CN117043209A

CN117043209A - Curable composition containing two perfluoropolyethers

Info

Publication number: CN117043209A
Application number: CN202280023684.XA
Authority: CN
Inventors: 胁田健吾
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2021-03-25
Filing date: 2022-03-25
Publication date: 2023-11-10
Also published as: WO2022203060A1; JPWO2022203060A1; KR20230160236A; TW202307040A

Abstract

The present invention provides a homogeneous curable composition free from suspended matters and precipitates, which can form a hard coat layer having both durability and sliding properties at a high level of properties and having high liquid repellency in addition to the actual use. The present invention provides a curable composition comprising: (a) An active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) A perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (except for (c) perfluoropolyether described later); (c) A perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and (d) a polymerization initiator generating radicals by active energy rays.

Description

Curable composition containing two perfluoropolyethers

Technical Field

The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surfaces of various display elements, and relates to a homogeneous curable composition which can form a hard coat layer excellent in slidability, scratch resistance, abrasion resistance and water repellency and free from suspended matters and precipitates.

The term "perfluoropolyether" used in the present invention means a compound having an active energy ray polymerizable group at the terminal of a molecular chain containing a poly (oxidized perfluoroalkylene) group. Among them, even when all hydrogen atoms such as a molecular chain including the poly (oxidized perfluoroalkylene) group or a hydrocarbon group of the active energy ray polymerizable group are not replaced with fluorine atoms, "a compound having an active energy ray polymerizable group at the terminal of the molecular chain including the poly (oxidized perfluoroalkylene) group" is referred to as "perfluoropolyether".

Background

In recent years, touch panels have been introduced into various devices such as portable information terminal devices such as mobile phones and tablet computers, notebook personal computers, home electric appliances, and interior and exterior articles of automobiles, and the surfaces of the touch panels of display elements such as liquid crystal displays and organic EL displays have been operated by finger or pen contact. When finger manipulation is assumed, the surface of the touch panel is required to have water repellency and oil repellency for facilitating removal of attached fingerprints, and further, abrasion resistance is required to maintain water repellency and oil repellency even by repeated rubbing with fingers. Further, in the case of operating the surface of the touch panel with a finger or a pen, the surface is required to have slidability from the viewpoint of the touch feeling of the finger or the pen. Further, the surface of the touch panel is required to have scratch resistance in order to prevent damage. In order to impart these characteristics to the surface of the touch panel, a surface coating such as a hard coating is provided.

Since the fluorine-containing compound exhibits high slidability and water and oil repellency, for example, a method of adding a small amount of a fluorine-based surface modifier to a coating liquid for forming a hard coat layer to prepare a composition is used as a material for forming a hard coat layer. The fluorine-based surface modifier is known to segregate on the surface of the hard coat layer due to the low surface energy of fluorine atoms.

In general, in order to impart scratch resistance and abrasion resistance to a hard coat layer, a method of improving the surface hardness of the hard coat layer by forming a high-density crosslinked structure to thereby provide resistance to external force is employed. As a material for forming such a hard coat layer, a multifunctional acrylate material which is three-dimensionally crosslinked by radicals generated by irradiation with active energy rays is currently used at most. In addition, a fluorine-based surface modifier added to a coating liquid for forming a hard coat layer is also generally used as a material having an active energy ray polymerizable group in order to impart scratch resistance and abrasion resistance to the hard coat layer (patent document 1). From the viewpoints of scratch resistance and abrasion resistance, a material having a low molecular weight capable of forming a high-density crosslinked structure and having a large number of active energy ray-polymerizable groups, so-called a material having a small acrylic equivalent weight, is preferable.

On the other hand, as described in patent document 2, since durability characteristics such as scratch resistance and abrasion resistance are required for the hard coat layer, for example, in the case of using a fluorine-based surface modifier having a crosslinkable group, immobilization of a molecular chain containing a fluorine atom occurs, and the sliding property of the hard coat layer is lowered. That is, it is difficult to achieve a high level of characteristics while the durability characteristics such as scratch resistance and abrasion resistance are in a trade-off relationship with the sliding properties.

In order to improve the trade-off relationship, there is a method of introducing a crosslinkable group only at one end of a molecular chain containing a fluorine atom in order to improve the mobility of the molecular chain containing a fluorine atom. However, the hard coat layer tends to have inferior durability characteristics, though the sliding property is superior to the method of introducing crosslinkable groups at both ends of the molecular chain containing fluorine atoms. In addition, when crosslinkable groups are introduced only at one end of a fluorine atom-containing molecular chain, steric hindrance to the fluorine atom-containing molecular chain is small as compared with the case where crosslinkable groups are introduced at both ends of the fluorine atom-containing molecular chain, and therefore the fluorine atom-containing molecular chain tends to aggregate easily, and when a coating liquid for forming a hard coat layer is prepared, the coating liquid tends to be cloudy.

From the viewpoints of slidability and water repellency, a substance having a high fluorine atom content is generally considered to be preferable, but there is a possibility that the fluorine-based surface modifier will aggregate in the coating liquid. When the fluorine-based surface modifier is aggregated in a coating liquid for forming a hard coat layer, molecular chains containing fluorine atoms do not segregate sufficiently on the surface of the hard coat layer when the hard coat layer is formed using the coating liquid, and the original sliding property and water repellency characteristics cannot be exhibited.

In order to improve the solubility of the fluorine-based surface modifier, a method of reducing the content of fluorine atoms in the fluorine-based surface modifier is considered, and as described above, it is considered that the slidability and water repellency of the hard coating layer are reduced, and it is difficult to satisfy the high characteristic level of slidability and water repellency.

As a method for improving the solubility of a fluorine-based surface modifier, patent document 3 reports the use of a fluorine-containing polyether which becomes a agglomerate when a hard coat agent composition is obtained and becomes a factor of clouding of the composition, and a fluorine-containing block copolymer excellent in compatibility with the composition.

Patent document 4 reports that a linear polymer having a fluorine content of 48 to 62 mass% and a linear polymer having a fluorine content of 25 to less than 45 mass% having a siloxane skeleton, in which a fluoropolyether is incorporated in the main chain, and an acrylic group is present at one or both ends of the molecular chain, and a fluoropolyether is present in the main chain, and that a linear polymer having a fluorine content of 48 to 62 mass% has improved solubility in a composition of the linear polymer, and excellent water repellency and sliding property. However, the abrasion resistance is described as "abrasion resistance represented by slidability" in paragraph 0006 of patent document 4, and the abrasion resistance is evaluated indirectly by slidability. Therefore, there is no specific example regarding scratch resistance, abrasion resistance.

Prior art literature

Patent literature

Patent document 1: international publication No. 2016/163479

Patent document 2: japanese patent No. 6497449

Patent document 3: japanese patent laid-open No. 2005-179613

Patent document 4: international publication No. 2020/170698

Disclosure of Invention

Problems to be solved by the invention

Patent document 3 describes that the fluorinated block copolymer described in the document has poor water repellency and lubricity compared to the fluorinated polyether, and therefore, the fluorinated block copolymer has a lower fluorine concentration than the fluorinated polyether, and it is easily conceivable that compatibility with the composition, slidability, and water repellency are difficult to be simultaneously achieved.

Patent document 4 describes the following results regarding slidability: in the above linear polymer having a fluorine content of 48 to 62 mass%, the slidability is the same in the case where the molecular chain has an acrylic group at one end and in the case where the molecular chain has an acrylic group at both ends. Therefore, it can be assumed that the sufficient level of characteristics with respect to the sliding property is not achieved.

In the present invention, there is a problem in that a homogeneous curable composition free from suspended matters and precipitates is provided which enables the formation of a hard coat layer having both of durability characteristics and sliding properties in a trade-off relationship at a high characteristic level. In addition, the hard coat layer is required to have high liquid repellency in addition to the actual use.

Solution for solving the problem

That is, the present invention is a curable composition comprising: (a) An active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) A perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (except for (c) perfluoropolyether described later); (c) A perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and (d) a polymerization initiator generating radicals by active energy rays.

A curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) 0.05 to 3 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, excluding the (c) perfluoropolyether described later; (c) 0.05 to 3 parts by mass of a perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and (d) 0.5 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.

A curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) 0.05 to 3 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (excluding (c) perfluoropolyether described later); (c) 0.05 to 3 parts by mass of a perfluoropolyether which is a reaction product of a raw material perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group; and (d) 0.5 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.

