WO2015060458A1

WO2015060458A1 - Polymerizable composition containing perfluoropolyether having hydroxyl group

Info

Publication number: WO2015060458A1
Application number: PCT/JP2014/078499
Authority: WO
Inventors: 将幸原口
Original assignee: 日産化学工業株式会社
Priority date: 2013-10-25
Filing date: 2014-10-27
Publication date: 2015-04-30
Also published as: JPWO2015060458A1; JP2020023717A

Abstract

[Problem] To provide a material for forming a hardcoat layer that exhibits superior abrasion resistance and high lubricity even in thin-film regions. [Solution] A polymerizable composition including: (a) 100 parts by mass of an active energy beam-curable polyfunctional monomer; (b) 0.1-10 parts by mass of a perfluoropolyether having an active energy beam-polymerizable group that is bonded via a poly(oxyalkylene) group to one end of a molecular chain that includes a poly(oxyperfluoroalkylene) group, and a hydroxyl group that is bonded via a poly(oxyalkylene) group to the other end of the molecular chain; and (c) 1-20 parts by mass of a polymerization initiator that generates radicals when exposed to the active energy beam. A hardcoat film comprising a hardcoat layer formed from said composition.

Description

Polymerizable composition containing perfluoropolyether having hydroxy groups

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

A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is rapidly increasing.

Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface. In order to impart scratch resistance to the surface of a plastic film, for example, a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
Most of these polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator. The acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity. As a means for forming a hard coat layer on the surface of the plastic film, for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, and the organic solvent is dried and then cured by ultraviolet rays. Then, a means for forming a hard coat layer is employed. In order to express functions such as hardness and scratch resistance in the formed hard coat layer at a level having no practical problem, the thickness of the hard coat layer is usually 5 to 10 μm.

By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired. The fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
In addition, the touch panel display of many smartphones employs a multi-touch function, which allows you to use multiple fingers to expand (pinch out) or reduce (pinch in) the screen, or to flick a finger in a certain direction on the screen. And swipe operation. In order to obtain a smooth tactile sensation without being caught by such finger movement, there is a demand for slipperiness when the display surface is touched with a finger.
From such a viewpoint, it is desired that the surface of the touch panel display has slipperiness when operated with a finger in addition to antifouling properties against fingerprints and the like. However, in a capacitive touch panel, since a person touches it with a finger every day, even if the initial antifouling property and slipperiness reach a considerable level, their functions often deteriorate during use. Therefore, the antifouling property and the durability of slipperiness during use have been problems.

Furthermore, in recent years, attempts have been made to reduce the thickness of the hard coat layer. As described above, as the polyfunctional acrylate having a highly crosslinked structure is used, the scratch resistance of the hard coat layer is improved while the curing shrinkage rate of the hard coat layer is increased. The thicker the hard coat layer, the higher the shrinkage before and after curing. If the cure shrinkage rate of the hard coat layer is increased, wrinkles and curls are increased, and cracks and peeling of the hard coat layer are likely to occur. Thus, there is a great demand for a hard coat layer having a very thin thickness, for example, 1 to 5 μm. However, if the hard coat layer having excellent mechanical strength such as scratch resistance is thinned, the scratch resistance of the hard coat tends to be lowered. Thus, it was difficult to achieve both a reduction in the thickness of the hard coat layer and the scratch resistance.

Up to now, as a hard coat layer having scratch resistance, antifouling property and slipperiness, as a component for imparting antifouling property and slipperiness to the hard coat layer surface, both ends of the poly (oxyperfluoroalkylene) chain, A compound having a (meth) acryloyl group via a urethane bond having an isophorone skeleton and a (meth) via a urethane bond having a fluoroalkyl group at one end of the poly (oxyperfluoroalkylene) chain and an isocyanuric acid skeleton at the other end A technique using a compound having an acryloyl group as a surface modifier is disclosed (Patent Document 1).

