JP6871526B2 - Hydrophilic fluorine-containing highly branched polymer and polymerizable composition containing the same - Google Patents

Description

The present invention relates to a hydrophilic fluorine-containing highly branched polymer and a polymerizable composition containing the same, and more particularly to a polymerizable composition capable of forming a cured film having hydrophilicity on the surface.

Plastic materials such as acrylic resin, polycarbonate resin, and ABS resin have well-balanced mechanical properties, and are excellent in moldability, light weight, and transparency. Taking advantage of these characteristics, housings for electronic devices and cosmetics, etc. It is widely used as. In order to improve various properties such as surface hardness, barrier property, chemical resistance, flame retardancy, and heat resistance of such plastic materials, a method by hard coating treatment by UV curing using a polyfunctional acrylate containing a photopolymerization initiator. Is widely used.

In recent years, there has been an increasing demand for surface performance that prevents water droplets from adhering to organic resin lenses such as automobile headlamps and back monitor cameras and shields for motorcycle helmets made of plastic. ing. However, in products and members having a transparent function, there is a problem that diffused reflection of light occurs due to adhesion of water droplets and light transmission is impaired.
As a solution to such a problem of surface performance, not only the property of repelling water droplets "water repellency" which has been conventionally evaluated by measuring the contact angle, but also the property of "hydrophilicity" which spreads wet even if water droplets adhere to it is attracting attention.

As one of the methods for producing a hydrophilic surface, for example, etching treatment, plasma treatment and the like are known, and although these methods are highly hydrophilic, only a temporary effect can be obtained. Further, although the use of titanium oxide as a photocatalyst has been known conventionally (Patent Document 1), there is a problem that it is necessary to expose it to sunlight for a long time in order to develop hydrophilicity. Further, the coating composition contains a copolymerization component composed of a vinyl-based monomer containing a hydrolyzable silyl group, an alcoholic hydroxyl group-containing vinyl-based monomer, and a tertiary amino group-containing vinyl-based monomer. A curable composition (Patent Document 2) and a coating composition containing a hydrolyzate or partial condensate of organosilane and a vinyl-based copolymer (Patent Document 3) have been proposed, but they are not hydrophilic. It was enough. Further, a hydrophilic treatment agent composition using a polymerizable unsaturated monomer having a betaine structure (Patent Document 4), and a curable composition using an active energy ray-curable quaternary ammonium salt to improve fingerprint resistance (Patent Document 4). Although various proposals have been made for the effect of surface modification such as Patent Document 5), it has not been possible to obtain sufficient hydrophilicity even with these techniques.

JP-A-2002-361800 Japanese Unexamined Patent Publication No. 7-82529 Japanese Unexamined Patent Publication No. 10-273623 Japanese Unexamined Patent Publication No. 2012-25820 Japanese Unexamined Patent Publication No. 2010-132818

As described above, various methods for producing a hydrophilic surface by using a photocatalyst using titanium oxide or a coating composition have been proposed, but there have been problems that the usage environment is limited and the hydrophilicity is not sufficient. Further, in order to impart durability to the plastic surface, it has been a problem that the film hardness is insufficient.
As described above, the conventional hydrophilic surface is not satisfactory in terms of hydrophilicity and durability, and a coating composition capable of imparting excellent hydrophilicity and sufficient hardness has been desired.

As a result of diligent studies to achieve the above object, the present inventors have adopted a hydrophilic hyperbranched polymer obtained by introducing a hydrophilic moiety and a fluorine functional group as a surface modifier for a resin. The present invention has been completed by finding that a hard coat layer capable of improving surface hydrophilicity and exhibiting high hardness by a polyfunctional hard coat can be formed.

（式中、Ｒ¹はそれぞれ独立して水素原子又はメチル基を表し、Ｌ¹はヒドロキシ基で置換されていてもよい炭素原子数２乃至１２のアルキレン基を表し、ａは１乃至３０の整数を表す。）
第９観点として、前記Ｌ¹がエチレン基である、第８観点に記載の親水性高分岐ポリマーに関する。
第１０観点として、前記ａが１乃至１０の整数である、第８観点又は第９観点に記載の親水性高分岐ポリマーに関する。
第１１観点として、前記モノマーＡと前記モノマーＢの合計モル数に対して５０〜１，２００モル％量の前記モノマーＣを用いて得られる、第１観点乃至第１０観点のうち何れか一項に記載の親水性高分岐ポリマーに関する。
第１２観点として、前記モノマーＣが、式［２］乃至式［４］で表される化合物群から選ばれる少なくとも１種の化合物である、第３観点乃至第１１観点に記載の親水性高分岐ポリマーに関する。