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

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

The fluorine atom content ratio of the perfluoropolyether (c) is 35 to 65 mass%.

The poly (oxidized perfluoroalkylene) groups of the (c) perfluoropolyether have repeating units- (CF) ₂ O) -and/or repeating units- (CF) ₂ CF ₂ O) -, in the case of having both repeating units, the poly (oxyperfluoroalkylene) group of the (c) perfluoropolyether is prepared by block bonding, random bonding, or both block bonding and random bonding of these repeating unitsAnd a bonded group.

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

(above formula [1]]In which m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 0 to 20. )

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

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

(in the above formula [2], m, n and q have the same meanings as defined in the above formula [1], 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 formula [ A2 ].

(above formula [ A1]]And [ A2]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [ 2]]The urethane bonds of the compounds shown are bonding bonds. )

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

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

(above formula [3]]In which r is a repeating unit- (CF) ₂ CF ₂ Number of O) -and s is the repeating unit- (CF) ₂ O) -number is 5-40, r and s are each independently integers of 0 or more, and when the two repeating units are present, the repeating units are bonded by block bonding, random bonding, or block bonding and random bonding. )

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

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

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

(above formula [ A1 ]]And [ A2 ]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [4 ]]The urethane bonds of the compounds shown are bonding bonds. )

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

A cured film obtained from the curable composition.

A hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer is composed of the cured film.

And a lower layer having a hard coat layer between the surface of the film base material and the hard coat layer, wherein the film base material is a resin film.

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

A method for producing a hard coat film, comprising: a step of forming a coating film by applying the curable composition to a film substrate; and a step of forming a hard coat layer by irradiating the coating film with an active energy ray to cure the coating film.

A method for producing a hard coat film, comprising: a step of forming a coating film by applying the curable composition to a film substrate; a step of removing the solvent from the coating film by heating; and a step of forming a hard coat layer by irradiating the coating film with an active energy ray to cure the coating film.

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

A surface modifying agent comprising: a perfluoropolyether (a) having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (excluding a perfluoropolyether (B) described later); and a perfluoropolyether (B) having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500.

A surface modifying agent comprising: a perfluoropolyether (a) having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (excluding a perfluoropolyether (B) described later); and a perfluoropolyether (B) which is a reaction product of a starting perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group.

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

The fluorine atom content of the perfluoropolyether (B) is 35 to 65 mass%.

The perfluoropolyether (a) has the active energy ray-polymerizable group at both ends of a molecular chain containing the poly (oxidized perfluoroalkylene) group.

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

(above formula [1]]And [3]]In which m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -number, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups, represents an integer of 0 to 20, r is a repeating unit- (CF) ₂ CF ₂ Number of O) -and s is the repeating unit- (CF) ₂ O) -number of 5.ltoreq.r+s.ltoreq.40, r and s each independently representing an integer of 0 or more, in a polyester resin having a repeating unit- (CF) ₂ CF ₂ O) -and repeating units- (CF) ₂ In the case of both O) -these repeating units are bonded by block bonding, random bonding, or both block bonding and random bonding. )

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

(in the above formulae [2] and [4], m, n and q have the same meanings as defined in the above formula [1], r and s have the same meanings as defined in the above formula [3], A represents a terminal group having the above active energy ray-polymerizable group, and this terminal group A is a group represented by the following formula [ A1] or formula [ A2 ])

(above formula [ A1]]And [ A2]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [2]]Or [4]]The urethane bonds of the compounds shown are bonding bonds. )

Effects of the invention

According to the present invention, a curable composition useful for forming a cured film and a hard coating layer which are excellent in both scratch resistance/abrasion resistance and excellent slidability even in a film having a thickness of 1 μm to 20 μm can be provided. Further, according to the present invention, a cured film obtained from the curable composition or a hard coating film having a hard coating layer composed of the cured film can be provided, and a hard coating film excellent in both durability characteristics such as scratch resistance and abrasion resistance and sliding properties in a trade-off relationship can be provided. The present invention can provide a curable composition useful for forming a cured film and a hard coating layer which have both the above characteristics and also have high water repellency, and a hard coating film having a hard coating layer excellent in these characteristics.

Detailed Description

Curable composition

The components of the curable composition of the present invention will be described below.

[ (a) active energy ray-curable multifunctional monomer having two or more (meth) acryloyl groups in one molecule ]

(a) The active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule of the component (hereinafter, also simply referred to as "(a) polyfunctional monomer") means a monomer that undergoes polymerization reaction and curing by irradiation of active energy rays such as ultraviolet rays.

In the curable composition of the present invention, (a) a polyfunctional monomer is preferably exemplified by: a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound, a monomer selected from the group consisting of a polyfunctional urethane (meth) acrylate compound described later, and a monomer selected from the group consisting of a lactone-modified polyfunctional (meth) acrylate compound. In the present invention, as the (a) polyfunctional monomer, one selected from the group consisting of the above polyfunctional (meth) acrylate compounds may be used alone, or two or more kinds may be used in combination. In the present invention, (meth) acrylate compounds include both acrylate compounds and methacrylate compounds, and for example, (meth) acrylic acid includes acrylic acid and methacrylic acid.

The (a) polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene modification include: oxymethylene modification, oxyethylene modification and oxypropylene modification. Examples of the oxyalkylene-modified polyfunctional monomer include those modified with an oxyalkylene group among the polyfunctional (meth) acrylate compounds and polyfunctional urethane (meth) acrylate compounds described above. The oxyalkylene-modified polyfunctional monomer may be used singly or in combination of two or more.

Further, in the present invention, as the preferable (a) polyfunctional monomer, polyfunctional monomers having at least three (meth) acryloyl groups in one molecule, for example, polyfunctional monomers having at least four (meth) acryloyl groups in one molecule, are exemplified. In the present invention, the (a) polyfunctional monomer includes a monomer selected from the group consisting of oxyalkylene-modified polyfunctional (meth) acrylate compounds having at least three (meth) acryloyl groups in one molecule.

Examples of the polyfunctional (meth) acrylate compound (among them, a compound having no urethane bond) include: trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) ) Acrylic acid esters, ethoxylated pentaerythritol tetra (meth) acrylic acid esters, ethoxylated dipentaerythritol hexa (meth) acrylic acid esters, ethoxylated glycerol tri (meth) acrylic acid esters, ethoxylated bisphenol A di (meth) acrylic acid esters, 1, 3-propanediol di (meth) acrylic acid esters, 1, 3-butanediol di (meth) acrylic acid esters, 1, 4-butanediol di (meth) acrylic acid esters, 1, 6-hexanediol di (meth) acrylic acid esters, 2-methyl-1, 8-octanediol di (meth) acrylic acid esters, 1, 9-nonanediol di (meth) acrylic acid esters, 1, 10-decanediol di (meth) acrylic acid esters, neopentyl glycol di (meth) acrylic acid esters, ethylene glycol di (meth) acrylic acid esters, diethylene glycol di (meth) acrylic acid esters, triethylene glycol di (meth) acrylic acid esters, tetraethylene glycol di (meth) acrylic acid esters, propylene glycol di (meth) acrylic acid esters, dipropylene glycol di (meth) acrylic acid esters, bis (2-hydroxyethyl) isocyanurate di (meth) acrylic acid esters, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic acid esters, tricyclo [ 5.2.1.0.0 ^2，6 ]Decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy propane, 2-hydroxy-1, 3-di (meth) acryloyloxy propane, 9-bis [4- (2- (meth) acryloyloxy) ethoxy) phenyl ]Fluorene, bis [4- (meth) acryloylthiophenyl ]]Thioether, bis [2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Among them, preferable polyfunctional (meth) acrylate compounds include: pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the oxyalkylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of a polyol modified with an oxyalkylene group. Examples of the polyol include: glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, di (trimethylol) propane, pentaerythritol and dipentaerythritol.

The above-mentioned polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryl groups or methacryl groups in one molecule and having one or more urethane bonds [ -NHC (=O) O- ], and may further have urea bonds [ -NHC (=O) NH- ]. Examples of the polyfunctional urethane (meth) acrylate compound include: the compound obtained by the reaction of the polyfunctional isocyanate and the (meth) acrylate having a hydroxyl group, and the compound obtained by the reaction of the polyfunctional isocyanate and the (meth) acrylate having a hydroxyl group and the polyol, but the polyfunctional urethane (meth) acrylate compound usable in the present invention is not limited to these examples.

