CN113423513B - Light-resistant hard coating curable composition - Google Patents

Light-resistant hard coating curable composition Download PDF

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CN113423513B
CN113423513B CN202080013139.3A CN202080013139A CN113423513B CN 113423513 B CN113423513 B CN 113423513B CN 202080013139 A CN202080013139 A CN 202080013139A CN 113423513 B CN113423513 B CN 113423513B
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curable composition
film
hard coat
active energy
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CN113423513A (en
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辻本晴希
原口将幸
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Abstract

The present invention provides a hard coat layer forming material exhibiting high scratch resistance and light resistance. A curable composition and a hard coating film comprising a hard coating layer formed from the composition, wherein the curable composition comprises: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) 0.05 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain thereof via urethane bonds (excluding a 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 generating radicals by active energy rays.

Description

Light-resistant hard coating curable composition
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 to be applied to the surface of various display elements such as a touch panel display and a liquid crystal display.
Background
In many electronic devices such as home appliances including televisions, communication devices including cellular phones, office devices including copiers, entertainment devices including game machines, medical devices including X-ray imaging devices, and living devices including microwave ovens, touch panel displays using liquid crystal display elements or Organic Light Emitting Diode (OLED) display elements are provided which can be operated by a finger of a person. A hard coat film in which a hard coat layer is provided on a transparent plastic film as a base material is used on the outermost surface of these touch panel displays, wherein the hard coat layer has: scratch resistance for preventing a surface of the touch panel from being damaged by a nail or the like when a person operates with a finger; and stain resistance for making a fingerprint stain, which is attached when a person touches with a finger, difficult to attach and easy to wipe off.
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, forming a crosslinked structure with low molecular mobility, is employed. As a material for forming these hard coat layers, a multifunctional acrylate-based material which is 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, and 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, and functions such as hardness and scratch resistance are exhibited at a level practically free from problems.
Further, among the devices provided with the touch panel display, there are devices used outdoors, in which the touch panel surface and the hard coat film are exposed to ultraviolet rays. Some of the transparent plastic films used as substrates for hard coating films also become significantly yellow and deteriorate due to short-time exposure to ultraviolet light. Since the hard coat film is required to have high transparency in the touch panel display, the hard coat film is required to have light resistance to prevent yellowing, deterioration of the hard coat film caused by ultraviolet rays. As a method for imparting light resistance to a hard coat layer, 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, formation of a three-dimensional crosslinked structure of the multifunctional acrylate is generally hindered. As described above, the scratch resistance and the light resistance of the hard coat layer have a trade-off relationship, and the characteristics of both layers are problematic. On the other hand, there is reported a technique: by using a combination of a multifunctional urethane (meth) acrylate oligomer and a triazine ultraviolet light absorber, a hard coat layer having both light resistance and scratch resistance is obtained on a plastic film having a problem in light resistance (patent document 1).
Prior art literature
Patent literature
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 high light resistance to ultraviolet rays in a wavelength region of 300nm or more, but has a problem of insufficient scratch resistance.
Solution for solving the problem
As a result of intensive studies to achieve the above object, the present inventors have found that a curable composition capable of forming a hard coating layer having excellent light resistance and excellent scratch resistance not only for a region having a wavelength of 300nm or more but also for ultraviolet rays in a region smaller than 300nm on a plastic film having a problem in light resistance, the curable composition comprising: a perfluoropolyether containing a poly (oxyperfluoroalkylene) group having an active energy ray polymerizable group at both ends of its molecular chain via a urethane bond without via a poly (oxyperfluoroalkylene) group; and a specific ultraviolet absorber.
That is, in the present invention, as a first aspect, there is provided a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) 0.05 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain thereof via urethane bonds (excluding a 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 generating radicals by active energy rays.
As a second aspect, the curable composition according to the first aspect, wherein the (c) ultraviolet absorber has at least two hydroxyl groups.
As a third aspect, the curable composition according to the first or second aspect, wherein the perfluoropolyether (b) has at least two active energy ray polymerizable groups at both ends of its molecular chain via urethane bonds, respectively.
As a fourth aspect, the curable composition according to the third aspect, wherein the (b) perfluoropolyether has at least three active energy ray polymerizable groups at both ends of its molecular chain via urethane bonds, respectively.
