CN113423513A - Curable composition for light-resistant hard coating - Google Patents

Curable composition for light-resistant hard coating Download PDF

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CN113423513A
CN113423513A CN202080013139.3A CN202080013139A CN113423513A CN 113423513 A CN113423513 A CN 113423513A CN 202080013139 A CN202080013139 A CN 202080013139A CN 113423513 A CN113423513 A CN 113423513A
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curable composition
group
hard coat
active energy
film
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CN113423513B (en
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辻本晴希
原口将幸
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Nissan Chemical Corp
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • 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
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    • C08J7/04—Coating
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The invention provides a material for forming a hard coat layer, which exhibits high scratch resistance and light resistance. A curable composition and a hard coat film provided with a hard coat layer formed from the composition, the curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 0.1 to 30 parts by mass of an ultraviolet absorber having a benzophenone skeleton; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

Description

Curable composition for light-resistant hard coating
Technical Field
The present invention relates to a light-resistant hard coat material (curable composition) useful as a material for forming a hard coat layer applied to the surface of various display elements such as touch panel displays and liquid crystal displays.
Background
A touch panel display using a liquid crystal display element or an OLED (organic EL) display element, which can be operated by a finger of a person, is provided in many electronic devices such as home electric appliances such as televisions, communication devices such as mobile phones, office equipment such as copiers, entertainment equipment such as game machines, medical equipment such as X-ray imaging devices, and living equipment such as microwave ovens. A hard coat film in which a hard coat layer is provided on a transparent plastic film as a substrate is used on the outermost surface of these touch panel displays, wherein the hard coat layer has: scratch resistance for preventing the surface of the touch panel from being damaged by a nail or the like when the touch panel is operated by a human finger; and stain resistance for making it difficult for fingerprint stains attached to a finger to be attached and easy to be wiped off when touched by a person.
In general, as a method for imparting scratch resistance to a hard coat layer, for example, a method of improving surface hardness and providing resistance to external force by forming a high-density crosslinked structure, that is, a crosslinked structure having low molecular mobility is employed. As a material for forming these hard coatings, a multifunctional acrylate-based material three-dimensionally crosslinked by radical polymerization using active energy rays is most commonly used at present. As a method for forming a hard coat layer on the surface of a transparent plastic film, for example, a method is employed in which 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, the organic solvent is dried, and then cured by ultraviolet rays to form a hard coat layer. In the hard coat layer formed, the thickness of the hard coat layer is usually 1 μm to 15 μm to exhibit functions such as hardness and scratch resistance at a level that is practically free from problems.
Further, some of the devices provided with a touch panel display are used outdoors, and the surface of the touch panel and the hard coat film are exposed to ultraviolet rays. Some of transparent plastic films used as substrates for hard coat films are significantly yellowed and deteriorated by exposure to ultraviolet light for a short period of time. Since a hard coat film is required to have high transparency in a touch panel display, the hard coat layer is required to have light resistance to prevent yellowing and deterioration of the hard coat film caused by ultraviolet rays. As a method for imparting light resistance to a hard coat layer in general, there is a method of adding an ultraviolet absorber to a curable composition for forming a hard coat layer in advance. However, since the ultraviolet absorber absorbs active energy rays for causing a curing reaction by radical polymerization, the formation of a three-dimensional crosslinked structure of the polyfunctional acrylate is generally hindered. As described above, the scratch resistance and light resistance of the hard coat layer are in a trade-off relationship, and the compatibility of the properties of both becomes a problem. On the other hand, there is reported a technique of: by using a combination of a polyfunctional urethane (meth) acrylate oligomer and a triazine-based ultraviolet absorber, a hard coat layer having both a certain light resistance and scratch resistance is obtained on a plastic film having a problem in light resistance (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6020670
Disclosure of Invention
Problems to be solved by the invention
However, the hard coat layer described in patent document 1 has a high light resistance to ultraviolet rays having a wavelength of 300nm or more, but has a problem of insufficient scratch resistance.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a curable composition capable of forming a hard coat layer having excellent light resistance and excellent scratch resistance not only in a region having a wavelength of 300nm or more but also in an ultraviolet ray region having a wavelength of less than 300nm on a plastic film having a problem in light resistance, has completed the present invention, the curable composition comprising: a perfluoropolyether containing a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group at both ends of a molecular chain thereof via a urethane bond without via the poly (oxyalkylene) group; and a specific ultraviolet absorber.
