TW202244122A - Curable composition for hard coat - Google Patents

Abstract

To provide a homogeneous curable composition that is free of suspended matter and sediment, and is capable of forming a hard coat layer provided with high-standard characteristics, both in durability and in smoothness, as well as high liquid repellency when actual use thereof is assumed. Provided is a curable composition that includes: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule; (b) 0.05 -2 parts by mass of perfluoropolyether having, via a poly(oxyalkylene) group, an active energy ray-polymerizable group only in one end of a molecular chain which includes a poly(oxyperfluoroalkylene) group, and having a weight average molecular weight of 1500-3500; and (c) 1-20 parts by mass of a polymerization initiator which generates radicals due to active energy rays.

Description

Curing composition for hard coating

The present invention relates to a curable composition useful as a material for forming a hard coat layer on the surface of various display elements, and to a hard coat capable of forming a hard coat excellent in smoothness, scratch resistance, abrasion resistance and water repellency Layer, and a homogeneous hardening composition without floating and sediment.

In recent years, touch panels have been introduced into portable information terminals such as mobile phones and tablet computers, notebook personal computers, home appliances, and interior and exterior parts of automobiles, and touch liquid crystal displays and organic EL displays with fingers or pens. There are more and more cases where the surface of the touch panel of the display device such as the display device is operated. In the case of operating with fingers, in order to make it easy to remove attached fingerprints, the surface of the touch panel requires water and oil repellency, and wear resistance that maintains the water and oil repellency even if it is repeatedly rubbed by fingers is required. In addition, when the surface of the touch panel is operated with a finger or a pen, smoothness is required for the surface from the viewpoint of the touch feeling of the finger or the pen. Moreover, scratch resistance is required for the surface of a touch panel in order to prevent damage. In order to impart these characteristics to the surface of the touch panel, a surface coating layer, such as a hard coating layer, is provided.

Since fluorine-containing compounds exhibit high smoothness and water and oil repellency, they are used as hard coat layer forming materials, for example, by adding a small amount of fluorine-based surface modifier to the coating solution for forming a hard coat layer. The method of things. It is known that fluorine-based surface modifiers will segregate to the surface of the hard coating layer due to the low surface energy of fluorine atoms.

In general, in order to impart scratch resistance and abrasion resistance to the hard coat layer, a method of increasing the surface hardness of the hard coat layer by forming a high-density crosslinked structure to impart resistance to external force is used. As a material for forming such a hard coat layer, a multifunctional acrylate-based material that undergoes three-dimensional crosslinking by free radicals generated by irradiation of active energy rays is most commonly used at present. The fluorine-based surface modifying agent added to the coating liquid for forming the hard coat layer is also a material having an active energy ray polymerizable group ( Patent Document 1).

On the other hand, as described in Patent Document 2, since durable properties such as scratch resistance and wear resistance are required for the hard coat layer, for example, in the case of using a fluorine-based surface modifier having a crosslinkable group , will cause the immobilization of molecular chains containing fluorine atoms, and the smoothness of the hard coating layer will decrease. That is, durability characteristics such as scratch resistance and abrasion resistance have a trade-off relationship with smoothness, and it is difficult to achieve a high level of characteristics.

In order to improve the above-mentioned trade-off relationship and improve the mobility of molecular chains containing fluorine atoms, there is a method of introducing a crosslinkable group at only one end of a molecular chain containing fluorine atoms. However, compared with the method of introducing crosslinkable groups at both ends of the molecular chain containing fluorine atoms, although the smoothness of the hard coat layer is excellent, the durability tends to be generally poor, and there is a tendency for the hard coat layer to contain fluorine atoms. The molecular chains of the hard coating tend to be easily aggregated, and the coating liquid tends to become cloudy when preparing a coating liquid for forming a hard coat layer. When the fluorine-based surface modifying agent is condensed in the coating solution for forming the hard coat layer, when the coating solution is used to form the hard coat layer, the molecular chains containing fluorine atoms cannot be sufficiently segregated to the surface of the hard coat layer, And become unable to show the original characteristics of smoothness, water repellency, and scratch resistance.

In order to improve the solubility of fluorine-based surface modifiers, it is considered that the content ratio of fluorine atoms in fluorine-based surface modifiers is reduced, such as shortening the molecular chain containing fluorine atoms, but it is conceivable that the result will lead to hard coating. The smoothness and water-repellency of the layer decrease, and it becomes difficult to satisfy the high characteristic level of smoothness or water-repellency.

As a method for improving the solubility of a fluorine-based surface modifier, Patent Document 3 reports that when obtaining a hard coating agent composition, a fluorine-containing polyether that forms an aggregate and is the main cause of the white turbidity of the composition is reported. , and, a fluorine-containing block copolymer having excellent compatibility with the composition. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2016/163479 [Patent Document 2] Japanese Patent No. 6497449 [Patent Document 3] Japanese Patent Laid-Open No. 2005-179613

[Problem to be Solved by the Invention]

Since the fluorine-containing block copolymer described in Patent Document 3 is inferior in water repellency and lubricity compared with the fluorine-containing polyether, it can be easily assumed that the fluorine concentration of the above-mentioned fluorine-containing block copolymer is between Compared with the above-mentioned fluorine-containing polyether, it is relatively low, and it is difficult to achieve compatibility with the composition and smoothness or water repellency. The object of the present invention is to provide a homogeneous curable composition free of floats and sediments that can form a hard coating layer, and the hard coating layer can achieve a trade-off between durability and smoothness at a high property level. sexual coexistence. In addition, in terms of envisaged and practical use, the hard coating layer becomes required to have high liquid-repellent properties. [Means to solve the problem]

A first aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryl groups in one molecule, (b ) has an active energy ray polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene group) group, and has a weight-average molecular weight of 1,500 to 3,500 0.05 to 2 parts by mass of fluoropolyether, and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals due to active energy rays.

Another aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of perfluoropolyether, which has a poly(oxyalkylene) group bonded to only one end of a molecular chain containing a poly(oxygen perfluoroalkylene) group The reaction product of a raw material perfluoropolyether having a hydroxyl number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group; and (c) produced by the active energy ray 1 to 20 parts by mass of a radical polymerization initiator.

The aforementioned (b) perfluoropolyether has the aforementioned active energy ray polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group via the aforementioned poly(oxyalkylene) group. , and the weight average molecular weight is from 1500 to 3500.

The aforementioned (b) perfluoropolyether has the aforementioned active energy ray polymerizable group via a urethane bond bonded to the aforementioned poly(oxyalkylene) group.

The aforementioned poly(oxyalkylene) group is a poly(oxyethylene) group.

