WO2020162323A1

WO2020162323A1 - Curable composition for flexible hard coating

Info

Publication number: WO2020162323A1
Application number: PCT/JP2020/003467
Authority: WO
Inventors: 健吾脇田; 将幸原口
Original assignee: 日産化学株式会社
Priority date: 2019-02-06
Filing date: 2020-01-30
Publication date: 2020-08-13
Also published as: KR20210123324A; TW202045553A; JPWO2020162323A1; CN113396127A

Abstract

[Problem] To provide a material for forming a hard coat layer having excellent abrasion-resistance and stretchability. [Solution] The present invention pertains to: a curable composition containing (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer selected from the group consisting of (a-1) active energy ray-curable oxyethylene modified polyfunctional monomers and (a-2) active energy ray-curable lactone modified polyfunctional monomers, (b) 0.05-10 parts by mass of a perfluoropolyether including a poly(oxy perfluoro alkylene) group, (c) 10-65 parts by mass of silica particles having respective surfaces thereof modified with a silane coupling agent including a nitrogen-containing proton-donating functional group, and (d) 1-20 parts by mass of a polymerization initiator that generates radicals by active energy rays; and a hard coat film provided with a hard coat layer formed by said curable composition.

Description

Curable composition for flexible hard coat

The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as a flexible display, which has excellent scratch resistance and stretchability, and further has antistatic property and/or antistatic property. The present invention relates to a curable composition capable of forming a hard coat layer capable of imparting antiglare properties.

Smartphones have become popular as the most common form of mobile phone, and have become an indispensable part of our daily lives. A cover glass is used on the surface of the smartphone to prevent the display from being scratched. In recent years, bendable displays, so-called flexible displays, have been developed as the above displays. The flexible display is expected to have a wide range of applications as a display that can be deformed such as bent and wound. However, since glass is generally hard and difficult to bend back, it cannot be applied to flexible displays. Therefore, instead of glass, it has been attempted to apply a plastic film having a hard coat layer having scratch resistance for scratch protection to the surface of a flexible display. When a flexible display applied with a plastic film having a hard coat layer on its surface is curved with its display side facing outward (that is, with the hard coat layer facing outward), the outermost hard coat layer has Since the stress is generated, the hard coat layer is required to have a certain stretchability.

Further, generally, as a method of imparting scratch resistance to the hard coat layer, for example, by forming a high-density crosslinked structure, that is, by forming a crosslinked structure having low molecular mobility, surface hardness is increased and resistance to external force is increased. The method of giving is adopted. As a material for forming these hard coat layers, a polyfunctional acrylate-based material that is three-dimensionally crosslinked by radicals is currently most used. However, the polyfunctional acrylate-based material is usually inferior in stretchability due to its high crosslink density. As described above, the stretchability of the hard coat layer and the scratch resistance are in a trade-off relationship, and it is an issue to make both properties compatible.

As one of the methods for improving scratch resistance, a method of imparting slipperiness to the cured film surface by mixing a curable composition for forming a hard coat layer with a silicone or fluorine-based surface modifier has been known. ing.
In addition, a technique of a hard coat layer that achieves both scratch resistance and stretchability by using a polyfunctional acrylate in combination with high hardness silica fine particles has been reported (Patent Document 1).

On the other hand, when a hard coat film is used as a front protective material for a display, antistatic property may be required in order to suppress adhesion of dust and the like due to static electricity generated during lamination and to prevent malfunction of the display. As a countermeasure against such static electricity, it is desirable that the surface resistance value is about 10 ¹⁰ Ω/□.

JP, 2011-131409, A

In the silica particle-added hard coat layer described in Patent Document 1 proposed so far, the physical interaction between the polyfunctional acrylate and the silica particles is weak, and it is difficult to obtain sufficient scratch resistance, and the stretchability is improved. Was not at a satisfactory level.

The present inventors have conducted extensive studies to achieve the above object, and as a result, the surface was modified with an oxyethylene-modified or lactone-modified polyfunctional monomer and a silane coupling agent having a nitrogen-containing proton-donating functional group. A curable composition containing silica particles and a perfluoropolyether containing a poly(oxyperfluoroalkylene) group as a surface modifier forms a hard coat layer capable of improving stretchability while maintaining scratch resistance. They have found that they can be formed and can also impart antistatic performance and/or antiglare properties, and have completed the present invention.

That is, the first aspect of the present invention is as follows.
An active energy ray-curable polyfunctional monomer selected from the group consisting of (a) (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer and (a-2) active energy ray-curable lactone-modified polyfunctional monomer. 100 parts by mass of functional monomer,
(B) 0.05 to 10 parts by mass of perfluoropolyether containing a poly(oxyperfluoroalkylene) group,
(C) 10 to 65 parts by mass of silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton donating functional group, and
(D) A curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
As a second aspect, the nitrogen-containing proton-donating functional group is at least one group selected from the group consisting of an amino group, an amide group, a urea group, a thiourea group, a urethane group, a thiourethane group, a ureido group, and a thioureido group. Which is a curable composition according to the first aspect.
As a third aspect, the curable composition according to the second aspect, wherein the nitrogen-containing proton donating functional group is at least one group selected from the group consisting of an amino group, a urea group, a thiourea group, and a ureido group. Regarding
A fourth aspect relates to the curable composition according to any one of the first to third aspects, wherein the (c) silica particles are silica fine particles having an average particle diameter of 40 nm to 500 nm.
As a fifth aspect, the (b) perfluoropolyether has an active energy ray-polymerizable group at the end of its molecular chain via a urethane bond, according to any one of the first to fourth aspects. Of the curable composition.
As a sixth aspect, the above-mentioned (b) perfluoropolyether has at least two active energy ray-polymerizable groups via urethane bonds at the ends of its molecular chain. And a curable composition according to item 1.
As a seventh aspect, the above-mentioned (b) perfluoropolyether has at least two active energy ray-polymerizable groups at one end of its molecular chain via a urethane bond. One relates to the curable composition.
As an eighth aspect, any one of the first to sixth aspects, wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain. The curable composition according to any one of the above.
As a ninth aspect, the poly(oxyperfluoroalkylene) group has both a repeating unit —[OCF ₂ ]— and a repeating unit —[OCF ₂ CF ₂ ]—, and these repeating units are block-bonded or random-bonded. Or the curable composition according to any one of the first to eighth aspects, which is a group formed by a block bond and a random bond.
As a tenth aspect, the curable composition according to the ninth aspect, wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].

(In the above formula [1],
n is the total number of repeating units -[OCF ₂ CF ₂ ]- and the number of repeating units -[OCF ₂ ]-, and represents an integer of 5 to 30,
The repeating unit —[OCF ₂ CF ₂ ]— and the repeating unit —[OCF ₂ ]— are bonded by a block bond, a random bond, or a block bond and a random bond. )
As an eleventh aspect, in the first to tenth aspects, a part or all of the (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer is composed of an oxyethylene-modified polyfunctional (meth)acrylate compound. The curable composition according to any one of the above.
A twelfth aspect is that the (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer is a monomer having 3 or more active energy ray-polymerizable groups in one molecule, and has an average oxyethylene-modified amount of The curable composition according to any one of the first to eleventh aspects, which is a monomer of less than 3 mol per 1 mol of the active energy ray-polymerizable group.
As a thirteenth aspect, the (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer is a monomer having an average oxyethylene-modified amount of less than 2 mol with respect to 1 mole of the active energy ray-polymerizable group. And the curable composition described in 1.
As a fourteenth aspect, any one of the first to thirteenth aspects, wherein a part or all of (a-2) the active energy ray-curable lactone-modified polyfunctional monomer is composed of a lactone-modified polyfunctional (meth)acrylate compound. The curable composition according to any one of the above.
A fifteenth aspect relates to the curable composition according to the fourteenth aspect, wherein part or all of the (a-2) active energy ray-curable lactone-modified polyfunctional monomer is an ε-caprolactone-modified polyfunctional monomer.
As a sixteenth aspect, the (c) silica particles are silica particles whose surface is modified with a silane coupling agent having a thiourea group or a ureido group, and
(E) The curable composition according to any one of the first to fifteenth aspects, further including 10 parts by mass to 55 parts by mass of the antistatic agent.
A seventeenth aspect relates to the curable composition according to the sixteenth aspect, which comprises metal oxide particles as the (e) antistatic agent.
As an eighteenth aspect, the curable composition according to the seventeenth aspect, wherein the metal oxide particles contain an oxide of at least one element selected from the group consisting of tin, zinc, and indium.
A nineteenth aspect relates to the curable composition according to the eighteenth aspect, wherein the metal oxide particles contain tin oxide.
As a twentieth aspect, the metal oxide particles contain at least one of phosphorus-doped tin oxide and tin oxide whose surface is coated with antimony pentoxide. Of the curable composition.
As a twenty-first aspect, the curable composition according to any one of the first to twentieth aspects further including (f) 1 part by mass to 40 parts by mass of fine particles having an average particle size of 0.2 μm to 15 μm. Regarding things.
A twenty-second aspect relates to the curable composition according to the twenty-first aspect, wherein (f) the fine particles having an average particle size of 0.2 μm to 15 μm are organic fine particles.
A twenty-third aspect relates to the curable composition according to the twenty-second aspect, wherein the organic fine particles are polymethylmethacrylate fine particles.
A twenty-fourth aspect relates to the curable composition according to any one of the first to twenty-third aspects, further including (g) a solvent.
A twenty-fifth aspect relates to a cured film obtained from the curable composition according to any one of the first to twenty-fourth aspects.
A twenty-sixth aspect relates to a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to the twenty-fifth aspect.
A 27th aspect relates to the hardcoat film according to the 26th aspect, wherein the hard coat layer has a layer thickness of 1 μm to 10 μm.
A twenty-eighth aspect is a method for producing a hard coat film, comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is described in any one of the first to twenty-fourth aspects. It relates to a method for producing a hard coat film, which comprises a step of forming a coating film by applying the curable composition of 1. to a film substrate and a step of irradiating the coating film with an active energy ray to cure the coating film.
A twenty-ninth aspect relates to silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group.
A thirtieth aspect relates to the silica particles according to the twenty-ninth aspect, which have an average particle diameter of 40 nm to 500 nm.
A 31st aspect relates to the silica particles according to the 29th aspect or the 30th aspect, wherein the nitrogen-containing proton-donating functional group is a thiourea group or a thiourethane group.

