KR20230160236A - Curable composition containing two perfluoropolyethers - Google Patents

Abstract

The present invention relates to a homogeneous curable composition free from suspended matter and sediment, which has both durability and slipperiness at a high level, and is capable of forming a hard coat layer with high liquid-repellent properties when practical use is assumed. , (a) an active energy ray-curable multifunctional monomer having two or more (meth)acryloyl groups per molecule, (b) active energy ray polymerization at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group. Perfluoropolyether having a group and having a weight average molecular weight of 1400 to 3500 (however, excluding (c) perfluoropolyether described later), (c) containing a poly(oxyperfluoroalkylene) group A perfluoropolyether having the active energy ray polymerizable group only at one end of the molecular chain and having a weight average molecular weight of 1550 to 3500, (d) a curable polymer comprising a polymerization initiator that generates radicals by active energy rays. A composition is provided.

Description

Curable composition containing two perfluoropolyethers

The present invention relates to a curable composition useful as a forming material for a hard coat layer applied to the surface of various display elements, and is capable of forming a hard coat layer with excellent slipperiness, scratch resistance, abrasion resistance, and water repellency, and is free from suspended matter and sediment. It relates to a homogeneous curable composition.

On the other hand, “perfluoropolyether” used in the present invention refers to one having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group. Here, even when the molecular chain or active energy ray polymerizable group containing the poly(oxyperfluoroalkylene) group does not have all of its hydrogen atoms, such as its hydrocarbon group, replaced with fluorine atoms, "poly(oxyperfluoroalkylene) “those having an active energy ray polymerizable group at the terminal of the molecular chain containing a (roalkylene) group” are called “perfluoropolyethers.”

Recently, touch panels have been introduced into various devices such as portable information terminals such as mobile phones and tablet computers, laptops, home appliances, and automobile interior and exterior products, and the surface of the touch panel of display elements such as liquid crystal displays and organic EL displays has been touched with a finger. Or, the number of cases of manipulation by touching it with a pen is increasing. When assuming operation with a finger, the surface of the touch panel is required to have water and oil repellency to facilitate removal of attached fingerprints, and furthermore, it is required to have abrasion resistance to maintain the water and oil repellency even when repeatedly rubbed with a finger. Furthermore, when the surface of the touch panel is manipulated with a finger or pen, this surface is required to have slipperiness from the viewpoint of the tactile feel of the finger or pen. Additionally, the surface of the touch panel is required to have scratch resistance to prevent scratches. In order to impart these properties to the surface of the touch panel, a surface coat layer, for example, a hard coat layer, is provided.

Fluorine-containing compounds are used as forming materials for hard coat layers because they exhibit high slipperiness and water and oil repellency. For example, a method of making a composition by adding a small amount of a fluorine-based surface modifier to the coating liquid for forming the hard coat layer. This is being used. It is known that fluorine-based surface modifiers segregate on the surface of the hard coat layer due to the low surface energy of fluorine atoms.

Generally, in order to provide scratch resistance and wear resistance to a hard coat layer, a method of forming a high-density cross-linked structure to increase the surface hardness of the hard coat layer and provide resistance to external force is adopted. As a material for forming such a hard coat layer, a multifunctional acrylate-based material that is three-dimensionally crosslinked by radicals generated by active energy ray irradiation is currently most used. Additionally, as a fluorine-based surface modifier added to the coating liquid forming the hard coat layer, a material having an active energy ray polymerizable group is generally used to provide scratch resistance and wear resistance to the hard coat layer (Patent Document 1). From the viewpoint of scratch resistance and wear resistance, materials with a low acrylic equivalent weight, so-called low acrylic equivalent weight, which are small molecules capable of forming a high-density crosslinked structure and have a large number of active energy ray polymerizable groups are preferred.

On the other hand, as described in Patent Document 2, the hard coat layer is required to have durability characteristics such as scratch resistance and abrasion resistance, so for example, when a fluorine-based surface modifier having a crosslinkable group is used, the molecular chain containing a fluorine atom Fixation occurs, and the slipperiness of the hard coat layer decreases. In other words, durability characteristics such as scratch resistance and wear resistance and slipperiness are in a trade-off relationship, and it is difficult to achieve both high characteristic levels.

In order to improve the above trade-off relationship and increase the mobility of the molecular chain containing a fluorine atom, there is a method of introducing a crosslinkable group only to one end of the molecular chain containing a fluorine atom. However, compared to the method of introducing crosslinkable groups at both ends of the molecular chain containing fluorine atoms, the slipperiness of the hard coat layer is excellent, but the durability characteristics tend to be inferior. Furthermore, compared to the case where a crosslinkable group is introduced at both ends of the molecular chain containing a fluorine atom, in the case where a crosslinkable group is introduced only at one end of the molecular chain containing a fluorine atom, the molecular chain containing a fluorine atom Since steric hindrance is small, molecular chains containing fluorine atoms tend to aggregate, and when preparing a coating liquid for forming a hard coat layer, the coating liquid tends to become cloudy.

From the viewpoint of slipperiness and water repellency, it is generally said that a high content of fluorine atoms is desirable, but there is a risk that the fluorine-based surface modifier may aggregate in the coating solution. If the fluorine-based surface modifier is aggregated in the coating liquid forming the hard coat layer, when the hard coat layer is formed using this coating liquid, the molecular chains containing fluorine atoms are not sufficiently segregated on the surface of the hard coat layer, and the original The slipperiness and water-repellent properties cannot be expressed.

In order to improve the solubility of the fluorine-based surface modifier, a method of lowering the content of fluorine atoms in the fluorine-based surface modifier is considered. As described above, as a result, the slipperiness and water repellency of the hard coat layer decreases, and the slipperiness and water repellency decrease. It can be assumed that satisfying this high characteristic level becomes difficult.

As a method of improving the solubility of a fluorine-based surface modifier, Patent Document 3 discloses a fluorine-containing polyether that forms aggregates when obtaining a hard coat composition and causes the composition to become cloudy, and a fluorine-containing block that has excellent compatibility with this composition. The combined use of copolymers has been reported.

In Patent Document 4, a linear polymer having a fluoropolyether in the main chain and having an acrylic group at one or both ends of the molecular chain and having a fluorine content of 48 to 62% by mass, and fluoropolyether in the main chain, By using together a straight chain polymer having a siloxane skeleton and having a fluorine content of 25% by mass or more and less than 45% by mass, which has a plurality of acrylic groups at both ends of the molecular chain, a composition of the linear polymer having a fluorine content of 48% to 62% by mass is provided. It has been reported that solubility in water is improved and a hard coat layer with excellent water repellency and slipperiness is obtained. However, regarding abrasion resistance, Patent Document 4 describes in paragraph [0006] “abrasion resistance represented by slipperiness,” and abrasion resistance is indirectly evaluated by slipperiness. Therefore, there are no specific examples regarding scratch resistance or wear resistance.

International Publication No. 2016/163479 Japanese Patent No. 6497449 Japanese Patent Publication No. 2005-179613 International Publication No. 2020/170698

Since it is described in the same document that the fluorine-containing block copolymer described in Patent Document 3 has inferior water repellency and lubricity compared to the fluorine-containing polyether, the fluorine concentration of the fluorine-containing block copolymer is lower than that of the fluorine-containing polyether. It can be easily assumed that it is low and that compatibility with the composition and coexistence of slipperiness and water repellency are difficult.

In Patent Document 4, with respect to slipperiness, in the case where the linear polymer having the above-mentioned fluorine content is 48% by mass to 62% by mass, the case where it has an acrylic group at one end of the molecular chain and the case where it has an acrylic group at both ends of the molecular chain, The results of equivalent slip properties are described. Therefore, it can be assumed that there is no sufficient characteristic level regarding slipperiness.

In the present invention, the object is to provide a homogeneous curable composition free from suspended matter and sediment, capable of forming a hard coat layer that has both durability and slipperiness, which are in a trade-off relationship, at a high level of properties. In addition to these, when assuming actual use, it is necessary for the hard coat layer to have high liquid-repellent properties.

That is, the present invention provides (a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule,

(b) a perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, (c) described later) (excluding perfluoropolyether),

(c) a perfluoropolyether having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500, and

(d) A curable composition containing a polymerization initiator that generates radicals by active energy rays.

(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule,

(b) a perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, (c) described later) (excluding perfluoropolyether) 0.05 parts by mass to 3 parts by mass,

(c) 0.05 to 3 parts by mass of a perfluoropolyether having the active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500. wealth, and

(d) A curable composition containing 0.5 parts by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

(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 to 3 parts by mass of perfluoropolyether ( However, (c) perfluoropolyether described later is excluded),

(c) Raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a functional group that reacts with the hydroxyl group, and the above 0.05 to 3 parts by mass of perfluoropolyether, which is a reaction product with a compound having an active energy ray polymerizable group, and

(d) A curable composition containing 0.5 parts by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

The (c) perfluoropolyether has the active energy ray polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1550 to 3500.