The aforementioned poly(oxyperfluoroalkylene) group has a repeating unit -(CF ₂ O)- and/or a repeating unit -(CF ₂ CF ₂ O)-, and in the case of having both repeating units, these repeating units It is a group formed by block bonding, random bonding, or block bonding and random bonding.

(上述式[1]中，m為重複單位-(CF ₂CF ₂O)-之數，及n為重複單位-(CF ₂O)-之數，且滿足5≦(m+n)≦30，m及n係各自獨立表示0以上之整數，q表使氧伸乙基之數且為2至20之整數。) The aforementioned molecular chain including the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1].

(In the above formula [1], m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30 , m and n each independently represent an integer of 0 or more, and q represents the number of oxyethylidene groups and is an integer of 2 to 20.)

In the aforementioned formula [1], m and n each independently represent an integer of 1 or more.

(上述式[2]中，m、n及q係與前述式[1]之定義為同義，A表示前述具有活性能量線聚合性基之末端基。) The aforementioned (b) perfluoropolyether is a compound represented by the following formula [2].

(In the above formula [2], m, n and q are synonymous with the definition of the aforementioned formula [1], and A represents the aforementioned terminal group having an active energy ray polymerizable group.)

(上述式[A1]及式[A2]中，R ¹及R ²係各自獨立表示氫原子或甲基，＊表示與前述式[2]所示之化合物中之胺基甲酸酯鍵之鍵結處。) The aforementioned terminal group A is a group represented by the following formula [A1] or formula [A2].

(In the above-mentioned formula [A1] and formula [A2], R ¹ and R ² are each independently representing a hydrogen atom or a methyl group, and * represents the bond with the urethane bond in the compound shown in the aforementioned formula [2] knot.)

The curable composition of the present invention further includes (d) a solvent.

Another aspect of the present invention is a cured film obtained from the curable composition of the present invention.

Another aspect of the present invention is a hard coat film comprising a hard coat layer on at least one surface of a film substrate, and the hard coat layer is composed of the aforementioned cured film.

The film base has a hard coat underlayer between the surface of the film base and the hard coat layer, and the film base is a resin film.

The aforementioned hard coat layer has a film thickness of 1 μm to 20 μm.

Another aspect of the present invention is a method for producing a hard-coated film, which includes the steps of applying the curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with active energy rays A step of hardening to form a hard coat layer.

Another aspect of the present invention is a method for producing a hard coat film, which includes: applying the curable composition of the present invention on a film substrate to form a coating film; The step of solvent, and the step of irradiating the coating film with active energy rays to harden it to form a hard coating layer.

A method for producing a hard coat film, further comprising the step of forming an underlayer of the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film, and the underlayer of the hard coat layer is formed on the underlayer of the hard coat layer. the aforementioned coating.

Another aspect of the present invention is a perfluoropolyether compound having active energy at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene group) A linear polymeric base with a weight average molecular weight of 1500 to 3500.

Another aspect of the present invention is a perfluoropolyether compound having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group The reaction product of a raw material perfluoropolyether having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group.

The perfluoropolyether compound has the active energy ray polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group via the poly(oxyalkylene) group, and The weight average molecular weight is 1500 to 3500.

(上述式[1]中，m為重複單位-(CF ₂CF ₂O)-之數，及n為重複單位-(CF ₂O)-之數，且滿足5≦(m+n)≦30，m及n係各自獨立表示0以上之整數，在具有兩者之重複單位之情況，該等重複單位係以嵌段鍵結、無規鍵結，或，嵌段鍵結及無規鍵結進行鍵結而成，q表示氧伸乙基之數且為2至20之整數。) The aforementioned molecular chain including the poly(oxyperfluoroalkylene) group has a structure represented by the following formula [1].

(In the above formula [1], m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30 , m and n each independently represent an integer of 0 or more, and in the case of repeating units of both, the repeating units are block bonding, random bonding, or block bonding and random bonding Formed by bonding, q represents the number of oxyethylene groups and is an integer from 2 to 20.)

In the aforementioned formula [1], m and n each independently represent an integer of 1 or more.

(上述式[2]中，m、n及q係與前述式[1]之定義為同義，A表示具有前述活性能量線聚合性基之下述式[A1]或式[A2]所示之末端基。)

(上述式[A1]及式[A2]中，R ¹及R ²係各自獨立表示氫原子或甲基，＊表示與前述式[2]所示之化合物中之胺基甲酸酯鍵之鍵結處。) [發明效果] The aforementioned perfluoropolyether compound is a compound represented by the following formula [2].

(In the above formula [2], m, n and q are synonymous with the definition of the aforementioned formula [1], and A represents the following formula [A1] or formula [A2] having the aforementioned active energy ray polymerizable group end group.)

(In the above-mentioned formula [A1] and formula [A2], R ¹ and R ² are each independently representing a hydrogen atom or a methyl group, and * represents the bond with the urethane bond in the compound shown in the aforementioned formula [2] knot.) [Effect of the invention]

According to the present invention, it is possible to provide a curable composition with excellent homogeneity, which can be used to form a cured film with excellent scratch resistance, abrasion resistance and excellent smoothness even in a thin film with a thickness of 1 μm to 20 μm. and hard coating. Also, according to the present invention, it is possible to provide a cured film obtained from the aforementioned curable composition or a hard coat film having a hard coat layer composed of the cured film, and to provide scratch resistance, abrasion resistance, It is a hard coating film with excellent wear resistance and smoothness. Furthermore, according to the present invention, in addition to the coexistence of the above two properties, it is also possible to provide a cured film with high water-repellent properties and a curable composition for forming a hard coat layer, and a hard coat with excellent properties. layer of hard coating film.

＜Hardening composition＞

Each component of the curable composition of the present invention will be described below.

[(a) Active energy ray-curable polyfunctional monomer having two or more (meth)acryl groups in one molecule] (a) An active energy ray-curable polyfunctional monomer having two or more (meth)acryl groups in one molecule of the component (hereinafter, also simply referred to as "(a) polyfunctional monomer") means A monomer that is irradiated with active energy rays such as ultraviolet rays to undergo a polymerization reaction and hardens.

Preferred (a) polyfunctional monomers in the curable composition of the present invention include monomers selected from the group of polyfunctional (meth)acrylate compounds, and, for example, those described below Monomers selected from the group of polyfunctional urethane (meth)acrylate compounds, and monomers selected from the group of lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, as (a) the polyfunctional monomer, one selected from the group consisting of the above-mentioned polyfunctional (meth)acrylate compounds may be used alone, or two or more types may be used in combination. Furthermore, the (meth)acrylate compound in the present invention includes both acrylate compounds and methacrylate compounds. For example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

Also (a) the polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer. Examples of the oxyalkylene denaturation include oxymethylene denaturation, oxyethylene denaturation, and oxypropylene denaturation. transsexual. Examples of the above-mentioned oxyalkylene-modified polyfunctional monomer include, for example, in the above-mentioned polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound, those modified by oxyalkylene group compound. The aforementioned oxyalkylene-modified polyfunctional monomers may be used alone or in combination of two or more.