That is, the present invention relates to, as a first aspect, a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 0.1 to 30 parts by mass of an ultraviolet absorber having a benzophenone skeleton; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
A second aspect relates to the curable composition according to the first aspect, wherein the ultraviolet absorber (c) has at least two hydroxyl groups.
A third aspect relates to the curable composition according to the first or second aspect, wherein the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A fourth aspect of the present invention relates to the curable composition according to the third aspect, wherein the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A fifth aspect of the present invention is the curable composition according to any one of the first to fourth aspects, wherein the poly (oxyperfluoroalkylene) group has a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
A sixth aspect relates to the curable composition according to the fifth aspect, wherein the perfluoropolyether (c) has a partial structure represented by the following formula [1 ].
Figure BDA0003200134660000031
(the above formula [1]]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-a total number of numbers of 5 to 30, said repeating units- [ OCF2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding. )
A seventh aspect relates to the curable composition of any one of the first to sixth aspects, wherein a part or all of the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
An eighth aspect relates to the curable composition of any one of the first to seventh aspects, wherein the (a) polyfunctional monomer is an oxyalkylene-modified polyfunctional monomer.
A ninth aspect relates to the curable composition of any one of the first to eighth aspects, wherein the polyfunctional monomer (a) is a polyfunctional monomer having at least three active energy ray-polymerizable groups.
A tenth aspect relates to the curable composition according to any one of the first to ninth aspects, further comprising (e) a solvent.
An eleventh aspect relates to a cured film obtained from the curable composition according to any one of the first to tenth aspects.
A twelfth aspect relates to a hard coat film comprising a hard coat layer formed from the cured film according to the eleventh aspect on at least one side of a film base.
A thirteenth aspect of the present invention relates to a method for producing a hard coat film, including a hard coat layer provided on at least one surface of a film base, the hard coat layer including: a step of applying the curable composition according to any one of the first to tenth aspects to a film substrate to form a coating film; and a step of irradiating the coating film with an active energy ray to cure the coating film.
Effects of the invention
The present invention provides a curable composition useful for forming a cured film and a hard coat layer having excellent scratch resistance and excellent light resistance even in a thin film having a thickness of about 1 to 15 μm.
Further, according to the present invention, a hard coating film having a surface provided with a cured film obtained from the curable composition or a hard coating layer formed therefrom can be provided, and a hard coating film excellent in scratch resistance and light resistance can be provided.
In particular, according to the present invention, a hard coat film having a hard coat layer excellent in light resistance and scratch resistance not only in a wavelength region of 300nm or more but also in ultraviolet rays in a wavelength region of less than 300nm, which is preferably applied to the surface of a substrate such as the surface of a display used outdoors, can be provided.
Detailed Description
< curable composition >
More specifically, the curable composition of the present invention relates to a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 0.1 to 30 parts by mass of an ultraviolet absorber having a benzophenone skeleton; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
Hereinafter, the respective components (a) to (d) will be described first.
[ (a) active energy ray-curable polyfunctional monomer ]
(a) The active energy ray-curable polyfunctional monomer (hereinafter, simply referred to as "polyfunctional monomer (a)") of the component (a) means a monomer having two or more active energy ray-polymerizable groups which are cured by a polymerization reaction by irradiation with an active energy ray such as ultraviolet ray. Examples of the active energy ray-polymerizable group include a (meth) acryloyl group, a vinyl group, and the like.
In the curable composition of the present invention, the active energy ray-curable polyfunctional monomer (a) is preferably a monomer selected from the group consisting of polyfunctional (meth) acrylate compounds, a monomer selected from the group consisting of polyfunctional urethane (meth) acrylate compounds described later, and a monomer selected from the group consisting of lactone-modified polyfunctional (meth) acrylate compounds. In the present invention, the active energy ray-curable polyfunctional monomer (a) may be used alone or in combination of two or more from the group consisting of the polyfunctional (meth) acrylate compounds.
In the present invention, the (meth) acrylate compound means both of an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
The polyfunctional monomer (a) may be an oxyalkylene-modified polyfunctional monomer, and the oxyalkylene modification includes: oxymethylene modification, oxyethylene modification, oxypropylene modification, and the like. Examples of the oxyalkylene-modified polyfunctional monomer include compounds obtained by modifying the above polyfunctional (meth) acrylate compound (or polyfunctional urethane (meth) acrylate compound) with an oxyalkylene group. The oxyalkylene-modified polyfunctional monomer may be used singly or in combination of two or more.
In the present invention, as the above-mentioned (a) polyfunctional monomer, a polyfunctional monomer having at least three, for example, at least four active energy ray-polymerizable groups can be used.