According to the present invention, it is possible to provide a curable composition which is useful for forming a cured film and a hard coat layer that have both excellent scratch resistance and high stretchability even in a thin film having a thickness of about 1 μm to 10 μm. ..
Further, according to the present invention, it is possible to provide a hard coat film having a cured film obtained from the curable composition or a hard coat layer formed from the cured film provided on the surface, scratch resistance, and stretching. A hard coat film having excellent properties can be provided.
Furthermore, according to the present invention, in addition to the above-mentioned properties, a curable composition useful for forming a hardened film and a hard coat layer having antistatic properties and/or antiglare properties, and a hard coat layer excellent in these properties. It is possible to provide a hard coat film having a surface coated with.

<Curable composition>
The curable composition of the present invention specifically comprises
An active energy ray-curable polyfunctional monomer selected from the group consisting of (a) (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer and (a-2) active energy ray-curable lactone-modified polyfunctional monomer. 100 parts by mass of functional monomer,
(B) 0.05 to 10 parts by mass of perfluoropolyether containing a poly(oxyperfluoroalkylene) group,
(C) 10 to 65 parts by mass of silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton donating functional group, and
(D) Relating to a curable composition containing a curable composition containing 1 part by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. First, each component of the above (a) to (d) Will be described.

[(A) Active energy ray curable polyfunctional monomer]
In the present invention, as the active energy ray-curable polyfunctional monomer of the component (a), (a-1) an active energy ray-curable oxyethylene-modified polyfunctional monomer or (a-2) an active energy ray-curable lactone described later is used. A modified polyfunctional monomer is used. These (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomers and (a-2) active energy ray-curable lactone-modified polyfunctional monomers may be used in combination.
The component (a) has two or more active energy ray-polymerizable groups that undergo a polymerization reaction to be cured by irradiation with an active energy ray such as ultraviolet rays, and also has a group derived from an oxyethylene group or a lactone. It is a functional monomer. Examples of the active energy ray-polymerizable group include (meth)acryloyl group and vinyl group.

[(A-1) Active energy ray-curable oxyethylene-modified polyfunctional monomer]
The active energy ray-curable oxyethylene-modified polyfunctional monomer used in the present invention is a monomer having two or more active energy ray-polymerizable groups. Preferably, the average amount of modified oxyethylene is less than 3 mol per 1 mol of the active energy ray-polymerizable group.

The preferable (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer in the curable composition of the present invention has at least three active energy ray-polymerizable groups and has an average oxyethylene-modified amount of the above-mentioned active energy. A monomer selected from the group consisting of oxyethylene-modified polyfunctional (meth)acrylate compounds, which is less than 3 mol with respect to 1 mol of the linear polymerizable group, and, for example, from the group consisting of oxyethylene-modified polyfunctional urethane (meth)acrylate compounds. Mention may be made of the monomers selected.
In addition, in this invention, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the oxyethylene-modified polyfunctional (meth)acrylate compound include (oxy)ethylene-modified polyol (meth)acrylate compounds.
Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.

In the active energy ray-curable oxyethylene-modified polyfunctional monomer (a-1), the average oxyethylene-modified amount is less than 3 mol with respect to 1 mol of the active energy ray-polymerizable group contained in the monomer, and preferably the monomer Can be less than 2 mol per 1 mol of the active energy ray-polymerizable group. The average oxyethylene modification amount is larger than 0 mol with respect to 1 mol of the active energy ray-polymerizable group contained in the monomer, preferably 0.1 mol or more with respect to 1 mol of the active energy ray-polymerizable group contained in the monomer, More preferably, it can be 0.5 mol or more.
Further, the addition number of oxyethylene to 1 molecule of the (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer can be 1 to 30, preferably 1 to 12.

In the present invention, one type of the above (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer can be used alone, or two or more types can be used in combination.

[(A-2) active energy ray-curable lactone-modified polyfunctional monomer]
The (a-2) active energy ray-curable lactone-modified polyfunctional monomer used in the present invention is a lactone-modified polyfunctional monomer which undergoes a polymerization reaction upon irradiation with an active energy ray such as ultraviolet rays and is cured. Refers to monomers.
The preferable (a) active energy ray-curable lactone-modified polyfunctional monomer in the curable composition of the present invention is a monomer selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds.

Examples of the lactone-modified polyfunctional (meth)acrylate compound include polyols modified with lactones such as γ-butyrolactone, δ-valerolactone, ε-caprolactone (that is, ring-opening addition or ring-opening addition polymerization of lactone). Alternatively, a (meth)acrylate compound of polythiol can be used.
Examples of the polyol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, bisphenol A, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, ethoxylated dipentaerythritol, ethoxylated glycerin, ethoxylated. Bisphenol A, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1 ,10-decanediol, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 1,3-adamantane diol, 1,3-adamantane dimethanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol , Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, dioxane glycol, bis(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate, 9,9-bis(4-hydroxy) Examples thereof include phenyl)fluorene and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene.
Further, examples of the thiol include bis(2-mercaptoethyl)sulfide and bis(4-mercaptophenyl)sulfide.

Examples of such a lactone-modified polyfunctional (meth)acrylate compound include lactone-modified trimethylolpropane tri(meth)acrylate, lactone-modified ditrimethylolpropane tetra(meth)acrylate, lactone-modified pentaerythritol di(meth)acrylate, and lactone. Modified pentaerythritol tri(meth)acrylate, lactone modified pentaerythritol tetra(meth)acrylate, lactone modified dipentaerythritol penta(meth)acrylate, lactone modified dipentaerythritol hexa(meth)acrylate, lactone modified 2-hydroxy-1,3 -Di(meth)acryloyloxypropane, lactone modified 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, lactone modified glycerin tri(meth)acrylate, lactone modified bisphenol A di(meth)acrylate, lactone modified ethoxylated tri Methylolpropane tri(meth)acrylate, lactone modified ethoxylated pentaerythritol tetra(meth)acrylate, lactone modified ethoxylated dipentaerythritol hexa(meth)acrylate, lactone modified ethoxylated glycerin tri(meth)acrylate, lactone modified ethoxylated bisphenol A Di(meth)acrylate, lactone-modified 1,3-propanediol di(meth)acrylate, lactone-modified 1,3-butanediol di(meth)acrylate, lactone-modified 1,4-butanediol di(meth)acrylate, lactone-modified 1,6-hexanediol di(meth)acrylate, lactone-modified 2-methyl-1,8-octanediol di(meth)acrylate, lactone-modified 1,9-nonanediol di(meth)acrylate, lactone-modified 1,10- Decanediol di(meth)acrylate, lactone modified tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate, lactone modified 1,3-adamantane diol di(meth)acrylate, lactone modified 1, 3-adamantane dimethanol di(meth)acrylate, lactone modified ethylene glycol di(meth)acrylate, lactone modified diethylene glycol di(meth)acrylate, lactone modified triethylene glycol di(meth)acrylate, lactone modified tetraethylene glycol di(meth)acrylate Acrylate, lactone modified polyethylene glycol di (Meth)acrylate, lactone modified propylene glycol di(meth)acrylate, lactone modified dipropylene glycol di(meth)acrylate, lactone modified polypropylene glycol di(meth)acrylate, lactone modified neopentyl glycol di(meth)acrylate, lactone modified dioxane Glycol di(meth)acrylate, lactone-modified bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, lactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, lactone-modified 9,9-bis(4 -(Meth)acryloyloxyphenyl)fluorene, lactone-modified 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, lactone-modified bis[2-(meth)acryloylthioethyl]sulfide, lactone Examples thereof include modified bis[4-(meth)acryloylthiophenyl]sulfide.