As preferred (a) polyfunctional monomers in the present invention, for example, there are at least 2 (meth)acryloyl groups in 1 molecule, preferably at least 3 in 1 molecule, more preferably 1 There are at least 4 multifunctional monomers in the molecule.

Examples of the polyfunctional (meth)acrylate compound (however, a compound not having a urethane bond) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane Tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate base) acrylate, glycerol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated Dipentaerythritol hexa(meth)acrylate, Ethoxylated glycerol tri(meth)acrylate, Ethoxylated bisphenol A di(meth)acrylate, 1,3-Propanediol di(meth)acrylate Acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2- Methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, new Pentylene Glycol Di(meth)acrylate, Ethylene Glycol Di(meth)acrylate, Diethylene Glycol Di(meth)acrylate, Triethylene Glycol Di(meth)acrylate, Tetraethylene Glycol Di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, reference (2-Hydroxyethyl)isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decanedimethanol di(meth)acrylate, dioxanediol di( Meth)acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 2-hydroxy-1,3-di(meth)acryloxypropane, 9,9- Bis[4-(2-(meth)acryloxyethoxy)phenyl] fluorine, bis[4-(meth)acrylthiophenyl]sulfide, bis[2-(methyl) Acrylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate ) acrylate, and polypropylene glycol di(meth)acrylate. Among them, as preferred polyfunctional (meth)acrylate compounds, for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

As said oxyalkylene-denatured polyfunctional (meth)acrylate compound, the (meth)acrylate compound of the polyalcohol denatured with an oxyalkylene group is mentioned, for example. Examples of the aforementioned polyalcohol include glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, triglycerol, Methylpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

The above polyfunctional urethane (meth)acrylate compound has a plurality of acryl groups or methacryl groups in one molecule, and has more than one urethane bond [-NHC(=O)O The compound of -] may also have a urea bond [-NHC(=O)NH-]. As the polyfunctional urethane (meth)acrylate compound, for example, a compound obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and a compound obtained by reacting a polyfunctional isocyanate with a Compounds obtained by reacting hydroxyl (meth)acrylates with polyalcohols, but the polyfunctional urethane (meth)acrylate compounds that can be used in the present invention are not limited to these examples.

Furthermore, examples of the polyfunctional isocyanate include toluene diisocyanate, isophorone diisocyanate, stubble diisocyanate, and hexamethylene diisocyanate. Furthermore, examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. Furthermore, examples of the polyalcohol include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol. ; Polyester polyols; polyether polyols; and polycarbonate diols, which are the reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid .

(a) The polyfunctional monomer may also be a lactone-modified polyfunctional (meth)acrylate compound, and as the denatured lactone, ε-caprolactone is preferred. Examples of the lactone-denatured polyfunctional (meth)acrylate compound include ε-caprolactone-denatured pentaerythritol tri(meth)acrylate, ε-caprolactone-denatured pentaerythritol tetra(meth)acrylate, ε-caprolactone-denatured dipentaerythritol penta(meth)acrylate, and ε-caprolactone-denatured dipentaerythritol hexa(meth)acrylate.

[having an active energy ray polymerizable group at only one end of the molecular chain containing the poly(oxyperfluoroalkylene) group via the poly(oxyalkylene) group and having a weight average molecular weight of 1500 to 3500 Perfluoropolyether] In the following, the component (b) has an active energy ray polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene group) group, and the weight average molecular weight is 1500 to 3500 perfluoropolyether, also known as "(b) perfluoropolyether". (b) Perfluoropolyether is, for example, the aforementioned poly(oxyperfluoroalkylene) group-containing molecular chain having a hydroxyl group bonded to the poly(oxyalkylene group) at only one end and having a number average molecular weight of 1500 The raw material perfluoropolyether up to 3000 is obtained by reacting with a compound having a functional group that can react with the hydroxyl group and the aforementioned active energy ray polymerizable group. Examples of the functional group that reacts with a hydroxyl group include a hydroxyl group, a carboxyl group, and an isocyanate group. The preferred (b) perfluoropolyether in the curable composition of the present invention is that only one end of the molecular chain containing the poly(oxygen perfluoroalkylene) group is separated from the aforementioned poly(oxyalkylene group). ) group-bonded urethane bond having the aforementioned active energy ray polymerizable group.

(b) Perfluoropolyether has a poly(oxyalkylene) group, so it has excellent compatibility with (a) multifunctional monomers, and only (b) perfluoropolyether can achieve the present invention. Function as a surface modifier in the hard coat layer formed by the curable composition. As said poly(oxyalkylene) group, a poly(oxyethylene) group is preferable.

(b) The perfluoropolyether is not limited to having one active energy ray polymerizability via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group The group may have two or more active energy ray polymerizable groups. Examples of the active energy ray polymerizable group include (meth)acryl and vinyl groups, and examples of the terminal group having the active energy ray polymerizable group include the aforementioned formula [A1] or formula [ The basis shown in A2]. Among these terminal groups, the group represented by the formula [A2] having two active energy ray polymerizable groups is preferable.

As the above-mentioned poly(oxyperfluoroalkylene) group, from the viewpoint of obtaining a cured film with good scratch resistance, it is preferable to have -[CF ₂ O]-(oxyperfluoromethylene) and -[CF ₂ CF ₂ O Both of ]-(oxyperfluoroethylenyl) are preferably used as the base of the repeating unit. In this case, the bonding of these oxyperfluoroalkylene groups may be any of block bonding and random bonding.

(b) The perfluoropolyether preferably has a content ratio of fluorine atoms of not less than 35 mass % and not more than 60 mass %, more preferably not less than 40 mass % and not more than 55 mass %. If the content of fluorine atoms is at least 35% by mass, a hard coating layer with excellent water repellency or slipperiness can be obtained, and if it is at most 60% by mass, it can be sufficiently compatible with (a) the polyfunctional monomer to obtain White turbidity is a rare hard coating layer.

(b) The weight average molecular weight of the perfluoropolyether is 1500 to 3500, preferably 1600 to 3500, more preferably 1700 to 3000. (b) When the weight-average molecular weight of perfluoropolyether is within the above-mentioned range, (b) perfluoropolyether is easily retained on the surface of the hard coating layer obtained from the curable composition of the present invention, and the surface of the layer The shear stress will be sufficiently reduced, so a hard coating layer with excellent smoothness can be obtained. In addition, when the weight average molecular weight of (b) perfluoropolyether is in the above-mentioned range, the hardness of the layer surface can be adjusted appropriately, and a hard coat layer excellent in durability such as scratch resistance can be obtained. That is, when the weight average molecular weight of (b) perfluoropolyether is in the above-mentioned range, smoothness and durability can be coexisted.