Examples of the polyfunctional isocyanate include: toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. Examples of the (meth) acrylate having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. Examples of the polyol include: diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, etc.; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, adipic acid, etc.; polyether polyols; and (3) polycarbonate diol.

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

[ (b) perfluoropolyether having an active energy ray-polymerizable group at the end of a molecular chain comprising a poly (oxidized perfluoroalkylene) group and having a weight-average molecular weight of 1400 to 3500 ]

Hereinafter, the perfluoropolyether having an active energy ray polymerizable group at the terminal of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 is also referred to simply as "(b) perfluoropolyether". (b) Among the perfluoropolyethers, the perfluoropolyether (c) described later is excluded. In the curable composition of the present invention, the perfluoropolyether (b) preferably has an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group via a urethane bond. The terminal of the molecular chain containing the poly (oxidized perfluoroalkylene) group may be any of the entire terminal and a part of the terminal of the molecular chain. In the case where the molecular chain is linear, all ends and a part of the ends of the molecular chain are both ends and one end of the linear molecular chain, respectively. As the linking group between the poly (oxyperfluoroalkylene) group and the urethane bond, for example, a hydrocarbon group having an ether bond, at least one of hydrogen atoms of which is optionally substituted with a fluorine atom, may be cited. Furthermore, (b) perfluoropolyethers having no silicon atoms in their chemical structure are preferred.

(b) The perfluoropolyether functions as a surface modifier in the hard coat layer formed from the curable composition of the present invention, along with the component (c) described later. In addition, (b) the perfluoropolyether has excellent compatibility with the polyfunctional monomer (a), and therefore, cloudiness is suppressed, and a hard coat layer having a transparent appearance can be formed.

The poly (oxyperfluoroalkylene) group is preferably present in the cured film from the viewpoint of obtaining a cured film having excellent scratch resistance ₂ O]- (oxidized perfluoromethylene) and- [ CF ₂ CF ₂ O]Both of the (perfluoroethylene oxide) groups are repeating units. In this case, the bonding of these oxidized perfluoroalkylenes may be any of block bonding and random bonding.

(b) The perfluoropolyether is not limited to having one active energy ray polymerizable group at the terminal of the molecular chain containing the poly (oxidized perfluoroalkylene) group, and may have two or more active energy ray polymerizable groups. Examples of the active energy ray-polymerizable group include a (meth) acryloyl group and a vinyl group, and examples of the terminal group having the active energy ray-polymerizable group include a group represented by the formula [ A1] or the formula [ A2 ]. Of these terminal groups, those having two active energy ray-polymerizable groups and represented by the formula [ A2] are preferable.

From the viewpoint of obtaining a cured film having good scratch resistance, (b) the perfluoropolyether more preferably has active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group, and further preferably the number of the active energy ray polymerizable groups in one molecule is large. The number of the polymerizable groups is preferably two or more, more preferably three or more, at each end of the molecular chain containing the poly (oxidized perfluoroalkylene) group.

By (b) the perfluoropolyether having a weight average molecular weight of 1400 to 3500, a hard coat layer excellent in scratch resistance, abrasion resistance and sliding property can be obtained.

In the curable composition of the present invention, the content of the perfluoropolyether (b) is, for example, 0.05 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the polyfunctional monomer (a). The content of (b) perfluoropolyether is 0.05 parts by mass or more to impart sufficient scratch resistance to the hard coat layer, and the content of (b) perfluoropolyether is 3 parts by mass or less to be sufficiently compatible with (a) the polyfunctional monomer to give a hard coat layer with little cloudiness.

(b) The perfluoropolyether may be used singly or in combination of two or more. In the case of combining two or more kinds, the following perfluoropolyethers may be contained: the active energy ray-polymerizable group is provided at one end (one end) of a molecular chain containing a poly (oxidized perfluoroalkylene) group via a urethane bond, and a hydroxyl group is provided at the other end (the other end) of the molecular chain.

[ (c) perfluoropolyether having the active energy ray-polymerizable group only at one end of the molecular chain comprising a poly (oxidized perfluoroalkylene) group and having a weight-average molecular weight of 1550 to 3500 ]

Hereinafter, the perfluoropolyether having the active energy ray polymerizable group only at one end of the molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500 is also referred to simply as "(c) perfluoropolyether". (c) The perfluoropolyether is obtained, for example, by reacting a starting perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing the poly (oxidized perfluoroalkylene) group with a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group, and having a number average molecular weight of 1200 to 3000. Examples of the functional group that reacts with the hydroxyl group include: hydroxyl, carboxyl, and isocyanate groups.

"furthermore, the starting perfluoropolyether preferably has a fluorine atom-containing group at one end thereof on the opposite side of the hydroxyl group-containing one end, more preferably has a trifluoromethoxy group. The perfluoropolyether (c) having a group containing the fluorine atom at the end opposite to the end having the active energy ray-polymerizable group can be sufficiently transferred to the surface of the hard coat layer, and can exhibit excellent water repellency and slidability. "

(c) The perfluoropolyether is not limited to having one active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group, and may have two or more active energy ray polymerizable groups. Examples of the active energy ray-polymerizable group include a (meth) acryloyl group and a vinyl group, and examples of the terminal group having the active energy ray-polymerizable group include a group represented by the formula [ A1] or the formula [ A2 ]. Of these terminal groups, those having two active energy ray-polymerizable groups and represented by the formula [ A2] are preferable.

(c) The perfluoropolyether functions as a surface modifier in the hard coat layer formed from the curable composition of the present invention, along with the (b) perfluoropolyether. In addition, (c) the perfluoropolyether is excellent in compatibility with (b) the perfluoropolyether, so that cloudiness is suppressed and a hard coat layer having a transparent appearance can be formed. In addition, from the viewpoint of compatibility with (a) the polyfunctional monomer, (c) the perfluoropolyether preferably has a poly (oxyalkylene) group. As the poly (oxyalkylene) group, a poly (oxyethylene) group is preferable.

In the curable composition of the present invention, the perfluoropolyether (c) preferably has an active energy ray polymerizable group via a urethane bond at one end of a molecular chain containing only a poly (oxidized perfluoroalkylene) group. The poly (oxyperfluoroalkylene) group is preferably present in the cured film from the viewpoint of obtaining a cured film having excellent scratch resistance ₂ O]- (oxidized perfluoromethylene) and- [ CF ₂ CF ₂ O]Both of the (perfluoroethylene oxide) groups are repeating units. In this case, the bonding of these oxidized perfluoroalkylenes may be any of block bonding and random bonding.

(c) The fluorine atom content of the perfluoropolyether is, for example, 35% by mass or more and 65% by mass or less, preferably 40% by mass or more and 65% by mass or less, and more preferably 45% by mass or more and 65% by mass or less. When the fluorine atom content is 35 mass% or more, a hard coat layer excellent in water repellency and sliding properties can be obtained, and when it exceeds 65 mass%, there is a possibility that the hard coat layer is insufficiently compatible with the (a) polyfunctional monomer and cannot obtain sufficient characteristics.

(c) The perfluoropolyether has a weight average molecular weight of 1550 to 3500, preferably 1600 to 3500, more preferably 1700 to 3500. When the weight average molecular weight of the perfluoropolyether (c) is in the above range, the perfluoropolyether (c) tends 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 surface of the layer becomes sufficiently small, so that a hard coat layer excellent in sliding properties can be obtained. In addition, when the weight average molecular weight of the perfluoropolyether (c) is in the above range, a hard coat layer excellent in durability such as scratch resistance can be obtained by appropriately adjusting the hardness of the layer surface. That is, when the weight average molecular weight of the perfluoropolyether (c) is in the above range, both slidability and durability can be achieved.

In the curable composition of the present invention, the content of the (c) perfluoropolyether is, for example, 0.05 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.05 to 3 parts by mass with respect to 100 parts by mass of the (a) polyfunctional monomer. Since the content of the perfluoropolyether (c) is 0.05 parts by mass or more, and the perfluoropolyether (c) is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, a hard coat layer excellent in sliding properties can be obtained. In addition, the content of the perfluoropolyether (c) is 3 parts by mass or less, whereby the perfluoropolyether (b) is sufficiently compatible with the perfluoropolyether to give a hard coat layer with little cloudiness. The content of the perfluoropolyether (c) is, for example, 10 to 800 parts by mass, more preferably 10 to 500 parts by mass, and still more preferably 10 to 400 parts by mass, based on 100 parts by mass of the perfluoropolyether (b).