As a fifth aspect, the curable composition according to any one of the first to fourth aspects, wherein the poly (oxidized perfluoroalkylene) group of the (b) perfluoropolyether is a polymer having a repeating unit- [ OCF ] 2 ]-and repeating units- [ OCF 2 CF 2 ]-both of these repeating units are bonded in a block bond, a random bond, or a combination of block bond and random bond.
As a sixth aspect, the curable composition according to the fifth aspect, wherein the perfluoropolyether (b) has a partial structure represented by the following formula [1 ].
(above formula [1 ]]In which n represents a repeating unit- [ OCF ] 2 CF 2 ]Number and repeating units- [ OCF ] 2 ]The total number of said repeating units- [ OCF ] is an integer ranging from 5 to 30 2 CF 2 ]-said repeating unit- [ OCF 2 ]-, block bonded, random bonded, or any one of block bonded and random bonded. )
As a seventh aspect, the curable composition according to any one of the first to sixth aspects, wherein part or all of the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
As an eighth aspect, the curable composition according to any one of the first to seventh aspects, wherein the (a) polyfunctional monomer is an oxyalkylene-modified polyfunctional monomer.
As a ninth aspect, the curable composition according to any one of the first to eighth aspects, wherein the (a) polyfunctional monomer is a polyfunctional monomer having at least three active energy ray polymerizable groups.
As a tenth aspect, the curable composition according to any one of the first to ninth aspects, further comprising (e) a solvent.
As an eleventh aspect, there is provided a cured film obtained from the curable composition according to any one of the first to tenth aspects.
As a twelfth aspect, the present invention 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 material.
As a thirteenth aspect, the present invention relates to a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film base material, the hard coat layer comprising: 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 curing the coating film by irradiation with active energy rays.
Effects of the invention
According to the present invention, 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 film having a thickness of about 1 μm to 15 μm can be provided.
Further, according to the present invention, a hard coat film having a surface provided with a cured film obtained from the curable composition or a hard coat layer formed therefrom can be provided, and a hard coat film excellent in scratch resistance and light resistance can be provided.
In particular, according to the present invention, a hard coat film suitable for a substrate surface such as a display surface used outdoors, which has excellent light resistance and abrasion resistance not only for a wavelength region of 300nm or more but also for ultraviolet rays in a wavelength region of less than 300nm, can be provided.
Detailed Description
Curable composition
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) 0.05 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain thereof via urethane bonds (excluding a 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 generating radicals by active energy rays.
The components (a) to (d) will be described below.
[ (a) active energy ray-curable polyfunctional monomer ]
(a) The active energy ray-curable polyfunctional monomer (hereinafter, simply referred to as "(a) polyfunctional monomer") of the component (a) is a monomer having two or more active energy ray-polymerizable groups that are cured by polymerization reaction by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray-polymerizable group include a (meth) acryl group and a vinyl group.
In the curable composition of the present invention, the preferable (a) active energy ray-curable polyfunctional monomer is 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, as the active energy ray-curable polyfunctional monomer (a), one kind of the polyfunctional (meth) acrylate compound may be used alone or two or more kinds may be used in combination.
In the present invention, the (meth) acrylate compound refers to both of an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
The (a) polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene modification include: an oxymethylene group modification, an oxyethylene group modification, an oxypropylene group modification, etc. Examples of the oxyalkylene-modified polyfunctional monomer include compounds in which an oxyalkylene group is modified in the above-mentioned polyfunctional (meth) acrylate compound (or polyfunctional urethane (meth) acrylate compound). The oxyalkylene-modified polyfunctional monomer may be used alone 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, 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) acrylate, tetraethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0 2，6 ]Decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy propane, 2-hydroxy-1, 3-di (meth) acryloyloxy propane, 9-bis [4- (2- (meth) acryloyloxy) ethoxy) phenyl]Fluorene, bis [4- (meth) acryloylthiophenyl ]]Thioether, bis [2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) propaneOlefine acid esters, polypropylene glycol di (meth) acrylate esters, 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 polyols modified with an oxyalkylene group.
Examples of the polyol include: glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, di (trimethylol) propane, pentaerythritol, dipentaerythritol, and the like.
The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryl groups or methacryl groups in 1 molecule and having one or more urethane bonds (-NHCOO-).
