TW201700634A - Coating curable composition having marring resistance - Google Patents

Abstract

To provide a material for forming a hard coat layer which has an outer appearance without unevenness and exhibits high scratch resistance. This curable composition contains (a) 100 parts by mass of an active energy beam-curable multifunctional monomer, (b) 0.1-10 parts by mass of a perfluoropolyether which has an active energy beam-polymerizable group on both terminals of a poly(oxyperfluoroalkylene) group-containing molecular chain, with a poly(oxyalkylene) group, or a poly(oxyalkylene) group and one urethane bond, in that order, interposed therebetween, and (c) 1-20 parts by mass of a polymerization initiator that generates radicals by means of active energy rays. A hard coat film has a hard coat layer formed from said composition.

Description

Scratch-resistant coating hardenable composition

The present invention relates to a curable composition which is useful as a material for forming a hard coat layer which is applied to the surface of various display elements such as a touch panel display or a liquid crystal display.

Most of the products equipped with touch panels for flat panel displays such as personal computers, mobile phones, portable game devices, and ATMs are commercially available. In particular, with the advent of smart phones or tablets, the capacitive touch panel with multi-touch capability immediately increases the number of mounts.

Thinner tempered glass has been used on the surface of such touch panel displays, and a protective film is attached to the surface of the display in order to prevent the glass from scattering. Since the protective film is easily scratched by the glass because of the use of the plastic film, it is necessary to provide a hard coat layer excellent in scratch resistance on the surface. The scratch resistance of the surface of the plastic film is imparted, for example, by forming a highly crosslinked structure, that is, a crosslinked structure having a low molecular mobility, thereby improving the surface hardness and imparting resistance to external force.

As the hard coat forming material of these, the most used polyfunctional C The enoate-based material, which is mostly a monomer which is liquid at normal temperature, is subjected to 3-dimensional crosslinking by a radical generated from a photopolymerization initiator. Since the acrylate is cured by ultraviolet rays (UV), the time for irradiating UV is very short and energy-saving, so that it has high productivity. As a means for forming a hard coat layer on the surface of the plastic film, for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator, and an organic solvent is applied to a plastic film by gravure coating or the like, and after drying the organic solvent, ultraviolet rays are used. A means of hardening to form a hard coat. The hard coat layer to be formed is usually formed to have a thickness of 5 to 10 μm in order to exhibit a function of hardness, scratch resistance, and the like in a practically problematic level.

Moreover, the electrostatic capacitance type touch panel is operated by being touched by a human finger. Therefore, each time an operation is performed, a fingerprint is attached to the surface of the touch panel, which significantly impairs the visibility of the image of the display or impairs the appearance of the display. Since the fingerprint contains oil derived from sweat and oil derived from sebum, it is difficult to adhere to any of these, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the surface of the display.

From such a viewpoint, it is desirable that the surface of the touch panel display has antifouling properties against fingerprints and the like. However, in the electrostatic capacitance type touch panel, since the human eye touches with the finger, even if the initial antifouling property reaches a certain level, the function is often lowered during use. Therefore, there is a problem of durability against the antifouling property of the use process.

Conventionally, as a method of imparting antifouling properties to the surface of a hard coat layer, a method of adding a fluorine-based surface modifier to a coating liquid for forming a hard coat layer is used. The added fluorine compound is segregated due to its low surface energy The surface of the hard coat imparts water repellency and oil repellency. As the fluorine-based compound, an oligomer having a number average molecular weight of about 1,000 to 5,000, which is called a perfluoropolyether having a poly(oxyperfluoroalkylene) chain, is used from the viewpoint of water repellency and oil repellency. However, since perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in an organic solvent used for a coating liquid for forming a hard coat layer. Also, the hard coat layer formed causes aggregation.

In such a perfluoropolyether, in order to impart solubility to an organic solvent and dispersibility in a hard coat layer, a method of adding an organic moiety to a perfluoropolyether is used. Further, in order to impart scratch resistance, a method of bonding an active energy ray-curable portion represented by a (meth) acrylate group is used.

Heretofore, an antifouling hard coat layer having scratch resistance has been disclosed, and as a component for imparting antifouling properties to the surface of the hard coat layer, the end of the poly(oxyperfluoroalkylene) chain is different. A technique in which a compound having a (meth)acrylinyl group is used as a surface modifier in a complex urethane bond of a phorone skeleton (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-76029

The method specifically described in Patent Document 1 is a reaction of the first stage, that is, a perfluoropolyether having a hydroxyl group at both terminals and a diisocyanate. The reaction is difficult to control by the molecular weight of the formation of the polyurethane. Further, it is necessary to add the second-stage reaction, that is, a polyfunctional acrylate having a hydroxyl group, in a stepwise manner, and the synthesis method is troublesome. Further, since the highly polar urethane bond is added, there is a problem that the scratch resistance is lowered.