(c) The perfluoropolyether may be used singly or in combination of two or more.

[ (d) polymerization initiator ]

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

Examples of the polymerization initiator (d) include: benzoin, alkylbenzene, thioxanthone, azo, azide, diazonium, o-quinone diazide, acylphosphine oxide, oxime ester, organic peroxide, benzophenone, biscoumarin, bisimidazole, titanocene, thiol, halogenated hydrocarbon, trichloromethyl triazine, iodonium salt, sulfonium salt, and other onium salts. These polymerization initiators may be used singly or in combination of two or more. In the present invention, an alkylbenzene type is preferably used as the polymerization initiator (d) from the viewpoints of transparency, surface curability and film curability. By using the alkylbenzene, a cured film having further improved scratch resistance can be obtained.

Examples of the alkylbenzene ketones include: alpha-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one, and the like; α -aminoalkyl phenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl phenylglyoxylate.

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

[ (e) solvent ]

The curable composition of the present invention may contain (e) a solvent as an optional component, that is, may be in the form of a varnish. The solvent (e) may be appropriately selected in consideration of the solubility/dispersibility of the above-mentioned components (a) to (d), workability at the time of application of a curable composition related to formation of a cured film (hard coat layer) to be described later, drying property before and after curing, and the like.

Examples of the solvent (e) include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and o-dichlorobenzene; esters or ester ethers such as ethyl acetate, propyl acetate, butyl methoxyacetate, methyl cellosolve acetate, ethyl cellosolve acetate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA); ethers such as diethyl ether, tetrahydrofuran (THF), 1, 4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene Glycol Monoethyl Ether (PGME), propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO), and a solvent obtained by mixing two or more of these solvents.

In the curable composition of the present invention, the content of the solvent (e) is not particularly limited, and is, for example, a concentration of 1 to 70 mass%, preferably 5 to 50 mass% of the solid content of the curable composition of the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of the solid component (the portion from which the solvent component is removed from the entire components) of the curable composition of the present invention relative to the total mass (total mass) of the components (a) to (e) and other additives.

[ other additives ]

In the curable composition of the present invention, as long as the effect of the present invention is not impaired, a usual additive may be appropriately blended, for example, one of a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, or the like, alone or in combination of two or more of them may be appropriately blended as required.

< cured film >)

The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and the coating film is irradiated with an active energy ray to polymerize (cure) the coating film to form a cured film, which is also the object of the present invention. As the hard coat layer in the hard coat film described later, a hard coat layer composed of the cured film described above may be used.

Examples of the base material include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic Polyurethanes (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, cellulose Triacetate (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin), metals, wood, paper, glass, and slate (slate). The shape of these substrates may be plate-like, film-like or three-dimensional molded bodies. In addition, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, an antistatic layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and the like may be formed as an underlayer of a hard coat layer on the surface of the substrate, or a plurality of underlayer of the hard coat layer may be laminated. The layer formed on the surface of the substrate is not particularly limited as long as the effect of the present invention is not impaired.

The coating method on the substrate may be appropriately selected from a cast coating method (cast coat method), a spin coating method, a doctor blade method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, a printing method (a relief printing method, a gravure printing method, a lithographic printing method, a screen printing method, etc.), among which a relief printing method is preferably used from the viewpoint of availability of a roll-to-roll method, and a gravure coating method is particularly preferably used from the viewpoint of film coatability. The curable composition of the present invention is preferably applied by filtration using a filter having a pore diameter of about 0.2 μm or the like. In the case of coating, a solvent may be further added to the curable composition as needed. The solvent in this case includes various solvents listed in the above [ (e) solvent ].

After the curable composition of the present invention is applied to a substrate to form a coating film, the coating film is pre-dried by a heating unit such as a heating plate or an oven as necessary to remove the solvent (solvent removal step). The conditions for the heat drying at this time are preferably, for example, 40 to 120℃for about 30 seconds to 10 minutes. After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray include: ultraviolet rays, electron beams, and X-rays, ultraviolet rays being particularly preferred. As a light source for ultraviolet irradiation, for example, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. Further, the polymerization may be completed by post-baking, specifically, heating by a heating unit such as a heating plate or an oven.

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

< hard coating film >)

The curable composition of the present invention can be used to produce a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate. The hard coat film is also an object of the present invention, and is preferably used for protecting the surfaces of various display elements such as touch panels and liquid crystal displays, for example.

The hard coat layer in the hard coat film of the present invention can be formed by a method comprising: a step of forming a coating film by applying the curable composition of the present invention to a film substrate; a step of removing the solvent by heating as needed; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays. The method for producing a hard coat film comprising these steps and having a hard coat layer on at least one surface of a film base material is also an object of the present invention.

As the film base material, various transparent resin films which can be used for optical applications among the base materials listed in the above-mentioned < cured film > can be used. Preferable resin films include, for example: films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic Polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefin, polyamide, polyimide, and cellulose Triacetate (TAC).

The film base material may be formed by stacking a plurality of layers. For example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, an antistatic layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and other layers different from the resin film may be laminated on the surface of the resin film as an underlayer of the hard coat layer, or a plurality of layers of the underlayer of the hard coat layer may be laminated. The layer to be laminated on the surface of the resin film is not particularly limited as long as the effect of the present invention is not impaired.

The method for applying the curable composition of the present invention to the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) can be the methods listed in the above < cured film >. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film to remove the solvent may be included as necessary after the coating film forming step. In this case, a method of drying the coating film (solvent removal step) listed in the above-mentioned < 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 >)

The following surface modifying agents are also objects of the present invention, which comprise: a perfluoropolyether (a) having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (excluding a perfluoropolyether (B) described later); and a perfluoropolyether (B) having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500.

Also, a surface modifier comprising: a perfluoropolyether (a) having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500 (excluding a perfluoropolyether (B) described later); and a perfluoropolyether (B) which is a reaction product of a starting perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group.

The "perfluoropolyether (a)" is the same as the (B) perfluoropolyether, and the "perfluoropolyether (B)" is the same as the (c) perfluoropolyether.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples. In the examples, the apparatus and conditions for preparing the sample and analyzing the physical properties are as follows.

(1) Coating with bar coater

The device comprises: PM-9050MC manufactured by SMT.

Rod: OSG SYSTEM PRODUCTS A-Bar OSP-15, manufactured by Kagaku Kogyo Co., ltd.) had a maximum wet film thickness of 15 μm (film thickness after drying was 3 μm).

Coating speed: 4 m/min.

(2) Film thickness measurement

The device comprises: f20 film thickness measuring system manufactured by Filmetrics Inc.

(3) Baking oven

The device comprises: a double-layer clean oven (upper and lower formula) PO-250-45-D manufactured by Sanji instruments (Co., ltd.).

(4) UV curing

The device comprises: CV-110QC-G manufactured by Heraeus Co.

A lamp: electrodeless lamp H-bulb manufactured by Heraeus Co.

(5) Scratch resistance test and abrasion resistance test

The device comprises: TRIBOGEAR TYPE, a reciprocating abrasion tester manufactured by New east science Co., ltd.): 30S.

Scanning speed: 3200 mm/min.

Scanning distance: 50mm.

(6) Contact angle measurement

The device comprises: dropMaster DM-501, available from Kyowa interface science, inc.

Measuring temperature: 23 ℃.

(7) Dynamic coefficient of friction measurement

The device comprises: load-variable friction abrasion test system TRIBOGEAR (registered trademark) TYPE, manufactured by New DONG scientific Co., ltd.): HHS2000.

And (3) probe: 0.6mmR sapphire needle.

Load: 200g.

Scanning speed: 2 mm/s.

Scanning distance: 10mm.

(8) Total light transmittance, haze measurement

The device comprises: haze meter NDH5000 manufactured by japan electrochromic industry co.

(9) Weight average molecular weight determination

Gel Permeation Chromatography (GPC).

The device comprises: HLC-8420GPC manufactured by Tosoh Co., ltd.