Examples of the polyfunctional urethane (meth) acrylate compound include: the compound obtained by the reaction of the polyfunctional isocyanate with the (meth) acrylate having a hydroxyl group, the compound obtained by the reaction of the polyfunctional isocyanate with the (meth) acrylate having a hydroxyl group and the polyol, and the like, but the polyfunctional urethane (meth) acrylate compound usable 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: diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, etc.; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, adipic acid, etc.; polyether polyols; polycarbonate diol, and the like.
(a) The active energy ray multifunctional monomer may be a lactone-modified multifunctional (meth) acrylate compound, preferably epsilon-caprolactone as a modified lactone. Examples of the lactone-modified polyfunctional (meth) acrylate compound include: epsilon-caprolactone modified pentaerythritol tri (meth) acrylate, epsilon-caprolactone modified pentaerythritol tetra (meth) acrylate, epsilon-caprolactone modified dipentaerythritol penta (meth) acrylate, epsilon-caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.
[ (b) a perfluoropolyether containing a poly (oxidized perfluoroalkylene) group having an active energy ray-polymerizable group via a urethane bond at both ends of its molecular chain (wherein except for the perfluoropolyether having a poly (oxidized alkylene) group between the poly (oxidized perfluoroalkylene) group and the urethane bond) ]
In the present invention, as the component (b), a perfluoropolyether having a poly (oxyalkylene) group and an active energy ray polymerizable group at both ends of a molecular chain thereof via a urethane bond without via the poly (oxyalkylene) group (hereinafter, simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of a 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.
In addition, the compatibility of the component (b) with the component (a) is excellent, and thus the occurrence of cloudiness in the hard coat layer is suppressed, and a hard coat layer having a transparent appearance can be formed.
The poly (oxyalkylene) group is a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
The number of carbon atoms of the alkylene group in the poly (oxidized perfluoroalkylene) group is not particularly limited, but is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group is a group having a structure in which a divalent fluorinated hydrocarbon group having 1 to 4 carbon atoms is alternately linked to an oxygen atom, and the oxyperfluoroalkylene group is a group having a structure in which a divalent fluorinated hydrocarbon group having 1 to 4 carbon atoms is linked to an oxygen atom. Specifically, there may be mentioned- [ OCF 2 ]- (oxidized perfluoromethylene), - [ OCF ] 2 CF 2 ]- (oxidized perfluoroethylene), - [ OCF ] 2 CF 2 CF 2 ]- (oxidized perfluoropropane-1, 3-diyl), - [ OCF 2 C(CF 3 )F]- (oxidized perfluoropropane-1, 2-diyl), and the like.
The above-mentioned oxidized perfluoroalkylene groups may be used singly or in combination of two or more, and in this case, the bonding of the plurality of oxidized perfluoroalkylene groups may be any of block bonding and random bonding.
Among them, from the viewpoint of obtaining a cured film excellent in scratch resistance, it is preferable to use a cured film having- [ OCF ] as the poly (oxidized perfluoroalkylene) group 2 ]- (oxidized perfluoromethylene) and- [ OCF 2 CF 2 ]Both- (oxidized perfluoroethylene) groups are the repeating unit groups.
Among them, as the above poly (oxidized perfluoroalkylene) group, it is preferable that, in terms of the repeating unit: - [ OCF ] 2 ]-and- [ OCF 2 CF 2 ]-in molar ratio [ repeating units: - [ OCF ] 2 ]－]: [ repeating units: - [ OCF ] 2 CF 2 ]－]=2: 1 to 1:2, more preferably, according to a ratio of about 1:1 comprises the above-mentioned repeating units. The bonding of these repeating units may be any of block bonding and random bonding.
The number of repeating units of the oxidized perfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, based on the total number of repeating units.
The weight average molecular weight (Mw) of the poly (oxidized perfluoroalkylene) group as measured by Gel Permeation Chromatography (GPC) in terms of polystyrene is 1000 to 5000, preferably 1500 to 3000.
Examples of the active energy ray-polymerizable group include a (meth) acryloyl group and a vinyl group.
(b) The perfluoropolyether having a polymerizable group at both ends of the molecular chain is not limited to having one active energy ray polymerizable group such as a (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 containing an active energy ray polymerizable group include structures represented by the following formulas [ A1] to [ A5], and structures in which an acryloyl group in the structures is substituted with a methacryloyl group.
Examples of the perfluoropolyether having polymerizable groups at both ends of the molecular chain (b) include compounds represented by the following formula [2 ].
