the curable composition of Comparative Example 14 with SMA3 added. Therefore, it showed inferior results in slipperiness. This is because SMA1 has eight acrylic groups in one molecule, and thus has a high fixing ability in the film. it is conceivable that.
• the curable composition of Comparative Example 15 has one hydroxy group only at one end of the molecular chain containing the polyfunctional acrylate PA1 and the poly(oxyperfluoroalkylene) group. It contains SMA3 with a weight average molecular weight of 1908 obtained by reacting a perfluoropolyether compound PFPE3 with a molecular weight of 1900 with the isocyanate compound N1 having the active energy ray-polymerizable group, and further contains an antistatic agent AN1. Then, as shown in Table 4, although the curable composition of Comparative Example 15 is excellent in homogeneity, the hard coat film provided with the hard coat layer obtained from the curable composition has the curability of Comparative Example 15.

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