In addition, a compound having a (meth) acryloyl group via a urethane bond having a tolylene skeleton at both ends of the poly (oxyperfluoroalkylene) chain, a polysiloxane chain at one end of the poly (oxyperfluoroalkylene) chain, A technique using a compound having a (meth) acryloyl group as a surface modifier via a urethane bond having a hexamethylene skeleton at the other end is disclosed (Patent Document 2).

JP 2013-76029 A JP 2010-143092 A

In any of the methods described in Patent Documents 1 and 2, a compound having (meth) acryloyl groups at both ends of a poly (oxyperfluoroalkylene) chain is used as a surface modifier. The compound has a problem that the poly (oxyperfluoroalkylene) chain is immobilized at both ends, so that the compound loses flexibility and is inferior in slipperiness. Furthermore, the above compounds have a structure having (meth) acryloyl groups at both ends via a urethane bond having an isophorone skeleton or a tolylene skeleton, etc., but these rigid skeletons work to increase the friction coefficient. Further, there was a risk of lowering the slipperiness.
In Patent Document 1, a compound having a fluoroalkyl group at one end of a poly (oxyperfluoroalkylene) chain and a silicone chain in one end of a poly (oxyperfluoroalkylene) chain in Patent Document 2 are used together. Since groups and silicone chains are concentrated on the outermost surface of the hard coat layer, it is effective for expressing slipperiness, but on the other hand, it is not fixed to the matrix resin, so it is inferior in scratch resistance. There was a problem.
Furthermore, the hard coat layer described in any of the literature has excellent scratch resistance. The thickness of the hard coat layer is as thick as 10 μm, and the scratch resistance in the thin film region of 1 to 5 μm is as follows. There is no mention. That is, there has been a demand for a hard coat layer that is excellent in scratch resistance even in a thin film region and that exhibits high slipperiness.

As a result of intensive studies in order to achieve the above object, the present inventors have determined that a hydroxyl group is bonded to one end of a molecular chain containing a poly (oxyperfluoroalkylene) structure via a poly (oxyalkylene) group at one end. And a polymerizable composition using a compound having an active energy ray polymerizable group via a poly (oxyalkylene) group at the other end as a fluorine-based surface modifier has a thickness of 1 to 5 μm. The inventors have found that a hard coat layer having excellent scratch resistance and high slipperiness can be formed even in a thin film, and completed the present invention.

That is, the present invention provides, as a first aspect, (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) having an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and via a poly (oxyalkylene) group at the other end The present invention relates to a polymerizable composition comprising 0.1 to 10 parts by mass of a perfluoropolyether having a hydroxy group and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
As a second aspect, the polymerizable composition according to the first aspect, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. About.
As a third aspect, the present invention relates to the polymerizable composition according to the first aspect or the second aspect, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
As a fourth aspect, the component (a) the polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the polymerizable composition according to any one of the above.
As a fifth aspect, the present invention relates to the polymerizable composition according to any one of the first aspect to the fourth aspect, in which the component (c) polymerization initiator is a mixture of alkylphenones and thioxanthones.
As a sixth aspect, the present invention relates to the polymerizable composition according to any one of the first aspect to the fifth aspect, further including (d) a solvent.
As a seventh aspect, the present invention relates to a cured film obtained from the polymerizable composition according to any one of the first aspect to the sixth aspect.
As an eighth aspect, there is provided a hard coat film comprising a hard coat layer on at least one surface of the film substrate, wherein the hard coat layer is polymerizable according to any one of the first to sixth aspects. The present invention relates to a hard coat film formed by a step of applying a composition on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays and curing.
As a ninth aspect, the hard coat film according to the eighth aspect, wherein the hard coat layer has a thickness of 0.1 to 10 μm.
As a tenth aspect, the hard coat film according to the ninth aspect, wherein the hard coat layer has a thickness of 1 to 5 μm.
As an eleventh aspect, there is an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and a poly (oxyalkylene) group at the other end. The present invention relates to a perfluoropolyether compound having a hydroxy group via
As a twelfth aspect, the present invention relates to a surface modifier comprising the perfluoropolyether compound described in the eleventh aspect.
A thirteenth aspect relates to the use of the perfluoropolyether compound described in the eleventh aspect as a surface modifier.