(2)]Wherein A represents the formula [ A1]]-type [ A5]]The structure shown and the substitution of the acryl group in their structure to one of the methacryl groups, PFPE represents the poly (oxidized perfluoroalkylene) group (wherein, with L 1 The direct bond side is an oxygen radical terminal and the bond side with the oxygen atom is a perfluoroalkylene terminal. ) L, L 1 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 L 2 Represents an m+1 valent residue from which OH is removed from an m+1 polyol. )
Examples of the alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms include: -CH 2 CHF－、－CH 2 CF 2 －、－CHFCF 2 －、－CH 2 CH 2 CHF－、－CH 2 CH 2 CF 2 －、－CH 2 CHFCF 2 -etc., preferably-CH 2 CF 2 －。
As the above [ 2]]The partial Structure (A-NHC (=O) O) of the compound m L 2 As the "C", there may be mentioned the following formula [ B1]]-type [ B12]]The illustrated construction, etc.
(in the formulae [ B1] to [ B12], A represents one of the structures represented by the formulae [ A1] to [ A5] and the structure in which an acryl group in the structures is replaced with a methacryl group.)
In the structures represented by the above formulas [ B1] to [ B12], the formulas [ B1] and [ B2] correspond to the case where m=1, the formulas [ B3] to [ B6] correspond to the case where m=2, the formulas [ B7] to [ B9] correspond to the case where m=3, and the formulas [ B10] to [ B12] correspond to the case where m=5.
Of these, the structure represented by the formula [ B3] is preferable, and a combination of the formula [ B3] and the formula [ A3] is particularly preferable.
As the preferable perfluoropolyether having polymerizable groups at both ends of the molecular chain, there can be mentioned a compound having a partial structure represented by the following formula [1 ].
The partial structure represented by the above formula [1] corresponds to a portion in which A-NHC (=O) is removed from the compound represented by the above formula [2 ].
The above-mentioned [1]]N in (a) represents a repeating unit- [ OCF ] 2 CF 2 ]Number and repeating units- [ OCF ] 2 ]The total number of the amounts is preferably an integer in the range of 5 to 30, more preferably an integer in the range of 7 to 21. In addition, the repeating unit- [ OCF 2 CF 2 ]The number of said repeating units- [ OCF ] 2 ]The ratio of the number of-preferably 2:1 to 1:2, more preferably about 1: 1. The bonding of these repeating units may be any of block bonding and random bonding.
In the present invention, (b) a perfluoropolyether having polymerizable groups at both ends of a molecular chain is used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).
The use of (b) a perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 0.05 parts by mass or more can impart sufficient scratch resistance to the hard coat layer. Further, by using (b) a perfluoropolyether having polymerizable groups at both ends of a molecular chain in a proportion of 10 parts by mass or less, it is possible to sufficiently compatibilize (a) an active energy ray-curable polyfunctional monomer and to obtain a hard coat layer having less cloudiness.
The perfluoropolyether having polymerizable groups at both ends of the molecular chain (b) can be obtained by reacting a hydroxyl group present at both ends of a compound represented by the following formula [3], with an isocyanate compound having a polymerizable group, that is, a compound having an isocyanate group bonded to a bond in the structure represented by the formulae [ A1] to [ A5] and a structure in which an acryl group in the structure is replaced with a methacryl group (for example, 2- (meth) acryloyloxyethyl isocyanate, 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, or the like), to form a urethane bond.
(HO) m L 2 -O-L 1 -PFPE-O-L 1 -O-L 2 (OH) m [3]
(A method of [3]]Among them, PFPE, L 1 、L 2 M represents the same as the formula [2 ]]The same meaning. )
The curable composition of the present invention may contain: (b) A perfluoropolyether comprising a poly (oxyperfluoroalkylene) group having an active energy ray polymerizable group at both ends of its molecular chain via a urethane bond (wherein there is no poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond), and may further comprise: a perfluoropolyether comprising a poly (oxidized perfluoroalkylene) group having an active energy ray polymerizable group via a urethane bond at one end (one end terminus) of a molecular chain thereof and a hydroxyl group at the other end (the other end terminus) of the molecular chain (wherein there is no poly (oxidized alkylene) group between the poly (oxidized perfluoroalkylene) group and the urethane bond and between the poly (oxidized perfluoroalkylene) group and the hydroxyl group); a perfluoropolyether comprising a poly (oxidized perfluoroalkylene) group as represented by the above formula [3], wherein the perfluoropolyether has hydroxyl groups at both ends of a molecular chain thereof (wherein there is no poly (oxidized alkylene) group between the poly (oxidized perfluoroalkylene) group and the hydroxyl groups) [ a compound having no active energy ray polymerizable group ].