Chromatographic column: TSKgelG2000HXL, TSKgelG3000HXL manufactured by Tosoh corporation.

Measuring temperature: 40 ℃.

Eluent: tetrahydrofuran.

And (3) detection: RI.

(10) Combustion ion chromatography

Automatic sample combustion device system: AQF-2100H was manufactured by Nitto Seiko analytical technique (Mitsubishi chemical analytical technique, original Co.).

Ion chromatograph: thermoFisher Scientific Dionex Interon, inc.

Sample: 2mg.

Absorption liquid: 2.7mM sodium carbonate+0.3 mM sodium bicarbonate aqueous solution.

Eluent: 2.7mM sodium carbonate+0.3 mM sodium bicarbonate aqueous solution.

Chromatographic column: thermoFisher Scientific AG-12A/AS-12A.

Flow rate: 1.5 mL/min.

A detector: conductivity (using suppressors).

Standard sample: fluoride ion standard solution (F-1000) Fuji film and Wako pure chemical industries, ltd.

When the solvent in the sample does not contain a fluorine atom-containing solvent, the fluorine concentration is measured while the solvent is contained, and the fluorine concentration in the solute is calculated from the solid content concentration. When the solvent containing fluorine atoms is contained in the solvent in the sample, the solvent in the sample is volatilized at 120 ℃ for 20 minutes using a halogen moisture meter, and the fluorine concentration is measured using the sample which is judged to have a constant mass change and in which all the solvent is volatilized.

Further, the shorthand notation indicates the following meanings.

Multifunctional acrylate PA1: dipentaerythritol pentaacrylate/hexaacrylate mixture [ ARONIX (registered trademark) M-403, manufactured by Toyama Synthesis Co., ltd ].

Multifunctional acrylate PA2: an oxyethylene modified multifunctional acrylate [ New front (registered trademark) MF-001 manufactured by first industry Co., ltd.).

Multifunctional acrylate PA3: multifunctional urethane acrylate [ ART RESIN (registered trademark) UN-3320HS, manufactured by Kogyo Co., ltd.).

Multifunctional acrylate PA4: pentaerythritol triacrylate/pentaerythritol tetraacrylate [ PET30 manufactured by Japanese chemical Co., ltd ].

PFPE1: perfluoropolyethers having two hydroxyl groups at both ends thereof without a poly (oxyalkylene) group, respectively [ Solvay Specialty Polymers company Fomblin (registered trademark) T4, having the following structure, are based on ¹⁹ F-NMR ¹ Number average molecular weight 2200 calculated from analysis results of H-NMR]。

(in the above formula, r is a repeating unit- (CF) ₂ CF ₂ Number of O) -and s is the repeating unit- (CF) ₂ O) -amount, satisfying 5.ltoreq.r+s.ltoreq.40, r and s each independently represent an integer of 0 or more. )

PFPE2: the perfluoropolyether having one hydroxyl group at only one end and not via a poly (oxyalkylene) group (7324X, manufactured by Solvay Specialty Polymers Co., ltd.) having the following structure is based on ¹⁹ F-NMR ¹ Number average molecular weight 1750 to 1950 calculated from analysis result of H-NMR]。

(in the above formula, m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more. )

PFPE3: the perfluoropolyether having one hydroxyl group at only one end via a poly (oxyethylene) group, having the following structure [ Fomblin (registered trademark) 4102X, manufactured by Solvay Specialty Polymers Co., ltd., based on ¹⁹ F-NMR ¹ Number average molecular weight 1900 calculated from the analysis result of H-NMR ]。

(in the above formula, m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 2 to 20. )

PFPE4: a perfluoropolyether having one hydroxyl group at only one end thereof without a poly (oxyalkylene) group, FO2 made by the company Apollo Scientific, having the following structure, having a molecular weight of 978.15.

PFPE5: a perfluoropolyether having one hydroxyl group at only one end thereof without passing through a poly (oxyalkylene) group (1H, 1H-perfluoro-3, 6, 9-trioxatridecan-1-ol) [ C10GOL, manufactured by the company Exfluor Research, molecular weight 548.1].

PFPE6: perfluoropolyethers having one hydroxyl group at each end thereof without a poly (oxyalkylene) group (Fomblin (registered trademark) manufactured by the company Solvay Specialty Polymers) D2 having the following structure ¹⁹ F-NMR ¹ Number average molecular weight 1550 calculated from analysis result of H-NMR]。

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

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

SMA6: perfluoropolyether having an active energy ray polymerizable group at the terminal of the molecular chain containing a poly (oxidized perfluoroalkylene) group [ OPTOOL (registered trademark) DAC-HP, manufactured by DAIKIN Co., ltd.), a nonvolatile matter 20 mass% solution, weight average molecular weight measured in terms of polystyrene based on GPC: mw is 1521, dispersity: mw/Mn was 1.1 (Mn is a number average molecular weight), and the fluorine atom content in the perfluoropolyether compound calculated by combustion ion chromatography was 35 mass%.

SMA7: perfluoropolyethers having a total of four active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group [ Fluorolink (registered trademark) AD-1700, manufactured by Solvay Specialty Polymers company), a nonvolatile 70 mass% solution, weight average molecular weight measured in terms of polystyrene based on GPC: mw is 3973, dispersity: mw/Mn was 2.1, and the fluorine atom content in the perfluoropolyether compound was 29 mass% as calculated by combustion ion chromatography.

DOTDD: dioctyltin di neodecanoate [ NEOSTANN (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 Co., ltd.).

AN1: an aqueous dispersion of PEDOT-PSS [ 3.0 to 4.0 mass% of an aqueous dispersion of PEDOT-PSS manufactured by Sigma-Aldrich Co., ltd., high conductivity grade, product No. 655201].

PREPARATION EXAMPLE 1 preparation of the component SMA1 of the surface modifier

Into the screw tube, 1.19g (0.5 mmol) of PFPE, 0.52g (2.0 mmol) of N, 0.017g of DOTDD (0.01 times the total mass of PFPE1 and N1) and PGMEA1.67g were charged. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 1. Weight average molecular weight of SMA1 obtained, measured in terms of polystyrene based on GPC: mw of 2494, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA1 calculated by combustion ion chromatography was 42 mass%.

PREPARATION EXAMPLE 2 preparation of SMA2 as a component of the surface modifier

Into the screw tube were charged 2.20g (1.2 mmol) of PFPE, 0.28g (1.2 mmol) of N, 0.025g (0.01 times the total mass of PFPE2 and N1) of DOTDD, and 0.6g of MEK. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to give an 80 mass% MEK solution of the target perfluoropolyether compound SMA 2. Weight average molecular weight of the obtained SMA2 as measured in terms of polystyrene based on GPC: mw is 1710, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA2 calculated by combustion ion chromatography was 63 mass%.

PREPARATION EXAMPLE 3 preparation of SMA3 as a component of the surface modifier

Into the screw tube were charged 3.08g (1.6 mmol) of PFPE, 0.39g (1.6 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE3 and N1) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 3. Weight average molecular weight of SMA3 obtained, measured in terms of polystyrene based on GPC: mw of 1908, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA3 calculated by combustion ion chromatography was 47 mass%.

PREPARATION EXAMPLE 4 preparation of SMA4 as a component of the surface modifier

Into the screw tube were charged 2.78g (2.9 mmol) of PFPE4, 0.68g (2.9 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE4 and N1) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 4. Weight average molecular weight of SMA4 obtained, measured in terms of polystyrene based on GPC: mw of 1299, dispersity: mw/Mn was 1.0. The content of fluorine atoms in SMA4 calculated by combustion ion chromatography was 51 mass%, and a value equivalent to the content of fluorine atoms of 51 mass% calculated theoretically from the structure of SMA4 was shown.

PREPARATION EXAMPLE 5 preparation of the component SMA5 of the surface modifier

Into the screw tube were charged 2.41g (4.4 mmol) of PFPE5, 1.05g (4.4 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE5 and N1) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 5. Weight average molecular weight of the obtained SMA5 as measured in terms of polystyrene based on GPC: mw was 1029, dispersity: mw/Mn was 1.0. The content of fluorine atoms in SMA5 calculated by combustion ion chromatography was 46 mass%, and a value equivalent to 47 mass% of the content of fluorine atoms calculated theoretically from the structure of SMA5 was shown.