As a result of repeated efforts by the present inventors to achieve the above object, it has been found that both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group pass through a poly(oxyalkylene) group or a poly(oxyalkylene). a base and one urethane bond, and the perfluoropolyether having an active energy ray polymerizable group is excellent in solubility in a coating liquid for forming a hard coat layer and dispersibility in a hard coat layer, The curable composition used as the fluorine-based surface modifier as the fluorine-containing surface modifier has excellent scratch resistance and can form a hard coat layer exhibiting a non-uniform appearance, and the present invention has been completed.

In other words, the present invention relates to a curable composition comprising the following (a) to (c), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) The two ends of the molecular chain comprising a poly(oxyperfluoroalkylene) group are active through a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane bond. 0.1 to 10 parts by mass of the perfluoropolyether of the energy ray polymerizable group, and (c) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray.

The second aspect is the curable composition according to the first aspect, wherein the poly(oxyperfluoro-cyclohexane) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as a repeat The basis of the unit.

The third aspect of the invention is the curable composition according to the first aspect or the second aspect, wherein the poly(oxyalkylene) group is a poly(oxyalkylene) group having a repeating unit number of 5 to 12.

The curable composition according to any one of the first aspect to the third aspect, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group.

The curable composition according to any one of the first aspect to the fourth aspect, wherein the active energy ray-polymerizable group is a group having at least two or more active energy ray-polymerizable moieties.

The curable composition according to any one of the first aspect to the fifth aspect, wherein the polyfunctional single system of the component (a) is selected from the group consisting of polyfunctional (meth) acrylate compounds and At least one of the group consisting of polyfunctional urethane (meth) acrylate compounds.

The curable composition according to any one of the first aspect to the sixth aspect, further comprising (d) a solvent.

The eighth aspect relates to a cured film obtained by the curable composition according to any one of the first to seventh aspects.

According to a ninth aspect, a hard coat film comprising a hard coat film having a hard coat layer on a surface of at least one side of a film substrate, wherein the hard coat layer is formed of a cured film of the eighth aspect.

According to a tenth aspect, a hard coat film comprising a hard coat film having a hard coat layer on a surface of at least one side of a film substrate, the hard coat layer being The method comprising the steps of: applying a curable composition according to any one of the first to seventh aspects to a film substrate to form a coating film, and a step of curing the coating film by irradiating an active energy ray; Formed.

The hard coat film according to the ninth aspect or the tenth aspect, wherein the hard coat layer has a film thickness of from 1 to 10 μm.

The twelfth aspect relates to a perfluoropolyether compound which is bonded to a poly(oxyalkylene) group or a poly(oxyalkylene) at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group. The base and one urethane bond are in this order and have an active energy ray polymerizable group.

The perfluoropolyether compound according to the twelfth aspect, wherein the poly(oxyperfluoroalkylene) group has -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- Repeat the base of the unit.

The perfluoropolyether compound according to the twelfth aspect or the thirteenth aspect, wherein the poly(oxyalkylene) group is a poly(oxyalkylene) group having a repeating number of 5 to 12.

The perfluoropolyether compound according to any one of the fourteenth aspect, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group.

The perfluoropolyether compound according to any one of the above aspects, wherein the active energy ray-polymerizable group is a group having at least two or more active energy ray-polymerizable moieties.

The seventeenth aspect relates to a surface modifying agent comprising the perfluoropolyether compound according to any one of the twelfth to sixteenth aspects.

The ninth aspect relates to a surface modification of the perfluoropolyether compound according to any one of the twelfth to sixteenth aspects.

According to the present invention, it is possible to provide a cured film which is excellent in scratch resistance and excellent in appearance even in a film having a thickness of about 1 to 10 μm, and a curable composition which is useful for formation of a hard coat layer.

Moreover, according to the present invention, it is possible to provide a hard coat film which is provided on the surface by a cured film obtained from the curable composition or a hard coat layer formed therefrom, and provides a hard coat film excellent in scratch resistance and appearance.

<Sclerosing composition>

The curable composition of the present invention relates in detail to a curable composition comprising (a) to (c), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) comprising a poly(oxyperfluoroalkylene) group having both ends of a molecular chain passing through a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane bond in this order, and having an active energy 0.1 to 10 parts by mass of the perfluoropolyether of the linear polymerizable group, and (c) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray.

Hereinafter, each component of the above (a) to (c) will be described.

[(a) Active energy ray-curable polyfunctional monomer]

The active energy ray-curable polyfunctional monomer refers to a monomer which is cured by a polymerization reaction by irradiation with an active energy ray such as ultraviolet rays.

The curable composition of the present invention is preferably selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (methyl) as the (a) active energy ray-curable polyfunctional monomer. a monomer in the group consisting of acrylate compounds.