The (c) perfluoropolyether has an active energy ray polymerizable group via a urethane bond.

The (c) perfluoropolyether has a fluorine atom content of 35% by mass to 65% by mass.

The poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a repeating unit-(CF ₂ O)- and/or a repeating unit-(CF ₂ CF ₂ O)-, and repeats both. When it has units, it is a group formed by combining these repeating units by block combinations, random combinations, or block combinations and random combinations.

The molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a structure represented by the following formula [1].

[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)-, 5≤(m+n)≤30 m and n each independently represent an integer of 0 or more, and q is the number of oxyethylene groups and represents an integer of 0 to 20.)

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

The (c) perfluoropolyether is a compound represented by the following formula [2].

[Formula 2]

(In the above formula [2], m, n and q are the same as the definitions of the above formula [1], and A represents a terminal group having the above active energy ray polymerizable group.)

The terminal group A is a group represented by the following formula [A1] or [A2].

[Formula 3]

(In the formula [A1] and formula [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the number of bonds with the urethane bond of the compound represented by the formula [2]. )

The (b) perfluoropolyether has the active energy ray polymerizable group at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.

The molecular chain containing the poly(oxyperfluoroalkylene) group of the (b) perfluoropolyether has a structure represented by the following formula [3].

[Formula 4]

(In the above formula [3], r is the number of repeating units-(CF ₂ CF ₂ O)-, and s is the number of repeating units-(CF ₂ O)-, 5≤(r+s)≤40 and r and s each independently represent an integer of 0 or more, and when both have repeating units, these repeating units are combined by block combination, random combination, or block combination and random combination.)

In the above formula [3], r and s each independently represent an integer of 1 or more.

The (b) perfluoropolyether is a compound represented by the following formula [4].

[Formula 5]

(In the above formula [4], r and s have the same definition as the above formula [3], and A represents a terminal group having the above active energy ray polymerizable group.)

The terminal group A is a group represented by the following formula [A1] or [A2].

[Formula 6]

(In the above formulas [A1] and [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the number of bonds with the urethane bond of the compound represented by the above formula [4]. )

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

A cured film obtained from the above curable composition.

A hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer is made of the cured film.

There is a lower layer of the hard coat layer between the surface of the film substrate and the hard coat layer, and this film substrate is a resin film.

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

A method of producing a hard coat film, comprising the steps of applying the curable composition on a film substrate to form a coating film, and forming a hard coat layer by irradiating the coating film with active energy rays and curing it.

A process of applying the curable composition on a film substrate to form a coating film, a process of removing the solvent from the coating film by heating, and a process of forming a hard coat layer by irradiating the coating film with active energy rays and curing it. Including, a method of manufacturing a hard coat film.

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

A perfluoropolyether (A) having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, perfluoropolymer ether (A) described later) (excluding polyether (B)), and perfluorocarbons having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500. A surface modifier containing polyether (B).

A perfluoropolyether (A) having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, perfluoropolymer ether (A) described later) (excluding polyether (B)), and a raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and A surface modifier comprising perfluoropolyether (B), which is a reaction product between a functional group that reacts with a hydroxy group and a compound having the active energy ray polymerizable group.

The perfluoropolyether (B) has the active energy ray polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1550 to 3500.

The perfluoropolyether (B) has a fluorine atom content of 35% by mass to 65% by mass.

The perfluoropolyether (A) has the active energy ray polymerizable group at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group.

The molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether (A) has a structure represented by the following formula [3], and the poly(oxyperfluoroalkylene) group of the perfluoropolyether (B) is A molecular chain containing a perfluoroalkylene group has a structure represented by the following formula [1].

[Formula 7]

(In the above formulas [1] and formulas [3], m is the number of repeating units-(CF ₂ CF ₂ O)-, and n is the number of repeating units-(CF ₂ O)-, 5≤(m+ n) ≤ 30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer from 0 to 20, and r is a repeating unit - (CF ₂ CF ₂ O) - The number and s are the number of repeating units-(CF ₂ O)-, satisfying 5≤(r+s)≤40, r and s each independently represent an integer of 0 or more, and the repeating units-(CF ₂ In the case of having both CF ₂ O)- and repeating unit-(CF ₂ O)-, these repeating units are formed by combining block combinations, random combinations, or block combinations and random combinations.)

In the formula [1], m and n each independently represent an integer of 1 or more, and in the formula [3], r and s each independently represent an integer of 1 or more.

The perfluoropolyether (A) is a compound represented by the following formula [4], and the perfluoropolyether (B) is a compound represented by the following formula [2].

[Formula 8]

(In the formula [2] and formula [4], m, n and q are the same as the definition of the formula [1], r and s are the same as the definition of the formula [3], and A is the activation energy It represents a terminal group having a pre-polymerizable group, and this terminal group A is a group represented by the following formula [A1] or formula [A2].)

[Formula 9]

(In the formula [A1] and formula [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the urethane bond of the compound represented by formula [2] or formula [4]. Indicates the number of bonds.)

According to the present invention, it is possible to provide a curable composition useful for forming a cured film and a hard coat layer that have both excellent scratch resistance and wear resistance and excellent slipperiness even in thin films with a thickness of 1 μm to 20 μm. In addition, according to the present invention, it is possible to provide a hard coat film comprising a cured film obtained from the above curable composition or a hard coat layer made of this cured film, and durability characteristics such as scratch resistance and abrasion resistance in a trade-off relationship. A hard coat film with excellent slipperiness can be provided. Furthermore, according to the present invention, it is possible to provide a curable composition useful for forming a cured film and a hard coat layer that provides both high water repellency properties in addition to both of the above properties, and a hard coat film having a hard coat layer excellent in these properties. there is.

<Curable composition>

Each component of the curable composition of the present invention is explained below.

[(a) Active energy ray-curable multifunctional monomer having two or more (meth)acryloyl groups per molecule]

The active energy ray-curable polyfunctional monomer (hereinafter also simply referred to as “(a) polyfunctional monomer”) having two or more (meth)acryloyl groups per molecule of component (a) refers to active energy rays such as ultraviolet rays. By irradiating, the polymerization reaction proceeds and indicates the monomer that hardens.

(a) Polyfunctional monomers preferred in the curable composition of the present invention include monomers selected from the group consisting of polyfunctional (meth)acrylate compounds, and monomers selected from the group consisting of polyfunctional urethane (meth)acrylate compounds described later. , and monomers selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds. In the present invention, as the (a) polyfunctional monomer, one type from the group consisting of the above-mentioned polyfunctional (meth)acrylate compounds can be used individually or in combination of two or more types. Meanwhile, in the present invention, the (meth)acrylate compound includes both an acrylate compound and a methacrylate compound, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

In addition, (a) the polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene-modified monomer include oxymethylene-modified, oxyethylene-modified, and oxypropylene-modified monomers. Examples of the oxyalkylene-modified polyfunctional monomer include compounds obtained by oxyalkylene modification of the polyfunctional (meth)acrylate compound or polyfunctional urethane (meth)acrylate compound. The above-mentioned oxyalkylene-modified polyfunctional monomers can also be used individually or in combination of two or more types.

In addition, preferred polyfunctional monomers (a) in the present invention include polyfunctional monomers having at least 3 (meth)acryloyl groups per molecule, for example, at least 4 groups per molecule. In the present invention, as the (a) polyfunctional monomer, a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth)acrylate compounds having at least three (meth)acryloyl groups per molecule can be mentioned. .

Examples of the above-mentioned multifunctional (meth)acrylate compound (however, a compound that does not have a urethane bond) include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritoldi. (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate Latex, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate , neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate Tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3 -Methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl] Fluorene, bis[4-(meth)acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanedioldi(meth)acrylate, 1, Examples include 3-adamantane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Among these, preferred polyfunctional (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Acrylate can be mentioned.

Examples of the oxyalkylene-modified polyfunctional (meth)acrylate compound include (meth)acrylate compounds of polyol modified with oxyalkylene. Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. there is.

The polyfunctional urethane (meth)acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule, one or more urethane bonds [-NHC(=O)O-], and a urea bond [ It may additionally have -NHC(=O)NH-]. Examples of the polyfunctional urethane (meth)acrylate compound include a compound obtained by reaction between a polyfunctional isocyanate and a (meth)acrylate having a hydroxy group, and a (meth)acrylate having a polyfunctional isocyanate and a hydroxy group. and compounds obtained by the reaction of polyol, but the polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.

Meanwhile, examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. In addition, (meth)acrylates having the above-mentioned hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta. (meth)acrylate, and tripentaerythritol hepta(meth)acrylate. Furthermore, examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols that are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, and adipic acid; polyetherpolyol; and polycarbonate diol.