（式中、Ｒ²は水素原子又はメチル基を表し、Ｒ³乃至Ｒ⁵はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ²は炭素原子数２乃至１２のアルキレン基を表し、Ｘ^-は対アニオンを表し、ｋは１乃至３０の整数を表す。）

（式中、Ｒ⁶は水素原子又はメチル基を表し、Ｒ⁷及びＲ⁸はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ³は炭素原子数２乃至１２のアルキレン基を表し、Ｌ⁴はヒドロキシ基で置換されていてもよい炭素原子数１乃至１２のアルキレン基を表し、Ｚ^-はＣＯＯ^-基又はＳＯ₃ ^-基を表し、ｍは１乃至３０の整数を表す。）

（式中、Ｒ⁹は水素原子又はメチル基を表し、Ｒ¹⁰乃至Ｒ¹²はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ⁵及びＬ⁶はそれぞれ独立して炭素原子数２乃至１２のアルキレン基を表し、ｎは１乃至３０の整数を表す。）
第１３観点として、前記モノマーＡと前記モノマーＢの合計モル数に対して５０〜３００モル％量の前記モノマーＤを用いて得られる、第１観点乃至第１２観点のうち何れか一項に記載の親水性高分岐ポリマーに関する。
第１４観点として、前記モノマーＤが式［５］で表される化合物である、第３観点乃至第１３観点に記載の親水性高分岐ポリマーに関する。

（式中、Ｒ¹³は水素原子又はメチル基を表し、Ｒ¹⁴は炭素原子数１乃至１２のフルオロアルキル基を表す。）
第１５観点として、前記重合開始剤Ｅがアゾ系重合開始剤である、第１観点乃至第１４観点のうち何れか一項に記載の親水性高分岐ポリマーに関する。
第１６観点として、（ａ）活性エネルギー線重合性多官能モノマー１００質量部、（ｂ）第１観点乃至第１５観点のうち何れか一項に記載の親水性高分岐ポリマー０．００１〜２０質量部、及び（ｃ）活性エネルギー線によりラジカルを発生する重合開始剤１〜２０質量部を含む重合性組成物に関する。
第１７観点として、前記（ａ）多官能モノマーが多官能（メタ）アクリレート化合物である、第１６観点に記載の重合性組成物に関する。
第１８観点として、前記（ｃ）重合開始剤がアルキルフェノン化合物である、第１６観点又は第１７観点に記載の重合性組成物に関する。
第１９観点として、第１６観点乃至第１８観点のうち何れか一項に記載の重合性組成物より得られる硬化膜に関する。
第２０観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムであって、該ハードコート層が、第１６観点乃至第１８観点のうち何れか一項に記載の重合性組成物の紫外線硬化膜である、ハードコートフィルムに関する。
第２１観点として、前記ハードコート層が１〜３０μｍの膜厚を有する、第２０観点に記載のハードコートフィルムに関する。
第２２観点として、フィルム基材の少なくとも一方の面にハードコート層を備えるハードコートフィルムの製造方法であって、第１６観点乃至第１８観点のうち何れか一項に記載の重合性組成物をフィルム基材上に塗布し塗膜を形成する工程、塗膜に紫外線を照射し硬化する工程、を含む、ハードコートフィルムの製造方法に関する。That is, as a first aspect of the present invention, a hydrophilic high branch having at least one hydrophilic moiety selected from the group consisting of an amino group, an amide structure, an ammonium group and a phosphoric acid structure and a fluoroalkyl group in the molecule. A polymer, wherein the polymer has a monomer A having two or more radically polymerizable double bonds in the molecule, the at least one hydrophilic moiety and two or more radically polymerizable double bonds in the molecule. At least two types are selected from the group consisting of the monomer B having the monomer B and the monomer C having the at least one hydrophilic site and one radically polymerizable double bond in the molecule, or the hydrophilic monomer composed of the monomer B. , 5 to 200 mol% with respect to the total number of moles of the polymerizable compound containing the fluoroalkyl group and the monomer D having at least one radically polymerizable double bond in the molecule, and the monomer A and the monomer B. It relates to a hydrophilic hyperbranched polymer which is a polymer with an amount of a polymerization initiator E.
As a second aspect, the polymerizable compound has an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond in the molecule, and a monomer F having one radically polymerizable double bond. The hydrophilic hyperbranched polymer according to the first aspect, further comprising.
As a third aspect, the hydrophilic hyperbranched polymer according to the first or second aspect, wherein the radically polymerizable double bond is independently a vinyl group or a (meth) acryloyl group, respectively.
As a fourth aspect, the hydrophilic hyperbranched polymer according to the third aspect, wherein the monomer B is a divinyl compound or a di (meth) acrylate compound.
A fifth aspect of the present invention relates to the hydrophilic hyperbranched polymer according to any one of the first to fourth aspects, wherein the monomer B is a compound having a phosphoric acid structure.
As a sixth aspect, the monomer B is bis (2- (meth) acryloyloxyethyl) = hydroxyloyloxyethyl or 1,3-bis ((meth) acryloyloxy) propyl-2-yl = dihydrogen = phosphate. The present invention relates to the hydrophilic hyperbranched polymer according to the fifth aspect.
As a seventh aspect, the hydrophilic hyperbranched polymer according to the third aspect, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.
The eighth aspect relates to the hydrophilic hyperbranched polymer according to the seventh aspect, wherein the monomer A is a compound represented by the formula [1].