Further, the term "(meth)acrylate compound" as used in the present invention means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic means acrylic acid and methacrylic acid.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri(meth) acrylate, ditrimethylolpropane tetra(meth) acrylate, and pentaerythritol di(meth) acrylate. , pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethoxy Trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerol Acrylate, ethoxylated bisphenol A di(meth) acrylate, 1,3-propanediol di(meth) acrylate, 1,3-butanediol di(meth) acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1, 9-decanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate Two two Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylic acid Ester, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6] decane-dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-methyl-3-Bing Xixi Bing Xixi propane, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, 9,9-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]anthracene, bis[4 -(Meth)acryloylsulfonylphenyl]sulfide, bis[2-(methyl)propenylsulfonylethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1 3-adamantane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and the like.

Preferred examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

The above polyfunctional urethane (meth) acrylate compound is a compound having a propylene fluorenyl group or a methacryl fluorenyl group and having one or more urethane linkages (-NHCOO-) in one molecule.

For example, examples of the polyfunctional urethane (meth) acrylate include those obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a polyfunctional isocyanate having a hydroxyl group ( a reaction of a methyl group acrylate with a polyol, etc., but can be used in the present invention The polyfunctional urethane (meth) acrylate compound is not limited to this example only.

Further, examples of the polyfunctional isocyanate include toluene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, and hexamethylene diisocyanate.

Further, examples of the (meth) acrylate having the above hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.

Further, examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; A polyester polyol such as a reaction product of a diol and an aliphatic dicarboxylic acid or a dicarboxylic acid anhydride such as succinic acid, maleic acid or adipic acid; a polyether polyol; a polycarbonate diol or the like.

In the present invention, the (a) active energy ray-curable polyfunctional monomer may be selected from the above polyfunctional (meth) acrylate compound and the above polyfunctional urethane (meth) acrylate compound. One of the constituent groups is used alone or in combination of two or more. From the viewpoint of the scratch resistance of the obtained cured product, it is preferably used in combination as a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. Moreover, as the polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 5 or more functional groups and a polyfunctional (meth) acrylate compound having 4 or less functional groups are preferably used in combination.

Further, combining the above polyfunctional (meth) acrylate compound with the above When the functional urethane (meth) acrylate compound is used, it is preferred to use the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. ~100 parts by mass, more preferably 30 to 70 parts by mass.

Further, when the above-mentioned polyfunctional (meth) acrylate compound is used in combination with the above-described pentafunctional or higher polyfunctional (meth) acrylate compound and the above-described tetrafunctional or lower polyfunctional (meth) acrylate compound, 100 parts by mass of the polyfunctional (meth) acrylate compound having a functional or higher functional group is preferably 10 to 100 parts by mass, more preferably 20 to 60 parts by mass, based on the polyfunctional (meth) acrylate compound having 4 or less functional groups.

Further, it is preferred to use a polyfunctional urethane (meth) acrylate compound in an amount of 20 to 100 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and to have a polyfunctional function with respect to 5 or more functional groups. 100 parts by mass of the acrylate compound, 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, and a polyfunctional urethane for 100 parts by mass of the polyfunctional (meth) acrylate compound. 20 to 100 parts by mass of the (meth) acrylate compound, and 20 to 60 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functional groups, based on 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functional groups. The polyfunctional urethane (meth) acrylate compound is used in an amount of 30 to 70 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate compound, and is polyfunctional (meth) acrylate with respect to 5 or more functional groups. 100 parts by mass of the compound using a polyfunctional (meth) acrylate compound 10 of 4 or less functional groups ~100 parts by mass, based on 100 parts by mass of the polyfunctional (meth) acrylate compound, 30 to 70 parts by mass of a polyfunctional urethane (meth) acrylate compound and more than 5 functional groups or more 100 parts by mass of the acrylate compound is used in an amount of 20 to 60 parts by mass based on the polyfunctional (meth) acrylate compound having 4 or less functional groups.

[(b) at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group, through a poly(oxyalkylene) group or through a poly(oxyalkylene) group and a urethane bond Sequential, perfluoropolyether having active energy ray polymerizable groups]

In the present invention, as the component (b), it is used at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, through a poly(oxyalkylene) group or through a poly(oxyalkylene) group and one A perfluoropolyether having an active energy ray polymerizable group in the order of a urethane bond (hereinafter also referred to as "(b) a perfluoropolyether having a polymerizable group at both terminals"). The component (b) functions as a surface modifier for applying a hard coat layer of the curable composition of the present invention.

The number of carbon atoms of the alkyl group of the poly(oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly(oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorinated carbon group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and an oxyperfluoroalkylene group means having A structural group in which a divalent fluorinated carbon group having 1 to 4 carbon atoms is bonded to an oxygen atom. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene), -[OCF ₂ CF ₂ ]-(oxyperfluorovinyl), -[OCF ₂ CF ₂ CF ₂ ]-( A group such as oxyperfluoropropane-1,3-diyl), -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl).

The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more. In this case, the bonding of the plurality of oxyperfluoroalkylene groups may be block bonding or random bonding. Everything is fine.