[ (c) ultraviolet absorber having 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 above-mentioned ultraviolet absorber having a benzophenone skeleton, that is, a compound in which at least two hydrogen atoms are substituted with hydroxyl groups in two benzene rings constituting the benzophenone skeleton.
In this way, in the present invention, a hard coat layer having excellent light resistance not only for a region having a wavelength of 300nm or more but also for ultraviolet rays in a region smaller than 300nm can be formed by using (c) an ultraviolet absorber having a benzophenone skeleton. The hard coat film having the hard coat layer can be preferably used as a hard coat film excellent in light resistance on a substrate surface such as a display surface suitable for outdoor use.
Examples of the ultraviolet absorber having a benzophenone skeleton include: 2, 4-dihydroxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 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-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, and the like.
In the present invention, it is desirable to use (c) an ultraviolet absorber having a benzophenone skeleton in an amount of 0.1 to 30 parts by mass, preferably 1 to 15 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).
[ (d) polymerization initiator for generating radical by active energy ray ]
In the curable composition of the present invention, the polymerization initiator that generates radicals by the active energy rays (hereinafter, also simply referred to as "polymerization initiator") is, for example, a polymerization initiator that generates radicals by the active energy rays such as electron rays, ultraviolet rays, X-rays, and the like, particularly by irradiation with ultraviolet rays.
Examples of the polymerization initiator (d) include: benzoin, alkylbenzene, thioxanthone, azo, azide, diazonium, o-quinone diazide, acylphosphine oxide, oxime ester, organic peroxide, benzophenone, biscoumarin, bisimidazole, titanocene, thiol, halogenated hydrocarbon, trichloromethyl triazine, onium salts such as iodonium salt and sulfonium salt, and the like. They may be used singly or in combination of two or more.
Among them, in the present invention, from the viewpoints of transparency, surface curability, and film curability, it is preferable to use an acylphosphine oxide or an alkylbenzene as the polymerization initiator (d). By using the acylphosphine oxides and the alkylbenzene, a cured film having further improved scratch resistance can be obtained.
Examples of the acylphosphine oxides include phenyl bis (2, 4, 6-trimethoxybenzoyl) phosphine oxide and diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Examples of the alkylbenzene ketones include: alpha-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one, and the like; α -aminoalkyl phenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 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 desirable to use (d) the polymerization initiator in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, per 100 parts by mass of the active energy ray-curable polyfunctional monomer (a) described above.
[ (e) solvent ]
The curable composition of the present invention may further contain (e) a solvent, that is, may be in the form of a varnish (film-forming material).
The solvent may be appropriately selected in consideration of workability at the time of application of a cured film (hard coat layer) to be described later, drying properties before and after curing, and the like, by dissolving the components (a) to (d). Examples 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 species 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, t-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 solvents among these solvents.
(e) The amount of the solvent to be used is not particularly limited, but is, for example, 1 to 70% by mass, preferably 5 to 50% by mass, based on the solid content in the curable composition of the present invention. Here, the solid content concentration (also referred to as nonvolatile content concentration) means the content of the solid content (the portion from which the solvent component is removed from the entire components) relative to the total mass (total mass) of the above-mentioned 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, as long as the effect of the present invention is not impaired, additives which are 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 required.
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 (coated) on 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, the hard coat layer in the hard coat film described later may be a layer formed of the cured film.
Examples of the substrate in this case include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., polyurethanes, thermoplastic Polyurethanes (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metals, wood, paper, glass, slate, etc. The shape of these substrates may be plate-like, film-like or three-dimensional molded bodies.
The coating method on the substrate may be appropriately selected from a casting 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 inkjet method, a printing method (a relief printing method, a gravure printing method, a lithographic printing method, a screen printing method, etc.), among which a relief printing method is preferably used from the viewpoint of availability of a roll-to-roll method and film coatability, and a gravure coating method is particularly preferably used. It is preferable that the curable composition is filtered by using a filter having a pore diameter of about 0.2 μm in advance and then applied. In the case of coating, a solvent may be further added to the curable composition as needed. The solvent in this case may be any of the solvents listed in the above [ (e) solvent ].