(In the formula, R ¹ independently represents a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 2 to 12 carbon atoms which may be substituted with a hydroxy group, and a is an integer of 1 to 30. Represents.)
As a ninth aspect, the L ¹ is an ethylene group, relates to a hydrophilic hyperbranched polymer according to the eighth aspect.
As a tenth aspect, it relates to the hydrophilic hyperbranched polymer according to the eighth or ninth aspect, wherein a is an integer of 1 to 10.
As the eleventh viewpoint, any one of the first to tenth viewpoints obtained by using the monomer C in an amount of 50 to 1,200 mol% with respect to the total number of moles of the monomer A and the monomer B. The present invention relates to a hydrophilic hyperbranched polymer.
As a twelfth aspect, the hydrophilic high branch according to the third to eleventh viewpoints, wherein the monomer C is at least one compound selected from the compound group represented by the formulas [2] to [4]. Regarding polymers.

(In the formula, R ² represents a hydrogen atom or a methyl group, R ^{3 to} R ⁵ represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ² represents a carbon. represents an alkylene group of atoms having 2 to 12, X ^- represents a counter anion, k is an integer of 1 to 30).

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ³ represents a carbon. represents an alkylene group of atoms having 2 to 12, L ⁴ represents an alkylene group which optionally may 1 to 12 carbon atoms be substituted with a hydroxy group, Z ^- is COO ^- group or a SO ₃ ^- represents a group, m Represents an integer from 1 to 30.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, and R ^{10 to} R ¹² represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, respectively, and L ⁵ and L ⁶ independently represents an alkylene group having 2 to 12 carbon atoms, and n represents an integer of 1 to 30.)
As a thirteenth viewpoint, it is described in any one of the first to twelfth viewpoints obtained by using the monomer D in an amount of 50 to 300 mol% with respect to the total number of moles of the monomer A and the monomer B. With respect to hydrophilic hyperbranched polymers.
A fourteenth aspect relates to the hydrophilic hyperbranched polymer according to the third to thirteenth aspects, wherein the monomer D is a compound represented by the formula [5].

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a fluoroalkyl group having 1 to 12 carbon atoms.)
A fifteenth aspect relates to the hydrophilic hyperbranched polymer according to any one of the first to fourteenth aspects, wherein the polymerization initiator E is an azo-based polymerization initiator.
As a sixteenth viewpoint, (a) 100 parts by mass of an active energy ray-polymerizable polyfunctional monomer, and (b) 0.001 to 20 parts by mass of the hydrophilic highly branched polymer according to any one of the first to fifteenth viewpoints. The present invention relates to a polymerizable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by (c) active energy rays.
A seventeenth aspect relates to the polymerizable composition according to the sixteenth aspect, wherein the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
As the eighteenth aspect, it relates to the polymerizable composition according to the sixteenth aspect or the seventeenth aspect, wherein the polymerization initiator (c) is an alkylphenone compound.
The 19th aspect relates to a cured film obtained from the polymerizable composition according to any one of the 16th to 18th viewpoints.
As a twentieth viewpoint, the hard coat film is provided with a hard coat layer on at least one surface of the film base material, and the hard coat layer is the polymerizable property according to any one of the 16th to 18th viewpoints. The present invention relates to a hard coat film, which is an ultraviolet curable film of a composition.
The twenty-first aspect relates to the hard coat film according to the twentieth aspect, wherein the hard coat layer has a film thickness of 1 to 30 μm.
As a 22nd viewpoint, a method for producing a hard coat film having a hard coat layer on at least one surface of a film base material, wherein the polymerizable composition according to any one of the 16th to 18th viewpoints is used. The present invention relates to a method for producing a hard coat film, which comprises a step of applying the film onto a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays to cure the coating film.

The hydrophilic highly branched polymer of the present invention can impart excellent hydrophilicity on the surface of a resin (cured product) when blended with a resin. Further, the resin is obtained by further copolymerizing a monomer having an aliphatic hydrocarbon group having 1 to 30 carbon atoms and one radically polymerizable double bond, which may contain an ether bond in the molecule. The surface uniformity of the (cured product) can be further improved.
The resin composition containing the hydrophilic hyperbranched polymer of the present invention can form a cured film (hard coat) having excellent hydrophilicity.