Among these, from the viewpoint of obtaining a cured film having excellent scratch resistance, it is preferred to use -[OCF ₂ ]-(oxyperfluoromethylene) as the poly(oxyperfluoroalkylene) group. Both base and -[OCF ₂ CF ₂ ]-(oxyperfluorovinyl) are used as the basis of the repeating unit.

Wherein, as the poly(oxyperfluoroalkylene) group, it is preferred to include a repeating unit: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]-in a molar ratio [repeating unit: -[OCF ₂ ]-]: [Repeating unit: -[OCF ₂ CF ₂ ]-]= 2:1 to 1:2 ratio base, more preferably comprising a ratio of about 1:1. The bonding of these repeating units can be any of block bonding and random bonding.

The total number of repeating units of the above-mentioned oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21, as the total number of repeating units.

Further, the poly(oxyperfluoro-cyclohexane) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 2,000, as measured by polystyrene conversion by gel permeation chromatography.

The number of carbon atoms of the alkyl group of the poly(oxyalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the above poly(oxyalkylene) group means a group having a structure in which an alkylene group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and an oxygen-extended alkyl group means a valence of 2 to 4 carbon atoms. The base of the structure in which an alkyl group is bonded to an oxygen atom. Examples of the above alkylene group include a vinyl group, a 1-methylvinyl group, a trimethylene group, and a tetramethylene group. Wait.

The above-mentioned oxygen alkyl group may be used singly or in combination of two or more. In this case, the bonding of the plurality of oxygen-extended alkyl groups may be either a block bond or a random bond.

Among them, the above poly(oxyalkylene) group is preferably a poly(oxyethylene) group.

The number of repeating units of the oxygen-alkylene group in the poly(oxyalkylene) group is more preferably in the range of, for example, 1 to 15, for example, in the range of 5 to 12, for example, in the range of 7 to 12.

Examples of the active energy ray-polymerizable group bonded to the poly(oxyalkylene) group or the poly(oxyalkylene) group and the one urethane bond in this order include (meth)acryl fluorenyl group. Amino (meth) acrylonitrile, vinyl, and the like.

The active energy ray polymerizable group is not limited to an active energy ray polymerizable portion having one (meth) acrylonitrile group or the like, and may have two or more active energy ray polymerizable portions, and examples thereof include the following The structure of A1 to A5 and the structure in which the acryl fluorenyl group in the structure is substituted with a methacryl fluorenyl group.

The perfluoropolyether having a polymerizable group at both ends of (b) is exemplified by the ease of industrial production, and the compounds shown below and the propylene sulfhydryl groups in the compounds are methacryl A thiol-substituted compound is preferred. Further, in the structural formula, the A system represents one of the structures represented by the above formula [A1] to the formula [A5], the PFPE means the poly(oxyperfluoroalkylene) group, and n each independently represents the repetition of the oxyethylene group. The number of units is preferably from 1 to 15, more preferably from 5 to 12, and even more preferably from 7 to 12.

Wherein the perfluoropolyether having a polymerizable group at both ends of the (b) of the present invention is attached to the poly(oxyalkylene) group at both ends of the molecular chain including the poly(oxyperfluoroalkylene) group; a urethane bond in this order, that is, preferably a poly(oxyalkylene) group bonded to both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group, respectively Each poly(oxyalkylene) group at the end is bonded to a urethane bond, and each of the urethane bonds at the two ends is bonded to an active energy ray-polymerizable perfluoropolyether. Further, the perfluoropolyether is preferably a perfluoropolyether having at least two or more active energy ray-polymerizable moieties of active energy ray-polymerizable groups.

In the present invention, (b) the perfluoropolyether having a polymerizable group at both terminals is preferably 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the above (a) active energy ray-curable polyfunctional monomer. Use in a ratio of 0.2 to 5 parts by mass.

The above (b) a perfluoropolyether having a polymerizable group at both terminals, for example, a compound having a hydroxyl group which is transmitted through a poly(oxyalkylene) group at both ends of a poly(oxyperfluoroalkylene) group The hydroxyl group at both ends is an amine compound having a polymerizable group such as 2-(meth)acryloxyethyl isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate. a method for the esterification reaction, a method for dehydrochlorination of (meth)acrylic acid chloride or chloromethylstyrene, and a (meth)acrylic acid A method of performing a dehydration reaction, a method of subjecting itaconic anhydride to an esterification reaction, and the like.

Wherein, a compound having a hydroxyl group which passes through a poly(oxyalkylene) group at both ends of a poly(oxyperfluoroalkylene) group, and a 2-(meth)acryloxyethyl group for a hydroxyl group at both ends thereof a method for performing a urethanization reaction of an isocyanate compound having a polymerizable group such as an isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate, or The method of dehydrochlorination of acrylic acid chloride or chloromethylstyrene is particularly preferable in terms of easy reaction.