According to the present invention, it is possible to provide a polymerizable composition useful for forming a cured film and a hard coat layer having excellent scratch resistance and high slipperiness even in a thin film having a thickness of 1 to 5 μm.
Further, according to the present invention, it is possible to provide a hard coat film provided with a hard coat layer formed using the polymerizable composition on the surface, and are excellent in antifouling property, slipperiness and scratch resistance. A hard coat film can be provided.

<Polymerizable composition>
The present invention relates to a polymerizable composition comprising a perfluoropolyether having a hydroxy group.
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) having an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and via a poly (oxyalkylene) group at the other end The present invention relates to a polymerizable composition comprising 0.1 to 10 parts by mass of a perfluoropolyether having a hydroxy group and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
Hereinafter, the components (a) to (c) will be described first.

[(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
The preferable (a) active energy ray-curable polyfunctional monomer in the polymerizable composition of the present invention is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate , Ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated bisphenol Nord A di (meth) acrylate, 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, propylene glycol di (meth) acrylate, dipropylene glycol di ( Me ) 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-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecyleneoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] Sulfide, , 3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, etc. it can.
Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
For example, the polyfunctional urethane (meth) acrylate is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. Although what is obtained etc. are mentioned, the polyfunctional urethane (meth) acrylate compound which can be used by this invention is not limited only to this illustration.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.

In the present invention, as the (a) active energy ray-curable polyfunctional monomer, one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination.
When the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound are used in combination, polyfunctional (meth) acrylate compound: polyfunctional urethane (meth) acrylate compound = 90: 10 to 10 : It is preferable to use it in the ratio (mass ratio) of 90.

[(B) Perfluoropolyether having a hydroxy group]
In the present invention, the component (b) has an active energy ray-polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and poly (oxy) at the other end. A perfluoropolyether having a hydroxy group via an (oxyalkylene) group (hereinafter, also simply referred to as “(b) a perfluoropolyether having a hydroxy group”) is used. The component (b) serves as a surface modifier in the hard coat layer to which the polymerizable composition of the present invention is applied.

The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked. Specifically, — [OCF ₂ ] — (oxyperfluoromethylene group), — [OCF ₂ CF ₂ ] — (oxyperfluoroethylene group), — [OCF ₂ CF ₂ CF ₂ ] — (oxyperfluoropropane) -1,3-diyl group) and-[OCF ₂ C (CF ₃ ) F]-(oxyperfluoropropane-1,2-diyl group).
The above oxyperfluoroalkylene groups may be used alone or in combination of two or more. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.

Among these, from the viewpoint of obtaining a cured film having good slipperiness, as the poly (oxyperfluoroalkylene) group, — [OCF ₂ ] — (oxyperfluoromethylene group) and — [OCF ₂ CF ₂ ] — It is preferable to use a group having both (oxyperfluoroethylene group) as a repeating unit.
Among them, as the poly (oxyperfluoroalkylene) group, the repeating unit: — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — are represented by a molar ratio of [Repeating unit: — [OCF ₂ ] —]: [Repeating Unit: — [OCF ₂ CF ₂ ] —] = 2: 1 to 1: 2 is preferable, and a group including about 1: 1 is more preferable. The bond of these repeating units may be either a block bond or a random bond.
The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
The weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. .

The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked.
The oxyalkylene groups may be used singly or in combination of two or more. In that case, the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
Among these, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is more preferably in the range of 1 to 10.

Examples of the active energy ray polymerizable group bonded through the poly (oxyalkylene group) include a (meth) acryloyl group, a urethane (meth) acryloyl group, and a vinyl group.

Examples of the urethane moiety constituting the urethane (meth) acryloyl group include the structures U1 to U28 shown below.