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

[(b) Perfluoropolyether having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500]

The perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing the poly(oxyperfluoroalkylene) group of component (b) and having a weight average molecular weight of 1400 to 3500 is hereinafter simply referred to as "( b) It is also called “perfluoropolyether”. (b) Perfluoropolyether excludes (c) perfluoropolyether described later. The (b) perfluoropolyether preferred in the curable composition of the present invention has an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. The terminals of the molecular chain containing the poly(oxyperfluoroalkylene) group may be all terminals or partial terminals of the molecular chain. When the molecular chain is linear, all ends and some ends of the molecular chain are both ends and one end of the linear molecular chain, respectively. Examples of the linking group between the poly(oxyperfluoroalkylene) group and the urethane bond include a hydrocarbon group having an ether bond, and in this hydrocarbon group, at least one hydrogen atom may be substituted with a fluorine atom. there is. Additionally, the preferred (b) perfluoropolyether does not have a silicon atom in its chemical structure.

(b) The perfluoropolyether, together with the component (c) described later, serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention. In addition, (b) perfluoropolyether has excellent compatibility with (a) polyfunctional monomer, so white turbidity is suppressed and it is possible to form a hard coat layer with a transparent appearance.

As the poly(oxyperfluoroalkylene) group, from the viewpoint of obtaining a cured film with good scratch resistance, -[CF ₂ O]-(oxyperfluoromethylene group) and -[CF ₂ CF ₂ O]-( A group having both oxyperfluoroethylene groups) as repeating units is preferable. In that case, the bond between these oxyperfluoroalkylene groups may be either a block bond or a random bond.

(b) Perfluoropolyether is not limited to having one active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group, but two or more active energy ray polymerizable groups. It may be possible to have a . Examples of this active energy ray polymerizable group include (meth)acryloyl group and vinyl group, and examples of the terminal group having this active energy ray polymerizable group include the above formula [A1] or formula [A2] A group represented by can be mentioned. Among these terminal groups, the group represented by the formula [A2], which has two active energy ray polymerizable groups, is preferable.

(b) It is more preferable that the perfluoropolyether has an active energy ray polymerizable group at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film with excellent scratch resistance. , it is more preferable that the number of active energy ray polymerizable groups in one molecule is large. The number of these polymerizable groups is preferably two or more, more preferably three or more, at each end of the molecular chain containing the poly(oxyperfluoroalkylene) group.

(b) When the weight average molecular weight of the perfluoropolyether is 1400 to 3500, a hard coat layer with excellent scratch resistance, wear resistance, and slipperiness can be obtained.

In the curable composition of the present invention, the content of (b) perfluoropolyether is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass to 5 parts by mass, based on 100 parts by mass of the polyfunctional monomer (a). part, or 0.05 parts by mass to 3 parts by mass, preferably 0.1 part by mass to 3 parts by mass, more preferably 0.1 part by mass to 1 part by mass. (b) When the perfluoropolyether content is 0.05 parts by mass or more, sufficient scratch resistance can be provided to the hard coat layer, and (b) when the perfluoropolyether content is 3 parts by mass or less, ( a) It is sufficiently compatible with multifunctional monomers, and a hard coat layer with less cloudiness can be obtained.

(b) Perfluoropolyether can be used individually or in combination of two or more types. When two or more types are combined, an active energy ray polymerizable group is provided at one end (one end) of the molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond, and the molecular chain also has an active energy ray polymerizable group. The other end may contain perfluoropolyether having a hydroxy group.

[(c) Perfluoropolyether having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500]

The perfluoropolyether having the above active energy ray polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group of component (c) and having a weight average molecular weight of 1550 to 3500 is as follows: It is also simply referred to as “(c) perfluoropolyether.” (c) Perfluoropolyether is, for example, a raw material perfluoropolymer having a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group. It is obtained by reacting ether with a compound having a functional group that reacts with the hydroxy group and the active energy ray polymerizable group. Examples of the functional group that reacts with the hydroxy group include a hydroxy group, a carboxyl group, and an isocyanate group.

“In addition, it is preferable to have a group containing a fluorine atom at the end opposite to the end having a hydroxy group of the raw material perfluoropolyether, and more preferably to have a trifluoromethoxy group. The (c) perfluoropolyether, which has a group containing a fluorine atom at one end opposite to the other end having the active energy ray polymerizable group, can sufficiently transfer to the surface of the hard coat layer and has excellent water repellency and It can exhibit slipperiness.”

(c) Perfluoropolyether is not limited to having one active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, and can be polymerized with two or more active energy rays. It can also be having a penis. Examples of this active energy ray polymerizable group include (meth)acryloyl group and vinyl group, and examples of the terminal group having this active energy ray polymerizable group include the above formula [A1] or formula [A2] A group represented by can be mentioned. Among these terminal groups, the group represented by the formula [A2], which has two active energy ray polymerizable groups, is preferable.

(c) Perfluoropolyether, together with (b) perfluoropolyether, serves as a surface modifier in the hard coat layer formed from the curable composition of the present invention. In addition, since (c) perfluoropolyether has excellent compatibility with (b) perfluoropolyether, white turbidity is suppressed and it is possible to form a hard coat layer with a transparent appearance. In addition, the (c) perfluoropolyether preferably has a poly(oxyalkylene) group from the viewpoint of compatibility with the (a) polyfunctional monomer. As this poly(oxyalkylene) group, a poly(oxyethylene) group is preferable.

The (c) perfluoropolyether preferred in the curable composition of the present invention has an active energy ray polymerizable group via a urethane bond only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. As the poly(oxyperfluoroalkylene) group, from the viewpoint of obtaining a cured film with good scratch resistance, -[CF ₂ O]-(oxyperfluoromethylene group) and -[CF ₂ CF ₂ O]-( A group having both oxyperfluoroethylene groups) as repeating units is preferable. In that case, the bond between these oxyperfluoroalkylene groups may be either a block bond or a random bond.

(c) The perfluoropolyether has a fluorine atom content of, for example, 35% by mass or more and 65% by mass or less, preferably 40% by mass or more and 65% by mass, and more preferably 45% by mass or more. It is 65% by mass. If the content of fluorine atoms is 35% by mass or more, a hard coat layer with excellent water repellency and slipperiness can be obtained, and if it exceeds 65% by mass, there is a risk that (a) it will not be sufficiently compatible with the polyfunctional monomer and sufficient properties may not be obtained. There is.

(c) The weight average molecular weight of the perfluoropolyether is 1550 to 3500, preferably 1600 to 3500, and more preferably 1700 to 3500. When the weight average molecular weight of (c) perfluoropolyether is within the above range, (c) perfluoropolyether becomes easy to remain on the surface of the hard coat layer obtained from the curable composition of the present invention, and the shear stress on the layer surface is reduced. Since it is sufficiently small, a hard coat layer with excellent slipperiness can be obtained. Furthermore, when the weight average molecular weight of the (c) perfluoropolyether is within the above range, the hardness of the layer surface is appropriately adjusted, and a hard coat layer with excellent durability such as scratch resistance can be obtained. That is, when the weight average molecular weight of (c) perfluoropolyether is within the above range, both slipperiness and durability become possible.

In the curable composition of the present invention, the content of (c) perfluoropolyether is, for example, 0.05 parts by mass to 10 parts by mass, 0.05 parts by mass to 5 parts by mass, based on 100 parts by mass of the polyfunctional monomer (a). parts, or 0.05 parts by mass to 3 parts by mass. (c) The content of perfluoropolyether is 0.05 parts by mass or more, so that (c) perfluoropolyether is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, resulting in a hard coat layer excellent in slipperiness. can be obtained. Moreover, when the content of (c) perfluoropolyether is 3 parts by mass or less, a hard coat layer that is sufficiently compatible with (b) perfluoropolyether and has little cloudiness can be obtained. In addition, the content of the (c) perfluoropolyether relative to 100 parts by mass of the (b) perfluoropolyether is, for example, 10 to 800 parts by mass, more preferably 10 to 500 parts by mass. parts, more preferably 10 to 400 parts by mass.

(c) Perfluoropolyether can be used individually or in combination of two or more types.

[(d) Polymerization initiator]

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

(d) As a polymerization initiator, for example, benzoins, alkylphenones, thioxanthone, azones, azides, diazides, o-quinone diazides, acylphosphine oxides, oxime esters, organic peroxides. , benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These polymerization initiators may be used individually or in combination of two or more types. In the present invention, it is preferable to use alkylphenones as the (d) polymerization initiator from the viewpoints of transparency, surface hardenability, and thin film hardenability. By using alkylphenones, a cured film with improved scratch resistance can be obtained.

Examples of the alkylphenones include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4-(2- Hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl α-hydroxyalkylphenones such as propan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1- α-aminoalkylphenones such as onone; 2,2-dimethoxy-1,2-diphenylethan-1-one; and methyl phenylglyoxylate.