Among them, ε-caprolactone is preferable as the lactone to be modified, and for example, a compound in which the lactone of the lactone-modified polyfunctional (meth)acrylate compound is ε-caprolactone is preferable.
More preferable lactone-modified polyfunctional (meth)acrylate compounds include, for example, ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth). ) Acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate and the like.

Examples of the lactone-modified polyfunctional (meth)acrylate compound include lactone-modified polyfunctional urethane (meth)acrylate compounds. The lactone-modified polyfunctional urethane (meth)acrylate compound has a plurality of (meth)acryloyl groups in one molecule, and has a urethane bond (-NHCOO-) and, for example, γ-butyrolactone, δ-valerolactone, ε- It is a compound having a ring-opening structure of a lactone such as caprolactone.
For example, as the lactone-modified polyfunctional urethane (meth)acrylate, those obtained by reacting a polyfunctional isocyanate with a lactone-modified (meth)acrylate having a hydroxy group, a polyfunctional isocyanate having a hydroxy group (meth) Examples thereof include those obtained by reacting an acrylate with a polyol modified with a lactone, but the lactone-modified polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.

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

In the present invention, the active energy ray-curable lactone-modified polyfunctional monomer (a-2) may be used alone or in combination of two or more.

[(B) Perfluoropolyether containing poly(oxyperfluoroalkylene) group]
The number of carbon atoms of the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but it is 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 an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is a carbon atom. It 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 Examples thereof include groups such as -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, and in that case, the bonds of plural kinds of oxyperfluoroalkylene groups are a block bond and a random bond. Either of them may be used.

Among these, from the viewpoint of obtaining a cured film having good scratch resistance, as poly(oxyperfluoroalkylene) groups, -[OCF ₂ ]-(oxyperfluoromethylene group) and -[OCF ₂ CF ₂ ] are used. It is preferable to use a group having both —(oxyperfluoroethylene group) as a repeating unit.
Among them, as the above poly(oxyperfluoroalkylene) group, repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- are in a molar ratio of [repeating unit: -[OCF ₂ ]-]: [repeat Unit: —[OCF ₂ CF ₂ ]—] is preferably a group containing at a ratio of 2:1 to 1:2, and more preferably a group containing at a ratio of about 1:1. The bond of these repeating units may be either a block bond or a random bond.
The total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
The weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured by gel permeation chromatography in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3,000. ..

In the present invention, the component (b) is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at the end of its molecular chain via a urethane bond. A polyether (hereinafter, also simply referred to as “(b) perfluoropolyether having a polymerizable group at the end of the molecular chain”) can be used. The terminals of the molecular chain of the perfluoropolyether may be all terminals or some terminals of the molecular chain. When the molecular chain of the perfluoropolyether is linear, all ends and some ends of the molecular chain are both ends and one end of the linear molecular chain, respectively. As the component (b), a perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond can be excluded. The component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.
Further, the component (b) has excellent compatibility with the component (a), thereby suppressing the clouding of the hard coat layer and enabling the formation of a hard coat layer having a transparent appearance.

As the above-mentioned active energy ray-polymerizable group, a (meth)acryloyl group, a vinyl group and the like can be mentioned.

(B) The perfluoropolyether having a polymerizable group at the terminal of the molecular chain is not limited to one having one active energy ray-polymerizable group at the terminal of the molecular chain, but may be two or more active energy ray-polymerizable groups. May be present at the end of the molecular chain. For example, as the terminal structure containing an active energy ray-polymerizable group, the structures of formulas [A1] to [A5] shown below, and And a structure in which the acryloyl group of is substituted with a methacryloyl group.

Examples of such (b) perfluoropolyether having a polymerizable group at the end of the molecular chain include compounds represented by the following formula [2].

(In the formula [2], A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group, and PFPE represents Represents a poly(oxyperfluoroalkylene) group (provided that the side directly bonded to L ¹ is an oxy terminal and the side bonded to an oxygen atom is a perfluoroalkylene terminal), and L ¹ is 1 to 3 fluorine atoms. Represents an alkylene group having 2 or 3 carbon atoms, each of which is independently substituted with m, independently represents an integer of 1 to 5, and L ² represents an m+1-valent residue obtained by removing OH from an m+1-valent alcohol. Represents.)

The alkylene group of the fluorine atom 1 to carbon atoms substituted with three 2 or _{_{_{3, -CH 2 CHF -, -}}} CH 2 CF 2 -, - CHFCF 2 -, - CH 2 CH 2 CHF-, Examples thereof include —CH ₂ CH ₂ CF ₂ — and —CH ₂ CHFCF ₂ —, and —CH ₂ CF ₂ — is preferable.

Examples of the partial structure (A-NHC(═O)O) _m L ² — in the compound represented by the above formula [2] include structures represented by the following formulas [B1] to [B12]. To be

(In the formulas [B1] to [B12], A represents one of the structures represented by the above formulas [A1] to [A5] and the structure in which the acryloyl group in these structures is substituted with a methacryloyl group. Represents.)
In the structures represented by the above formulas [B1] to [B12], the formula [B1] and the formula [B2] correspond to the case where m=1, and the formulas [B3] to [B6] are m= This corresponds to the case of 2, the expression [B7] to the expression [B9] correspond to the case of m=3, and the expression [B10] to the expression [B12] correspond to the case of m=5.
Among these, the structure represented by the formula [B3] is preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.

Among the perfluoropolyethers having a polymerizable group at the end of the molecular chain (b), particularly preferred are compounds having a partial structure represented by the following formula [1].

The partial structure represented by the formula [1] corresponds to a portion obtained by removing A—NHC(═O) from the compound represented by the formula [2].
In the formula [1], n represents the total number of repeating units -[OCF ₂ CF ₂ ]- and the number of repeating units -[OCF ₂ ]-, and preferably an integer in the range of 5 to 30, An integer in the range of to 21 is more preferable. The ratio of the number of repeating units -[OCF ₂ CF ₂ ]- to the number of repeating units -[OCF ₂ ]- is preferably in the range of 2:1 to 1:2, and is approximately 1:1. It is more preferable to set the range to. The bond of these repeating units may be either a block bond or a random bond.

In the present invention, (b) the perfluoropolyether having a polymerizable group at the terminal of the molecular chain is 0.05 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Parts, preferably 0.1 to 5 parts by weight.
(B) By using perfluoropolyether having a polymerizable group at the end of the molecular chain in a proportion of 0.05 parts by mass or more, sufficient scratch resistance can be imparted to the hard coat layer. Further, by using (b) the perfluoropolyether having a polymerizable group at the end of the molecular chain in a proportion of 10 parts by mass or less, it is sufficiently compatible with (a) the active energy ray-curable polyfunctional monomer, A hard coat layer with less white turbidity can be obtained.

The perfluoropolyether having a polymerizable group at the end of the molecular chain (b) is, for example, one represented by the following formula [3]

(In the formula [3], PFPE, L ¹ , L ² and m have the same meanings as those in the formula [2].) A polymerizable group for the hydroxy group present at both terminals of the compound represented by the formula [2]. An isocyanate compound having, that is, a compound in which an isocyanato group is bonded to a bond in a structure represented by the above formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is replaced with a methacryloyl group (for example, It can be obtained by reacting 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.) to form a urethane bond.

The (b) perfluoropolyether containing a poly(oxyperfluoroalkylene) group of the curable composition of the present invention is a perfluoropolyether containing a poly(oxyperfluoroalkylene) group and has a molecular chain of A perfluoropolyether having an active energy ray-polymerizable group at one end (one end) via a urethane bond and a hydroxy group at the other end (the other end) of the molecular chain, or the above formula A perfluoropolyether having a poly(oxyperfluoroalkylene) group as represented by [3], which has hydroxy groups at both ends of its molecular chain [active energy ray-polymerizable group A compound having no.] may be included. Adding a condition that there is no poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond and between the poly(oxyperfluoroalkylene) group and the hydroxy group. You can

[(C) Silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group]
The component (c) is a silica particle whose surface has been modified with a silane coupling agent having a nitrogen-containing proton donating functional group described below (hereinafter, also simply referred to as “(c) silica particle”).
In the curable composition of the present invention, (c) silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group has scratch resistance due to interaction with (a) a polyfunctional monomer. The stretchability can be imparted without impairing.