For example, in the present invention, as the above-mentioned (a) polyfunctional monomer, a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth) acrylate compounds having at least three active energy ray-polymerizable groups can be used.
Examples of the polyfunctional (meth) acrylate compound (compound having no urethane bond) 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, glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerol tri (meth) 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, glycerol tri (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, and mixtures thereof, 1, 6-hexanediol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylateEthylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.02，6]Decane dimethanol di (meth) acrylate, dioxane diol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl]Fluorene, bis [ 4- (meth) acryloyl-thiophenyl]Thioether, bis [ 2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like.
Among them, preferable polyfunctional (meth) acrylate compounds include: pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the oxyalkylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of polyhydric alcohols modified with an oxyalkylene group.
Examples of the polyol include: glycerin, diglycerin, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
The polyfunctional urethane (meth) acrylate compound has a plurality of acryloyl groups or methacryloyl groups in 1 molecule and has one or more urethane bonds (-NHCOO-).
Examples of the polyfunctional urethane (meth) acrylate compound include: a compound obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, a compound obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group and a polyol, and the like, but the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to these examples.
Examples of the polyfunctional isocyanate include: toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.
Examples of the (meth) acrylate having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.
Examples of the polyol include: glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids such as succinic acid, maleic acid and adipic acid, or dicarboxylic anhydrides; a polyether polyol; polycarbonate diols, and the like.
(a) The active energy ray-polyfunctional monomer may be a lactone-modified polyfunctional (meth) acrylate compound, and preferably epsilon-caprolactone as a modified lactone. Examples of the lactone-modified polyfunctional (meth) acrylate compound include: and epsilon-caprolactone-modified pentaerythritol tri (meth) acrylate, epsilon-caprolactone-modified pentaerythritol tetra (meth) acrylate, epsilon-caprolactone-modified dipentaerythritol penta (meth) acrylate, and epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate.
[ (b) a perfluoropolyether having a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group at both ends of the molecular chain via a urethane bond (except for the perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond) ]
In the present invention, as the component (b), a perfluoropolyether containing a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group via a urethane bond without via the poly (oxyalkylene) group at both ends of the molecular chain thereof (hereinafter, simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain) is used. (b) The component (a) functions as a surface modifier in a hard coat layer to which the curable composition of the present invention is applied.
Further, the hard coat layer having a transparent appearance can be formed by suppressing the generation of white turbidity by the excellent compatibility of the component (b) and the component (a).
The poly (oxyalkylene) group is a group in which the number of repeating units of an oxyalkylene group is 2 or more and an alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately bonded, and the oxyperfluoroalkylene group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are bonded. Specifically, it includes- [ OCF ]2]- (perfluoromethylene oxide), - [ OCF2CF2]- (perfluoroethylene oxide), - [ OCF2CF2CF2]- (Oxoperfluoropropane-1, 3-diyl), [ OCF2C(CF3)F]- (perfluoropropane oxide-1, 2-diyl), and the like.
The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more, and in this case, the bonding of the multiple oxyperfluoroalkylene groups may be either of a block bonding and a random bonding.
Among them, it is preferable to use a poly (oxyperfluoroalkylene) group having- [ OCF ] as a poly (oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film having good scratch resistance2]- (perfluoromethylene oxide) and- [ OCF2CF2]Both of (perfluoroethylene oxide) are heavyA group of multiple units.
Among them, as the poly (oxyperfluoroalkylene) group, preferred is a poly (oxyperfluoroalkylene) group in which: - [ OCF2]And- [ OCF2CF2]-as [ repeating units: - [ OCF2]－]: [ repeating unit: - [ OCF2CF2]－]2: 1-1: 2, more preferably, in a ratio of about 1: the ratio of 1 comprises the groups of the above repeating units. The bonding of these repeating units may be either block bonding or random bonding.
The number of the repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, in terms of the total number of the repeating units.
The poly (oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1000 to 5000, preferably 1500 to 3000, as measured in terms of polystyrene by Gel Permeation Chromatography (GPC).
Examples of the active energy ray-polymerizable group include a (meth) acryloyl group, a vinyl group and the like.
(b) The perfluoropolyether having polymerizable groups at both ends of the molecular chain is not limited to those having active energy ray-polymerizable groups such as one (meth) acryloyl group at both ends of the molecular chain, and may have two or more active energy ray-polymerizable groups at both ends of the molecular chain, and examples of the terminal structure including active energy ray-polymerizable groups include structures represented by the following formulas [ a1] to [ a5], and structures in which acryloyl groups in these structures are substituted with methacryloyl groups.