In the curable composition of the present invention, the content of the polymerization initiator (d) is, for example, 0.5 parts by mass to 20 parts by mass, preferably 1 part by mass to 20 parts by mass, based on 100 parts by mass of the polyfunctional monomer (a). , more preferably 2 to 10 parts by mass.

[(e) Solvent]

The curable composition of the present invention may contain a solvent (e) as an optional component, that is, it may be in the form of a varnish. (e) The solvent includes the dissolution and dispersibility of the components (a) to (d), workability during application of the curable composition according to the formation of the cured film (hard coat layer) described later, and before and after curing. It can be selected appropriately considering drying properties, etc.

Examples of the solvent (e) include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; Aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Halogenates such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, and o-dichlorobenzene; Esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); Diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGME), propylene glycol ethers such as mono-n-propyl ether, propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, and cyclohexanone; Alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO), and solvents in which two or more of these solvents are mixed.

The content of the solvent (e) in the curable composition of the present invention is not particularly limited, but for example, the solid content concentration of the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass. This is the concentration. Here, the solid content concentration (also referred to as non-volatile content concentration) refers to the solid content (solvent component from all components) relative to the total mass (total mass) of the components (a) to (e) and other additives of the curable composition of the present invention. Indicates the content of (excluding items).

[Other additives]

In addition, to the curable composition of the present invention, additives generally added as necessary, as long as they do not impair the effect of the present invention, such as polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion imparting agents, One type of plasticizer, ultraviolet absorber, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, etc. can be appropriately mixed alone or in combination of two or more types.

<cured film>

The curable composition of the present invention can be applied (coated) on a substrate to form a coating film, and polymerized (cured) by irradiating the coating film with active energy rays to form a cured film, and this cured film is also the subject of the present invention. am. Additionally, as a hard coat layer in the hard coat film described later, what is made of the above cured film can be used.

As the substrate, for example, 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, triacetylcellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal , wood, paper, glass, and slate. The shape of these substrates may be plate-shaped, film-shaped, or a three-dimensional molded body. In addition, on the surface of the substrate, for example, a primer layer, an ultraviolet ray absorption layer, an infrared absorption layer, a near-infrared absorption layer, an electromagnetic wave absorption layer, a color correction layer, a refractive index adjustment layer, a weather resistance layer, an anti-reflection layer, an anti-static layer, a discoloration prevention layer, and a gas barrier layer. , a vapor barrier layer, a light scattering layer, an electrode layer, etc. may be formed as a lower layer of the hard coat layer, and a plurality of lower layers of this hard coat layer may be laminated. The layer formed on the surface of the substrate is not particularly limited as long as it does not impair the effect of the present invention.

Application methods on the substrate include cast coating, spin coating, blade coating, dip coating, roll coating, spray coating, bar coating, die coating, inkjet printing, and printing (relief printing). , intaglio printing, flat printing, screen printing, etc.) can be appropriately selected, and among them, the roll-to-roll method can be used, and from the viewpoint of thin film applicability, the convex printing method can be used. It is preferable to use a printing method, especially a gravure coat method. Meanwhile, it is preferable to filter the curable composition of the present invention in advance using a filter with a pore diameter of about 0.2 μm, and then apply it for application. On the other hand, when applying, a solvent may be additionally added to this curable composition as needed. Solvents in this case include various solvents exemplified in [(e) Solvent] above.

After applying the curable composition of the present invention on a substrate to form a coating film, if necessary, the coating film is pre-dried using a heating means such as a hot plate or oven to remove the solvent (solvent removal process). The conditions for heat drying at this time are preferably, for example, 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 preferable. Light sources used for ultraviolet irradiation include, for example, solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. Furthermore, polymerization may be completed thereafter by performing post-bake, specifically by heating using a heating means such as a hot plate or oven.

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

<Hard coat film>

Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. This hard coat film is also the object of the present invention, and this hard coat film is suitably used to protect 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 includes the steps of applying the curable composition of the present invention on a film substrate to form a coating film, a step of removing the solvent by heating if necessary, and exposing the coating film to ultraviolet rays. It can be formed by a method including a step of irradiating active energy rays such as curing the coating film. A method for producing a hard coat film including a hard coat layer on at least one side of a film substrate including these steps is also the subject of the present invention.

As the film substrate, among the substrates mentioned in the above <cured film>, various transparent resin films that can be used for optical purposes are used. Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethane, thermoplastic polyurethane (TPU), and polycarbonate. , polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetylcellulose (TAC).

The film substrate may be formed by stacking a plurality of layers. For example, on the surface of the resin film, a primer layer, an ultraviolet ray absorption layer, an infrared absorption layer, a near-infrared absorption layer, an electromagnetic wave absorption layer, a color correction layer, a refractive index adjustment layer, a weather resistance layer, an anti-reflection layer, an anti-static layer, a discoloration prevention layer, and a gas barrier layer. Layers different from this resin film, such as a water vapor barrier layer, a light scattering layer, and an electrode layer, may be laminated as a lower layer of the hard coat layer, and a plurality of lower layers of this hard coat layer may be laminated. The layer laminated on the surface of the resin film is not particularly limited as long as it does not impair the effect of the present invention.

In addition, the method of applying the curable composition of the present invention on the film substrate (coat film forming process) and the method of irradiating active energy rays to the coating film (curing process) can use the methods exemplified in the above <cured film>. there is. Additionally, when the curable composition of the present invention contains a solvent (in the form of a varnish), after the coating film forming process, a step of drying the coating film and removing the solvent may be included, if necessary. In that case, the coating film drying method (solvent removal process) mentioned as an example in the above <cured film> can be used.

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

<Surface modifier>

A perfluoropolyether (A) having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, perfluoropolymer ether (A) described later) (excluding polyether (B)), and perfluorocarbons having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500. A surface modifier containing polyether (B) is also the subject of the present invention.

Furthermore, a perfluoropolyether (A) having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, purple polyether (A) described later (excluding fluoropolyether (B)), and raw perfluoropolyether with a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. , a surface modifier containing perfluoropolyether (B), which is a reaction product between a functional group that reacts with the hydroxy group and a compound having the active energy ray polymerizable group, is also included in the present invention.

Meanwhile, “perfluoropolyether (A)” is the same as the above-mentioned (b) perfluoropolyether, and “perfluoropolyether (B)” is the same as the above-mentioned (c) perfluoropolyether. same.

Example

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the following examples. Meanwhile, in the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.

(1) Application by bar coater

Device: SMT Co., Ltd. PM-9050MC

Bar: A-Bar OSP-15 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 15μm (film thickness after drying 3μm)

Application speed: 4m/min

(2)Film thickness measurement

Device: F20 film thickness measurement system manufactured by Philmetrics Co., Ltd.

(3)Oven

Equipment: Sanki Keiso Co., Ltd. two-layer clean oven (top and bottom) PO-250-45-D

(4)UV curing

Device: CV-110QC-G manufactured by Heraeus Co., Ltd.

Lamp: Electrodeless lamp H-bulb manufactured by Heraeus Co., Ltd.

(5) Scratch resistance test and abrasion resistance test

Equipment: Reciprocating abrasion tester manufactured by Shinto Science Co., Ltd. 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.

Measurement temperature: 23℃

(7) Dynamic friction coefficient measurement

Equipment: Shinto Science Co., Ltd., load-variable friction wear test system TRIBOGEAR (registered trademark) TYPE: HHS2000

Probe: 0.6mmR sapphire pin

Load: 200g

Scanning speed: 2mm/sec

Scanning distance: 10mm

(8) Total light transmittance, haze measurement

Device: Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

(9) Weight average molecular weight measurement

Gel permeation chromatography (GPC)

Device: HLC-8420GPC manufactured by Tosoh Corporation

Column: TSKgelG2000HXL, TSKgelG3000HXL, manufactured by Tosoh Co., Ltd.

Measurement temperature: 40℃

Eluent: tetrahydrofuran

Detection: RI

(10)Combustion ion chromatography

Automatic sample combustion device system: AQF-2100 H manufactured by Nitto Seiko Analytech Co., Ltd. (formerly Mitsubishi Chemical Analytech Co., Ltd.)

Ion chromatograph: 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 manufactured by Thermo Fisher Scientific Co., Ltd.

Flow rate: 1.5mL/min

Detector: Electrical conductivity (with suppressor)

Standard sample: Fluoride ion standard solution (F-1000) manufactured by Fujifilm Wako Pure Chemical Co., Ltd. (formerly Wako Pure Chemical Industries, Ltd.)

When the solvent in the sample did not contain a solvent containing a fluorine atom, the fluorine concentration was measured as it was containing the solvent, and the fluorine concentration of the solute was calculated by converting from the solid content concentration. If the solvent in the sample contains a solvent containing a fluorine atom, use a halogen moisture meter to volatilize the sample solvent under conditions of 120°C for 20 minutes, and use the sample for which it is judged that the mass change has become constant and all of the solvent has been volatilized. The fluorine concentration was measured.