Further, the curable composition of the present invention contains, in addition to (b) a terminal of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a permeated poly(oxyalkylene). a perfluoropolyether having a base and one urethane bond in this order, and having an active energy ray polymerizable group, may comprise a perfluoropolyether: comprising a poly(oxyperfluoroalkylene) group One end of the molecular chain passes through a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane bond in this order, and has an active energy ray polymerizable group, and is polymerized at the other end thereof ( a perfluoropolyether having a hydroxyl group or a perfluoropolyether having a hydroxyl group which is transmitted through a poly(oxyalkylene) group at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group [ a compound having no active energy ray polymerizable group].

Further, the above (b) is at both ends of the molecular chain comprising a poly(oxyperfluoroalkylene) group, passes through a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane. A perfluoropolyether compound having an active energy ray polymerizable group in this order, and also a subject of the present invention, a surface modifier composed of a perfluoropolyether compound having a polymerizable group at both ends, The use of surface modification with the perfluoropolyether compound is also an object of the present invention.

[(c) Polymerization initiator which generates radicals by active energy rays]

In the curable composition of the present invention, a polymerization initiator which generates a radical by an active energy ray (hereinafter also referred to simply as "(c) polymerization initiator") is preferably used, for example, by electron beam, ultraviolet ray, An active energy ray such as X-ray or the like, especially a polymerization initiator which generates a radical by ultraviolet irradiation.

Examples of the (c) polymerization initiator include benzoin, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, and sulfhydryl groups. Phosphine oxides, oxime esters, organic peroxides, benzophenones, dicoumarins, biimidazoles, titanocarbons, mercaptans, halogenated hydrocarbons, trichloromethyltriazines, Or iodonium salts, barium salts, etc. These may be used alone or in combination of two or more.

In the present invention, from the viewpoint of transparency, surface hardenability, and film curability, it is preferred to use an alkyl benzophenone as the (c) polymerization initiator. By using an alkyl phenone, a cured film having improved scratch resistance can be obtained.

Examples of the alkylphenones include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-hydroxy-1-(4- (2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropenyl)benzyl) Alpha-hydroxyalkylphenones such as phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylpropane- 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) α-Aminoalkylphenones such as alkyl-1-ketone; 2,2-dimethoxy-1,2-diphenylethane-1-one; methyl phenylglyoxylate and the like.

In the present invention, it is desirable that the (c) polymerization initiator is used in an amount of from 1 to 20 parts by mass, preferably from 2 to 10 parts by mass, per 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.

[(d) Solvent]

The curable composition of the present invention may further comprise (d) a solvent, or may be in the form of a varnish (film forming material).

In the above-mentioned solvent, the components (a) to (c) described above may be dissolved, and the cured film (hard coat layer) to be described later may be appropriately selected in consideration of workability at the time of the coating work, drying property before and after curing, and the like. Examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, and cyclohexane; Methyl, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, etc.; ethyl acetate, butyl acetate Esters or ester ethers of esters, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate; diethyl ether, Tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether An ether such as propylene glycol mono-n-butyl ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone or cyclohexanone; methanol, ethanol, n -C , Isopropyl alcohol, N- butyl alcohol, isobutyl alcohol, ferf-butyl alcohol, 2-ethylhexyl alcohol, benzyl An alcohol such as an alcohol or an ethylene glycol; an amide such as N,N-dimethylformamide or N,N-dimethylacetamide; an anthracene such as dimethyl anthracene; N- A heterocyclic compound such as methyl-2-pyrrolidone or a mixed solvent of two or more of these.

The amount of the solvent used in the above (d) is not particularly limited. For example, the solid content of the curable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. The solid content concentration (also referred to as the non-volatile component concentration) herein means the total mass of the above components (a) to (d) (and other additives as desired) with respect to the curable composition of the present invention ( The total mass) solid content (the solvent component is removed from the total component).

[Other Additives]

Further, the curable composition of the present invention does not impair the effects of the present invention, and if necessary, may be appropriately blended with generally added additives such as a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, and a sealant. A property-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like.

<hardened film>

The curable composition of the present invention can be formed by coating on a substrate to form a coating film, and the coating film is irradiated with an active energy ray to be polymerized (hardened) to form a cured film. This cured film is also an object of the present invention. Further, a hard coat layer of a hard coat film to be described later may be formed of the cured film.

As the aforementioned substrate in this case, for example, various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) can be cited. Polyester, polyolefin, polyamide, polyimine, epoxy resin, melamine resin, triethylene glycol, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-benzene Ethylene copolymer (AS), decene-based resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these substrates may be a plate shape, a film shape or a ternary shape.

For the coating method on the substrate, a cast coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, or the like can be appropriately selected. Printing method (relief, gravure, lithography, screen printing, etc.), etc., which can be used in a roll-to-roll method, and from the viewpoint of film coating properties, it is desirable to use a relief printing method. In particular, gravure coating is used. Further, it is preferred to apply a filter curable composition such as a filter having a pore diameter of about 0.2 μm beforehand, and then apply it to the coating. Further, at the time of coating, if necessary, a solvent may be added to the curable composition to form a varnish. The solvent in this case is exemplified by the various solvents exemplified in the above [(d) solvent].