Figure BDA0003200134660000091
Examples of the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2 ].
Figure BDA0003200134660000092
(formula [2]]Wherein A represents the formula [ A1]]-formula [ A5]PFPE represents one of the structures shown and structures in which an acryloyl group in their structures is substituted with a methacryloyl group, and the poly (oxyperfluoroalkylene) group (wherein, with L, a group represented by formula1The side directly bonded is an oxy terminus and the side bonded to the oxygen atom is a perfluoroalkylene terminus. ) L is1Each represents an alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms, m independently represents an integer of 1 to 5, and L2Represents a residue of valence m +1 with OH removed from m +1 polyol. )
Examples of the alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms include: -CH2CHF－、－CH2CF2－、－CHFCF2－、－CH2CH2CHF－、－CH2CH2CF2－、－CH2CHFCF2-etc., preferably-CH2CF2－。
As the above formula [2]Partial structure of the shown compound (A-NHC (═ O)mL2Examples thereof include the following formula [ B1]-formula [ B12]The structure shown, etc.
Figure BDA0003200134660000101
Figure BDA0003200134660000111
(in the formulae [ B1] to [ B12], A represents one of the structures represented by the formulae [ A1] to [ A5] and a structure in which an acryloyl group in the structures is replaced by a methacryloyl group.)
In the structures represented by formulas [ B1] to [ B12], formula [ B1] and formula [ B2] correspond to the case where m is 1, formula [ B3] to formula [ B6] correspond to the case where m is 2, formula [ B7] to formula [ B9] correspond to the case where m is 3, and formula [ B10] to formula [ B12] correspond to the case where m is 5.
Among them, the structure represented by the formula [ B3] is preferable, and the combination of the formula [ B3] and the formula [ A3] is particularly preferable.
Preferable (b) perfluoropolyether having a polymerizable group at both ends of the molecular chain includes a compound having a partial structure represented by the following formula [1 ].
Figure BDA0003200134660000112
The partial structure represented by the above formula [1] corresponds to a portion where a — NHC (═ O) is removed from the compound represented by the above formula [2 ].
The above formula [1]Wherein n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]The total number of (a) is preferably an integer in the range of 5 to 30, more preferably an integer in the range of 7 to 21. Furthermore, the repeating unit- [ OCF ]2CF2]The number of-and the repeating unit- [ OCF ]2]The ratio of the quantities of-is preferably 2: 1-1: 2, more preferably about 1: 1, in the above range. The bonding of these repeating units may be either block bonding or random bonding.
In the present invention, (b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain is used in a proportion of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
By using (b) the perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 0.05 part by mass or more, sufficient scratch resistance can be imparted to the hard coat layer. Further, by using (b) perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 10 parts by mass or less, the (a) active energy ray-curable polyfunctional monomer can be sufficiently compatible, and a hard coat layer with less white turbidity can be obtained.
The perfluoropolyether (b) having polymerizable groups at both ends of the molecular chain can be obtained by reacting hydroxyl groups present at both ends of the compound represented by the following formula [3], for example, with an isocyanate compound having polymerizable groups, that is, a compound having isocyanate groups bonded to bonding bonds in the structures represented by the formulae [ a1] to [ a5] and structures in which the acryloyl groups in the structures are replaced with methacryloyl groups (for example, 2- (meth) acryloyloxyethyl isocyanate, 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, and the like), to form urethane bonds.
(HO)mL2-O-L1-PFPE-O-L1-O-L2(OH)m [3]
(formula [3]]Middle, PFPE, L1、L2And m represents the formula [2]]The same meaning is used. )
The curable composition of the present invention may contain: (b) a poly (oxyperfluoroalkylene) -based perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain thereof via a urethane bond (wherein no poly (oxyalkylene) group is present between the poly (oxyperfluoroalkylene) group and the urethane bond), and in addition, may comprise: a perfluoropolyether that contains a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at one end (one end terminal) of its molecular chain via a urethane bond and a hydroxyl group at the other end (the other end terminal) of the molecular chain (wherein there is no poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond and between the poly (oxyperfluoroalkylene) group and the hydroxyl group.); a perfluoropolyether containing a poly (oxyperfluoroalkylene) group as represented by the above formula [3], the perfluoropolyether having hydroxyl groups at both ends of the molecular chain thereof (wherein no poly (oxyperfluoroalkylene) group is present between the poly (oxyperfluoroalkylene) group and the hydroxyl group) [ a compound having no active energy ray-polymerizable group ].