In the curable composition of the present invention, the content of (b) perfluoropolyether is 0.05 to 2 parts by mass relative to 100 parts by mass of the aforementioned (a) multifunctional monomer. (b) When the content of perfluoropolyether is 0.05 parts by mass or more, since (b) perfluoropolyether is sufficiently present on the surface of the hard coating layer obtained from the curable composition of the present invention, it is possible to obtain Hard coating layer with excellent smoothness. Furthermore, since the content of (b) perfluoropolyether is 2 parts by mass or less, it is sufficiently compatible with (a) the polyfunctional monomer, and a hard coat layer with less cloudiness can be obtained.

(b) Perfluoropolyether may be used alone or in combination of two or more.

[(c) Polymerization initiator] The preferred (c) polymerization initiator in the curable composition of the present invention is, for example, a polymerization initiator that generates free radicals by active energy rays such as electron rays, ultraviolet rays, and X-rays, especially by irradiation of ultraviolet rays. .

Examples of (c) polymerization initiators include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, and o-quinonediazides. (o-quinone diazide), acylphosphine oxides, oxime esters, organic peracids, benzophenones, dicoumarins, biimidazoles, titanocenes, mercaptans, halogenated hydrocarbons Classes, trichloromethyltriazines, and onium salts such as iodonium salts and permeic acid salts. These polymerization initiators may be used alone or in combination of two or more. From the viewpoints of transparency, surface hardening and film hardening, it is preferable to use alkylphenones as (c) polymerization initiator in the present invention. By using alkyl phenones, a cured film with improved scratch resistance can be obtained.

Examples of the above-mentioned alkyl phenones include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-(4- (2-Hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-Hydroxy-1-(4-(4-(2-Hydroxy-2-methylpropionyl)benzyl) α-hydroxyalkylphenones such as phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- α-aminoalkylphenones such as 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; 2,2-di Methoxy-1,2-diphenylethan-1-one; and methyl phenylglyoxylate.

In the curable composition of the present invention, the content of the (c) polymerization initiator is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the aforementioned (a) polyfunctional monomer. good.

[(d) Solvent] The curable composition of the present invention may also contain (d) a solvent as an optional component, that is, it may also be in the form of a varnish. As the (d) solvent, in consideration of the solubility and dispersibility of the above-mentioned components (a) to (c) and the formation of the cured film (hard coat layer) described later, the curable composition The workability at the time, the dryness before and after hardening, etc. can be selected appropriately.

Examples of the solvent (d) above include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; n-hexane, n-heptane, mineral spirits, cyclohexane Aliphatic or alicyclic hydrocarbons such as; methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene Halides such as: ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Esters or ester ethers of acetate (PGMEA); diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol Ethers such as monomethyl ether, propylene glycol monoethyl ether (PGME), propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether; acetone, methyl ethyl ketone Ketones such as (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclohexanone, etc.; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isopropyl alcohol Alcohols such as butyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, etc.; N,N-dimethylformamide (DMF), N,N-dimethyl Amides such as acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc.; and sulfides such as dimethylsulfide (DMSO), and a mixture of two of these solvents above solvents.

The content of (d) solvent in the curable composition of the present invention is not particularly limited. For example, the solid content concentration of the curable composition of the present invention is 1 mass % to 70 mass %, preferably 5 mass % to 50 mass %. Concentration in % by mass. Here, the solid content concentration (also referred to as the non-volatile content concentration) refers to the solid content relative to the total mass (total mass) of the above-mentioned components (a) to (d) and other additives of the curable composition of the present invention (The content of the solvent component removed from the whole component).

[Other additives] In addition, as long as the effect of the present invention is not impaired, the curable composition of the present invention can be used alone or in combination of two or more additives that are generally added, such as polymerization inhibitors and photosensitizers. , leveling agent, surfactant, adhesion imparting agent, plasticizer, ultraviolet absorber, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, etc.

＜Cured film＞ The curable composition of the present invention can form a cured film by coating (coating) a base material to form a coating film, irradiating the coating film with active energy rays to polymerize (cure), and the cured film can also be formed. It is the object of the present invention. Moreover, what consists of the above-mentioned cured film can be used as a hard coat layer in the hard coat film mentioned later.

Examples of the substrate include various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc. Polyester, 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), metal, wood, paper, glass, slate. The shape of these substrates may be plate-like, film-like or 3-dimensional molded body. In addition, the surface of the above-mentioned base material may also be formed with, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correcting layer, a refractive index adjusting layer, a weather resistance layer, Anti-reflection layer, anti-static layer, anti-discoloration layer, gas barrier layer, water vapor barrier layer, light scattering layer, electrode layer, etc. are used as the lower layer of the hard coat layer, and the lower layer of the hard coat layer may be laminated in multiples . The layer formed on the surface of the base material is not particularly limited as long as the effects of the present invention are not impaired.

The method of coating on the above-mentioned substrates can be suitably selected from cast coating, spin coating, knife coating, dip coating, roll coating, spray coating, bar coating, and die coating. , inkjet method, printing method (letterpress printing method, gravure printing method, lithographic printing method, screen printing method, etc.), which may also use roll-to-roll (roll-to-roll) method, and from the film Coatability From this point of view, it is ideal to use a relief printing method, especially a gravure coating method. Furthermore, it is preferable to apply the curable composition of the present invention after filtering it with a filter having a pore size of about 0.2 μm in advance. In addition, when coating, a solvent may be further added to the curable composition as necessary. Examples of the solvent at this time include various solvents exemplified in the aforementioned [(e) solvent].

After coating the curable composition of the present invention on the base material to form a coating film, if necessary, use a heating means such as a hot plate or an oven to dry the coating film and remove the solvent (solvent removal step). As conditions for heat drying at this time, for example, it is preferable to set it at 40°C to 120°C for about 30 seconds to 10 minutes. After drying, the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron rays, and X-rays, and ultraviolet rays are particularly preferred. As a light source used for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. Thereafter, the polymerization is completely terminated by post-baking, specifically, by heating using heating means such as a hot plate and an oven.

Furthermore, the thickness of the formed cured film after drying and curing is usually 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm.

＜Hard Coating Film＞ A hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also the subject of the present invention, and is suitably used for protecting the surfaces of various display elements such as touch panels and liquid crystal displays, for example.