In addition, the abbreviated symbols indicate the following meanings.

Multifunctional acrylate PA1: Dipentaerythritol pentaacrylate/hexaacrylate mixture [Aronics (registered trademark) M-403 manufactured by Dong-A Synthetics Co., Ltd.]

Multifunctional acrylate PA2: Oxyethylene-modified multifunctional acrylate [New Frontier (registered trademark) MF-001 manufactured by Jeil Industrial Pharmaceutical Co., Ltd.]

Multifunctional acrylate PA3: Multifunctional urethane acrylate [Art Resin (registered trademark) UN-3320HS manufactured by Negami Industry Co., Ltd.]

Multifunctional acrylate PA4: Pentaerythritol triacrylate/pentaerythritol tetraacrylate [PET30 manufactured by Nippon Explosives Co., Ltd.]

PFPE1: Perfluoropolyether of the following structure having two hydroxy groups without a poly(oxyalkylene) group at each end [Fomblin (registered trademark) T4 ¹⁹ F-NMR and ¹ H- manufactured by Solbase Specialty Polymers, Inc. Number average molecular weight calculated from NMR analysis results: 2200]

[Formula 10]

(In the above formula, r is the number of repeating units-(CF ₂ CF ₂ O)-, and s is the number of repeating units-(CF ₂ O)-, satisfying 5≤(r+s)≤40, r and s each independently represent an integer greater than or equal to 0.)

PFPE2: Perfluoropolyether of the following structure having one hydroxy group only at one end without a poly(oxyalkylene) group (7324X manufactured by Solbase Specialty Polymers, Inc. From analysis results by ¹⁹ F-NMR and ¹ H-NMR) Calculated number average molecular weight 1750~1950]

[Formula 11]

(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)-, satisfying 5≤(m+n)≤30, m and n each independently represent an integer of 0 or more.)

PFPE3: Perfluoropolyether of the following structure, with a poly(oxyethylene) group only at one end and ^one hydroxy group (Fomblin (registered trademark) ⁴¹⁰² Number average molecular weight calculated from the analysis results: 1900]

[Formula 12]

(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)-, satisfying 5≤(m+n)≤30, m and n each independently represent an integer of 0 or more, and q is the number of oxyethylene groups and represents an integer of 2 to 20.)

PFPE4: Perfluoropolyether of the following structure having one hydroxy group only at one end without a poly(oxyalkylene) group (FO2 molecular weight 978.15, manufactured by Apollo Scientific)

[Formula 13]

PFPE5: Perfluoropolyether (1H,1H-perfluoro-3,6,9-trioxatridecan-1) having the following structure and having one hydroxy group only at one end without a poly(oxyalkylene) group. -All) [C10GOL molecular weight 548.1 manufactured by Exfluor Research]

[Formula 14]

PFPE6: Perfluoropolyether of the following structure having one hydroxy group without a poly(oxyalkylene) group at each end (Fomblin (registered trademark) D2, manufactured by Solbase Specialty Polymers, Inc. ¹⁹ F-NMR and ¹ H- Number average molecular weight calculated from NMR analysis results: 1550]

[Formula 15]

(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)-, satisfying 5≤(m+n)≤30, m and n each independently represent an integer of 0 or more.)

N1: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI, manufactured by Showa Denko Co., Ltd.]

N2: 2-acryloyloxyethyl isocyanate [Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.]

SMA6: Perfluoropolyether having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group (Optul (registered trademark) DAC-HP, manufactured by Daikin Industry Co., Ltd., non-volatile content) 20 mass% solution, weight average molecular weight measured in polystyrene conversion by GPC: Mw is 1521, dispersion: Mw/Mn is 1.1 (Mn is number average molecular weight), perfluoropolyether calculated by combustion ion chromatography Fluorine atom content in the compound: 35 mass%]

SMA7: A perfluoropolyether having a total of four active energy ray polymerizable groups at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group (Fluorolink (registered trademark) AD-1700, manufactured by Solbase Specialty Polymers, Inc.) Non-volatile matter 70 mass% solution, weight average molecular weight measured in polystyrene conversion by GPC: Mw is 3973, dispersion: Mw/Mn is 2.1, fluorine atom in perfluoropolyether compound calculated by combustion ion chromatography Content ratio 29% by mass]

DOTDD: Dioctyltin dineodecanoate [Neostane (registered trademark) U-830 manufactured by Nitto Chemical Co., Ltd.]

MEK: Methyl ethyl ketone

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

MeOH: methanol

O2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [OMNIRAD (registered trademark) 2959, manufactured by IGM Resins]

AN1: PEDOT-PSS aqueous dispersion [PEDOT-PSS 3.0% to 4.0% by mass aqueous dispersion highly conductive grade manufactured by Sigma-Aldrich, product number 655201]

[Preparation Example 1] Preparation of surface modifier component SMA1

Into the screw tube, 1.19 g (0.5 mmol) of PFPE1, 0.52 g (2.0 mmol) of N1, 0.017 g of DOTDD (0.01 times the total mass of PFPE1 and N1), and 1.67 g of PGMEA were added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA1. The weight average molecular weight of the obtained SMA1 measured in polystyrene conversion by GPC: Mw was 2494, and the dispersity: Mw/Mn was 1.0. Additionally, the content ratio of fluorine atoms in SMA1 calculated by combustion ion chromatography was 42% by mass.

[Preparation Example 2] Preparation of surface modifier component SMA2

Into the screw tube, 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 added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain an 80% by mass MEK solution of the target perfluoropolyether compound SMA2. The weight average molecular weight of the obtained SMA2 measured in polystyrene conversion by GPC: Mw was 1710, and the dispersity: Mw/Mn was 1.0. Additionally, the content ratio of fluorine atoms in SMA2 calculated by combustion ion chromatography was 63% by mass.

[Preparation Example 3] Preparation of surface modifier component SMA3

Into the screw tube, 3.08 g (1.6 mmol) of PFPE3, 0.39 g (1.6 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 added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA3. The weight average molecular weight of the obtained SMA3 measured in terms of polystyrene by GPC: Mw was 1908, and the dispersity: Mw/Mn was 1.0. Additionally, the content of fluorine atoms in SMA3 calculated by combustion ion chromatography was 47% by mass.

[Preparation Example 4] Preparation of surface modifier component SMA4

Into the screw tube, 2.78 g (2.9 mmol) of PFPE4, 0.68 g (2.9 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 added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA4. The weight average molecular weight of the obtained SMA4 measured in polystyrene conversion by GPC: Mw was 1299, and the dispersion degree: Mw/Mn was 1.0. In addition, the fluorine atom content in SMA4 calculated by combustion ion chromatography was 51% by mass, which was equivalent to the fluorine atom content of 51% by mass theoretically calculated from the structure of SMA4.

[Preparation Example 5] Preparation of surface modifier component SMA5

Into the screw tube, 2.41 g (4.4 mmol) of PFPE5, 1.05 g (4.4 mmol) of N1, 0.035 g of DOTDD (0.01 times the total mass of PFPE5 and N1), and 3.5 g of PGMEA were added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA5. The weight average molecular weight of the obtained SMA5 measured in polystyrene conversion by GPC: Mw was 1029, and the dispersion degree: Mw/Mn was 1.0. In addition, the fluorine atom content in SMA5 calculated by combustion ion chromatography was 46% by mass, which was similar to the fluorine atom content of 47% by mass theoretically calculated from the structure of SMA5.

[Preparation Example 6] Preparation of surface modifier component SMA8

Into the screw tube, 3.66 g (2.4 mmol) of PFPE6, 0.67 g (4.8 mmol) of N2, 0.054 g of DOTDD (0.01 times the total mass of PFPE6 and N2), and 4.4 g of PGMEA were added. This mixture was stirred at room temperature (about 23°C) for 72 hours using a stirrer chip to obtain a 50% by mass PGMEA solution of the target perfluoropolyether compound SMA8. The weight average molecular weight of the obtained SMA8 measured in polystyrene conversion by GPC: Mw was 1609, and the dispersion degree: Mw/Mn was 1.0. Additionally, the content ratio of fluorine atoms in SMA8 calculated by combustion ion chromatography was 54% by mass.

[Examples 1 to 9, Comparative Examples 1 to 13]

Each component shown in Table 1 was mixed to prepare a curable composition having the solid concentration shown in Table 1. Here, solid content refers to components other than the solvent. In addition, in Table 1, [part] indicates [part by mass], and [%] indicates [mass%]. Meanwhile, the solid content of the multifunctional acrylate and surface modifier in Table 1 is shown.