The (meth) acryloyl moiety constituting the urethane (meth) acryloyl group includes, for example, the following structures A1 to A5 and structures obtained by substituting the acryloyl group in these structures with methacryloyl groups.

Specific examples of such a perfluoropolyether having a hydroxy group include the following compounds and compounds obtained by substituting acryloyl groups in these compounds with methacryloyl groups. In the structural formulas, A1 to A5 represent structures represented by the formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n represents a repeating unit of an oxyethylene group. Represents a number, preferably a number from 1 to 10.

In the present invention, (b) the perfluoropolyether having a hydroxy group is 0.1 to 10 parts by mass, preferably 0.2 to It is desirable to use at a ratio of 5 parts by mass.

The (b) perfluoropolyether having a hydroxy group is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, A method of urethanizing 2- (meth) acryloyloxyethyl isocyanate to a group, a method of dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, itaconic anhydride It can be obtained by a method of esterifying an acid.
Among them, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, 2- (meth) acryloyloxyethyl isocyanate is used with respect to the hydroxy group at one end. A method in which urethanization reaction is carried out or a method in which (meth) acrylic acid chloride or chloromethylstyrene is dehydrochlorinated with respect to the hydroxy group is particularly preferred in terms of easy reaction.
The (b) poly (oxyperfluoroalkylene) group has an active energy ray polymerizable group at one end of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group, and the other end has a poly (oxyalkylene) group. A perfluoropolyether compound having a hydroxy group via the above is also an object of the present invention, and a surface modifier comprising the perfluoropolyether compound, and use of the perfluoropolyether compound as a surface modifier. Is also an object of the present invention.

[(C) Polymerization initiator that generates radicals by active energy rays]
In the polymerizable composition of the present invention, a polymerization initiator that generates radicals by a preferable active energy ray (hereinafter, also simply referred to as “(c) polymerization initiator”) is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
Examples of the polymerization initiator (c) include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones. Biscumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, or onium salts such as iodonium salts and sulfonium salts. You may use these individually by 1 type or in mixture of 2 or more types.
Among them, in the present invention, it is preferable to use a mixture of alkylphenones and thioxanthones as the polymerization initiator (c) from the viewpoint of transparency, surface curability, and thin film curability. By using a mixture of alkylphenones and thioxanthones, it is possible to obtain a cured film that is more excellent in slipperiness and further improved in scratch resistance.

Examples of the alkylphenones include 1-hydroxycyclohexyl = phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4- (2-hydroxyethoxy) phenyl) -2. Α-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one, etc. -Hydroxyalkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 Α-aminoalkylphenones such as -one; 2,2-dimethoxy-1,2-diphenylethane-1-one; And methyl oxylate.
Examples of the thioxanthones include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone and the like.

In the present invention, (c) the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.
Further, when a mixture of alkylphenones and thioxanthones is used, it is preferably used in a mass ratio of alkylphenones: thioxanthones = 100: 1 to 1: 100, and 100: 5 to 1: 1. It is more preferable to use in the ratio.

[(D) Solvent]
The polymerizable composition of the present invention may further contain (d) a solvent, that is, may be in the form of a varnish (film forming material).
The solvent is appropriately selected in consideration of the workability at the time of coating and the drying before and after curing for dissolving the components (a) to (c) and forming a cured film (hard coat layer) described later. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, Halides such as methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene S such as glycol monomethyl ether acetate Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl Ethers such as ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol , Tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, etc. Alcohols; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone; and two or more of these A mixed solvent is mentioned.
The amount of the solvent (d) used is not particularly limited. For example, the solvent is used at a concentration such that the solid content in the polymerizable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) refers to the solid content (excluding solvent components from all components) relative to the total mass (total mass) of the components (a) to (d) of the polymerizable composition of the present invention. Content).

[Other additives]
In addition, to the polymerizable composition of the present invention, additives generally added as necessary, for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a surface activity, unless the effects of the present invention are impaired. An agent, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended.