The hard coat layer in the hard coat film of the present invention can be obtained by including: a step of forming a coating film by applying the curable composition of the present invention on a film substrate; and removing the solvent by heating if necessary. step, and the step of irradiating the coating film with active energy rays such as ultraviolet rays to harden 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 substrate, various transparent resin films that can be used for optical applications are used among the substrates exemplified in the aforementioned <cured film>. As a preferable resin film, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and other polyesters, polyesters, etc. Urethane, thermoplastic polyurethane (TPU), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose ( TAC) and other films.

As said film base material, the thing formed by laminating|stacking plural layers may be sufficient. For example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistance layer, an antireflection layer, etc. layer, antistatic layer, antidiscoloration layer, gas barrier layer, water vapor barrier layer, light scattering layer, electrode layer, etc., which are layers different from the resin film as the lower layer of the hard coat layer, the hard coat layer The layer under the layer may also be a layered plural one. The layer to be laminated on the surface of the above-mentioned resin film is not particularly limited as long as the effect of the present invention is not impaired.

In addition, the method of coating the curable composition of the present invention on the above-mentioned film substrate (coating film forming step), and the method of irradiating the coating film with active energy rays (curing step) can use the aforementioned <cured film>. Example method. Also, when the curable composition of the present invention contains a solvent (in the form of a varnish), after the coating film forming step, a step of drying the coating film to remove the solvent may be included as necessary. In this case, the drying method (solvent removal step) of the coating film listed in the aforementioned <cured film> can be used.

The layer thickness (film thickness) of the hard coat layer obtained by this operation is, for example, 1 μm to 20 μm, preferably 1 μm to 10 μm.

＜Perfluoropolyether compounds＞ Raw material perfluoropolyethers having a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a number average molecular weight of 1,500 to 3,000, and The perfluoropolyether compound, which is a reaction product of a compound having a functional group that reacts with the hydroxyl group and an active energy ray polymerizable group, is also an object of the present invention. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, in the Examples, the apparatus and conditions used to prepare the samples and the properties of the analytes are as follows.

(1) Coating with rod coater Device: (stock) PM-9050MC made by SMT Coating rod: OSG System Products Co., Ltd. A-Bar OSP-30 with a maximum wet film thickness of 30 μm (6 μm after drying) or OSP-15 with a maximum wet film thickness of 15 μm (3 μm after drying) Coating speed: 4m/min (2) Film thickness measurement Device: F20 film thickness measurement system manufactured by Filmmetrics Co., Ltd. (3) Oven Device: Double-layer dust-free oven (upper and lower type) PO-250-45-D made by Sanji Jizhuang Co., Ltd. (4) UV hardening Device: CV-110QC-G manufactured by Heraeus Lamp: Electrodeless lamp H-bulb made by Heraeus Co., Ltd. (5) Scratch resistance test and abrasion resistance test Device: Shinto Science Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30S Scanning speed: 3200mm/min Scanning distance: 50mm (6) Contact angle measurement Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measuring temperature: 23°C (7) Dynamic friction coefficient measurement Device: Shinto Science Co., Ltd., load-variable friction and wear test system TRIBOGEAR (registered trademark) TYPE: HHS2000 Probe: 0.6mmR sapphire needle Load: 200g Scanning speed: 2mm/sec Scanning distance: 10mm (8) Total light transmittance, haze measurement Device: Nippon Denshoku Industry Co., Ltd. haze meter NDH5000 (9) Weight average molecular weight measurement Gel Permeation Chromatography (GPC) Device: HLC-8420GPC manufactured by Tosoh Co., Ltd. Tube string: TSKgelG2000HXL, TSKgelG3000HXL manufactured by Tosoh Co., Ltd. Measuring temperature: 40°C Eluent: Tetrahydrofuran Detection: RI (10) Combustion ion chromatography Automatic sample combustion device system: AQF-2100 H manufactured by Nitto Seiko Analytical Co., Ltd. (formerly Mitsubishi Chemical Analytical Co., Ltd.) Ion chromatography: Dionex Integrion manufactured by Thermo Fisher Scientific Co., Ltd. Sample: 2mg Absorption solution: 2.7mM sodium carbonate + 0.3mM sodium bicarbonate aqueous solution Eluent: 2.7mM sodium carbonate + 0.3mM sodium bicarbonate aqueous solution Column: AG-12A/AS-12A made by Thermo Fisher Scientific Co., Ltd. Flow: 1.5mL/min Detector: Conductivity (with suppressor) Standard sample: Fluoride ion standard solution (F-1000) manufactured by Fujifilm Wako Pure Chemical Industries Ltd. (formerly Wako Pure Chemical Industries Ltd.) When the solvent in the sample does not contain a solvent containing fluorine atoms, the fluorine concentration is directly measured in the state containing the solvent, and the fluorine concentration of the solute is converted from the solid content concentration and calculated.

(上述式中，m為重複單位-(CF ₂CF ₂O)-之數，及n為重複單位-(CF ₂O)-之數，且滿足5≦(m+n)≦30，m及n係各自獨立表示0以上之整數，q為氧伸乙基之數且表示2至20之整數。) PFPE2：在僅單末端上不隔著聚(氧伸烷基)基而具有1個羥基之下述構造之全氟聚醚[蘇威特殊聚合物公司製7324X 從利用 ¹⁹F-NMR及 ¹H-NMR之分析結果來算出之數平均分子量1750~1950]

(上述式中，m為重複單位-(CF ₂CF ₂O)-之數，及n為重複單位-(CF ₂O)-之數，且滿足5≦(m+n)≦30，m及n係各自獨立表示0以上之整數。) PFPE3：在僅單末端上不隔著聚(氧伸烷基)基而具有1個羥基之下述構造之全氟聚醚[Apollo Scientific公司製FO2　分子量978.15]

PFPE4：在僅單末端上不隔著聚(氧伸烷基)基而具有1個羥基之下述構造之全氟聚醚(1H,1H-全氟-3,6,9-三氧雜十三烷-1-醇)[Exfluor Research公司製C10GOL 分子量548.1]