[Table 1]

These curable compositions were applied using a bar coater onto an A4 size PET film (Lumiller (registered trademark) U403 (alias U40) manufactured by Toray Co., Ltd. (alias U40), thickness 100 μm] on which both sides were easily adhesive treated and a primer layer was formed. By applying, a coating film was obtained. This coating film was dried in an oven at 60°C for 8 minutes to remove the solvent. The obtained film was irradiated and exposed to UV light at an exposure amount of 300 mJ/cm ² under a nitrogen atmosphere to produce a hard coat film having a hard coat layer (cured film).

[Examples 10 to 11, Comparative Examples 14 to 15]

Each component shown in Table 2 was mixed to prepare a curable composition having a solid concentration shown in Table 2. Here, solid content refers to components other than the solvent. In addition, in Table 2, [part] indicates [part by mass], and [%] indicates [mass%]. Meanwhile, the solid content of the multifunctional acrylate and surface modifier in Table 2 is shown.

[Table 2]

These curable compositions were applied by a bar coater on an A4 size PET film (Lumiller (registered trademark) U403 (alias U40) manufactured by Toray Co., Ltd. (alias U40), thickness 100 μm] of A4 size on which both sides were treated with easy adhesive treatment and a primer layer was formed, I got a paint film. This coating film was dried in an oven at 65°C for 3 minutes to remove the solvent. The obtained film was irradiated and exposed to UV light at an exposure amount of 300 mJ/cm ² under a nitrogen atmosphere to produce a hard coat film having a hard coat layer (cured film).

The homogeneity of each curable composition and the scratch resistance, water repellency, abrasion resistance, slipperiness, and haze of the obtained hard coat film were evaluated. The evaluation procedure is shown below. The results are shown together in Tables 3 and 4.

[Composition homogeneity]

The appearance of each prepared curable composition was visually confirmed and evaluated according to the following standards.

A: Clear solution (no suspended matter, sediment or phase separation)

C: Either suspended solids, sediment, or phase separation is present.

[Scratch resistance]

The surface of the hard coat layer of the obtained hard coat film was rubbed with steel wool (BONSTAR (registered trademark) #0000 (ultrafine)) mounted on a reciprocating abrasion tester for 5,000 reciprocations at a stroke of 50 mm by applying a load of 1 kg. After that, the degree of the scratches in the area excluding the 5 mm width at both ends of the stroke of 50 mm was visually confirmed, and further, it was confirmed with a microscope (Keyence Co., Ltd.) that the scratches were on the surface of the hard coat layer, and the following criteria A, Evaluated according to B and C. On the other hand, when actual use as a hard coat layer is assumed, at least B is required, and A is preferable.

A: No scratches (0 scratches)

B: Scratches (1 to 4 scratches with a length of 1 mm to 9 mm)

C: Scratches (5 or more scratches with a length of 1 mm to 9 mm, or 1 or more scratches with a length of 1 cm or more)

[Water repellency]

1 μL of water was adhered to the surface of the hard coat layer, the contact angle θ after 5 seconds was measured five times, and the average value was evaluated according to the following standards. On the other hand, when actual use as a hard coat layer is assumed, A is preferable. On the other hand, if the contact angle is measured immediately after water is attached, the value is high and not stable, so in this measurement, the contact angle was measured 5 seconds after water was attached.

A: θ>105°

B: 100°≤θ≤105°

C: θ<100°

[Abrasion resistance]

The surface of the hard coat layer was rubbed 2,500 times with a 1kg load using a cylindrical eraser (RUBBER STICK, ϕ6.0mm manufactured by Minoan) mounted on a reciprocating abrasion tester. 1 μL of water was attached to the rubbed area, the contact angle θ after 5 seconds was measured at 5 points, the average value was taken as the contact angle value, and evaluation was made according to the following standards. On the other hand, when actual use as a hard coat layer is assumed, at least B is required, and A is preferable.

A: θ≥90°

B: 85°≤θ°<90°

C: 85°<θ

[Slippery]

The dynamic friction coefficient was measured at five locations on the surface of the hard coat layer and evaluated from the average value. On the other hand, the smaller the dynamic friction coefficient value, the smaller the friction with the probe used, and it serves as a standard for slipperiness. The smaller the dynamic friction coefficient value, the better the slipperiness when in contact, so the smaller the dynamic friction coefficient value, the more desirable it is.

[Hayes]

As a reference value, the haze was measured at three locations on the surface of the hard coat layer, and the average value was calculated. On the other hand, as a substrate, the PET film used this time (Lumiller (registered trademark) U403 (alias U40) manufactured by Toray Co., Ltd., thickness 100 μm) had a haze of 1.6.

[Table 3]

[Table 4]

As shown in Table 1, the curable compositions of Examples 1 to 8 are polyfunctional acrylates PA1 to PA4, and active energy rays are applied to both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group. A molecular chain containing a perfluoropolyether SMA1 having a polymerizable group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group. SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE2 or PFPE3 having a number average molecular weight of 1750 to 1950 and having one hydroxy group only at one end of , or SMA3 with a weight average molecular weight of 1908. As shown in Table 3, the curable compositions of Examples 1 to 8 exhibit excellent homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition has excellent slipperiness, scratch resistance, water repellency, and It showed wear resistance.

As shown in Table 1, the curable composition of Example 9 has polyfunctional acrylate PA1, an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of It is 1521, and it contains perfluoropolyether SMA6 with a fluorine atom content of 35% by mass, and further has one hydroxy group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. It includes SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950. As shown in Table 3, the curable composition of Example 9 exhibited excellent homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition exhibited excellent slipperiness, water repellency, and abrasion resistance. The hard coat film provided with the hard coat layer obtained from the curable composition of Example 9 is slightly inferior to the hard coat film provided with the hard coat layer obtained from the curable composition of Examples 1 to 8 with respect to scratch resistance. However, other items shown in Table 2 showed excellent characteristic levels.

On the other hand, as shown in Table 1, the curable composition of Comparative Example 1 has an active energy ray polymerizable group at each end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. , it also contains perfluoropolyether SMA1 with a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and only at one end of the molecular chain which further contains a poly(oxyperfluoroalkylene) group. SMA4 with a weight average molecular weight of 1299 and a fluorine atom content of 51% by mass obtained by reacting the isocyanate compound N1 having the above active energy ray polymerizable group with the perfluoropolyether compound PFPE4 having a molecular weight of 978.15 having one hydroxy group. It includes. As shown in Table 3, the curable composition of Comparative Example 1 exhibits excellent homogeneity, but the hard coat film having a hard coat layer obtained from this curable composition has Compared to hard coat films, slipperiness and scratch resistance were inferior. From these results, even if a perfluoropolyether having an active energy ray polymerizable group is used only at one end of the molecular chain containing an (oxyperfluoroalkylene) group with a high content of fluorine atoms, the slipperiness and scratch resistance are maintained. It was found that the weight average molecular weight of this perfluoropolyether was important in terms of slipperiness and scratch resistance.

In addition, as shown in Table 1, the curable composition of Comparative Example 2 has an active energy ray polymerizable group at each end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. , it also contains perfluoropolyether SMA1 with a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and only at one end of the molecular chain which further contains a poly(oxyperfluoroalkylene) group. SMA5, which has a weight average molecular weight of 1029 and a fluorine atom content of 47% by mass, was obtained by reacting the isocyanate compound N1 having the above active energy ray polymerizable group with the perfluoropolyether compound PFPE5 having a molecular weight of 548.10 having one hydroxy group. It includes. As shown in Table 3, the curable composition of Comparative Example 2 exhibits excellent homogeneity, but the hard coat film provided with a hard coat layer obtained from this curable composition has poor slipperiness, scratch resistance, and wear resistance. showed. From these results, it is clear that slipperiness and scratch resistance are maintained even when perfluoropolyether, which has an active energy ray polymerizable group only at one end of the molecular chain containing an (oxyperfluoroalkylene) group with a high content of fluorine atoms, is used. , and abrasion resistance were not excellent, and the size of the weight average molecular weight of this perfluoropolyether was shown to be important in slipperiness, scratch resistance, and abrasion resistance.

In addition, as shown in Table 1, the curable compositions of Comparative Examples 3 to 4 contain a hydroxyl group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. SMA4 or weight average molecular weight obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE4 having a molecular weight of 978.15 or the perfluoropolyether compound PFPE5 having a molecular weight of 548.10. Regarding the perfluoropolyether compound PFPE2 with a number average molecular weight of 1750 to 1950, which contains SMA5 with a molecular weight of 1029 and has one hydroxy group only at one end of the molecular chain further containing a poly(oxyperfluoroalkylene) group. , and SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group. As shown in Table 3, the curable compositions of Comparative Examples 3 to 4 were inferior in homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition had slipperiness, scratch resistance, and wear resistance. showed inferior results. This is believed to be because the weight average molecular weights of SMA4 and SMA5 are small, so the aggregation structure of SMA2 cannot be broken down and solubility in the coating liquid cannot be supported. Therefore, it is believed that SMA2 aggregated in the coating liquid and could not sufficiently segregate on the surface of the hard coat layer, resulting in poor slipperiness, scratch resistance, and wear resistance.