<Curing film>
The polymerizable composition of the present invention can form a cured film by coating (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray for polymerization (curing). The cured film is also an object of the present invention.
Examples of the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The coating method on the base material is 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 plate, an intaglio plate). , Lithographic printing, screen printing, etc.) can be selected as appropriate, and in particular, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the polymerizable composition is filtered in advance using a filter having a pore diameter of about 0.2 μm and then applied. In addition, when apply | coating, it is good also as a varnish form by adding a solvent to this polymeric composition as needed. Examples of the solvent in this case include the various solvents mentioned in [(d) Solvent].
After the polymerizable composition is applied on the substrate to form a coating film, the coating film is preliminarily dried with a hot plate or an oven as necessary to remove the solvent. The heat drying conditions at this time are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
After drying, the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. As a light source used 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.
Furthermore, after that, polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
The thickness of the formed cured film is usually 0.01 to 50 μm, preferably 0.05 to 20 μm after drying and curing.

<Hard coat film>
Using the polymerizable composition of the present invention, a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced. The hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.

The hard coat layer in the hard coat film of the present invention is formed by a step of coating the above-described polymerization of the present invention on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays to cure the coating film. Can be formed.

As the film substrate, various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned <cured film> are used. Preferably, for example, a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc. A film is mentioned.
Moreover, the method quoted in the above-mentioned <cured film> can be used for the coating method (coating film formation process) of the polymeric composition on the said film base material, and the ultraviolet irradiation method (curing process) to a coating film. . Moreover, when the solvent is contained in the polymerization composition of this invention (varnish form), the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process. In that case, the drying method (solvent removal process) of the coating film quoted to the above-mentioned <cured film> can be used.
The thickness of the hard coat layer thus obtained is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Bar coat application device: PM-9050MC manufactured by SMT Co., Ltd.
Bar: OSG Systems Products A-Bar OSP-25, maximum film thickness 25μm (corresponding to wire bar # 10)
Application speed: 4 m / min (2) Oven Equipment: Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
(3) UV irradiation device Device: H02-L41 manufactured by Eye Graphics Co., Ltd.
(4) Film thickness measurement device: Filmetrics F20 film thickness measurement system (5) Contact angle measurement device: Kyowa Interface Science Co., Ltd. DropMaster DM-501
Measurement temperature: 20 ° C
(6) Dynamic friction coefficient measurement apparatus: Shinto Kagaku Co., Ltd. load fluctuation type friction abrasion tester TRIBOGEAR HHS2000
Probe: 0.6mmR Sapphire pin Load: 50g
Measurement speed: 1 mm / sec Scanning distance: 1 cm
(7) Pencil hardness measurement apparatus: Electric pencil scratch hardness tester No. 1 manufactured by Yasuda Seiki Seisakusho Co., Ltd. 553M
Load: 750g
Pencil: Uni (registered trademark) series manufactured by Mitsubishi Pencil Co., Ltd.

Abbreviations represent the following meanings.
PFPE1: Perfluoropolyether having a poly (oxyalkylene) group and a hydroxy group at both ends [Fluorolink (registered trademark) 5147X manufactured by Solvay Specialty Polymers]
PFPE2: Perfluoropolyether having hydroxy groups at both ends [Fluorolink (registered trademark) D10H manufactured by Solvay Specialty Polymers]
PFPE3: Perfluoropolyether having acryloyl groups at both ends (Fluorolink (registered trademark) AD1700, Solvay Specialty Polymers, Inc., nonvolatile content: 70% by mass butyl acetate / ethyl acetate solution)
PFPE4: Perfluoropolyether having methacryloyl groups at both ends [Fluorolink (registered trademark) 5101X, Solvay Specialty Polymers, Inc., 80% by mass MEK solution in nonvolatile content]
PFPE5: Perfluoropolyether having a (meth) acryloyl group at one end [Optool (registered trademark) DAC-HP, manufactured by Daikin Industries, Ltd., non-volatile content: 20% by mass solution]
PFPE6: Perfluoropolyether having a (meth) acryloyl group at one end [Fluorine antifouling additive KY-1203, manufactured by Shin-Etsu Chemical Co., Ltd., MEK / MIBK solution with a nonvolatile content of 20% by mass]
AOI: 2-acryloyloxyethyl isocyanate [Karenz (registered trademark) AOI manufactured by Showa Denko KK]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko KK]
TFPI: 4- (trifluoromethoxy) phenyl isocyanate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DPHA: Dipentaerythritol hexaacrylate [KAYALAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.]
UA: 6 functional urethane acrylate [EBECRYL (registered trademark) 5129 manufactured by Daicel-Cytec Co., Ltd.]
I127: 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one [IRGACURE (registered trademark) 127 manufactured by BASF Japan Ltd.] ]
DETXS: 2,4-diethylthioxanthone [manufactured by Nippon Kayaku Co., Ltd. KAYACURE (registered trademark) DETX-S]
MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone PGME: propylene glycol monomethyl ether