N1：1,1-雙(丙烯醯氧基甲基)乙基異氰酸酯[昭和電工(股)製Kalenz(註冊商標)BEI] N2：2-丙烯醯氧基乙基異氰酸酯[昭和電工(股)製Kalenz(註冊商標)AOI] N3：2-甲基丙烯醯氧基乙基異氰酸酯[昭和電工(股)製Kalenz(註冊商標)MOI] DOTDD：二新癸酸二辛基錫[日東化成(股)製Neostan(註冊商標)U-830] SMA7：包含聚(氧全氟伸烷基)基之分子鏈之兩末端具有合計4個活性能量線聚合性基之全氟聚醚[蘇威特殊聚合物公司製Fluorolink(註冊商標)AD-1700，不揮發分70質量%溶液，利用GPC並以聚苯乙烯換算所測量之重量平均分子量：Mw為3973，分散度：Mw/Mn為2.1(Mn為數平均分子量)，藉由燃燒離子層析所算出之全氟聚醚化合物中之氟原子之含有比例29質量%] MEK：甲基乙基酮 PGME：丙二醇單甲基醚 PGMEA：丙二醇單甲基醚乙酸酯 O2959：2-羥基-1-(4-(2-羥基乙氧基)苯基)-2-甲基丙烷-1-酮[IGM Resins公司製OMNIRAD(註冊商標)2959] In addition, abbreviated symbols have the following meanings. Multifunctional acrylate PA1: Dipentaerythritol pentaacrylate/hexaacrylate mixture [Aronix (registered trademark) M-403 manufactured by Toagosei Co., Ltd.] Multifunctional acrylate PA2: Oxyethylene modified multifunctional acrylate [First Kogyo Pharmaceutical Co., Ltd. New Frontier (registered trademark) MF-001] Multifunctional acrylate PA3: Multifunctional urethane acrylate [Negami Industry Co., Ltd. Art Resin (registered trademark) UN-3320HS] Multifunctional Acrylate PA4: Pentaerythritol triacrylate/pentaerythritol tetraacrylate [Nippon Kayaku Co., Ltd. PET30] PFPE1: Only one terminal with a poly(oxyethylene) group interposed, and all of the following structures having one hydroxyl group Fluoropolyether [Fomblin (registered trademark) 4102X manufactured by Solvay Special Polymers, the number average molecular weight calculated from the analysis results of ¹⁹ F-NMR and ¹ H-NMR 1900]

(In the above formula, m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30, m and n is an integer independently representing 0 or more, and q is the number of oxyethylene groups and represents an integer of 2 to 20.) PFPE2: has one hydroxyl group without intervening a poly(oxyalkylene) group at only one end Perfluoropolyether with the following structure [Solvay Specialty Polymers Co., Ltd. 7324X, number average molecular weight calculated from the analysis results of ¹⁹ F-NMR and ¹ H-NMR 1750~1950]

(In the above formula, m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30, m and n each independently represents an integer of 0 or more.) PFPE3: Perfluoropolyether [FO2 manufactured by Apollo Scientific Co. 978.15]

PFPE4: Perfluoropolyether (1H,1H-perfluoro-3,6,9-trioxadeca Trialkan-1-ol) [C10GOL manufactured by Exfluor Research, molecular weight 548.1]

N1: 1,1-bis(acryloxymethyl)ethyl isocyanate [Kalenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.] N2: 2-acryloxyethyl isocyanate [manufactured by Showa Denko Co., Ltd. Kalenz (registered trademark) AOI] N3: 2-methacryloxyethyl isocyanate [Kalenz (registered trademark) MOI manufactured by Showa Denko Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [Nitto Kasei Co., Ltd.] Manufactured by Neostan (registered trademark) U-830] SMA7: Perfluoropolyether [Solvay Specialty Polymers] having a total of 4 active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group Fluorolink (registered trademark) AD-1700 manufactured by the company, 70% by mass solution of non-volatile matter, the weight average molecular weight measured by GPC in terms of polystyrene: Mw is 3973, the degree of dispersion: Mw/Mn is 2.1 (Mn is the number average Molecular weight), the content ratio of fluorine atoms in the perfluoropolyether compound calculated by combustion ion chromatography is 29% by mass] MEK: methyl ethyl ketone PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether ethyl Ester O2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959 manufactured by IGM Resins Co., Ltd.]

[Manufacture Example 1] Manufacture of perfluoropolyether compound SMA1 3.08 g (1.6 mmol) of PFPE1, 0.39 g (1.6 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N1), and 3.5 g of PGMEA were charged into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA1. The obtained SMA1 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1908, and a degree of dispersion: Mw/Mn was 1.0. Moreover, the content rate of the fluorine atom in SMA1 calculated by combustion ion chromatography was 47 mass %.

[Manufacturing example 2] Manufacture of perfluoropolyether compound SMA2 3.23 g (1.7 mmol) of PFPE1, 0.24 g (1.7 mmol) of N2, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N2), and 3.5 g of PGMEA were charged into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA2. The obtained SMA2 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1894, and a degree of dispersion: Mw/Mn was 1.1.

[Manufacture Example 3] Manufacture of perfluoropolyether compound SMA3 3.20 g (1.7 mmol) of PFPE1, 0.26 g (1.7 mmol) of N3, 0.035 g of DOTDD (0.01 times the total mass of PFPE1 and N3), and 3.5 g of PGMEA were charged into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA3. The obtained SMA3 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1868, and a degree of dispersion: Mw/Mn was 1.1.

[Manufacture Example 4] Manufacture of perfluoropolyether compound SMA4 2.20 g (1.2 mmol) of PFPE2, 0.28 g (1.2 mmol) of N1, 0.025 g of DOTDD (0.01 times the total mass of PFPE2 and N1), and 0.6 g of MEK were put into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain an 80 mass % MEK solution of the target perfluoropolyether compound SMA4. The obtained SMA4 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1710, and a degree of dispersion: Mw/Mn was 1.0. Moreover, the content rate of the fluorine atom in SMA4 calculated by combustion ion chromatography was 63 mass %.

[Manufacture Example 5] Manufacture of perfluoropolyether compound SMA5 2.78 g (2.9 mmol) of PFPE3, 0.68 g (2.9 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE3 and N1), and 3.5 g of PGMEA were charged into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA5. The obtained SMA5 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1299, and a degree of dispersion: Mw/Mn was 1.0. Also, the content ratio of fluorine atoms in SMA5 calculated by combustion ion chromatography was 51% by mass, which was about the same value as the content ratio of 51% by mass of fluorine atoms calculated theoretically from the structure of SMA5.

[Manufacture Example 6] Manufacture of perfluoropolyether compound SMA6 2.41 g (4.4 mmol) of PFPE4, 1.05 g (4.4 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE4 and N1), and 3.5 g of PGMEA were charged into the spiral tube. The mixture was stirred at room temperature (about 23° C.) for 72 hours using a stirring plate to obtain a 50 mass % PGMEA solution of the target perfluoropolyether compound SMA6. The obtained SMA6 had a weight average molecular weight measured in terms of polystyrene by GPC: Mw was 1029, and a degree of dispersion: Mw/Mn was 1.0. Also, the content ratio of fluorine atoms in SMA5 calculated by combustion ion chromatography was 46% by mass, which was about the same value as the content ratio of fluorine atoms calculated theoretically from the structure of SMA5, 47% by mass.

[Example 1 to Example 8, Comparative Example 1 to Comparative Example 4] The components described in Table 1 were mixed to prepare a curable composition having a solid content concentration described in Table 1. Here, the solid content refers to components other than the solvent. In addition, in Table 2, [part] represents [parts by mass], and [%] represents [mass %]. Furthermore, the multifunctional acrylate and the surface modifying agent in Table 1 represent solid components, respectively.