The shape of the silica particles themselves is not particularly limited, for example, may be a bead-like substantially spherical shape, may be an irregular shape such as powder, but a substantially spherical shape is preferable, more preferably, The particles are substantially spherical particles having an aspect ratio of 1.5 or less, and most preferably spherical particles.

The average particle size of the silica particles used in the present invention is in the range of 40 nm to 500 nm, for example, 40 nm to 350 nm, preferably 60 nm to 250 nm, or 70 nm to 250 nm. Here, the average particle diameter (nm) is a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction/scattering method based on Mie theory. By setting the average particle diameter of the silica particles within the above numerical range, a cured film having excellent scratch resistance can be obtained.
The particle size distribution of the silica particles is not particularly limited, but monodisperse particles having a uniform particle size are preferable.
The average particle size of the silica particles is such that the average particle size b of silica fine particles/film thickness a=0.01 to the film thickness of the cured film obtained from the curable composition of the present invention described later. It is preferable to select it so as to satisfy the range of 1.0.

As the silica particles, for example, colloidal silica having the above average particle diameter can be preferably used, and as the colloidal silica, silica sol can be used. As the silica sol, an aqueous silica sol produced by a known method using an aqueous solution of sodium silicate and an organosilica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent can be used.
In addition, alkoxysilanes such as methyl silicate and ethyl silicate are hydrolyzed and condensed in the presence of a catalyst (for example, ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide) in an organic solvent such as alcohol to obtain The silica sol to be used, or an organo silica sol obtained by substituting the silica sol with another organic solvent can also be used.

Examples of the organic solvent in the above-mentioned organosilica sol include lower alcohols such as methanol, ethanol and 2-propanol; ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); N,N-dimethylformamide (DMF), Linear amides such as N,N-dimethylacetamide (DMAc); cyclic amides such as N-methyl-2-pyrrolidone (NMP); ethers such as γ-butyrolactone; glycols such as ethyl cellosolve and ethylene glycol; Acetonitrile etc. are mentioned.
Substitution of water, which is a dispersion medium of the aqueous silica sol, or another target organic solvent can be performed by a usual method such as a distillation method or an ultrafiltration method.
The viscosity of the above organosilica sol is about 0.6 mPa·s to 100 mPa·s at 20°C.

As examples of commercially available products of the above aqueous silica sol and organo silica sol, for example, Seahoster (registered trademark) KE series [manufactured by Nippon Shokubai Co., Ltd.], Snowtex (registered trademark) series [manufactured by Nissan Kagaku Co., Ltd.] and the like are used. You can

In the present invention, a silane coupling agent having a nitrogen-containing proton donating functional group is used for surface modification of silica particles.
Examples of the nitrogen-containing proton donating functional group include an amino group, an amide group (-C(=O)NH-), a urea group (-NHC(=O)NH-), and a thiourea group (-NHC(=S)NH. -), urethane group (-NHC(=O)O-), thiourethane group (-NHC(=S)S-), ureido group (-NHC(=O)NH ₂ ), thioureido group (-NHC(= S) NH ₂ ), etc., among them, an amino group, a urea group, a thiourea group and a ureido group are preferable, and a urea group, a thiourea group and a ureido group are particularly preferable in view of the transparency of the cured film.
The silane coupling agent used for the surface modification of the silica particles used in the present invention may have one or more of the above nitrogen-containing proton-donating functional groups, may have two or more thereof, or a plurality of types. It may have a nitrogen-containing proton donating functional group.

The silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group are prepared by mixing the silane coupling agent having a nitrogen-containing proton-donating functional group with silica fine particles in the presence of water or alcohol. It can be prepared by A silane coupling agent having a nitrogen-containing proton-donating functional group is a silane having a nitrogen-containing proton-donating functional group, which forms a silanol group by hydrolysis and is condensed and bound to a silanol group existing on the surface of silica particles. It is believed that silica particles, the surface of which is modified by the coupling agent, are formed.
Specifically, for example, by mixing a colloidal solution of silica particles (silica sol) with a silane coupling agent having a nitrogen-containing proton donating functional group, a silane coupling agent having a nitrogen-containing proton donating functional group can be obtained. Surface modified silica particles can be prepared. The colloidal solution and the silane coupling agent may be mixed at room temperature or while heating. From the viewpoint of reaction efficiency, it is preferable to perform mixing while heating. When the mixing is performed while heating, the heating temperature can be appropriately selected depending on the solvent and the like. The heating temperature can be, for example, 30° C. or higher.
The mixing ratio of the silane coupling agent having a nitrogen-containing proton-donating functional group and the silica particles depends on the size of the silica particles and the type of the nitrogen-containing proton-donating functional group. ^{The amount} of the silane coupling agent molecule can be 0.01 to 5, preferably 0.05 to 2, and more preferably 0.1 to 1 with respect to 2). Here, the surface area of the silica particles is calculated from the specific surface area measured by the nitrogen adsorption method (BET method).

In the present invention, the silica particles (c) are 10 parts by mass to 65 parts by mass, for example, 10 parts by mass to 50 parts by mass, preferably 10 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is used in a proportion of from 45 to 45 parts by mass.

The present invention also covers silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group. For example, silica particles whose surface is modified with a silane coupling agent having a thiourea group or a ureido group, when used in combination with an antistatic agent (e) described later, not only imparts scratch resistance and stretchability to a cured film, It is preferable from the viewpoint of imparting the antistatic property of the cured film and obtaining a good coating film surface (appearance). Moreover, as a preferable example, silica particles whose surface is modified with a silane coupling agent having a thiourea group or a thiourethane group can be mentioned.

[(D) Polymerization initiator that generates radicals by active energy rays]
In the curable composition of the present invention, a polymerization initiator that generates a radical by a preferable active energy ray (hereinafter, also simply referred to as “(d) polymerization initiator”) is, for example, an active energy such as an electron beam, an ultraviolet ray or an X-ray. It is a polymerization initiator that generates radicals by irradiation of rays, especially by irradiation of ultraviolet rays.
Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, and benzophenone. And biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and 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 alkylphenones as the (d) polymerization initiator from the viewpoint of transparency, surface curability, and thin film curability. By using an alkylphenone, a cured film having further improved scratch resistance can be obtained.

Examples of the alkylphenones include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl) Α-hydroxy such as 2-methylpropan-1-one and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one Alkylphenones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one And α-aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate and the like.

In the present invention, the proportion of the polymerization initiator (d) is 1 part by mass to 20 parts by mass, preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Used in.

[(E) Antistatic agent]
The curable composition of the present invention may further contain metal oxide particles as the (e) antistatic agent. When the metal oxide particles are contained, the hard particles formed from the curable composition by using silica particles whose surface is modified with a silane coupling agent having a thiourea group or a ureido group as the (c) silica particles. It is possible to achieve both antistatic performance in the coat layer and good coating film surface (appearance).

The metal oxide particles can be fine particles having a primary particle diameter of 4 nm to 100 nm. By setting the primary particle diameter of the metal oxide particles within the above numerical range, antistatic properties can be imparted without affecting scratch resistance and stretchability, and a cured film that leads to the realization of transparency. Can be obtained.
In addition, in this invention, the primary particle diameter in a metal oxide particle refers to the particle diameter of each particle observed using a transmission electron microscope.

The metal oxide particles can include, for example, an oxide of at least one element selected from the group consisting of tin, zinc, and indium. Specifically, tin oxide (SnO ₂ ), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), gallium-doped zinc oxide (GZO), aluminum Examples thereof include doped zinc oxide (AlZO), antimony-doped zinc oxide (AZO), indium-doped zinc oxide or zinc oxide-doped indium oxide (IZO), and indium gallium zinc oxide (IGZO), of which phosphorus-doped tin oxide (PTO) is preferable.

The above-mentioned metal oxide particles may also include surface-coated metal oxide particles having a metal oxide as a nucleus and the surface of which is coated with an acidic or basic oxide. Examples of the nucleus include titanium oxide, a titanium oxide-tin oxide composite, a zirconium oxide-tin oxide composite, a tungsten oxide-tin oxide composite, a titanium oxide-zirconium oxide-, in addition to the metal oxide particles such as tin oxide. Mention may be made of tin oxide composites. Examples of the acidic or basic oxides include antimony pentoxide, silicon oxide-antimony pentoxide composite, and silicon oxide-tin oxide composite.