[Example 1] Production of perfluoropolyether SM1 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a hydroxy group at the other end 1.05 g of PFPE1 (0. 5 mmol), 0.07 g (0.5 mmol) of AOI, 0.01 g (0.02 mmol) of DBTDL, and 1.12 g of MEK. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50 mass% MEK solution of SM1.

[Example 2] Production of perfluoropolyether SM2 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a hydroxy group at the other end 1.05 g of PFPE1 (0. 5 mmol), 0.13 g (0.5 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL, and 1.18 g of MEK. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50 mass% MEK solution of SM2.

[Synthesis Example 1] Production of perfluoropolyether SM3 having a poly (oxyalkylene) group and an acryloyl group at both ends In a brown screw tube, 1.05 g (0.5 mmol) of PFPE1 and 0.14 g (1.0 mmol) of AOI , DBTDL 0.01 g (0.02 mmol), and MEK 1.19 g were charged. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50 wt% MEK solution of SM3.

[Synthesis Example 2] Production of perfluoropolyether SM4 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a trifluoromethoxy group at the other end 1.05 g of PFPE1 in a brown screw tube ( 0.5 mmol), TFPI 0.10 g (0.5 mmol), DBTDL 0.01 g (0.02 mmol), and MEK 1.22 g. The mixture was stirred for 24 hours at room temperature (approximately 25 ° C.) using a stirrer tip. To this reaction mixture, 0.07 g (0.5 mmol) of AOI was added, and the mixture was further stirred at room temperature (approximately 25 ° C.) for 24 hours to obtain a target 50% by mass SM4 solution of SM4.

[Synthesis Example 3] Production of perfluoropolyether SM5 having an acryloyl group at one end and a hydroxy group at the other end In a brown screw tube, 0.73 g (0.5 mmol) of PFPE2, 0.12 g (0.5 mmol) of BEI, DBTDL 0.01 g (0.02 mmol) and 0.85 g of MEK were charged. This mixture was stirred at room temperature (approximately 25 ° C.) for 24 hours using a stirrer chip to obtain a target 50% by mass SM5 solution of SM5.

[Examples 3 to 6 and Comparative Examples 1 to 4]
The following components were mixed to prepare a curable composition having a nonvolatile content concentration of 10% by mass.
(1) Polyfunctional monomer: 60 parts by mass of DPHA, 40 parts by mass of UA (2) Surface modifier: 2 parts by mass of the surface modifier described in Table 1 (as non-volatile content)
(3) Polymerization initiator: Polymerization initiator described in Table 1 Amount described in Table 1 (4) Solvent: PGME 995.2 parts by mass This curable composition was converted into an A4 size PET film [manufactured by Toyobo Co., Ltd. Cosmo Shine (registered trademark) A4100, thickness 125 μm] (easy adhesion treatment surface side) was bar-coated to obtain a coating film. This coating film was dried in an oven at 100 ° C. for 3 minutes to remove the solvent. The obtained film was exposed to UV light with an exposure amount of 200 mJ / cm ² under a nitrogen atmosphere to produce a hard coat film having a hard coat layer with a thickness of about 1 to 2 μm.