In addition, as shown in Table 1, the curable composition of Comparative Example 5 has an active energy ray polymerizable group at both ends of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group, In addition, it contains perfluoropolyether SMA7 with a weight average molecular weight of 3973 and a fluorine atom content of 29% by mass, and further contains hydride only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group. It includes SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE2 having a number average molecular weight of 1750 to 1950 having one hydroxyl group. As shown in Table 3, the curable composition of Comparative Example 5 exhibited excellent homogeneity and excellent slipperiness, but the hard coat film provided with a hard coat layer obtained from this curable composition was inferior in scratch resistance and abrasion resistance. indicated. From these results, it was shown that good slipperiness does not necessarily lead to good scratch resistance and good wear resistance. The hard coat film provided with the hard coat layer obtained from the curable composition of Comparative Example 5 is inferior in scratch resistance and wear resistance compared to the hard coat film provided with the hard coat layer obtained from the curable composition of Examples 1 to 9. The reason is thought to be that the weight average molecular weight of SMA7 is larger than that of SMA1 and SMA6, and the immobilization ability in the film is lowered. Furthermore, it is thought that this is because the fluorine atom content of SMA7 is small compared to SMA1 and SMA6, and the compatibility between SMA2 and SMA7 is poor, so that SMA2 and SMA7 are in a phase-separated state on the surface of the hard coat layer.

In addition, as shown in Table 1, the curable composition of Comparative Example 6 has a number average value having one hydroxy group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It includes SMA2 having a weight average molecular weight of 1710 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE2 having a molecular weight of 1750 to 1950. As shown in Table 3, the curable composition of Comparative Example 6 is inferior in homogeneity compared to the curable composition of Example 1 in which SMA1 was added to the curable composition of Comparative Example 6, and further, the curable composition of Comparative Example 6 Compared to the hard coat film provided with a hard coat layer obtained from the curable composition of Example 1, the hard coat film provided with the obtained hard coat layer showed inferior results in all slipperiness, scratch resistance, water repellency, and abrasion resistance. This includes a perfluoropolyether having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group, which acts as a solubility auxiliary for SMA2, and having a weight average molecular weight of 1400 to 3500. Since it did not, it is thought that this is because SMA2 aggregated in the coating liquid.

In addition, as shown in Table 1, the curable composition of Comparative Example 7 has a number average value having one hydroxy group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It includes SMA3 with a weight average molecular weight of 1908 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE3 with a molecular weight of 1900. As shown in Table 3, the curable composition of Comparative Example 7 has excellent homogeneity, but the hard coat film with a hard coat layer obtained from this curable composition is an example in which SMA1 was added to the curable composition of Comparative Example 7. Compared with the hard coat film provided with the hard coat layer obtained from the curable composition of Examples 2 to 4, the results showed inferior scratch resistance and water repellency. This is because SMA3 was used alone, and the cohesive force of SMA3 is strong, making it easy to aggregate inside the film, and in addition to the fact that SMA3 cannot sufficiently segregate on the surface of the hard coat layer, SMA3 has an active energy ray polymerizable group only at one end. This is thought to be because the immobilization ability in the film is low.

In addition, as shown in Table 1, the curable composition of Comparative Example 8 has a molecular weight of 978.15, which has one hydroxy group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It contains SMA4 with a weight average molecular weight of 1299 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE4. And, as shown in Table 3, the homogeneity is inferior to the curable composition of Comparative Example 1 in which SMA1 was added to the curable composition of Comparative Example 8, and a hard coat provided with a hard coat layer obtained from the curable composition of Comparative Example 8. The film showed poor results in all slipperiness, scratch resistance, and abrasion resistance. This is thought to be because SMA4 aggregates inside the film and cannot sufficiently segregate on the surface of the hard coat layer, and the molecular chain containing the poly(oxyperfluoroalkylene) group of SMA4 is short.

In addition, as shown in Table 1, the curable composition of Comparative Example 9 has a molecular weight of 548.1, which has one hydroxy group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It includes SMA5 having a weight average molecular weight of 1029 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE5. As shown in Table 3, the curable composition of Comparative Example 9 has excellent homogeneity, but the hard coat film including the hard coat layer obtained from this curable composition contains a molecule containing a poly(oxyperfluoroalkylene) group. Because the chains were short, slipperiness, water repellency, scratch resistance, and abrasion resistance all showed inferior results.

Furthermore, as shown in Table 1, the curable composition of Comparative Example 10 has an active energy ray polymerizable group at each end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. , and also contains perfluoropolyether SMA1 with a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass. As shown in Table 3, the curable composition of Comparative Example 10 is excellent in homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition is excellent in water repellency, scratch resistance, and abrasion resistance. Compared to the hard coat film provided with a hard coat layer obtained from the curable composition of Example 1 in which SMA2 was added to the curable composition of 10, the slipperiness result was inferior because it did not contain SMA2. This is because SMA1 has eight acrylic groups in one molecule and has a high immobilization ability in the film, so it is excellent in scratch resistance and abrasion resistance. However, since the immobilization ability is high, it is thought that SMA1 has low molecular mobility and is inferior in slipperiness.

Judging from the evaluation results of the hard coat films provided with hard coat layers obtained from the curable compositions of Comparative Examples 5 and 10 shown in Table 3, it was suggested that slipperiness and scratch resistance are in a trade-off relationship.

Furthermore, as shown in Table 1, the curable composition of Comparative Example 12 has an active energy ray polymerizable group at both ends of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group, It also contains perfluoropolyether SMA7, which has a weight average molecular weight of 3973 and a fluorine atom content of 29% by mass. As shown in Table 3, the curable composition of Comparative Example 12 has excellent homogeneity, but the hard coat film provided with a hard coat layer obtained from this curable composition is comparable to that obtained by adding SMA2 to the curable composition of Comparative Example 12. Compared to the hard coat film provided with a hard coat layer obtained from the curable composition of Example 5, all of them showed poor slipperiness results because they did not contain SMA2. From these results, the hard coat film obtained from a curable composition containing a perfluoropolyether having an active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier is poly. Compared to a hard coat film obtained from a curable composition containing only a perfluoropolyether having an active energy ray polymerizable group at both ends of the molecular chain containing an (oxyperfluoroalkylene) group as a surface modifier, it has excellent slipperiness. It has been suggested that

Furthermore, as shown in Table 1, the curable composition of Comparative Example 13 has an active energy ray polymerizable group at each end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. , It also contains perfluoropolyether SMA1 with a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and further contains a poly(oxyperfluoroalkylene) group at both ends of the molecular chain. The weight average molecular weight obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE6 having a number average molecular weight of 1550 having one hydroxy group is 1609, and the fluorine atom content ratio is 54. It includes SMA8 as a mass percent. As shown in Table 3, the curable composition of Comparative Example 13 exhibits excellent homogeneity, and the hard coat film having a hard coat layer obtained from this curable composition has excellent water repellency and scratch resistance, but Compared to the hard coat film provided with the hard coat layer obtained from the curable composition of Example 9, the slipperiness and abrasion resistance were inferior. From these results, the hard coat film obtained from a curable composition containing a perfluoropolyether having an active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group as a surface modifier has a surface Excellent slipperiness compared to a hard coat film obtained from a curable composition containing only perfluoropolyether having an active energy ray polymerizable group at both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group as a modifier. something appeared.

As shown in Table 2, the curable compositions of Examples 10 and 11 are polyfunctional acrylate PA1 or PA2, and active energy rays are applied to both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group. A molecular chain containing a perfluoropolyether SMA1 having a polymerizable group, a weight average molecular weight of 2494, and a fluorine atom content of 42% by mass, and further containing a poly(oxyperfluoroalkylene) group. SMA3 having a weight average molecular weight of 1908 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE3 having a number average molecular weight of 1900 and having one hydroxy group only at one end of It also contains antistatic agent AN1. As shown in Table 4, the curable compositions of Examples 10 and 11 exhibit excellent homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition has excellent slipperiness, scratch resistance, water repellency, and It showed wear resistance.

On the other hand, as shown in Table 2, the curable composition of Comparative Example 14 has an active energy ray polymerizable group at each end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. , it also contains perfluoropolyether SMA1 with a weight average molecular weight of 2494 and a fluorine atom content of 42% by mass, and further contains an antistatic agent AN1. As shown in Table 4, the curable composition of Comparative Example 14 is excellent in homogeneity, and the hard coat film provided with a hard coat layer obtained from this curable composition is excellent in water repellency, scratch resistance, and abrasion resistance. Compared to the hard coat film provided with a hard coat layer obtained from the curable composition of Example 10 in which SMA3 was added to the curable composition of Example 14, the slipperiness result was inferior because it did not contain SMA3. This is because SMA1 has eight acrylic groups in one molecule and has a high immobilization ability in the film, so it is considered to have excellent scratch resistance and wear resistance, but has low molecular mobility and is inferior to slipperiness.