In the present invention, when the metal oxide particles (e) are contained, 10 parts by mass to 55 parts by mass, preferably 10 parts by mass to 45 parts by mass relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Included in the ratio of parts by mass.

[(F) Fine particles having an average particle diameter of 0.2 μm to 15 μm]
The curable composition of the present invention may further contain (f) fine particles having an average particle diameter of 0.2 μm to 15 μm (hereinafter, simply referred to as “(f) fine particles”). The fine particles (f) impart an antiglare property by making the surface of the hard coat layer formed from the curable composition uneven.
In the present invention, it is preferable to use organic fine particles as the fine particles (f). The organic fine particles can also play a role of controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition that is the material for forming the hard coat layer.
The shape of the organic fine particles is not particularly limited, but may be, for example, a bead-shaped substantially spherical shape, or an irregular shape such as powder, but a substantially spherical shape is preferable, and an aspect is more preferable. The particles are substantially spherical particles having a ratio of 1.5 or less, and most preferably spherical particles.

Examples of the organic fine particles include polymethylmethacrylate fine particles (PMMA fine particles), silicone fine particles, polystyrene fine particles, polycarbonate fine particles, acrylic styrene fine particles, benzoguanamine fine particles, melamine fine particles, polyolefin fine particles, polyester fine particles, polyamide fine particles, polyimide fine particles, and polyfluorine fine particles. Ethylene oxide fine particles and the like. These organic fine particles may be used alone or in combination of two or more.
Among them, polymethylmethacrylate fine particles can be preferably used as the organic fine particles.

The average particle diameter of the organic fine particles used in the present invention is in the range of 0.2 μm to 15 μm, and preferably in the range of 1 μm to 10 μm. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by a laser diffraction/scattering method based on Mie theory. When the average particle diameter of the organic fine particles is larger than the above numerical range, the image clarity of the display is lowered, and when it is smaller than the above numerical range, sufficient antiglare properties cannot be obtained, and there is a problem that glare becomes large. It will be easier. The particle size distribution of the organic fine particles is not particularly limited, but monodisperse fine particles having a uniform particle size are preferable.
The organic fine particles are preferably organic fine particles having a refractive index that is 0 to 0.20 in difference in refractive index from the cured product of the active energy ray-curable polyfunctional monomer (a). The difference in refractive index is preferably 0 to 0.10.
The average particle size of the organic fine particles is such that the average particle size b of the organic fine particles/film thickness a=0.1 to the film thickness of the cured film obtained from the curable composition of the present invention described later. It is preferable to select it so as to satisfy the range of 1.0.

As the organic fine particles, commercially available products can be preferably used, and examples thereof include Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series [above, Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive・Performance Materials Japan (same)]; Eposter (registered trademark) series, same MA series, same ST series, same MX series [above, Nippon Shokubai Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Co., Ltd.]; Flow Bead Series [Sumitomo Seika Co., Ltd.]; Trepearl (registered trademark) PPS, PAI, PES, EP [above, Toray Industries, Inc.]; 3M (registered trademark) ) Dyion TF micro powder series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series [above, Manufactured by Soken Chemical Industry Co., Ltd.]; Tuftic (registered trademark) AR650 series, same AR-750 series, same FH-S series, same A-20, same YK series, same ASF series, same HU series, same F series, same C series, WS series [above, manufactured by Toyobo Co., Ltd.]; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series [above , Manufactured by Negami Kogyo Co., Ltd.; Shin-Etsu Silicone (registered trademark) KMP series [manufactured by Shin-Etsu Chemical Co., Ltd.] and the like can be used.

In the present invention, the fine particles (f) are 1 part by mass to 40 parts by mass, for example, 5 parts by mass to 30 parts by mass, preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is used in a ratio of 1 part to 25 parts by mass.

[(G) solvent]
The curable composition of the present invention may further contain (g) a solvent, that is, in the form of a varnish (film forming material).
As the solvent, the components (a) to (d), optionally the components (e) and (f) are dissolved/dispersed, and a coating for forming a cured film (hard coat layer) described later is applied. It may be appropriately selected in consideration of workability at the time, drying property before and after curing, and the like. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits and cyclohexane; methyl chloride, methyl bromide, Halides such as methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGME) ), propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether and the like; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclohexanone Such as ketones; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; N,N-dimethylformamide ( DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) and other amides; dimethylsulfoxide (DMSO) and other sulfoxides, and two or more of these solvents were mixed. Solvents may be mentioned.

Further, a solvent having a high boiling point can be used for the purpose of controlling the dispersibility of the fine particles at the time of drying after coating.
Examples of such a solvent include cyclohexyl acetate, propylene glycol diacetate, 1,3-butynylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol monobutyl ether acetate. , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol- Methyl-propyl-ether and the like can be mentioned.

The amount of the solvent (g) used is not particularly limited, but for example, the curable composition of the present invention is used at a concentration such that the solid content concentration is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) means the components (a) to (d) (and optionally the component (e), the component (f) and other additives in the curable composition of the present invention. ) Represents the content of solid content (all components excluding the solvent component) relative to the total mass (total mass).

[Other additives]
Further, the curable composition of the present invention, unless impairing the effects of the present invention, additives generally added as necessary, for example, a polymerization accelerator, a polymerization inhibitor, a photosensitizer, leveling Agents, surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately mixed.

<Cured film>
The curable composition of the present invention can form a cured film by applying (coating) on a substrate to form a coating film, and irradiating the coating film with an active energy ray to polymerize (curing). The cured film is also an object of the present invention. Further, the hard coat layer in the hard coat film described later can be made of the cured film.
Examples of the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polyolefin, polyamide, Polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, 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 substrate 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 inkjet method, a printing method (a relief printing method). , An intaglio printing method, a lithographic printing method, a screen printing method, etc. can be appropriately selected, and among them, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating properties, a relief printing method can be used. In particular, it is desirable to use the gravure coating method. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm and then applied to the coating. When applying, a solvent may be further added to the curable composition, if necessary. As the solvent in this case, the various solvents mentioned in the above [(g) solvent] can be mentioned.
After the curable composition is applied on a substrate to form a coating film, the coating film is preliminarily dried by a heating means such as a hot plate or an oven to remove the solvent, if necessary (solvent removing step). The conditions for heat drying at this time are preferably, for example, 40° C. to 120° C. and about 30 seconds to 10 minutes.
After drying, the coating film is cured by irradiating with 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 ray irradiation, sun rays, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.
After that, the polymerization may be completed by performing post-baking, specifically, heating with a heating means such as a hot plate or an oven.
The thickness of the formed cured film is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm after drying and curing.

<Hard coat film>
By using the curable 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 preferably used for protecting the surface of various display elements such as touch panels and liquid crystal displays.

The hard coat layer in the hard coat film of the present invention, a step of forming a coating film by applying the curable composition of the present invention on a film substrate, and a step of removing the solvent by heating if necessary, It can be formed by a method including a step of irradiating the coating film with an active energy ray such as ultraviolet rays to cure the coating film. A method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate including these steps is also an object of the present invention.

As the film base material, various transparent resin films that can be used for optical applications, among the base materials listed in the above <cured film>, are used. Examples of preferable resin films include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, Examples thereof include films of polyamide, polyimide, triacetyl cellulose (TAC) and the like.
Further, as the method for applying the curable composition on the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step), the method described in the above <cured film> should be used. You can When the curable composition of the present invention contains a solvent (in the form of varnish), a step of drying the coating film and removing the solvent may be included after the coating film forming step, if necessary. In that case, the coating film drying method (solvent removing step) described in the above <cured film> can be used.
The layer thickness (film thickness) of the hard coat layer thus obtained is preferably set to be 1 to 100 times the average particle diameter of the (c) silica particles. For example, the thickness of the hard coat layer is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Coating with a bar coater: PM-9050MC manufactured by SMT Co., Ltd.
Bar: A-Bar OSP-22 manufactured by OSG System Products, maximum wet film thickness 22 μm (corresponding to wire bar #9)
Coating speed: 4 m/min (2) Oven Device: Sanki Keiso Co., Ltd. 2-layer clean oven (upper and lower) PO-250-45-D
(3) UV curing device: Heraeus Co., Ltd. CV-110QC-G
Lamp: Heraeus High Pressure Mercury Lamp H-bulb
(4) Gel permeation chromatography (GPC)
Equipment: Tosoh Corp. HLC-8220GPC
Column: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko KK
Column temperature: 40°C
Eluent: Tetrahydrofuran Detector: RI
(5) Scratch resistance test device: Reciprocating abrasion tester TRIBOGEAR TYPE: 30S manufactured by Shinto Kagaku Co., Ltd.
Scanning speed: 5,000 mm/min Scanning distance: 50 mm
(6) Tensile test device: Shimadzu Corporation tabletop precision universal testing machine Autograph AGS-10kNX
Gripping tool: 1kN Manual screw type planar gripping tool Gripping tooth: High strength rubber coated gripping tooth Peeling speed: 10 mm/min Measuring temperature: 23°C
(7) Surface resistance measurement device: High resistivity meter Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation
Probe: URS probe Registration table: UFL
Applied voltage: 10V
(8) Total light transmittance, haze measurement device: Nippon Denshoku Industries Co., Ltd. haze meter NDH5000
(9) Glossiness measurement device: Konica Minolta Co., Ltd. Glossmeter GM-268Plus
Measuring angle: 60 degrees