The obtained hard coat layer was evaluated for film thickness, water and oleic acid contact angle, dynamic friction coefficient μk, slipperiness, scratch resistance and pencil hardness. The procedure for each evaluation is shown below. The results are also shown in Table 1.
[Film thickness]
The film thickness at three locations on the hard coat layer surface was measured, and the average value was taken as the film thickness value.
[Contact angle]
1 μL of probe liquid (water or oleic acid) was attached to the surface of the hard coat layer, the contact angle after 5 seconds was measured 5 times, and the average value was taken as the contact angle value.
[Dynamic friction coefficient]
The dynamic friction coefficients at five locations on the surface of the hard coat layer were measured, and the average value was taken as the dynamic friction coefficient value.
Note that the smaller the value of the dynamic friction coefficient value, the smaller the friction with the probe in use, which is a measure of slipperiness. The dynamic friction coefficient required for a hard coat layer applied to the surface of a display element such as a touch panel is required to be at least 0.1 or less, and preferably 0.05 or less.
[Slippery]
The surface of the hard coat layer was touched with a finger to operate the touch panel, and the touch at that time was evaluated according to the following criteria. In addition, when an actual use is assumed as a hard-coat layer, it is calculated | required that it is at least B, and it is desirable that it is A.
A: Does not feel a catch B: Feels a slight catch but can smoothly touch the surface C: Feels a catch and cannot touch the surface smoothly [Abrasion resistance]
The surface of the hard coat layer was rubbed back and forth 5000 times with a steel wool [Bonster Sales Co., Ltd. Bonstar (registered trademark) # 0000 (super extra fine)], and an oil marker [Zebra Co., Ltd. Made Mackey extra fine (blue), use fine side]. Subsequently, the drawn line was wiped off with a non-woven wiper [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Fibers Co., Ltd.], and the degree of scratches was visually confirmed and evaluated according to the following criteria. In addition, when an actual use is assumed as a hard-coat layer, it is calculated | required that it is at least B, and it is desirable that it is A.
A: The line drawn with the oil-based marker can be wiped clean without scratching B: The line drawn with the oil-based marker can be wiped off cleanly, but the ink drawn with the oil-based marker enters the scratch and cannot be wiped off [pencil hardness]
The measurement was performed according to JIS K5600-5-4.
A hard coat layer applied to the surface of a display element such as a touch panel, particularly a thin film having a thickness of 1 to 5 μm, usually requires a pencil hardness of H to 3H.

[Comparative Example 5]
The following components were mixed to prepare a curable composition having a nonvolatile content concentration of 10% by mass.
(1) Polyfunctional monomer: DPHA 60 parts by mass, UA 40 parts by mass (2) Surface modifier: PFPE3 1.4 parts by mass (as non-volatile content) and PFPE4 0.6 part by mass (as non-volatile content) Dissolved in 7.25 parts by mass of butyl (3) Polymerization initiator: I127 8 parts by mass, DETXS 0.8 parts by mass (4) Solvent: PGME 989.2 parts by mass Using this curable composition, Examples A hard coat film was prepared and evaluated in the same manner as in 3. The results are also shown in Table 1.

[Comparative Examples 6 to 7]
The following components were mixed to prepare a curable composition having a nonvolatile content concentration of 10% by mass.
(1) Polyfunctional monomer: 60 parts by mass of DPHA, 40 parts by mass of UA (2) Surface modifier: 2 parts by mass of the surface modifier described in Table 1 (as non-volatile content)
(3) Polymerization initiator: I127 8 parts by mass, DETXS 0.8 part by mass (4) Solvent: PGME 989.2 parts by mass Using this curable composition, a hard coat film was produced in the same manner as in Example 3. ,evaluated. The results are also shown in Table 1.