PREPARATION EXAMPLE 6 preparation of SMA8 As a component of the surface modifier

A screw tube was charged with 3.66g (2.4 mmol) of PFPE6, 0.67g (4.8 mmol) of N2, 0.054g (0.01 times the total mass of PFPE6 and N2) of DOTDD, and 4.4g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 8. Weight average molecular weight of the obtained SMA8 as measured in terms of polystyrene based on GPC: mw of 1609, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA8 calculated by combustion ion chromatography was 54 mass%.

Examples 1 to 9 and comparative examples 1 to 13

The components shown in table 1 were mixed to prepare curable compositions having the solid content concentrations shown in table 1. Herein, the solid component means a component other than a solvent. In table 1, [ parts ] means [ parts by mass ], [% ] means [ percent by mass ]. The polyfunctional acrylate and the surface modifier in table 1 each represent a solid component.

TABLE 1

A4-size PET film having a primer layer formed by subjecting both sides to an easy-to-adhere treatment by a bar coater [ Lumirror (registered trademark) U403 (known as U40, available from Toray Co., ltd.) had a thickness of 100. Mu.m]These curable compositions were applied thereon to obtain a coating film. The film was dried in an oven at 60℃for 8 minutes, and the solvent was removed. The film obtained was irradiated with a radiation exposure of 300mJ/cm under a nitrogen atmosphere ² By exposing to UV light, a hard coat film having a hard coat layer (cured film) is produced.

Examples 10 to 11 and comparative examples 14 to 15

The components shown in table 2 were mixed to prepare curable compositions having the solid content concentrations shown in table 2. Herein, the solid component means a component other than a solvent. In table 2, [ parts ] means [ parts by mass ], [% ] means [ percent by mass ]. The polyfunctional acrylate and the surface modifier in table 2 each represent a solid component.

TABLE 2

A4-size PET film having a primer layer formed by subjecting both sides to an easy-to-adhere treatment by a bar coater [ Lumirror (registered trademark) U403 (known as U40, available from Toray Co., ltd.) had a thickness of 100. Mu.m]These curable compositions were applied thereon to obtain a coating film. The film was dried in an oven at 65℃for 3 minutes, and the solvent was removed. The film obtained was irradiated with a radiation exposure of 300mJ/cm under a nitrogen atmosphere ² Is exposed to UV light to thereby produce a cured film having a hard coat layerA hard coat film.

The uniformity of each curable composition, and the scratch resistance, water repellency, abrasion resistance, sliding property, and haze of the obtained hard coating film were evaluated. The procedure of evaluation is shown below. The results are shown in tables 3 and 4.

[ homogeneity of composition ]

The appearance of each of the prepared curable compositions was visually confirmed, and evaluated according to the following criteria.

A: clear solution (no suspended matter, precipitate and phase separation).

C: there are any of suspended matter, precipitate, and phase separation.

[ scratch resistance ]

The hard coat surface of the obtained hard coat film was repeatedly rubbed 5000 times with a load of 1kg applied to steel wool [ BONSTAR (registered trademark) #0000 (ultra fine) ] mounted on a reciprocating abrasion tester at a stroke (stroke) of 50 mm. Then, the degree of the scratch in the region other than the 5mm width range at both ends of the stroke of 50mm was visually checked, and the scratch was checked on the hard coat surface by a microscope (KEYENCE corporation), and evaluated according to the following criteria A, B and C. In addition, when the hard coat layer is practically used, at least B, preferably a, is required.

A: no flaw (flaw 0 pieces).

B: the flaws (1 to 4 flaws of 1 to 9mm in length) were generated.

C: generating flaws (more than 5 flaws with the length of 1mm to 9mm or more than 1 flaw with the length of more than 1 cm).

[ Water repellency ]

The contact angle θ was measured five times after 5 seconds by allowing 1 μl of water to adhere to the hard coat layer surface, and the average value was evaluated according to the following criteria. Note that a is desirable when it is assumed that the composition is actually used as a hard coat layer. In addition, since the contact angle was measured immediately after water was allowed to adhere, the value was high and unstable, and in this measurement, the contact angle was measured after 5 seconds from the time of water adhesion.

A：θ＞105°。

B：100°≤θ≤105°。

C：θ＜100°。

[ abrasion resistance ]

The hard coat surface was reciprocally wiped 2500 times with a cylindrical eraser [ RUBBER STICK, phi 6.0mm ] mounted on a reciprocal abrasion tester, applied with a load of 1 kg. The wiped portion was allowed to adhere with 1 μl of water, and the contact angle θ was measured at five places for 5 seconds, and the average value was evaluated as a contact angle value according to the following criteria. In addition, when the hard coat layer is practically used, it is required to be at least B, and preferably a.

A：θ≥90°。

B：85°≤θ＜90°。

C：85°＜θ。

[ sliding Property ]

The coefficient of dynamic friction at five points on the hard coat surface was measured and evaluated based on the average value thereof. The smaller the coefficient of dynamic friction value is, the smaller the friction with the probe is, which is a criterion for slidability. The smaller the coefficient of dynamic friction value, the better the slidability upon contact, and therefore the smaller the coefficient of dynamic friction value, the more preferable.

[ haze ]

As a reference value, haze at three places of the hard coat surface was measured, and an average value thereof was calculated. The haze of the PET film [ LumirrorU 403 (registered trademark) manufactured by Toray Co., ltd.) (sometimes referred to as U40) used herein was 1.6 as a base material, and the thickness was 100. Mu.m.

TABLE 3

TABLE 4

As shown in table 1, the curable compositions of examples 1 to 8 include multifunctional acrylates PA1 to PA4 and the following: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further includes: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with a perfluoropolyether compound PFPE2 or PFPE3 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1750 to 1950, to obtain SMA2 or SMA3 having a weight average molecular weight of 1710 or a weight average molecular weight of 1908. As shown in table 3, the curable compositions of examples 1 to 8 showed excellent homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition showed excellent sliding properties, abrasion resistance, water repellency, and abrasion resistance.

As shown in table 1, the curable composition of example 9 includes a multifunctional acrylate PA1, the following: the perfluoropolyether SMA6 having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 1521, and a fluorine atom content of 35 mass%, further comprises: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA2 having a weight average molecular weight of 1710, which is obtained by reacting a perfluoropolyether compound PFPE2 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1750 to 1950. As shown in table 3, the curable composition of example 9 showed excellent homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition showed excellent slidability, water repellency, and abrasion resistance. The hard coat film having the hard coat layer obtained from the curable composition of example 9 was slightly inferior to the hard coat film having the hard coat layer obtained from the curable compositions of examples 1 to 8 in terms of scratch resistance, but 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 contains a multifunctional acrylate PA1 and the following substances: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further includes: an SMA4 having a weight average molecular weight 1299 and a fluorine atom content of 51 mass% obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE4 having a molecular weight 978.15 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 1 showed excellent homogeneity, but the hard coating film having the hard coating layer obtained from the curable composition showed inferior sliding properties and abrasion resistance as compared with the hard coating film obtained from the curable compositions of examples 1 to 9. From this result, it was shown that even if a perfluoropolyether having an active energy ray polymerizable group only at one end of a molecular chain containing a (oxidized perfluoroalkylene) group in a high proportion of fluorine atoms was used, the slidability and scratch resistance were poor, and that the size of the weight average molecular weight of the perfluoropolyether was important for slidability and scratch resistance.

Further, as shown in table 1, the curable composition of comparative example 2 contains a multifunctional acrylate PA1 and the following substances: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further includes: an SMA5 having a weight average molecular weight of 1029 and a fluorine atom content of 47 mass% which is obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE5 having a molecular weight of 548.10 having only one hydroxyl group at one end of a molecular chain including a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 2 showed excellent homogeneity, but the hard coat film having the hard coat layer obtained from the curable composition showed poor sliding properties, abrasion resistance and abrasion resistance. From this result, it was also shown that even if a perfluoropolyether having an active energy ray polymerizable group only at one end of a molecular chain containing a (oxidized perfluoroalkylene) group in a high proportion of fluorine atoms was used, the slidability, scratch resistance and abrasion resistance were not necessarily excellent, and that the size of the weight average molecular weight of the perfluoropolyether was important for slidability, scratch resistance and abrasion resistance.