The abbreviations have the following meanings.
A1: Oxyethylene-modified diglycerin tetraacrylate [Aronix (registered trademark) M-460, active energy ray-polymerizable group 4 mol, oxyethylene group 4 mol, manufactured by Toagosei Co., Ltd.]
A2: Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd.]
Surface modifier SM-2: Perfluoropolyether having two (meth)acryloyl groups at one end of the molecular chain [Fingerprint adhesion inhibitor Optool (registered trademark) DAC-HP manufactured by Daikin Industries, Ltd., nonvolatile content 20] Mass% solution]
Silica fine particles s-1: Silica fine particles having an average particle size of 200 nm [Organic silica sol MEK-ST-2040 (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 40 mass% MEK dispersion)]
Silica fine particles s-2: Silica fine particles having an average particle diameter of 80 nm [Organic silica sol MEK-ST-ZL (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by mass MEK dispersion)]
Silica fine particles s-3: Silica fine particles having an average particle size of 40 nm [Organic silica sol MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by mass MEK dispersion)]
Silane coupling agent c-1: trimethoxysilane having a urea group [Shin-Etsu Silicone (registered trademark) X-12-989MS manufactured by Shin-Etsu Chemical Co., Ltd.]
Silane coupling agent c-2: trimethoxysilane having a thiourea group [Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (registered trademark) X-12-1116]
Silane coupling agent c-3:3-ureidopropyltriethoxysilane [Tokyo Chemical Industry Co., Ltd., solid content concentration 50% alcohol solution]
Silane coupling agent c-4: N-(2-aminoethyl)-8-aminooctyltrimethoxysilane [Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (registered trademark) KBM-6803]
Silane coupling agent c-5: n-hexyltrimethoxysilane [Shin-Etsu Silicone (registered trademark) KBM-3063 manufactured by Shin-Etsu Chemical Co., Ltd.]
Silane coupling agent c-6:3-acryloylpropyltrimethoxysilane [Shin-Etsu Silicone (registered trademark) KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.]
PFPE: Perfluoropolyether having two hydroxy groups at both ends of the molecular chain without interposing poly(oxyalkylene) groups [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenzu (registered trademark) BEI manufactured by Showa Denko KK]
DOTDD: Dioctyltin dineodecanoate [Neostan (registered trademark) U-830 manufactured by Nitto Kasei Co., Ltd.]
O2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959 manufactured by IGM Resins]
MEK: Methyl ethyl ketone MeOH: Methanol antistatic agent e-1: Phosphorus-doped tin oxide 20 mass% isopropyl alcohol dispersion sol [Cernax (registered trademark) CX-S204IP, manufactured by Nissan Chemical Industries, Ltd., primary particle diameter: 5 nm to 20 nm, secondary Particle diameter: 10 nm to 20 nm] *Here, the primary particle diameter and the secondary particle diameter refer to the average particle diameter measured by observation with a transmission electron microscope. The particle size was measured by dripping a sol with a transmission electron microscope onto a copper mesh, drying it, and observing it with a transmission electron microscope (JEM-1020, manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV. The measured and averaged value was determined as the average primary particle diameter.
Antistatic agent e-2: Core-shell particles having a primary particle diameter of 30 nm to 40 nm whose core is tin oxide and whose surface is coated with antimony pentoxide 30% by mass methanol dispersion sol [Cernax (registered trademark) manufactured by Nissan Chemical Industries, Ltd.] HX-307M1]
FP1: Cross-linked polymethylmethacrylate true spherical particles [Techpolymer (registered trademark) SSX-101 manufactured by Sekisui Plastics Co., Ltd., average particle diameter 1 μm]

[Reference Example 1] Production of surface modifier SM-1 A screw tube was provided with 1.19 g (0.5 mmol) of PFPE, 0.52 g (2.0 mmol) of BEI, and 0.017 g of DOTDD (of the total mass of PFPE and BEI). 0.01 times amount), and MEK 1.67 g were charged. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer chip to obtain a 50% by mass MEK solution of the target compound, the surface modifier SM-1. The weight average molecular weight: Mw of the obtained SM-1 measured by GPC in terms of polystyrene was 3,000, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Reference Example 2] Production of silica fine particles s-4 (MEK dispersion) whose surface is modified with a silane coupling agent having a urea group In a four-necked flask, 35 g of silica fine particles s-1 and silane coupling agent c- 1 0.095 g and water 0.25 g were charged. This mixture was stirred with a stirrer chip at 65° C. for 3 hours to obtain 40% by mass of MEK silica fine particles s-4 having an average particle diameter of 200 nm modified with a target compound, a silane coupling agent having a urea group. A solution was obtained.

[Reference Example 3] Production of silica fine particles s-5 (MEK dispersion) whose surface was modified with a silane coupling agent having a thiourea group In a four-necked flask, 35 g of silica fine particles s-1 and silane coupling agent c- 2 0.093 g and water 0.25 g were charged. This mixture was stirred at 65° C. for 3 hours using a stirrer chip, and 40% by mass MEK of the target compound, silica fine particles s-5 modified with a silane coupling agent having a thiourea group and having an average particle diameter of 200 nm. A solution was obtained.

[Reference Example 4] Production of silica fine particles s-6 (MEK dispersion) whose surface was modified with a silane coupling agent having an ureido group In a four-necked flask, 35 g of silica fine particles s-1 and silane coupling agent c- 3 0.17 g and water 0.25 g were charged. This mixture was stirred with a stirrer chip at 65° C. for 3 hours to obtain 40% by mass of MEK silica fine particles s-6 having an average particle diameter of 200 nm modified with a silane coupling agent having a ureido group, which is a target compound. A solution was obtained.

[Reference Example 5] Production of silica fine particles s-7 (MEK dispersion liquid) whose surface was modified with a silane coupling agent having an amino group In a four-necked flask, 13 g of silica fine particles s-1 and silane coupling agent c- 4 0.03 g, MEK 13 g, and water 0.09 g were charged. This mixture was stirred for 3 hours at 65° C. using a stirrer chip to obtain 20% by mass MEK of the target compound, silica fine particles s-7 modified with a silane coupling agent having an amino group and having an average particle diameter of 200 nm. A solution was obtained.

[Reference Example 6] Production of silica fine particles s-8 (MEK dispersion liquid) whose surface was modified with a silane coupling agent having an n-propyl group In a four-necked flask, 35 g of silica fine particles s-1 and a silane coupling agent. C-5 (0.065 g) and water (0.25 g) were charged. This mixture was stirred at 65° C. for 3 hours using a stirrer chip, and 40 mass of the target compound, silica fine particles s-8 modified with a silane coupling agent having an n-propyl group and having an average particle diameter of 200 nm. % MEK solution was obtained.

[Reference Example 7] Production of silica fine particles s-9 (MEK dispersion) whose surface was modified with a silane coupling agent having an acryloyl group In a four-necked flask, 35 g of silica fine particles s-1 and silane coupling agent c- 6 0.065 g and water 0.25 g were charged. This mixture was stirred using a stirrer chip at 65° C. for 3 hours to obtain 40% by mass of MEK silica fine particles s-9 having an average particle diameter of 200 nm modified with a target compound, a silane coupling agent having an acryloyl group. A solution was obtained.

[Reference Example 8] Production of silica fine particles s-10 (MEK dispersion liquid) whose surface was modified with a silane coupling agent having a thiourea group In a four-necked flask, 35 g of silica fine particles s-2, silane coupling agent c- 2 0.17 g and water 0.18 g were charged. This mixture was stirred at 65° C. for 3 hours using a stirrer chip to obtain 30% by mass MEK of the target compound, silica fine particles s-10 modified with a silane coupling agent having a thiourea group and having an average particle diameter of 80 nm. A solution was obtained.