[ (c) UV absorbers having a benzophenone skeleton ]
The curable composition of the present invention is characterized by using an ultraviolet absorber having a benzophenone skeleton as the component (c).
In particular, in the present invention, it is preferable to use a compound having at least two hydroxyl groups in the ultraviolet absorber having a benzophenone skeleton, that is, a compound in which at least two hydrogen atoms in two benzene rings constituting the benzophenone skeleton are substituted with hydroxyl groups.
As described above, in the present invention, a hard coat layer having excellent light resistance not only to a region of a wavelength of 300nm or more but also to ultraviolet rays of a region of less than 300nm can be formed by using (c) an ultraviolet absorber having a benzophenone skeleton. In addition, a hard coat film having excellent light resistance which is preferably suitable for use on the surface of a substrate such as the surface of a display used outdoors can be used as the hard coat film having the hard coat layer.
Examples of the ultraviolet absorber having a benzophenone skeleton include: 2, 4-dihydroxybenzophenone, 2 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ', 4, 4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone (Oxybenzone-3), 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 ' -phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone and the like.
In the present invention, it is preferable to use (c) the ultraviolet absorber having a benzophenone skeleton in a proportion of 0.1 to 30 parts by mass, preferably 1 to 15 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
[ (d) polymerization initiator generating free radical by active energy ray ]
In the curable composition of the present invention, the polymerization initiator which generates radicals by irradiation with an active energy ray such as an electron ray, an ultraviolet ray, or an X-ray (hereinafter, also simply referred to as "(d) polymerization initiator") is preferably a polymerization initiator which generates radicals by irradiation with an active energy ray.
Examples of the polymerization initiator (d) include: benzoins, alkylbenzones, thioxanthones, azos, azines, diazos, o-quinonediazines, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used alone or in combination of two or more.
Among them, in the present invention, from the viewpoint of transparency, surface curability, and film curability, acylphosphine oxides and alkylphenones are preferably used as the polymerization initiator (d). By using acylphosphine oxides and alkylphenones, a cured film having further improved scratch resistance can be obtained.
Examples of the acylphosphine oxides include phenylbis (2, 4, 6-trimethoxybenzoyl) phosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, and the like.
Examples of the above-mentioned alkylphenones include: α -hydroxyalkylbenzones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, and 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; α -aminoalkylbenzones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl phenylglyoxylate, and the like.
In the present invention, it is preferable to use (d) a polymerization initiator in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).
[ (e) solvent ]
The curable composition of the present invention may further contain (e) a solvent, and may be in the form of a varnish (film-forming material).
The solvent may be appropriately selected in consideration of workability in coating for forming a cured film (hard coat layer) described later, drying properties before and after curing, and the like, as long as the components (a) to (d) are dissolved. Examples thereof include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halogenated substances such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene and the like; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA); ethers such as diethyl ether, Tetrahydrofuran (THF), 1, 4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol and ethylene glycol; amides such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide (DMSO); and mixing two or more of these solvents.
(e) The amount of the solvent used is not particularly limited, but is used, for example, at a concentration of 1 to 70% by mass, preferably 5 to 50% by mass, of the solid content in the curable composition of the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of a solid content (a portion where a solvent component is removed from the entire components) with respect to the total mass (total mass) of the components (a) to (d) (and other additives as needed) of the curable composition of the present invention.
[ other additives ]
In the curable composition of the present invention, if necessary, additives usually added, for example, a polymerization accelerator, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber other than the above, a light stabilizer, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended as long as the effects of the present invention are not impaired.
For the purpose of controlling the haze value of the cured film, inorganic fine particles such as titanium oxide and organic fine particles such as polymethyl methacrylate particles may be blended.
< cured film >
The curable composition of the present invention is applied (coating) to a substrate to form a coating film, and the coating film is irradiated with active energy rays to polymerize (cure) the coating film, whereby a cured film can be formed. The cured film is also an object of the present invention. In addition, a hard coat layer in a hard coat film described later may be a layer formed of the cured film.
Examples of the base material in this case include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN), polyurethane, Thermoplastic Polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, and the like), metal, wood, paper, glass, slate, and the like. The shape of these substrates may be a plate, a film or a three-dimensional molded body.