These curable compositions were coated with a bar coater on an A4-size PET film [Lumirror (registered trademark) U403 (alias U40) manufactured by Toray Co., Ltd., manufactured by Toray Co., Ltd., which has undergone easy-adhesive treatment on both sides and formed a primer layer , Thickness 100μm] to obtain the coating film. The coating film was dried in an oven at 60° C. for 8 minutes to remove the solvent. A hard coat film having a hard coat layer (cured film) with a film thickness of 3 μm or 6 μm was produced by exposing the obtained film to UV light at an exposure dose of 300 mJ/cm ² in a nitrogen atmosphere.

The homogeneity of each curable composition was evaluated, as well as the scratch resistance, water repellency, abrasion resistance, smoothness, and haze of the obtained hard coating film. The operation sequence of evaluation is shown below. The results are shown in Table 2 together. [Composition Homogeneity] The appearance of each prepared curable composition was visually confirmed, and evaluated according to the following criteria. A: Transparent solution (there is no floating matter, sedimentation and phase separation) C: Any of floating solids, sediments and phase separation [scratch resistance] Using steel wool [BONSTAR (registered trademark) #0000 (ultra-fine)] installed on the reciprocating abrasion tester, add a load of 1 kg to the surface of the hard coating layer of the obtained hard coating film, and rub it back and forth 2500 times with a stroke of 50 mm Second-rate. Thereafter, visually confirm the degree of damage in the area of 5 mm width at both ends of the aforementioned stroke of 50 mm, and use a microscope (Keyence Co., Ltd.) to confirm the damaged surface of the hard coat layer, and according to the following criteria A, B and C for evaluation. Furthermore, when actual use is assumed as a hard coat layer, at least B is required, and A is ideal. A: No damage (damage 0) B: Damage (1 to 4 damages with a length of 1mm to 9mm) C: Lesions (more than 5 lesions with a length of 1 mm to 9 mm, or more than 1 lesions with a length of 1 cm or more) [water repellency] 1 μL of water was attached to the surface of the hard coat layer, and the contact angle θ after 10 seconds was measured five times, and the average value thereof was evaluated according to the following criteria. Also, in the case of assuming actual use as a hard coat layer, at least B is required, and A is considered ideal. A: θ≧105˚ B: 90˚≦θ<105˚ C: θ<90˚ [wear resistance] Using a cylindrical eraser [RUBBER STICK manufactured by Minoan Corporation, ϕ6.0mm] installed on a reciprocating abrasion tester, apply a load of 1 kg to the surface of the hard coating layer, and wipe 2,500 times reciprocating. 1 μL of water was applied to the wiped part, and the contact angle θ after 5 seconds was measured at 5 points, and the average value thereof was regarded as the contact angle value, and evaluated according to the following criteria. In addition, in the case of assuming actual use as a hard coat layer, A is ideal. A: θ≧90˚ B: 80˚≦θ<90˚ C: 80˚<θ [Smoothness] The dynamic friction coefficient μ´ at 5 places on the surface of the hard coating layer was measured, and the average value thereof was evaluated according to the following criteria. Moreover, the smaller the value of the coefficient of dynamic friction, the smaller the friction with the probe used, which is one of the basic standards of smoothness. Since the smaller the value of the coefficient of dynamic friction, the better the smoothness when touched, so the smaller the value of the coefficient of dynamic friction, the better. A: μ´≦0.035 B: 0.035＜μ´≦0.050 C: μ´＞0.050 [haze] As a reference value, the haze at 3 places on the surface of the hard coat layer was measured, and the average value thereof was calculated. In addition, as a base material, the haze of the PET film [Toray Co., Ltd. Lumirror (registered trademark) U403 (alternative name U40), thickness 100 μm] used this time was 1.6.

As shown in Table 1, the curable compositions of Examples 1 to 8 contain polyfunctional acrylates PA1 to PA4, and are used on only one end of the molecular chain containing poly(oxyperfluoroalkylene) groups. Perfluoropolyether PFPE1 having a hydroxyl group bonded to a poly(oxyethylene) group and having a number average molecular weight of 1900 reacts with any of the aforementioned isocyanate compound groups N1 to N3 having active energy ray polymerizable groups The resulting SMA1 with a weight average molecular weight of 1908, SMA2 with a weight average molecular weight of 1894, or SMA3 with a weight average molecular weight of 1868. And, as shown in Table 2, the curable compositions of Examples 1 to 8 exhibited excellent homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition exhibited excellent smoothness , Scratch resistance, water repellency and wear resistance.

On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 is composed of polyfunctional acrylate PA1, and only one end of the molecular chain containing poly(oxyperfluoroalkylene) group is not separated. Perfluoropolyether compound PFPE2 having a poly(oxyalkylene) group and having one hydroxyl group with a number average molecular weight of 1750 to 1950, the weight average molecular weight obtained by reacting with the aforementioned isocyanate compound N1 having an active energy ray polymerizable group is 1710 For SMA4, the curable composition of Comparative Example 2 is to include polyfunctional acrylate PA1, and only one end of the molecular chain containing poly(oxyperfluoroalkylene) groups is not separated by poly(oxyalkylene) SMA5 with a weight average molecular weight of 1299 obtained by reacting the perfluoropolyether compound PFPE3 with a molecular weight of 978.15 having one hydroxyl group and the aforementioned isocyanate compound N1 with an active energy ray polymerizable group. Moreover, as shown in Table 2, the homogeneity of the curable compositions of Comparative Example 1 and Comparative Example 2 was poor, and the hard coat film having the hard coat layer obtained from the curable composition was not as good as the difference between SMA4 and SMA5. The cohesion is high and SMA4 and SMA5 cannot sufficiently segregate to the surface of the hard coat layer, so compared with the hard coat film with the hard coat layer obtained from the curable compositions of Examples 1 to 8, its Become the result of poor smoothness and wear resistance.

In addition, as shown in Table 1, the curable composition of Comparative Example 3 contains polyfunctional acrylate PA1, and only one end of the molecular chain containing poly(oxyperfluoroalkylene) groups is not interposed by poly(oxygen perfluoroalkylene). Perfluoropolyether compound PFPE4 with a molecular weight of 548.1 having a hydroxyl group (oxyalkylene) group, and SMA6 with a weight average molecular weight of 1029 obtained by reacting the aforementioned isocyanate compound N1 with an active energy ray polymerizable group. And, as shown in Table 2, although the homogeneity of the curable composition of Comparative Example 3 is good, the hard coat film having the hard coat layer obtained from the curable composition is due to the inclusion of poly(oxygen peroxide) in SMA6. The molecular chain of the fluoroalkylene) group is short, so compared with the hard coating film equipped with the hard coating layer obtained by the curable composition of embodiment 1 to embodiment 8, it becomes slippery, resistant The result of poor abrasion resistance and wear resistance.