[Reference Example 9] Production of silica fine particles s-11 (MEK dispersion liquid) whose surface was modified with a silane coupling agent having a thiourea group In a four-necked flask, 35 g of silica fine particles s-3 and silane coupling agent c- 2 0.35 g and water 0.18 g were charged. This mixture was stirred with a stirrer chip at 65° C. for 3 hours to obtain 30% by mass of MEK silica fine particles s-11 having an average particle diameter of 40 nm modified with a silane coupling agent having a thiourea group, which is a target compound. A solution was obtained.

[Examples 1 to 8 and Comparative Examples 1 to 6]
The following components were mixed according to the description in Table 1 to prepare a curable composition having the solid content concentration shown in Table 1. Here, the solid content refers to components other than the solvent. In addition, in Table 1, “parts” means “parts by mass” and “%” means “mass %”. This curable composition was applied onto an A4 size double-sided easy-adhesion-treated PET film [Lumirror (registered trademark) U403 manufactured by Toray Industries, Inc., thickness 100 μm] with a bar coater to obtain a coating film. The coating film was dried in an oven at 65° C. for 3 minutes to remove the solvent. A hard coat having a hard coat layer (cured film) having a layer thickness (film thickness) of about 5 μm by irradiating the obtained film with UV light having an exposure dose of 300 mJ/cm ^{2 in} a nitrogen atmosphere. A film was made.

The scratch resistance and stretchability of the obtained hard coat film were evaluated. The procedure is shown below. The results are shown in Table 2 together with the haze value (reference value).
[Scratch resistance]
The surface of the hard coat layer of the hard coat film was rubbed with steel wool [BONSTAR (registered trademark) #0000 (ultrafine)] attached to a reciprocating abrasion tester under a load of 500 g/cm ² for 10 reciprocations to scratch the surface. Was visually confirmed and evaluated according to the following criteria A, B and C. When actually used as the hard coat layer, at least B is required, and A is desirable.
A: No scratches (0 scratches)
B: Scratch occurred (1 to 4 scratches)
C: Scratch occurred (5 or more scratches)
[Stretchability]
The hard coat film was cut into a rectangle having a length of 60 mm and a width of 10 mm to prepare a test piece. The test piece was attached to the grip of the universal tester so as to grip each 20 mm from both ends in the longitudinal direction, and the stretch ratio (=(increase in distance between grips)/(distance between grips)×100) was 2.5. %, 5%, 7.5%, and 10%, and a tensile test was performed in increments of 2.5%. The hard coat film after the tensile test was visually observed to confirm the maximum stretch ratio at which no crack was generated in the hard coat layer of the test piece. After that, the stretchability improvement rate was calculated based on the stretch rate of the hard coat film prepared using the curable compositions (Comparative Examples 1 and 6) excluding silica fine particles (=100%), and the value was calculated. The stretchability was evaluated according to the following criteria A, B and C. When actually used as the hard coat layer, at least B is required, and A is desirable.
A: 125% or more B: More than 100% and less than 125% C: 100% or less

As shown in Table 2, silica fine particles s obtained by modifying the surface of silica fine particles having an average particle diameter of 40 nm, 80 nm or 200 nm with an oxyethylene-modified polyfunctional monomer A1 with a silane coupling agent having a nitrogen-containing proton donating functional group. -4, s-5, s-6, s-7, s-10 or s-11, and a perfluoropolyether having four acryloyl groups at both ends of the molecular chain via urethane bonds as surface modifiers. A hard coat film having a hard coat layer obtained from the curable compositions of Examples 1 to 6 in which SM-1 was used was obtained from the curable composition of Comparative Example 1 in which silica fine particles were not added. As is clear from the comparison with the hard coat film having the hard coat layer, excellent stretchability was exhibited without impairing scratch resistance. Among them, silica fine particles modified with a silane coupling agent having a urea group (s-4), a thiourea group (s-5, s-10) or a ureido group (s-6) as a nitrogen-containing proton donating functional group are used. When it was present, it was shown that the transparency was also excellent.
In addition, silica fine particles s-10 having an average particle diameter of 80 nm whose surface is modified with a silane coupling agent having a thiourea group on the oxyethylene-modified polyfunctional monomer A1 and two ( The hard coat film provided with the hard coat layer obtained from the curable composition of Example 8 using the perfluoropolyether SM-2 having a (meth)acryloyl group had a curability of Comparative Example 1 in which silica fine particles were not added. As is clear from the comparison with the hard coat film having the hard coat layer obtained from the composition, excellent stretchability was exhibited without impairing scratch resistance.

On the other hand, the hard coat film provided with the hard coat layer obtained from the curable composition of Comparative Example 2 using the unmodified silica fine particles s-1 as the silica particles is inferior in scratch resistance, and has a poor scratch resistance. The results suggest that the interaction is weak. Similarly, a hard coat film having a hard coat layer obtained from the curable composition of Comparative Example 3 in which an n-hexyl group is adopted as a surface modifying group of silica particles (silica fine particles: s-8) is also used as acrylate and silica fine particles. It was shown that the interaction between them was weak and the scratch resistance was poor.
Further, the hard coat film provided with the hard coat layer obtained from the curable composition of Comparative Example 4 in which the acryloyl group was adopted as the surface modifying group of the silica particles (silica fine particles: s-9) was prepared from the acrylate and the silica fine particles. It was shown that the action is strong and the scratch resistance is excellent, but the stretchability is poor.
Then, the hard coat film including the hard coat layer of the curable composition of Comparative Example 6 having a layer thickness (film thickness) of 5 μm had a high surface friction coefficient because the surface modifier was not added. It was found that the scratch resistance was inferior.

Further, in the hard coat film including the hard coat layer obtained from the curable composition of Example 7 using the lactone modified polyfunctional monomer A2 instead of the oxyethylene modified polyfunctional monomer A1, silica fine particles are not added. As a result, scratch resistance and stretchability were improved as compared with Comparative Example 6.

[Examples 9 to 11, Reference Example 10 and Reference Example 11]
The following components were mixed according to the description in Table 3 to prepare a curable composition having a solid content concentration shown in Table 3. Here, the solid content refers to components other than the solvent. Further, in the table, "part" means "part by mass" and "%" means "% by mass". This curable composition was applied onto an A4 size double-sided easy-adhesion-treated PET film [Lumirror (registered trademark) U403 manufactured by Toray Industries, Inc., thickness 100 μm] with a bar coater to obtain a coating film. The coating film was dried in an oven at 65° C. for 3 minutes to remove the solvent. A hard coat having a hard coat layer (cured film) having a layer thickness (film thickness) of about 5 μm by irradiating the obtained film with UV light having an exposure dose of 300 mJ/cm ^{2 in} a nitrogen atmosphere. A film was made.

The obtained hard coat film was evaluated for appearance and surface resistance in addition to the evaluations of [scratch resistance] and [stretchability] described above. The procedure of appearance and surface resistance evaluation is shown below. The results are shown in Table 4 together with the haze value (reference value).
[appearance]
The appearance of the hard coat film was visually confirmed and evaluated according to the following criteria A and C.
A: There are no foreign matters over the entire hard coat layer C: Many foreign matters occur over the entire hard coat layer [surface resistance]
The hard coat film is placed with the surface of the hard coat layer facing upward on the registration table, the probe is pressed against the hard coat film (hard coat layer), the value after 10 seconds is measured at n=3, and the average value is the surface resistance value [ Ω/□].

As shown in Table 4, it contains oxyethylene-modified polyfunctional monomer A1, a surface modifier containing perfluoropolyether SM-1 having four acryloyl groups through urethane bonds at both ends of the molecular chain, and A silane coupling agent (s-5, s-10, or s-6) having a thiourea group (Examples 9 and 11) or a ureido group (Example 10) is used for surface modification of silica particles to prevent static electricity. The hard coat film provided with the hard coat layer obtained from the curable composition further containing the agents (e-1, e-2) has excellent scratch resistance and stretchability, and does not impair a good appearance, It has been shown that excellent antistatic properties can be imparted.
When silica fine particles (s-7) having a surface modified with a silane coupling agent having an amino group were used as the silica particles (Reference Example 10), good appearance and antistatic property could be imparted. However, when the silica fine particles (s-4) whose surface is modified with a silane coupling agent having a urea group are used (Reference Example 11), the scratch resistance and stretchability are adversely affected. Although the antistatic property could be imparted, it was confirmed that the scratch resistance and the appearance were affected. Thus, in imparting antistatic performance, it is suggested that the selection of metal oxide particles and silica particles is important so as not to adversely affect the scratch resistance and stretchability, and the surface appearance of the cured film. The result was

[Examples 12 and 13]
The following components were mixed according to the description in Table 5 to prepare a curable composition having a solid content concentration shown in Table 5. Here, the solid content refers to components other than the solvent. Further, in the table, "part" means "part by mass" and "%" means "% by mass". This curable composition was applied onto an A4 size double-sided easy-adhesion-treated PET film [Lumirror (registered trademark) U403 manufactured by Toray Industries, Inc., thickness 100 μm] with a bar coater to obtain a coating film. The coating film was dried in an oven at 65° C. for 3 minutes to remove the solvent. A hard coat having a hard coat layer (cured film) having a layer thickness (film thickness) of about 5 μm by irradiating the obtained film with UV light having an exposure dose of 300 mJ/cm ^{2 in} a nitrogen atmosphere. A film was made.