After applying a curable composition to a substrate to form a coating film, if necessary, the coating film is preliminarily dried by a hot plate or an oven to remove the solvent (solvent removal step). The heating and drying conditions at this time are, for example, preferably carried out at 40 to 120 ° C for about 30 seconds to 10 minutes.

After drying, the active energy rays such as ultraviolet rays are irradiated to harden the coating film. Examples of the active energy ray include ultraviolet rays, electron beams, and X-rays. For ultraviolet light. As a light source used for ultraviolet irradiation, a solar light, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.

Further, after the post-baking, specifically, heating can be carried out by using a hot plate, an oven or the like to complete the polymerization.

Further, the thickness of the formed cured film is usually 0.01 to 50 μm, preferably 0.05 to 20 μm after drying and hardening.

<hard coated film>

A hard coat film having a hard coat layer can be produced on the surface (surface) of at least one side of the film substrate by 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 example, to protect the surface of various display elements such as a touch panel or a liquid crystal display.

The hard coat layer of the hard coat film of the present invention may comprise a step of forming a coating film by applying the curable composition of the present invention to a film substrate, and an active energy ray for irradiating ultraviolet rays or the like on the coating film. The method of the step of hardening the coating film is formed.

As the film substrate, among the substrates listed in the above-mentioned "cured film", various transparent resin films which can be used for optical use are used. Preferred examples thereof include polyesters selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polycarbonate. A film made of a resin such as polymethacrylate, polystyrene, polyolefin, polyamine, polyimine or triacetyl cellulose.

Further, a method of applying a curable composition on the film substrate (The coating film forming step) and the active energy ray irradiation method (hardening step) for the coating film can be carried out by the method described in the above-mentioned "cured film". Further, in the case where the polymer composition of the present invention contains a solvent (varnish form), after the coating film forming step, a step of drying the coating film to remove the solvent may be included if necessary. In this case, the drying method (solvent removal step) of the coating film mentioned in the above-mentioned <hardened film> can be used.

The film thickness of the hard coat layer thus obtained is preferably from 1 to 20 μm, more preferably from 1 to 10 μm.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples described below.

Further, in the examples, the apparatus and conditions for the preparation of the sample and the analysis of the physical properties are as follows.

(1) Gel Permeation Chromatography (GPC)

Device: Tosoh (share) system HLC-8220GPC

Pipe column: Shodex (registered trademark) GPC K-804L, GPC K-805L by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Dissolution: tetrahydrofuran

Detector: RI

(2) Bar coating

Device: (share) SMT system PM-9050MC

Stick: OSG system product (stock) A-Bar OSP-30, maximum wet film thickness 30μm (equivalent to Wire bar#12)

Coating speed: 4m/min

(3) Oven

Device: Advantech Toyo Co., Ltd. Dust Free Dryer DRC433FA

(4) UV hardening

Device: Heraeus (share) system CV-110QC-G

Light: Heraeus (Holdings) High Pressure Mercury Lamp H-bulb

(5) Scratch test

Device: Xindong Science (share) system Round-trip friction test machine TRIBOGEAR TYPE: 30S

Scanning speed: 3,000mm/min

Scanning distance: 50mm

(6) Total light transmittance, haze

Device: Japan Electro-Color Industry Co., Ltd. Haze meter NDH5000

(7) Contact angle

Device: Concord Interface Science (share) system DropMaster DM-501

Measuring temperature: 20 ° C

Also, the abbreviation indicates the following meaning.

PFPE1: a perfluoropolyether having a hydroxyl group at a poly(oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers Co., Ltd.]

PFPE2: through the poly(oxyalkylene) group at both ends (repeating unit number 5~ 6) Perfluoropolyether having a hydroxyl group [Fluorolink 5158X manufactured by Solvay Specialty Polymers Co., Ltd.]

PFPE3: a perfluoropolyether having a hydroxyl group at a poly(oxyalkylene) group (repeating unit number of 3 to 4) at both ends [Fluorolink E10H manufactured by Solvay Specialty Polymers Co., Ltd.]

PFPE4: a perfluoropolyether having a hydroxyl group at both ends which does not pass through a poly(oxyalkylene) group [Fluorolink D10H manufactured by Solvay Specialty Polymers Co., Ltd.]

BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI by Showa Denko Co., Ltd.]

HDI: hexamethylene diisocyanate [DURANATE (registered trademark) 50M-HDI by Asahi Kasei Chemicals Co., Ltd.]

DBTDL: Dibutyltin dilaurate [Tokyo Chemical Industry Co., Ltd.]

DOTDD: Dioctyl tin decanoate [M5CAT-05, Japan Chemical Industry Co., Ltd.]

DPHA: dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD DPHA manufactured by Nippon Kayaku Co., Ltd.]