After the curable composition is applied to a substrate to form a coating film, the coating film is pre-dried by a heating unit such as a hot plate or an oven as necessary to remove the solvent (solvent removal step). The conditions for the heat drying at this time are preferably, for example, 40 to 120℃for about 30 seconds to 10 minutes.
After drying, active energy rays such as ultraviolet rays are irradiated to cure the coating film. The active energy ray may be: ultraviolet rays, electron rays, X-rays, and the like, and ultraviolet rays are particularly preferable. As a light source for ultraviolet irradiation, solar rays, 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, by heating using a heating unit such as a hot plate, an oven, or the like.
After drying and curing, the thickness of the cured film to be formed is usually 0.01 μm to 50. Mu.m, preferably 0.05 μm to 20. Mu.m.
< hard coating film >)
The curable composition of the present invention can be used to produce a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate. The hard coat film is also an object of the present invention, and for example, in order to protect the surfaces of various display elements such as touch panels and liquid crystal displays, the hard coat film can be preferably used.
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 forming a coating film by applying the curable composition of the present invention to a film substrate; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays. The method for producing a hard coat film comprising these steps and having a hard coat layer on at least one side of a film base material is also an object of the present invention.
As the film base material, various transparent resin films which can be used for optical applications among the above-mentioned base materials listed as < cured film > can be used. Preferable 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, polyolefin, polyamide, polyimide, and triacetyl cellulose (TAC).
The method of applying the curable composition to the film substrate (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step) may be the methods listed as < cured film >. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), the step of drying the coating film to remove the solvent may be included as necessary after the step of forming the coating film. In this case, the method of drying the coating film (solvent removal step) exemplified by < cured film > described above can be used.
The layer thickness (film thickness) of the hard coat layer thus obtained is preferably 1 μm to 20. Mu.m, more preferably 1 μm to 10. Mu.m.
Examples (example)
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples.
In the examples, the apparatus and conditions for preparation of the samples and analysis of physical properties were as follows.
(1) Coating with rod coater
The device comprises: PM-9050MC manufactured by SMT.
Rod: OSG SYSTEM PRODUCTS A-Bar OSP-22, manufactured by Wire BAR#9, has a maximum wet film thickness of 22. Mu.m.
Coating speed: 4 m/min.
(2) Baking oven
The device comprises: a dust free dryer DRC433FA manufactured by ADVANTEC TOYOBO Co.
(3) UV curing
The device comprises: CV-110QC-G manufactured by Heraeus Co.
A lamp: heraeus (Inc.) high pressure mercury lamp H-bulb.
(4) Gel Permeation Chromatography (GPC)
The device comprises: HLC-8220GPC manufactured by Tosoh Co., ltd.
Chromatographic column: shodex (registered trademark) GPC K-804L, GPC K-805L, manufactured by Showa Denko Co., ltd.
Chromatographic column temperature: 40 ℃.
Eluent: tetrahydrofuran.
A detector: RI.
(5) Scratch resistance test
The device comprises: TRIBOGEAR TYPE, a reciprocating abrasion tester manufactured by New east science Co., ltd.): 30S.
Scanning speed: 4500 mm/min.
Scanning distance: 50mm.
(6) Light fastness test
The device comprises: accelerated weathering tester QUV (registered trademark)/se manufactured by Q-Lab company.
Light source: UVB-313 type lamp.
Test conditions: 0.89W/cm 2 、50℃。
Test time: and 6 hours.
(7) Color difference meter
The device comprises: a spectrocolorimeter CM-700d manufactured by Konica Minolta Co.
Measurement mode: a transmissive mode.
Further, the shorthand notation indicates the following meanings.
A1: ethylene oxide modified multifunctional acrylate [ Aronix (registered trademark) MT-3553, manufactured by Toyama Synthesis Co., ltd.).
A2: ethylene oxide modified pentaerythritol tetraacrylate (KAYARAD (registered trademark) RP-1040, manufactured by Japanese chemical Co., ltd.).
A3: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ Kayarad (registered trademark) DN-0075, manufactured by Japanese chemical Co., ltd.).
A4:10 functional urethane acrylate [ ARTRESIN (registered trademark) UN-904, manufactured by Kogyo Co., ltd.).