Also, as shown in Table 1, the curable composition of Comparative Example 4 contains polyfunctional acrylate PA1, and has active energy ray polymerizable groups at both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups. Perfluoropolyether compound SMA7 with a weight average molecular weight of 3973. And, as shown in Table 2, although the homogeneity of the curable composition of Comparative Example 4 is good, the hard coat film having the hard coat layer obtained from the curable composition is because SMA7 contains poly(oxygen The two ends of the molecular chain of the perfluoroalkylene) group have an active ray energy polymerizable group, so the molecular mobility of the poly(oxyperfluoroalkylene) chain is reduced. As a result, the hard coat layer obtained from the curable composition is inferior in slipperiness and wear resistance compared to the hard coat film.

Claims (24)

A sclerosing composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryl groups in one molecule, (b) Having an active energy ray polymerizable group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene group) group, and having a weight average molecular weight of 1500 to 3500 0.05 to 2 parts by mass of perfluoropolyether, and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals due to active energy rays. A sclerosing composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryl groups in one molecule; (b) 0.05 parts by mass to 2 parts by mass of perfluoropolyether having poly(oxyalkylene) on only one end of the molecular chain containing poly(oxyperfluoroalkylene) groups The reaction product of a raw material perfluoropolyether with a number average molecular weight of 1,500 to 3,000 bonded hydroxyl groups and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group; and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals due to active energy rays. The curable composition as claimed in claim 2, wherein the aforementioned (b) perfluoropolyether is the aforementioned poly(oxyalkylene) group separated by the aforementioned poly(oxyalkylene group) ) group having the aforementioned active energy ray polymerizable group and having a weight average molecular weight of 1500 to 3500. The curable composition according to any one of claim 1 to claim 3, wherein the aforementioned (b) perfluoropolyether is formed via a urethane bond bonded to the aforementioned poly(oxyalkylene) group. It has the aforementioned active energy ray polymerizable group. The curable composition according to any one of claims 1 to 4, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group. The curable composition according to any one of claim 1 to claim 5, wherein the aforementioned poly(oxyperfluoroalkylene) group has repeating units -(CF ₂ O)- and/or repeating units-(CF ₂ CF ₂ O)-, and in the case of having both repeating units, these repeating units are a group formed by block bonding, random bonding, or block bonding and random bonding. The curable composition according to claim 6, wherein the molecular chain comprising the poly(oxyperfluoroalkylene) group has the structure shown in the following formula [1];

In the above formula [1], m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30, m and n each independently represent an integer of 0 or more, and q represents the number of oxyethylene groups and is an integer of 2 to 20. The curable composition according to claim 7, wherein in the aforementioned formula [1], m and n each independently represent an integer of 1 or more. The curable composition according to claim 7 or claim 8, wherein the aforementioned (b) perfluoropolyether is a compound represented by the following formula [2];

In the above-mentioned formula [2], m, n, and q are synonymous with the definitions of the aforementioned formula [1], and A represents the aforementioned terminal group having an active energy ray polymerizable group. The curable composition according to claim 9, wherein the terminal group A is a group represented by the following formula [A1] or formula [A2];

In the above formula [A1] and formula [A2], R1 and R2 are each independently representing ^{a hydrogen} atom or a methyl group, and * represents a bond with the urethane bond in the compound represented by the foregoing formula [2] place. The curable composition according to any one of claim 1 to claim 10, further comprising (d) a solvent. A cured film obtained from the curable composition according to any one of claim 1 to claim 11. A hard-coated film, which has a hard-coated layer on at least one side of a film substrate, and the hard-coated layer is composed of the cured film as claimed in claim 12. The hard coat film according to claim 13, wherein an underlayer of the hard coat layer is provided between the surface of the film base and the hard coat layer, and the film base is a resin film. The hard coat film according to claim 13 or claim 14, wherein the hard coat layer has a film thickness of 1 μm to 20 μm. A method for producing a hard coating film, comprising: A step of coating the curable composition according to any one of claim 1 to claim 11 on a film substrate to form a coating film, and A step of irradiating the coating film with active energy rays to harden it to form a hard coating layer. A method for producing a hard coat film, comprising: a step of applying the curable composition according to claim 11 on a film substrate to form a coating film, and a step of removing the aforementioned solvent from the coating film by heating, And, a step of irradiating the coating film with active energy rays to harden it to form a hard coating layer. The method for producing a hard coat film according to claim 16 or claim 17, further comprising: a step of forming a layer under the hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film, and The aforementioned coating film is formed on the layer under the hard coat layer. A perfluoropolyether compound having the aforementioned active energy ray polymerizable group via a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and The weight average molecular weight is 1500 to 3500. A perfluoropolyether compound having a number-average molecular weight of a hydroxyl group bonded to a poly(oxyalkylene) group at only one end of a molecular chain containing a poly(oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to The reaction product of perfluoropolyether, the raw material of 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group. Such as the perfluoropolyether compound of claim 20, which has the aforementioned active energy on only one end of the molecular chain containing the poly(oxygen perfluoroalkylene) group via the aforementioned poly(oxygenalkylene) group A linear polymeric base with a weight average molecular weight of 1500 to 3500. The perfluoropolyether compound according to any one of claim 19 to claim 21, wherein the aforementioned molecular chain comprising a poly(oxyperfluoroalkylene) group has the structure shown in the following formula [1];

In the above formula [1], m is the number of repeating units -(CF ₂ CF ₂ O)-, and n is the number of repeating units -(CF ₂ O)-, and satisfy 5≦(m+n)≦30, m and n are each independently representing an integer of 0 or more, and when there are repeating units of both, these repeating units are carried out by block bonding, random bonding, or block bonding and random bonding Bonded, q represents the number of oxyethylene groups and is an integer from 2 to 20. The perfluoropolyether compound according to Claim 22, wherein in the aforementioned formula [1], m and n each independently represent an integer of 1 or more. The perfluoropolyether compound according to Claim 22 or Claim 23, wherein the aforementioned perfluoropolyether compound is a compound represented by the following formula [2];

In the above formula [2], m, n and q are synonymous with the definition of the aforementioned formula [1], and A represents the terminal represented by the following formula [A1] or formula [A2] having the aforementioned active energy ray polymerizable group base;

In the above formula [A1] and formula [A2], R1 and R2 are each independently representing ^{a hydrogen} atom or a methyl group, and * represents a bond with the urethane bond in the compound represented by the foregoing formula [2] place.