The coating method on the substrate may be appropriately selected from a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief printing method, a gravure printing method, a planographic printing method, a screen printing method, and the like), and among them, a relief printing method is preferably used from the viewpoint of applicability to a roll-to-roll method and also from the viewpoint of film coatability, and particularly, a gravure coating method is preferably used. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm or the like and then applied. In the case of coating, a solvent may be further added to the curable composition as needed. Examples of the solvent in this case include various solvents listed in the above-mentioned [ (e) solvent ].
After a curable composition is applied to a substrate to form a coating film, the coating film is pre-dried by a heating means such as a hot plate or an oven as necessary to remove a solvent (solvent removal step). The conditions for the heat drying at this time are preferably, for example, about 30 seconds to 10 minutes at 40 to 120 ℃.
After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray include: ultraviolet rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferable. As a light source for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
Then, the polymerization can be completed by baking, specifically, heating using a heating means such as a hot plate or an oven.
After drying and curing, the thickness of the cured film formed is usually 0.01 to 50 μm, preferably 0.05 to 20 μm.
< hard coating film >
A hard coat film having a hard coat layer on at least one surface (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 is preferably 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 can be formed by a method comprising the steps of: a step of applying the curable composition of the present invention to a film substrate to form a coating film; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays. A method for producing a hard coat film comprising these steps and having a hard coat layer on at least one surface of a film substrate is also an object of the present invention.
As the film substrate, various transparent resin films that can be used for optical applications among the substrates listed as < cured film > above can be used. Preferred resin films include, for example: films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, Thermoplastic Polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefins, polyamides, polyimides, and triacetyl cellulose (TAC).
In addition, as the method of applying the curable composition to the film base material (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step), the methods listed under the above-mentioned < cured film > can be used. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), the coating film forming step may be followed by a step of drying the coating film to remove the solvent, if necessary. In this case, the coating film drying method (solvent removal step) listed as the above-mentioned < cured film > can be used.
The layer thickness (film thickness) of the hard coat layer thus obtained is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions for sample preparation and physical property analysis were as follows.
(1) Coating with a rod coater
The device comprises the following steps: PM-9050 MC (strain) prepared by SMT.
Stick: A-Bar OSP-22 manufactured by OSG SYSTEM PRODUCTS, Inc., and having a maximum wet film thickness of 22 μm (equivalent to WIRE BAR # 9).
Coating speed: 4 m/min.
(2) Baking oven
The device comprises the following steps: DRC433FA, a dust-free dryer manufactured by ADVANTEC Toyo (LTD.) Inc.
(3) UV curing
The device comprises the following steps: CV-110 QC-G was manufactured by Heraeus.
Lamp: high pressure mercury lamp H-bulb manufactured by Heraeus.
(4) Gel Permeation Chromatography (GPC)
The device comprises the following steps: HLC-8220 GPC, manufactured by Tosoh corporation.
A chromatographic column: shodex (registered trademark) GPC K-804L and GPC K-805L manufactured by Shorey electrician.
Temperature of the column: at 40 ℃.
Eluent: tetrahydrofuran.
A detector: and RI.
(5) Scratch resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): and (6) 30S.
Scanning speed: 4500 mm/min.
Scanning distance: 50 mm.
(6) Light resistance test
The device comprises the following steps: accelerated weather resistance QUV (registered trademark)/se manufactured by Q-Lab corporation.
Light source: UVB-313 type lamp.
The test conditions are as follows: 0.89W/cm2、50℃。
Test time: for 6 hours.
(7) Color difference meter
The device comprises the following steps: konica Minolta was CM-700 d, a spectrophotometer.
Measurement mode: a transmissive mode.
In addition, the abbreviation indicates the following meaning.
A1: oxyethylene-modified polyfunctional acrylate [ Aronix (registered trademark) MT-3553, manufactured by Toyo Seiya Kabushiki Kaisha ].
A2: ethylene oxide-modified pentaerythritol tetraacrylate [ KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kagaku Co., Ltd ].
A3: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ KAYARAD (registered trademark) DN-0075, manufactured by NIPPON CHEMICAL DISK.K. ].
A4: 10-functional urethane acrylate [ ARTRESIN (registered trademark) UN-904, manufactured by INDUSTRIAL CO., LTD.).
A5: caprolactone-modified dipentaerythritol hexaacrylate [ KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kagaku corporation ].
PFPE: perfluoropolyethers having two hydroxyl groups at both ends of the molecular chain without a poly (oxyalkylene) group [ Fomblin (registered trademark) T4, product of Solvay Specialty Polymers ].
BEI: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ Karenz (registered trademark) BEI, manufactured by Showa Denko K.K. ].