Further, as shown in table 1, the curable compositions of comparative examples 3 to 4 include a multifunctional acrylate PA1 and the following: the SMA4 having a weight average molecular weight 1299 or SMA5 having a weight average molecular weight 1029 obtained by reacting the isocyanate compound N1 having the active energy ray polymerizable group with the perfluoropolyether compound PFPE4 having a molecular weight 978.15 or the perfluoropolyether compound PFPE5 having a molecular weight 548.10, each having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group, further comprises: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA2 having a weight average molecular weight 1710, which is obtained by reacting a perfluoropolyether compound PFPE2 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight 1750 to 1950. As shown in table 3, the curable compositions of comparative examples 3 to 4 were poor in homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition showed poor slidability, scratch resistance and abrasion resistance. This is considered to be because SMA4 and SMA5 have small weight average molecular weights, and therefore cannot break the aggregation structure of SMA2, and cannot assist the solubility of SMA2 in the coating liquid. Therefore, it is considered that SMA2 is aggregated in the coating liquid, and SMA2 is not sufficiently segregated on the surface of the hard coat layer, so that slidability, scratch resistance, and abrasion resistance are poor.

Further, as shown in table 1, the curable composition of comparative example 5 includes a multifunctional acrylate PA1 and the following: the perfluoropolyether SMA7 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 3973, and a fluorine atom content of 29 mass%, further includes: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA2 having a weight average molecular weight 1710, which is obtained by reacting a perfluoropolyether compound PFPE2 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight 1750 to 1950. As shown in table 3, the curable composition of comparative example 5 showed excellent homogeneity and excellent slidability, but the hard coat film having the hard coat layer obtained from the curable composition showed poor abrasion resistance and abrasion resistance. From this result, it was found that good sliding properties were not necessarily well correlated with scratch resistance and abrasion resistance. The reason why the hard coat film having the hard coat layer obtained from the curable composition of comparative example 5 had inferior scratch resistance and abrasion resistance to the hard coat film having the hard coat layer obtained from the curable compositions of examples 1 to 9 is considered to be that SMA7 had a larger weight average molecular weight than SMA1 and SMA6 and had a lower immobilization ability in the film. This is considered to be because the content ratio of fluorine atoms in SMA7 is smaller than that in SMA1 and SMA6, and SMA2 is inferior in compatibility with SMA7, and SMA2 and SMA7 are in a state of being separated from each other on the hard coat surface.

Further, as shown in table 1, the curable composition of comparative example 6 contains a multifunctional acrylate PA1 and the following substances: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA2 having a weight average molecular weight 1710, which is obtained by reacting a perfluoropolyether compound PFPE2 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight 1750 to 1950. As shown in table 3, the curable composition of comparative example 6 was inferior in uniformity to the curable composition of example 1 obtained by adding SMA1 to the curable composition of comparative example 6, and the hard coat film having the hard coat layer obtained from the curable composition of comparative example 6 showed the results of inferior slidability, scratch resistance, water repellency, and abrasion resistance as compared with the hard coat film having the hard coat layer obtained from the curable composition of example 1. This is considered to be because the perfluoropolyether having an active energy ray polymerizable group at the end of the molecular chain containing a poly (oxidized perfluoroalkylene) group and a weight average molecular weight of 1400 to 3500 is not contained and functions as a solubility auxiliary for SMA2, and thus SMA2 is coagulated in the coating liquid.

Further, as shown in table 1, the curable composition of comparative example 7 includes a multifunctional acrylate PA1 and the following substances: an SMA3 having a weight average molecular weight of 1908, which is obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE3 having a number average molecular weight of 1900 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 7 was excellent in homogeneity, but the hard coating film having the hard coating layer obtained from the curable composition showed poor abrasion resistance and water repellency as compared with the hard coating film having the hard coating layer obtained from the curable compositions of examples 2 to 4 in which SMA1 was added to the curable composition of comparative example 7. This is considered to be because SMA3 alone has a strong cohesive force and is likely to aggregate inside the film, and SMA3 cannot be sufficiently segregated on the surface of the hard coat layer, but SMA3 has an active energy ray polymerizable group only at one end, so that the immobilization ability in the film is low.

Further, as shown in table 1, the curable composition of comparative example 8 contains a multifunctional acrylate PA1 and the following substances: an SMA4 having a weight average molecular weight 1299 obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE4 having a molecular weight 978.15 having one hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 8 was inferior in uniformity to the curable composition of comparative example 1 obtained by adding SMA1 to the curable composition of comparative example 8, and the hard coat film of the hard coat layer obtained from the curable composition of comparative example 8 exhibited poor sliding properties, abrasion resistance, and abrasion resistance. This is considered to be because SMA4 is aggregated in the film, SMA4 is not sufficiently segregated on the surface of the hard coat layer, and in addition, the molecular chain of SMA4 including a poly (oxidized perfluoroalkylene) group is short.

Further, as shown in table 1, the curable composition of comparative example 9 contains a multifunctional acrylate PA1 and the following substances: an SMA5 having a weight average molecular weight of 1029, which is obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE5 having a molecular weight of 548.1 having one hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 9 was excellent in homogeneity, but the hard coating film comprising the hard coating layer obtained from the curable composition had a short molecular chain containing a poly (oxyperfluoroalkylene) group, and therefore showed poor sliding properties, water repellency, scratch resistance, and abrasion resistance.

As shown in table 1, the curable composition of comparative example 10 includes a polyfunctional acrylate PA1 and the following substances: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%. As shown in table 3, the curable composition of comparative example 10 was excellent in homogeneity, and the hard coating film having the hard coating layer obtained from the curable composition was excellent in water repellency, scratch resistance, and abrasion resistance, but the hard coating film having the hard coating layer obtained from the curable composition of example 1 in which SMA2 was added to the curable composition of comparative example 10 showed a poor sliding property because SMA2 was not included. This is considered to be because SMA1 has eight acryl groups in one molecule, and thus has high immobilization ability in a film, and thus is excellent in scratch resistance and abrasion resistance, but on the other hand, SMA1 has low molecular mobility and poor sliding property due to high immobilization ability.

When judged from the evaluation results of the hard coat film having the hard coat layer obtained from the curable compositions of comparative examples 5 and 10 shown in table 3, it was suggested that the sliding property and the scratch resistance were in a trade-off relationship.

Further, as shown in table 1, the curable composition of comparative example 12 contains a multifunctional acrylate PA1 and the following substances: the perfluoropolyether SMA7 having active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 3973, and a fluorine atom content of 29 mass%. As shown in table 3, although the curable composition of comparative example 12 was excellent in homogeneity, the hard coat film having the hard coat layer obtained from the curable composition showed a poor sliding property as compared with the hard coat film having the hard coat layer obtained from the curable composition of comparative example 5 in which SMA2 was added to the curable composition of comparative example 12, since SMA2 was not included. From these results, it was suggested that the hard coat film obtained from the curable composition containing the perfluoropolyether having an active energy ray polymerizable group only at one end of the molecular chain containing a poly (oxidized perfluoroalkylene) group as a surface modifier was superior in slipperiness as compared with the hard coat film obtained from the curable composition containing the perfluoropolyether having an active energy ray polymerizable group only at both ends of the molecular chain containing a poly (oxidized perfluoroalkylene) group as a surface modifier.

Further, as shown in table 1, the curable composition of comparative example 13 contains a multifunctional acrylate PA1 and the following substances: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further includes: an SMA8 having a weight average molecular weight of 1609 and a fluorine atom content of 54 mass% obtained by reacting an isocyanate compound N1 having the active energy ray polymerizable group with a perfluoropolyether compound PFPE6 having a number average molecular weight of 1550 each having one hydroxyl group at each end of a molecular chain including a poly (oxidized perfluoroalkylene) group. As shown in table 3, the curable composition of comparative example 13 showed excellent homogeneity, and the hard coating film having the hard coating layer obtained from the curable composition showed excellent water repellency and abrasion resistance, but the hard coating film having the hard coating layer obtained from the curable compositions of examples 1 to 9 showed inferior sliding properties and abrasion resistance. From the results, it was shown that the hard coat film obtained from the curable composition containing the perfluoropolyether having an active energy ray polymerizable group only at one end of the molecular chain containing a poly (oxidized perfluoroalkylene) group as a surface modifier was excellent in slipperiness as compared with the hard coat film obtained from the curable composition containing the perfluoropolyether having an active energy ray polymerizable group only at both ends of the molecular chain containing a poly (oxidized perfluoroalkylene) group as a surface modifier.