PETA: pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Naka Nakamura Chemical Industry Co., Ltd. NK ester A-TMM-3LM-N]

UA: 6-functional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by DAICEL-ALLNEX Co., Ltd.]

I2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [BASF Japan IMGCURE 2959]

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

PGME: propylene glycol monomethyl ether

[Example 1] Production of perfluoropolyether SM1 having an acrylonitrile group through a poly(oxyalkylene) group and a urethane bond at both ends

PFPE1 1.05g (0.5mmol), BEI 0.26g (1.0mmol), DBTDL 0.01g (0.02mmol), and MEK 1.30g were placed in the threaded tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stirrer wafer. This reaction mixture was diluted with MEK 3.93 g to obtain a 20% by mass MEK solution of the objective compound, that is, SM1.

The weight average molecular weight measured by polystyrene conversion of the obtained GPC of SM1 was Mw of 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.1.

[Example 2] Production of perfluoropolyether SM2 having an acrylonitrile group through a poly(oxyalkylene) group and a urethane bond at both terminals

1.89 g (1.0 mmol) of PFPE2, 0.52 g (2.0 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL, and 2.41 g of MEK were placed in the screw tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stirrer wafer to obtain a 50% by mass MEK solution of the objective compound, that is, SM2.

The weight average molecular weight measured by polystyrene conversion of the obtained GPC of SM2 was Mw of 2,800 and the degree of dispersion: Mw/Mn was 1.2.

[Synthesis Example 1] Permeation of a poly(oxyalkylene) group and two urethanes at both ends Manufacture of perfluoropolyether SM3 with acrylonitrile group as a bond

HDI 0.3 g (2 mmol), PETA 1.1 g (2 mmol), DOTDD 0.03 g (0.05 mmol), and MEK 3.0 g were placed in a screw tube. This mixture was stirred at room temperature (about 23 ° C) for 4 hours using a stirrer wafer. 1.6 g (0.8 mmol) of PFPE3 was added thereto, and the mixture was further stirred for 24 hours to obtain a 50% by mass MEK solution of the target compound, SM3.

The weight average molecular weight measured by polystyrene conversion of the obtained GPC of SM3: Mw was 4,800, and the degree of dispersion: Mw/Mn was 1.1.

[Synthesis Example 2] Production of perfluoropolyether SM4 having an acrylonitrile group at both terminals

PFPE4 2.0 g (1.0 mmol), BEI 0.52 g (2.0 mmol), DBTDL 0.01 g (0.02 mmol), and MEK 2.52 g were placed in a threaded tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stirrer wafer to obtain a 50% by mass MEK solution of the intended compound, SM4.

The weight average molecular weight measured by polystyrene conversion of GPC of the obtained SM4: Mw was 2,200, and the degree of dispersion: Mw/Mn was 1.1.

[Examples 3 and 4, Comparative Examples 1, 2]

The following components were mixed as described in Table 1, and the curable composition of the solid content concentration shown in Table 1 was prepared. Further, the term "solid fraction" as used herein refers to a component other than a solvent. In addition, the "parts" in the table means [parts by mass].

(1) Polyfunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA

(2) Surface modifier: The surface modifier described in Table 1 is based on Table 1. The amount recorded (solid fraction conversion)

(3) Polymerization initiator: I2959 5 parts by mass

(4) Solvent: PGME 155 parts by mass

This curable composition was applied by a bar coating on both sides of the A4 size, and then a PET film (Lumilar (trademark) U403, thickness: 100 μm manufactured by Toray Industries, Inc.) was easily applied to obtain a coating film. The coating film was dried in an oven at 120 ° C for 3 minutes to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 200 mJ/cm ² in a nitrogen atmosphere to prepare a hard coat film having a hard coat layer (cured film) having a film thickness of about 6 μm.

The homogeneity of each of the curable compositions and the appearance, scratch resistance, total light transmittance, haze, and contact angle of water and oleic acid of the obtained hard coat film were evaluated. The evaluation order of the composition homogeneity, appearance, scratch resistance, and contact angle is shown below. The results are shown together in Table 2.

[composition homogeneity]

The appearance of the curable composition after the preparation for 2 hours was visually confirmed and evaluated based on the following criteria.

A: Become a transparent solution

C: It is white and turbid

[Exterior]

The appearance of the hard coat film was visually confirmed and evaluated based on the following criteria.

A: There is no non-uniformity through the hard coating.

C: the unevenness of the plaque in the hard coating completely precipitates the condensate is very obvious

[scratch resistance]

The surface of the hard coat layer was wound with a load of 1 kg/cm ² by a steel wool (Bonstar (registered trademark) #0000 (superfine) manufactured by Bonstar Trading Co., Ltd.), and 5,000 round-trip wipes were applied thereto. Partly marked with oily [Zebra's McKee is very fine (blue), using thin side] to draw lines. Then, the line to be drawn was wiped with a non-woven wiper [BEMCOT M-1 made by Asahi Kasei Fiber Co., Ltd.], and the degree of scratch was visually confirmed and evaluated according to the following criteria. Also, as a hard coat layer, assuming at the actual use, seek at least B, and expect A to be.