The obtained hard coat film was evaluated for antiglare property in addition to the evaluation of [surface resistance] described above. The procedure for evaluating the antiglare property is shown below. The results are shown in Table 6 together with the haze value and the total light transmittance (reference value).
[Anti-glare property]
The obtained hard coat film was placed on a black base having a gloss Gs (60°) of 11.8, and the gloss Gs (60°) of the hard coat layer surface of the hard coat film was measured. Evaluation was performed according to A, B and C. When actually used as the hard coat layer, at least B is required, and A is desirable.
A: Gs (60°)≦120
B: 120<Gs (60°)≦125
C: Gs (60°)>125

As shown in Table 6, oxyethylene-modified polyfunctional monomer A1 as a polyfunctional monomer was modified with a silane coupling agent having a thiourea group as a nitrogen-containing proton-donating functional group on the surface of silica fine particles having an average particle diameter of 80 nm. -10 silica fine particles, as a surface modifier, perfluoropolyether SM-1 having four acryloyl groups through urethane bonds at both ends of the molecular chain, phosphorus-doped tin oxide as metal oxide particles as an antistatic agent It was shown that the hard coat films obtained from the curable compositions of Example 12 and Example 13 using e-1 and organic fine particles FP1 respectively have antiglare properties and antistatic properties.

As described above, as shown in the results of the examples, it has an active energy ray-curable polyfunctional monomer, a perfluoropolyether containing a poly(oxyperfluoroalkylene) group as a surface modifier, and a nitrogen-containing proton-donating functional group. By using a curable composition in which silica particles whose surfaces are modified with a silane coupling agent are combined, a hard coat film having a hard coat layer with improved stretchability can be obtained while maintaining scratch resistance. .. Further, by selecting the nitrogen-containing proton-donating functional group, a hard coat film having a hard coat layer having excellent transparency can be obtained.
Further, using metal oxide particles as an antistatic agent in the above composition, particularly by using silica particles surface-modified with a silane coupling agent having a thiourea group or a ureido group as a nitrogen-containing proton-donating functional group, It is possible to prepare a hard coat film that does not deteriorate scratch resistance and stretchability, and has a good appearance and excellent antistatic properties.
Furthermore, by using fine particles having an average particle diameter of 0.2 μm to 15 μm in the above composition, a hard coat film having antiglare properties can be prepared.

Claims

An active energy ray-curable polyfunctional monomer selected from the group consisting of (a) (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer and (a-2) active energy ray-curable lactone-modified polyfunctional monomer. 100 parts by mass of functional monomer,
(B) 0.05 to 10 parts by mass of perfluoropolyether containing a poly(oxyperfluoroalkylene) group,
(C) 10 to 65 parts by mass of silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton donating functional group, and
(D) A curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
The nitrogen-containing proton donating functional group is at least one group selected from the group consisting of an amino group, an amide group, a urea group, a thiourea group, a urethane group, a thiourethane group, a ureido group, and a thioureido group. 1. The curable composition according to 1.
The curable composition according to claim 2, wherein the nitrogen-containing proton-donating functional group is at least one group selected from the group consisting of an amino group, a urea group, a thiourea group, and a ureido group.
The curable composition according to any one of claims 1 to 3, wherein the (c) silica particles are silica fine particles having an average particle size of 40 nm to 500 nm.
The curable composition according to any one of claims 1 to 4, wherein the (b) perfluoropolyether has an active energy ray-polymerizable group at the end of its molecular chain via a urethane bond. ..
The curing according to any one of claims 1 to 5, wherein the (b) perfluoropolyether has at least two active energy ray-polymerizable groups at the ends of its molecular chain via urethane bonds. Sex composition.
7. The perfluoropolyether (b) has at least two active energy ray-polymerizable groups at one end of its molecular chain via a urethane bond, according to any one of claims 1 to 6. Curable composition.
7. The perfluoropolyether (b) has at least three active energy ray-polymerizable groups via urethane bonds at both ends of its molecular chain, according to any one of claims 1 to 6. Curable composition.
The poly(oxyperfluoroalkylene) group has both a repeating unit —[OCF 2 ]— and a repeating unit —[OCF 2 CF 2 ]—, and these repeating units are block-bonded, random-bonded, or block-bonded. The curable composition according to any one of claims 1 to 8, which is a group formed by bonding with a random bond.
The curable composition according to claim 9, wherein the perfluoropolyether (b) has a partial structure represented by the following formula [1].

(In the above formula [1],
n is the total number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, and represents an integer of 5 to 30,
The repeating unit —[OCF 2 CF 2 ]— and the repeating unit —[OCF 2 ]— are bonded by a block bond, a random bond, or a block bond and a random bond. )
11. The active energy ray-curable oxyethylene-modified polyfunctional monomer as a whole or part thereof is composed of an oxyethylene-modified polyfunctional (meth)acrylate compound, according to any one of claims 1 to 10. The curable composition according to.
The above-mentioned (a-1) active energy ray-curable oxyethylene-modified polyfunctional monomer is a monomer having 3 or more active energy ray-polymerizable groups in one molecule, and has an average oxyethylene-modified amount of the active energy ray-polymerizable group. The curable composition according to any one of claims 1 to 11, which is a monomer of less than 3 mol per 1 mol of the group.
The curable product according to claim 12, wherein the active energy ray-curable oxyethylene-modified polyfunctional monomer (a-1) is a monomer having an average oxyethylene modification amount of less than 2 mol with respect to 1 mol of the active energy ray-polymerizable group. Composition.
The active energy ray-curable lactone-modified polyfunctional monomer (a-2) partially or wholly comprises a lactone-modified polyfunctional (meth)acrylate compound. Curable composition.
15. The curable composition according to claim 14, wherein a part or all of the (a-2) active energy ray-curable lactone-modified polyfunctional monomer is an ε-caprolactone-modified polyfunctional monomer.
The (c) silica particles are silica particles whose surface is modified with a silane coupling agent having a thiourea group or a ureido group, and
(E) The curable composition according to any one of claims 1 to 15, further comprising 10 parts by mass to 55 parts by mass of the antistatic agent.
The curable composition according to claim 16, comprising metal oxide particles as the (e) antistatic agent.
The curable composition according to claim 17, wherein the metal oxide particles contain an oxide of at least one element selected from the group consisting of tin, zinc, and indium.
The curable composition according to claim 18, wherein the metal oxide particles include tin oxide.
The curable composition according to any one of claims 17 to 19, wherein the metal oxide particles contain at least one of phosphorus-doped tin oxide and tin oxide whose surface is coated with antimony pentoxide. ..
The curable composition according to any one of claims 1 to 20, further comprising (f) 1 part by mass to 40 parts by mass of fine particles having an average particle size of 0.2 μm to 15 μm.
The curable composition according to claim 21, wherein the fine particles (f) having an average particle diameter of 0.2 μm to 15 μm are organic fine particles.
The curable composition according to claim 22, wherein the organic fine particles are polymethyl methacrylate fine particles.
The curable composition according to any one of claims 1 to 23, further comprising (g) a solvent.
A cured film obtained from the curable composition according to any one of claims 1 to 24.
A hard coat film comprising a hard coat layer on at least one surface of a film substrate, the hard coat layer comprising the cured film according to claim 25.
The hard coat film according to claim 26, wherein the hard coat layer has a layer thickness of 1 μm to 10 μm.
A method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is the curable composition according to any one of claims 1 to 24. A method for producing a hard coat film, comprising the steps of: applying a film on a film substrate to form a coating film; and irradiating the coating film with an active energy ray to cure the film.
Silica particles whose surface is modified with a silane coupling agent having a nitrogen-containing proton-donating functional group.
The silica particles according to claim 29, having an average particle diameter of 40 nm to 500 nm.
31. The silica particles according to claim 29 or 30, wherein the nitrogen-containing proton-donating functional group is a thiourea group or a thiourethane group.