DOTDD: dioctyltin dineodecanoate [ NEOSTAN (registered trademark) U-830, available from NIDDM CHEMICAL CRYSTAL CO., LTD.).
O819: bis (2, 4, 6-trimethoxybenzoyl) phenylphosphine oxide [ OMNIRAD (registered trademark) 819, manufactured by IGM Resins ].
O2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ OMNIRAD (registered trademark) 2959, manufactured by IGM Resins Co., Ltd ].
UVA-1: 2, 4-dihydroxybenzophenone [ manufactured by Tokyo chemical industry Co., Ltd ].
UVA-2: 2, 2, 4, 4-tetrahydroxybenzophenone [ UVINUL (registered trademark) 3050 manufactured by BASF Japan, Ltd ].
UVA-3: 2- (4- ((2-hydroxy-3-dodecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine/2- (4- ((2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine [ TINUVIN (registered trademark) 400, manufactured by BASF Japan, Ltd ].
UVA-4: 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy-octyl phenylpropionate [ TINUVIN (registered trademark) 384-2, manufactured by BASF Japan, Ltd.).
UVA-5: 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate [ UVINUL (registered trademark) 3039 manufactured by BASF Japan, Inc. ].
MEK: methyl ethyl ketone.
MeOH: methanol.
TPU: a polyurethane elastomer film [ Higress DUS 605-CER manufactured by Sheedom, Ltd., thickness 100 μm ].
PC: polycarbonate film [ Iipilon (registered trademark) film FS-2000, thickness 100 μm, manufactured by Mitsubishi gas chemical corporation ].
Reference example 1 production of surface modifier SM
Into the spiral tube were charged 1.19g (0.5mmol) of PFPE, 0.52g (2.0mmol) of BEI, 0.017g (an amount of 0.01 times the total mass of PFPE and BEI) of DOTDD, and 1.67g of MEK. The mixture was stirred using a stirrer Chip (Starer Chip) at room temperature (about 23 ℃) for 24 hours. A 50 mass% MEK solution of the surface modifier SM as the objective compound was obtained. Weight average molecular weight of the obtained SM as determined in terms of polystyrene based on GPC: mw of 3000, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Examples 1 to 12 and comparative examples 1 to 10
The following components were mixed as described in table 1 to prepare a curable composition. In Table 1, [ parts]Is expressed as [ parts by mass]. The curable composition was applied to a film substrate (a4 size) by a bar coater to obtain a coating film. The coating film was dried in an oven at 65 ℃ for 3 minutes to remove the solvent. The obtained film was irradiated with an exposure of 300mJ/cm in a nitrogen atmosphere2The hard coat film was formed to have a layer thickness (film thickness) of about 5 μm by exposure to UV light.
The hard coat film obtained was evaluated for scratch resistance and light resistance. The evaluation methods of scratch resistance and light resistance are shown below. The results are shown in Table 2.
[ scratch resistance ]
On the hard coat surface of the hard coat film, steel wool (BONSTAR (registered trademark) #0000 (ultra-fine) manufactured by BONSTAR, Inc.) attached to the reciprocating abrasion tester was used]Application of 350g/cm2The degree of the scratches (number of lines and length) was visually checked by wiping 10 times in a reciprocating manner under the load of (1), and evaluated according to the following criteria A, B and (C). It is to be noted that it is assumed that the hard coat layer is actually used as the hard coat layerIn this case, at least B, preferably A, is required.
A: has no scar.
B: producing fewer than 5 scars of less than 5mm in length.
C: more than 5 scars with the length less than 5mm or more than 1 scar with the length more than 5mm are generated.
[ light resistance ]
Before the light resistance test, a white backing plate [ L ] was placed on the back surface (surface on which the hard coat layer was not formed) of the hard coat film＊＝86.6，a＊＝－1.0，b＊＝－0.4]And a yellowness Index (Yellow Index, D1925) was measured using the colorimeter (YI 1). After the light resistance test using the accelerated weathering tester, the yellowness index (YI2) was measured by the same method as that using the color difference meter. The difference in yellowness index between before and after the light resistance test (YI 2-YI 1) was determined as Δ YI and evaluated according to the following criteria A and C.