A: No scratches are drawn with oily marks.

B: The line drawn by oily marks can be clearly wiped off by rare scratches.

C: oily mark ink penetrates into the wound and cannot be wiped off

[Contact angle]

1 μL of water or oleic acid was attached to the surface of the hard coat layer, and the contact angle θ after 5 seconds was measured at 5 points, and the average value was defined as a contact angle value.

As shown in Table 1, as a surface modifying agent for a hard coat layer, a perfluoropolyether SM1 having a propylene group based on a poly(oxyalkylene) group and a urethane bond at both ends is used. The hardenable compositions of Examples 3 and 4 of SM2 exhibited a transparent solution, and each of the hard coat films produced using these curable compositions was excellent in scratch resistance and had no non-uniform appearance.

On the other hand, as a surface modifier of a hard coat layer, a perfluoropolyether having a propylene fluorenyl group is used instead of a poly(oxyalkylene) group and a urethane bond at both ends. Passing poly(oxyalkylene) at both ends Comparative Example 1 in which the perfluoropolyether SM3 having an acryl fluorenyl group and two urethane groups and the urethane group have a large deterioration in scratch resistance, and the precipitation of the hard coat layer is fully exhibited. Condensate, the appearance of patchy non-uniformity is very obvious.

Further, as a surface modifying agent, in Comparative Example 2 in which a perfluoropolyether SM4 having an acryl fluorenyl group at the both ends thereof is not transmitted through a poly(oxyalkylene) group, the composition is cloudy and the homogeneity is deteriorated, and further, from the composition The hard coat layer obtained by the object was deteriorated in abrasion resistance as compared with the examples, and the appearance was also largely deteriorated.

As described above, as a result of the examples, the structure of the terminal of the perfluoropolyether used as the surface modifier is only slightly different, that is, a hardenable composition which is not homogeneous, and which is produced by the composition The hard coat layer is difficult to obtain satisfactory scratch resistance and appearance, and only the hardenable composition of the present invention can obtain a hard coat film which satisfies all of such properties.

Claims (18)

A curable composition comprising the following (a) to (c), (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, and (b) comprising a poly(oxyperfluoroalkylene) group; The two ends of the molecular chain pass through a poly(oxyalkylene) group or a poly(oxyalkylene) group and a urethane bond in this order, and the perfluoropolyether having an active energy ray polymerizable group is 0.1. ~10 parts by mass, and (c) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray. The hardenable composition of claim 1, wherein the poly(oxyperfluoro-cyclohexane) group has a group of -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as a repeating unit. The hardenable composition of claim 1 or claim 2, wherein the poly(oxyalkylene) group is a poly(oxyalkylene) group having a repeating number of 5 to 12. The curable composition according to any one of claims 1 to 3, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group. The curable composition according to any one of claims 1 to 4, wherein the active energy ray-polymerizable group is a group having at least two or more active energy ray-polymerizable moieties. The sclerosing composition according to any one of the preceding claims, wherein the polyfunctional single system of the component (a) is selected from the group consisting of polyfunctional (meth) acrylate compounds and polyfunctional urethanes. At least one of the group consisting of (meth) acrylate compounds. The sclerosing composition according to any one of claims 1 to 6, further comprising (d) a solvent. A cured film obtained by the curable composition according to any one of claims 1 to 7. A hard coat film comprising a hard coat film of a hard coat layer on a surface of at least one side of a film substrate, the hard coat layer being composed of the cured film of claim 8. A hard coat film comprising a hard coat film having a hard coat layer on a surface of at least one side of a film substrate, the hard coat layer comprising: hardening according to any one of claim 1 to claim 7 The step of applying a composition on a film substrate to form a coating film, and a step of curing the coating film by irradiating an active energy ray to form a film. The hard coat film of claim 9 or claim 10, wherein the hard coat layer has a film thickness of 1 to 10 μm. A perfluoropolyether compound which is bonded to a poly(oxyalkylene) group or a poly(oxyalkylene) group and an amine group at both ends of a molecular chain comprising a poly(oxyperfluoroalkylene) group. The formate bond is in this order and has an active energy ray polymerizable group. The perfluoropolyether compound according to claim 12, wherein the poly(oxyperfluoroalkylene) group has a group of -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as a repeating unit. The perfluoropolyether compound according to claim 12 or claim 13, wherein the poly(oxyalkylene) group is a poly(oxyalkylene) group having a repeating unit number of 5 to 12. The perfluoropolyether compound according to any one of claims 12 to 14, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group. The perfluoropolyether compound according to any one of claims 12 to 15, wherein the active energy ray-polymerizable group is a group having at least two or more active energy ray-polymerizable moieties. A surface modifying agent comprising the perfluoropolyether compound according to any one of claim 12 to claim 16. A use for surface modification of a perfluoropolyether compound according to any one of claims 12 to 16.