A5: caprolactone-modified dipentaerythritol hexaacrylate [ Kayarad (registered trademark) DPCA-20, manufactured by Japanese chemical Co., ltd.).
PFPE: perfluoropolyethers having two hydroxyl groups at both ends of the molecular chain without a poly (oxyalkylene) group (Fomblin (registered trademark) T4, manufactured by Solvay Specialty Polymers Co., ltd.).
BEI:1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ Karenz (registered trademark) BEI, manufactured by Showa electric Co., ltd ].
DOTDD: dioctyltin di neodecanoate [ NEOSTAN (registered trademark) U-830, manufactured by Nitto chemical Co., ltd.).
O819: bis (2, 4, 6-trimethoxybenzoyl) phenylphosphine oxide (OMNIRAD (registered trademark) 819, manufactured by IGM Resins Co., ltd.).
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 industries, ltd.).
UVA-2:2, 4-tetrahydroxybenzophenone [ UVINIUL (registered trademark) 3050, manufactured by BASF Japan Co., 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 [ manufactured by BASF Japan, inc. ] TINUVIN (registered trademark) 400].
UVA-4:3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy-benzoic acid octyl ester [ TINUVIN (registered trademark) 384-2 manufactured by BASF Japan Co., ltd.).
UVA-5: 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate [ UVINIUL (registered trademark) 3039, manufactured by BASF Japan Co., ltd.).
MEK: methyl ethyl ketone.
MeOH: methanol.
TPU (thermoplastic polyurethane): polyurethane elastomer film [ Higress DUS605-CER, manufactured by Sheeedom Co., ltd., thickness 100 μm ].
PC: polycarbonate film [ Iuppilon (registered trademark) film FS-2000, mitsubishi gas chemical corporation, thickness 100 μm ].
Reference example 1 production of surface modifier SM
1.19g (0.5 mmol) of PFPE, 0.52g (2.0 mmol) of BEI, 0.017g (an amount 0.01 times the total mass of PFPE and BEI) of DOTDD and 1.67g of MEK are charged into the spiral tube. 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 measured in terms of polystyrene based on GPC: mw was 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 in accordance with the descriptions in table 1 to prepare curable compositions. In Table 1, [ parts ]]Representation [ parts by mass ]]. The curable composition was applied to a film base material (A4 size) by a bar coater to obtain a coating film. The film was dried in an oven at 65℃for 3 minutes, and the solvent was removed. The film obtained was irradiated with light of 300mJ/cm under nitrogen atmosphere 2 By exposure to UV light, a hard coat film having a layer thickness (film thickness) of about 5 μm was produced.
The obtained hard coat film was evaluated for scratch resistance and light resistance. The evaluation modes of scratch resistance and light resistance are shown below. The results are shown in Table 2.
[ scratch resistance ]
For hard coatingThe hard coat layer of the film was formed by using a steel wool [ BONSTAR (registered trademark) #0000 (ultra fine) manufactured by BONSTAR Co., ltd.) mounted on the reciprocating abrasion tester]Applying 350g/cm 2 The number of scratches (number of scratches and length of the scratch) was visually checked by wiping the fabric repeatedly 10 times under the load of (a) and evaluated according to the following criteria A, B and C. In the case of assuming that the coating is actually used as a hard coat layer, it is required that the coating be at least B, and preferably a.
A: no flaw.
B: less than 5 lesions less than 5mm in length are produced.
C: generating more than 5 scratches with the length of less than 5mm or generating more than 1 scratch with the length of more than 5 mm.
[ light fastness ]
Before the light resistance test, a white backing plate L was placed on the back side of the hard coat film (side where the hard coat layer was not formed) ＊ ＝86.6，a ＊ ＝－1.0，b ＊ ＝－0.4]And the yellowness Index (D1925) was measured using the color difference meter (YI 1). After the light resistance test, the yellowness index (YI 2) was measured by the same method as that using the color difference meter using the accelerated weather resistance tester. The difference in yellowness index (YI 2-YI 1) between before and after the light fastness test was defined as DeltaYI, and evaluated according to the following criteria A and C.