A：ΔYI＜1.0。
C：ΔYI≥1.0。
[ Table 1]
Figure BDA0003200134660000211
[ Table 2]
Scratch resistance Light resistance
Example 1 A A
Example 2 B A
Example 3 B A
Example 4 A A
Example 5 B A
Example 6 A A
Example 7 A A
Example 8 B A
Example 9 B A
Example 10 B A
Example 11 B A
Example 12 B A
Comparative example 1 C A
Comparative example 2 C C
Comparative example 3 B C
Comparative example 4 C A
Comparative example 5 C C
Comparative example 6 C C
Comparative example 7 A C
Comparative example 8 B C
Comparative example 9 C A
Comparative example 10 C A
As shown in table 2, it was demonstrated that the hard coat films (examples 1 to 12) having a hard coat layer produced using a curable composition prepared by compounding a perfluoropolyether SM having four acryloyl groups via urethane bonds at both ends of the molecular chain as a surface modifier, with a polyfunctional monomer a1, a2, A3, a4, or a5, a uv-1 or UVA-2 having a benzophenone skeleton as an ultraviolet absorber, and a TPU or a PC film substrate exhibiting excellent light resistance in the UVB (ultraviolet B wave) region, without impairing scratch resistance.
On the other hand, it was shown that the hard coat films provided with hard coat layers produced from the curable compositions of comparative examples 1 and 4, in which a1 was used as a polyfunctional monomer, UVA-3 having a triazine skeleton was used as an ultraviolet absorber, SM was used as a surface modifier, and TPU and PC were used as film substrates, respectively, were excellent in light resistance, but poor in scratch resistance. Further, it was shown that the hard coat films provided with hard coat layers produced from the curable compositions of comparative examples 2 and 5, which used UVA-4 having a benzotriazole skeleton as an ultraviolet absorber and TPU and PC as film substrates, respectively, were inferior in scratch resistance and light resistance. Similarly, it was revealed that the hard coat films having hard coat layers produced from the curable compositions of comparative examples 3 and 6, in which UVA-5 having a cyanoacrylate skeleton was used as an ultraviolet absorber and TPU and PC were used as film substrates, respectively, had poor light resistance. Next, it was demonstrated that the hard coat films provided with the hard coat layers produced from the curable compositions of comparative examples 7 and 8, which used a1 as the polyfunctional monomer, no ultraviolet absorber, SM as the surface modifier, and TPU and PC as the film base materials, respectively, had excellent scratch resistance, but were inferior in light resistance because no ultraviolet absorber was added. It was also shown that the hard coat films having hard coat layers produced from the curable compositions of comparative examples 9 and 10, which used a1 as the polyfunctional monomer, UVA-1 having a benzophenone skeleton as the ultraviolet absorber, and no surface modifier, and used TPU and PC as the film base materials, respectively, had excellent light resistance, but had poor scratch resistance because no surface modifier was added.
As described above, as shown in the results of examples, only by using a curable composition in which a polyfunctional monomer, an ultraviolet absorber having a benzophenone skeleton, and perfluoropolyether are combined, a hard coating film satisfying scratch resistance and light resistance can be obtained.

Claims (13)

1. A curable composition comprising:
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;
(b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass, excluding the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond;
(c) 0.1 to 30 parts by mass of an ultraviolet absorber having a benzophenone skeleton; and
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
2. The curable composition according to claim 1,
the (c) ultraviolet absorber has at least two hydroxyl groups.
3. The curable composition according to claim 1 or 2,
the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at both ends of the molecular chain thereof via urethane bonds.
4. The curable composition according to claim 3,
the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
5. The curable composition according to any one of claims 1 to 4,
the poly (oxyperfluoroalkylene) group is a poly (oxyalkylene) group having a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
6. The curable composition according to claim 5,
the perfluoropolyether (c) has a partial structure represented by the following formula [1],
Figure FDA0003200134650000011
the above formula [1]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-the total number of the number of (a) is an integer of 5 to 30,
said repeating unit- [ OCF ]2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding.
7. The curable composition according to any one of claims 1 to 6,
some or all of the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
8. The curable composition according to any one of claims 1 to 7,
the (a) polyfunctional monomer is an oxyalkylene-modified polyfunctional monomer.
9. The curable composition according to any one of claims 1 to 8,
the (a) polyfunctional monomer is a polyfunctional monomer having at least three active energy ray-polymerizable groups.
10. The curable composition according to any one of claims 1 to 9,
further comprising (e) a solvent.
11. A cured film obtained from the curable composition according to any one of claims 1 to 10.
12. A hard coat film comprising a hard coat layer formed from the cured film according to claim 11 on at least one surface of a film substrate.
13. A method for producing a hard coat film, which comprises a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises:
a step of applying the curable composition according to any one of claims 1 to 10 to a film substrate to form a coating film; and
and a step of irradiating the coating film with an active energy ray to cure the coating film.
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