As shown in table 2, the curable compositions of examples 10 to 11 include the multifunctional acrylate PA1 or PA2 and the following: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain including a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further includes: AN isocyanate compound N1 having the active energy ray-polymerizable group is reacted with a perfluoropolyether compound PFPE3 having a number average molecular weight 1900 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group to obtain SMA3 having a weight average molecular weight 1908, and AN antistatic agent AN1 is contained. As shown in table 4, the curable compositions of examples 10 to 11 showed excellent homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition showed excellent sliding properties, abrasion resistance, water repellency, and abrasion resistance.

On the other hand, as shown in table 2, the curable composition of comparative example 14 contains a multifunctional acrylate PA1 and the following substances: the perfluoropolyether SMA1 having active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group, a weight average molecular weight of 2494, and a fluorine atom content of 42 mass%, further contains AN antistatic agent AN1. As shown in table 4, the curable composition of comparative example 14 was excellent in homogeneity, and the hard coating film having the hard coating layer obtained from the curable composition was excellent in water repellency, scratch resistance, and abrasion resistance, but the hard coating film having the hard coating layer obtained from the curable composition of example 10 in which SMA3 was added to the curable composition of comparative example 14 showed a poor sliding property because SMA3 was not included. This is considered to be because SMA1 has eight acryl groups in one molecule, and thus has high immobilization ability in a film, and thus is excellent in scratch resistance and abrasion resistance, but has low molecular mobility and poor sliding property.

Further, as shown in table 2, the curable composition of comparative example 15 contains a multifunctional acrylate PA1 and the following substances: the 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 having only one hydroxyl group at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group further contains AN antistatic agent AN1. As shown in table 4, although the curable composition of comparative example 15 was excellent in homogeneity, the hard coating film having the hard coating layer obtained from the curable composition showed excellent sliding properties as compared with the hard coating film having the hard coating layer obtained from the curable composition of example 10 in which SMA1 was added to the curable composition of comparative example 15, but on the other hand showed poor scratch resistance. This is thought to be because the immobilization ability in the film becomes low due to the separate use of SMA3 having active energy ray polymerizable groups only at one end.

Claims

1. A curable composition comprising:

(a) An active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule;

(b) A perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, wherein (c) the perfluoropolyether described later is excluded;

(c) A perfluoropolyether having the active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500; and

(d) Polymerization initiators which generate radicals by active energy rays.

2. A curable composition comprising:

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

(b) 0.05 to 3 parts by mass of a perfluoropolyether having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, with the exception of (c) a perfluoropolyether described later;

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

(d) And 0.5 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.

3. A curable composition comprising:

(c) 0.05 to 3 parts by mass of a perfluoropolyether which is a reaction product of a raw material perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group; and

4. The curable composition according to claim 3, wherein,

5. The curable composition according to any one of claim 1 to 4, wherein,

6. The curable composition according to any one of claims 1 to 5, wherein,

7. The curable composition according to any one of claims 1 to 6, wherein,

the poly (oxidized perfluoroalkylene) groups of the (c) perfluoropolyether have repeating units- (CF) ₂ O) -and/or repeating units- (CF) ₂ CF ₂ O) -, in the case of having both repeating units, the poly (oxidized perfluoroalkylene) group of the perfluoropolyether of (c) is a group in which these repeating units are bonded by block bonding, random bonding, or both block bonding and random bonding.

8. The curable composition according to claim 7, wherein,

the molecular chain of the perfluoropolyether (c) comprising a poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1],

the said [1]]In which m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 0 to 20.

9. The curable composition according to claim 8, wherein,

10. The curable composition according to claim 8 or 9, wherein,

the perfluoropolyether (c) is a compound represented by the following formula (2),

in the formula [2], m, n and q have the same meanings as defined in the formula [1], and A represents a terminal group having the active energy ray-polymerizable group.

11. The curable composition according to claim 10, wherein,

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

the [ A1]]And [ A2]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [2]]The urethane bonds of the compounds shown are bonding bonds.

12. The curable composition according to any one of claim 1 to 11, wherein,

13. The curable composition according to any one of claim 1 to 12, wherein,

the molecular chain of the perfluoropolyether (b) comprising a poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [3],

The above-mentioned [3]]In which r is a repeating unit- (CF) ₂ CF ₂ Number of O) -and s is a repeat unitMeta- (CF) ₂ O) -number is 5-40, r and s are each independently integers of 0 or more, and when the two repeating units are present, the repeating units are bonded by block bonding, random bonding, or block bonding and random bonding.

14. The curable composition according to claim 13, wherein,

15. The curable composition according to claim 13 or 14, wherein,

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

in the formula [4], r and s have the same meanings as defined in the formula [3], and A represents a terminal group having the active energy ray-polymerizable group.

16. The curable composition according to claim 15, wherein,

the [ A1]]And [ A2]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [4]]The urethane bonds of the compounds shown are bonding bonds.

17. The curable composition according to any one of claims 1 to 16, wherein,

The curable composition further comprises (e) a solvent.

18. A cured film obtained from the curable composition according to any one of claims 1 to 17.

19. A hard coat film comprising a hard coat layer comprising the cured film according to claim 18 on at least one surface of a film substrate.

20. The hard coat film according to claim 19, wherein,

21. The hard coat film according to claim 19 or 20, wherein,

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

22. A method for producing a hard coat film, comprising:

a step of forming a coating film by applying the curable composition according to any one of claims 1 to 17 to a film substrate; and

and a step of forming a hard coat layer by curing the coating film by irradiation with an active energy ray.

23. A method for producing a hard coat film, comprising:

a step of forming a coating film by applying the curable composition according to claim 17 to a film substrate;

a step of removing the solvent from the coating film by heating; and

24. The method for producing a hard coat film according to claim 22 or 23, wherein,

the method for producing a hard coat film further comprises: and forming a lower layer of a hard coat layer on the surface of the film base material, wherein the film base material is a resin film, and the coating film is formed on the lower layer of the hard coat layer.

25. A surface modifying agent comprising:

a perfluoropolyether (a) having an active energy ray polymerizable group at the end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1400 to 3500, except for a perfluoropolyether (B) described later; and

and a perfluoropolyether (B) having the active energy ray polymerizable group at only one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a weight average molecular weight of 1550 to 3500.

26. A surface modifying agent comprising:

and a perfluoropolyether (B) which is a reaction product of a starting perfluoropolyether having a hydroxyl group only at one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1200 to 3000, and a compound having a functional group reactive with the hydroxyl group and the active energy ray-polymerizable group.

27. The surface modifier of claim 26, wherein,

28. The surface modifier of any one of claims 25 to 27, wherein,

the fluorine atom content of the perfluoropolyether (B) is 35 to 65 mass%.

29. The surface modifier of any one of claims 25 to 28, wherein,

30. The surface modifier of any one of claims 25 to 29, wherein,

the molecular chain of the perfluoropolyether (A) comprising a poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [3], the molecular chain of the perfluoropolyether (B) comprising a poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1],

the said [1]]And [3]]In which m is a repeating unit- (CF) ₂ CF ₂ Number of O) -and n is the repeating unit- (CF) ₂ O) -number, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the number of oxyethylene groups, represents an integer of 0 to 20, r is a repeating unit- (CF) ₂ CF ₂ Number of O) -and s is the repeating unit- (CF) ₂ O) -number of 5.ltoreq.r+s.ltoreq.40, r and s each independently representing an integer of 0 or more, in a polyester resin having a repeating unit- (CF) ₂ CF ₂ O) -and repeating units- (CF) ₂ In the case of both O) -these repeating units are bonded by block bonding, random bonding, or both block bonding and random bonding.

31. The surface modifier of claim 30, wherein,

32. The surface modifier of claim 30 or 31, wherein,

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

in the formulae [2] and [4], m, n and q have the same meanings as defined in the formula [1], r and s have the same meanings as defined in the formula [3], A represents a terminal group having the active energy ray-polymerizable group, the terminal group A is a group represented by the following formula [ A1] or formula [ A2],

the [ A1]]And [ A2]]Wherein R is ¹ And R is ² Each independently represents a hydrogen atom or a methyl group, and the formula [2] ]Or [4 ]]The urethane bonds of the compounds shown are bonding bonds.