A：ΔYI＜1.0。
C：ΔYI≥1.0。
TABLE 1
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 revealed that the hard coat film (examples 1 to 12) having the hard coat layer produced using the curable composition in which A1, A2, A3, A4, or A5 was a polyfunctional monomer, UVA-1 or UVA-2 having a benzophenone skeleton was an ultraviolet absorber, and a perfluoropolyether SM having four acryl groups via urethane bonds at both ends of a molecular chain was blended as a surface modifier was able to exhibit excellent light resistance in the UVB (ultraviolet B wave) region in any one of the film substrates of TPU and PC without impairing the scratch resistance.
On the other hand, it was revealed that the hard coating film having the hard coating layer produced from the curable compositions of comparative examples 1 and 4, which used A1 as the polyfunctional monomer, UVA-3 having a triazine skeleton as the ultraviolet absorber, SM as the surface modifier, and TPU and PC as the film base material, respectively, was excellent in light resistance but poor in scratch resistance. Further, it was revealed that the hard coating film having the hard coating layer produced from the curable compositions of comparative examples 2 and 5 using UVA-4 having a benzotriazole skeleton as an ultraviolet absorber and TPU and PC as film substrates, respectively, had poor scratch resistance and light resistance. Also, it was revealed that the hard coat film having the hard coat layer produced from the curable compositions of comparative example 3 and comparative example 6 using UVA-5 having a cyanoacrylate skeleton as an ultraviolet absorber and TPU and PC as film substrates, respectively, had poor light resistance. Next, it was revealed that the hard coating film having the hard coating layer produced from the curable compositions of comparative examples 7 and 8 using A1 as the polyfunctional monomer, no ultraviolet absorber, SM as the surface modifier, and TPU and PC as the film base material, respectively, was excellent in scratch resistance, but was poor in light resistance because no ultraviolet absorber was added. It was also revealed that the hard coating film having the hard coating layer produced from the curable compositions of comparative examples 9 and 10 using A1 as the polyfunctional monomer, UVA-1 having a benzophenone skeleton as the ultraviolet absorber, and the TPU and PC as the film base materials, respectively, were excellent in light resistance, but were poor in scratch resistance because no surface modifier was added.
As shown in the results of the examples, a hard coat film satisfying scratch resistance and light resistance can be obtained only by using a curable composition comprising a combination of a polyfunctional monomer, an ultraviolet absorber having a benzophenone skeleton, and a perfluoropolyether.

Claims (8)

1. A curable composition, comprising:
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;
(b) 0.05 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain thereof via urethane bonds, wherein the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyalkylene) group and the urethane bond; (b) The poly (oxyperfluoroalkylene) group of the perfluoropolyether is a polyether having repeating units- [ OCF 2 ]-and repeating units- [ OCF 2 CF 2 ]Both sides, linking these repeating units in block bondsA group bonded, randomly bonded, or bonded by block bonding and random bonding, wherein the perfluoropolyether (b) is represented by the following formula [2 ]]The compounds of the formula (I) are shown,
above-mentioned [2 ]]Wherein A represents the following formula [ A3 ]]The structure shown or the structure in which the acryl group in the structure is substituted to methacryl group, PFPE represents the poly (oxidized perfluoroalkylene) group, wherein, with L 1 The side directly bonded is an oxygen radical terminal, the side bonded with the oxygen atom is a perfluoroalkylene terminal, L 1 Represents an alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms, and the partial structure (A-NHC (=O) O) m L 2 -represents the following formula [ B3 ]]The structure of the device is shown in the drawing,
(c) 0.1 to 30 parts by mass of an ultraviolet absorber having a benzophenone skeleton and having at least two hydroxyl groups; and
(d) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.
2. The curable composition according to claim 1, wherein,
part or all of the (a) polyfunctional monomers are polyfunctional (meth) acrylate compounds.
3. The curable composition according to claim 1 or 2, wherein,
the (a) polyfunctional monomer is an oxyalkylene-modified polyfunctional monomer.
4. The curable composition according to claim 1 or 2, wherein,
the (a) polyfunctional monomer is a polyfunctional monomer having at least three active energy ray polymerizable groups.
5. The curable composition according to claim 1 or 2, wherein,
further comprising (e) a solvent.
6. A cured film obtained from the curable composition according to any one of claims 1 to 5.
7. A hard coat film comprising a film substrate and, on at least one side thereof, a hard coat layer comprising the cured film according to claim 6.
8. A method for producing a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer comprises:
a step of applying the curable composition according to any one of claims 1 to 5 to a film substrate to form a coating film; and
and a step of curing the coating film by irradiation with active energy rays.
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