As shown in Table 1, perfluoropolyethers SM1 and SM2 having poly (oxyalkylene) and acryloyl groups at one end and poly (oxyalkylene) and hydroxy groups at the other end as surface modifiers in the hard coat layer. The hard coat films of Examples 3 and 4 used were excellent in antifouling property, slipperiness, scratch resistance and hardness at a film thickness of 1.4 to 1.6 μm.
Further, in Example 5 using an alkylphenone (I127) alone as a polymerization initiator and Example 6 using a thioxanthone (DETXS) alone, the film thickness is 1.8 μm, and the antifouling property and hardness are excellent. Regarding the slipping property and scratch resistance, the standard in consideration of actual use was satisfied as compared with the comparative examples described later.
Thus, by using together alkylphenones and thioxanthones (DETXS) as polymerization initiators (Example 3 and Example 4), compared to the case of using them alone (Example 5 and Example 6). As a result, it was confirmed that the slipperiness and scratch resistance when the film was thinned were further improved.

On the other hand, the hard coat film of Comparative Example 1 using perfluoropolyether SM3 having a poly (oxyalkylene) group and an acryloyl group at both ends as a surface modifier in the hard coat layer resulted in inferior slipperiness. It was.
The hard coat film of Comparative Example 2 using perfluoropolyether SM4 having a poly (oxyalkylene) group and an acryloyl group at one end and a poly (oxyalkylene) group and a trifluoromethoxy group at the other end, and an acryloyl group at both ends The hard coat film of Comparative Example 5 in which a perfluoropolyether having a methacryloyl group and a perfluoropolyether having a methacryloyl group at both ends were inferior in terms of slipperiness, scratch resistance and hardness.
Further, a hard coat film of Comparative Example 3 using perfluoropolyether SM5 having an acryloyl group at one end and a hydroxy group at the other end, and a perfluoropolyether having a poly (oxyalkylene) group and a hydroxy group at both ends The hard coat film of Comparative Example 4 used resulted in the hard coat layer becoming cloudy and inferior in slipperiness, scratch resistance and hardness.
And the hard coat film of the comparative example 6 and the comparative example 7 which used the perfluoropolyether which has a (meth) acryloyl group at one end brought a result that it was inferior to slipperiness and scratch resistance.

Thus, it is difficult to satisfy all the performances such as antifouling property, slipperiness, scratch resistance and hardness only by slightly different terminal structure of the perfluoropolyether used as the surface modifier. Only the polymerizable composition can obtain a hard coat film satisfying all these properties.

Claims

(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) having an active energy ray polymerizable group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, and via a poly (oxyalkylene) group at the other end A polymerizable composition comprising 0.1 to 10 parts by mass of a perfluoropolyether having a hydroxy group and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
2. The polymerizable composition according to claim 1, wherein the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units.
The polymerizable composition according to claim 1, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
The component (a) polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The polymerizable composition according to item.
The polymerizable composition according to any one of claims 1 to 4, wherein the component (c) polymerization initiator is a mixture of alkylphenones and thioxanthones.
The polymerizable composition according to any one of claims 1 to 5, further comprising (d) a solvent.
The cured film obtained from the polymeric composition as described in any one of Claims 1 thru | or 6.
A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the polymerizable composition according to any one of claims 1 to 6 as a film base. A hard coat film formed by a process of coating on a material to form a coating film and a process of irradiating the coating film with ultraviolet rays and curing.
The hard coat film according to claim 8, wherein the hard coat layer has a thickness of 0.1 to 10 µm.
The hard coat film according to claim 9, wherein the hard coat layer has a thickness of 1 to 5 μm.
One end of a molecular chain containing a poly (oxyperfluoroalkylene) group has an active energy ray polymerizable group via a poly (oxyalkylene) group, and the other end has a hydroxy group via a poly (oxyalkylene) group. A perfluoropolyether compound having
A surface modifier comprising the perfluoropolyether compound according to claim 11.
Use of the perfluoropolyether compound according to claim 11 as a surface modifier.