In addition, as shown in Table 2, the curable composition of Comparative Example 15 has a number average value having one hydroxy group only at one end of the molecular chain containing polyfunctional acrylate PA1 and a poly(oxyperfluoroalkylene) group. It contains SMA3 with a weight average molecular weight of 1908 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE3 with a molecular weight of 1900, and further contains an antistatic agent AN1. As shown in Table 4, the curable composition of Comparative Example 15 has excellent homogeneity, but the hard coat film with a hard coat layer obtained from this curable composition is an example in which SMA1 was added to the curable composition of Comparative Example 15. Compared to the hard coat film provided with the hard coat layer obtained from the curable composition of No. 10, it showed excellent slipperiness, but showed inferior scratch resistance. This is believed to be because SMA3, which has an active energy ray polymerizable group only at one end, was used alone, which lowered the immobilization ability in the film.

Claims (32)

(a) an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule,
(b) a perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, (c) described later) (excluding perfluoropolyether),
(c) a perfluoropolyether having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500, and
(d) A curable composition containing a polymerization initiator that generates radicals by active energy rays. (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule,
(b) a perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, (c) described later) (excluding perfluoropolyether) 0.05 parts by mass to 3 parts by mass,
(c) 0.05 to 3 parts by mass of a perfluoropolyether having the above active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500. wealth, and
(d) A curable composition containing 0.5 parts by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth)acryloyl groups per molecule,
(b) a perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, (c) described later) (excluding perfluoropolyether) 0.05 parts by mass to 3 parts by mass,
(c) Raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a functional group that reacts with the hydroxyl group, and the above 0.05 to 3 parts by mass of perfluoropolyether, which is a reaction product with a compound having an active energy ray polymerizable group, and
(d) A curable composition containing 0.5 parts by mass to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. According to paragraph 3,
The (c) perfluoropolyether has the active energy ray polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1550 to 3500. Composition. According to any one of claims 1 to 4,
A curable composition in which the (c) perfluoropolyether has an active energy ray polymerizable group via a urethane bond. According to any one of claims 1 to 5,
A curable composition in which the (c) perfluoropolyether has a fluorine atom content of 35% by mass to 65% by mass. According to any one of claims 1 to 6,
The poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a repeating unit-(CF ₂ O)- and/or a repeating unit-(CF ₂ CF ₂ O)-, and repeats both. In the case of having units, the curable composition is formed by combining these repeating units by block combinations, random combinations, or block combinations and random combinations. In clause 7,
A curable composition in which the molecular chain containing the poly(oxyperfluoroalkylene) group of the (c) perfluoropolyether has a structure represented by the following formula [1].
[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)-, 5≤(m+n)≤30 m and n each independently represent an integer of 0 or more, and q is the number of oxyethylene groups and represents an integer of 0 to 20.) According to clause 8,
In the formula [1], m and n each independently represent an integer of 1 or more. According to clause 8 or 9,
A curable composition wherein the (c) perfluoropolyether is a compound represented by the following formula [2].
[Formula 2]

(In the above formula [2], m, n and q are the same as the definitions of the above formula [1], and A represents a terminal group having the above active energy ray polymerizable group.) According to clause 10,
A curable composition wherein the terminal group A is a group represented by the following formula [A1] or [A2].
[Formula 3]

(In the formula [A1] and formula [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the number of bonds with the urethane bond of the compound represented by the formula [2]. ) According to any one of claims 1 to 11,
A curable composition in which the (b) perfluoropolyether has the active energy ray polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group. According to any one of claims 1 to 12,
A curable composition in which the molecular chain containing the poly(oxyperfluoroalkylene) group of the (b) perfluoropolyether has a structure represented by the following formula [3].
[Formula 4]

(In the above formula [3], r is the number of repeating units-(CF ₂ CF ₂ O)-, and s is the number of repeating units-(CF ₂ O)-, 5≤(r+s)≤40 and r and s each independently represent an integer of 0 or more, and when both have repeating units, these repeating units are combined by block combination, random combination, or block combination and random combination.) According to clause 13,
In the formula [3], r and s each independently represent an integer of 1 or more. According to claim 13 or 14,
A curable composition wherein the (b) perfluoropolyether is a compound represented by the following formula [4].
[Formula 5]

(In the above formula [4], r and s have the same definition as the above formula [3], and A represents a terminal group having the above active energy ray polymerizable group.) According to clause 15,
A curable composition wherein the terminal group A is a group represented by the following formula [A1] or [A2].
[Formula 6]

(In the above formulas [A1] and [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the number of bonds with the urethane bond of the compound represented by the above formula [4]. ) According to any one of claims 1 to 16,
(e) A curable composition further comprising a solvent. A cured film obtained from the curable composition according to any one of claims 1 to 17. A hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer consists of the cured film according to claim 18. According to clause 19,
A hard coat film having a lower layer of a hard coat layer between the surface of the film substrate and the hard coat layer, and the film substrate being a resin film. According to claim 19 or 20,
A hard coat film wherein the hard coat layer has a film thickness of 1 μm to 20 μm. Comprising the steps of applying the curable composition according to any one of claims 1 to 17 on a film substrate to form a coating film, and forming a hard coat layer by irradiating the coating film with active energy rays and curing it. , Manufacturing method of hard coat film. A process of applying the curable composition according to claim 17 on a film substrate to form a coating film, a process of removing the solvent from the coating film by heating, and irradiating the coating film with active energy rays and curing it to form a hard coat layer. A method of manufacturing a hard coat film, including a forming process. According to claim 22 or 23,
A method for producing a hard coat film, further comprising forming a lower layer of a hard coat layer on the surface of the film substrate, wherein the film substrate is a resin film, and forming the coating film on the lower layer of the hard coat layer. . A perfluoropolyether (A) having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, perfluoropolymer ether (A) described later) (excluding polyether (B)), and
A surface modifier comprising a perfluoropolyether (B) having the active energy ray polymerizable group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500. . A perfluoropolyether (A) having an active energy ray polymerizable group at the end of the molecular chain containing a poly(oxyperfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (however, perfluoropolymer ether (A) described later) (excluding polyether (B)), and
Raw material perfluoropolyether having a number average molecular weight of 1200 to 3000 having a hydroxyl group only at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, a functional group that reacts with the hydroxyl group, and the active energy ray A surface modifier comprising perfluoropolyether (B), which is a reaction product with a compound having a polymerizable group. According to clause 26,
The perfluoropolyether (B) has the active energy ray polymerizable group only at one end of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has a weight average molecular weight of 1550 to 3500. Modifier. According to any one of claims 25 to 27,
A surface modifier wherein the perfluoropolyether (B) has a fluorine atom content of 35% by mass to 65% by mass. According to any one of claims 25 to 28,
A surface modifier wherein the perfluoropolyether (A) has the active energy ray polymerizable groups at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group. According to any one of claims 25 to 29,
The molecular chain containing the poly(oxyperfluoroalkylene) group of the perfluoropolyether (A) has a structure represented by the following formula [3], and the poly(oxyperfluoroalkylene) group of the perfluoropolyether (B) is A surface modifier in which the molecular chain containing a perfluoroalkylene group has a structure represented by the following formula [1].
[Formula 7]

(In the above formulas [1] and formulas [3], m is the number of repeating units-(CF ₂ CF ₂ O)-, and n is the number of repeating units-(CF ₂ O)-, 5≤(m+ n) ≤ 30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups and represents an integer from 0 to 20, and r is a repeating unit - (CF ₂ CF ₂ O) - The number and s are the number of repeating units-(CF ₂ O)-, satisfying 5≤(r+s)≤40, r and s each independently represent an integer of 0 or more, and the repeating units-(CF ₂ In the case of having both CF ₂ O)- and repeating unit-(CF ₂ O)-, these repeating units are formed by combining block combinations, random combinations, or block combinations and random combinations.) According to clause 30,
In the formula [1], m and n each independently represent an integer of 1 or more, and in the formula [3], r and s each independently represent an integer of 1 or more. According to claim 30 or 31,
A surface modifier wherein the perfluoropolyether (A) is a compound represented by the following formula [4], and the perfluoropolyether (B) is a compound represented by the following formula [2].
[Formula 8]

(In the formula [2] and formula [4], m, n and q are the same as the definition of the formula [1], r and s are the same as the definition of the formula [3], and A is the activation energy It represents a terminal group having a pre-polymerizable group, and this terminal group A is a group represented by the following formula [A1] or formula [A2].)
[Formula 9]

(In the formula [A1] and formula [A2], R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and * represents the urethane bond of the compound represented by formula [2] or formula [4]. Indicates the number of bonds.)