<Hydrophilic highly branched polymer>
The present invention has an amino group (-NH ₂ etc.), an amide structure (-C (= O) -NH- etc.), an ammonium group (-N (CH ₃ ) ₃ ⁺ etc.) and a phosphoric acid structure (-N (CH 3) 3 + etc.) in the molecule. The target is a hydrophilic hyperbranched polymer having at least one hydrophilic moiety selected from the group consisting of OP (= O) (OH) -O-, etc. and a fluoroalkyl group.
Specifically, the present invention has a monomer A having two or more radically polymerizable double bonds in the molecule, the at least one hydrophilic moiety and two or more radically polymerizable double bonds in the molecule. At least two types are selected from the group consisting of the monomer B and the monomer C having at least one hydrophilic site and one radically polymerizable double bond in the molecule, or the hydrophilic monomer composed of the monomer B and Monomer D having the fluoroalkyl group and at least one radically polymerizable double bond in the molecule, and an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may optionally contain an ether bond in the molecule. In the presence of a polymerization initiator E in an amount of 5 to 200 mol% with respect to the total number of moles of the monomer A and the monomer B, and the polymerizable compound containing the monomer F having one radically polymerizable double bond. It relates to a hydrophilic hyperbranched polymer obtained by polymerizing with.
Further, the hydrophilic hyperbranched polymer requires the monomer A, the monomer B, the monomer C, the monomer D, and other monomers not belonging to the monomer F as long as the effects of the present invention are not impaired. May be copolymerized accordingly.
The hydrophilic hyperbranched polymer is a so-called initiator fragment-embedded (IFIRP) type hyperbranched polymer, and has a fragment of the polymerization initiator E used for polymerization at the terminal thereof.

[Monomer A having two or more radically polymerizable double bonds in the molecule]
In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule is preferably a compound having either or both of a vinyl group and a (meth) acryloyl group, particularly a divinyl compound or a divinyl compound. It is preferably a di (meth) acrylate compound. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

（式中、Ｒ¹はそれぞれ独立して水素原子又はメチル基を表し、Ｌ¹はヒドロキシ基で置換されていてもよい炭素原子数２乃至１２のアルキレン基を表し、ａは１乃至３０の整数を表す。）Among the above-mentioned monomer A, a compound represented by the following formula [1] is particularly preferable.

(In the formula, R ¹ independently represents a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 2 to 12 carbon atoms which may be substituted with a hydroxy group, and a is an integer of 1 to 30. Represents.)

In the above formula [1], examples of the alkylene group having 2 to 12 carbon atoms which may be substituted with the hydroxy group of ^{L 1 include an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group and a methylethylene group.} Examples thereof include tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, decamethylene group, dodecamethylene group and the like. Among them, an ethylene group or a hexamethylene group is preferable from the viewpoint of surface modification effect.
Further, a in the formula [1] is preferably an integer of 1 to 10.

Examples of the monomer A include the organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbons:
(A1-1) aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene Etc. (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadien, norbornadien, etc. (A1-3) Aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, tri Vinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (A2) Vinyl ester, allyl ester, vinyl ether, allyl ether and vinyl ketone:
(A2-1) Vinyl ester; Divinyl adipate, Divinyl maleate, Divinyl phthalate, Divinyl isophthalate, Divinyl itacone, Vinyl (meth) acrylate, etc. (A2-2) Allyl ester; Dialyl maleate, Dialyl phthalate, Dialyl isophthalate, diallyl adipate, allyl (meth) acrylate and the like (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyetane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetraallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl ketone, etc. (A3) (meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylene glycol di (meth) acrylate, glycerin = tri (meth) acrylate, glycerin = 1,3-di (meth) acrylate, 2-hydroxy -1-acryloyloxy-3-methacryloyloxypropane, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8- Octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethyl propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkoxytitanium tri (meth) acrylate, dioxane glycol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decandimethanol di (meth) acrylate, 1,3- Adamantane diol di (meth) acrylate, 1,3-adamantan dimethanol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) Acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, aromatic urethane di (meth) acrylate, isophorone urethane di (meth) acrylate, aliphatic urethane di (meth) acrylate, etc. (A4) Polyalkylene glycol chain Vinyl-based compounds with:
Polyethylene glycol (molecular weight: 200, 300, 400, 600, 1000, etc.) Di (meth) acrylate, polypropylene glycol (molecular weight: 400, 500, 700, etc.) Di (meth) acrylate, polytetramethylene glycol (molecular weight: 650, etc.) Di (meth) acrylate, ethoxylated polypropylene glycol (molecular weight: 700, etc.) Di (meth) acrylate, etc. (A5) Nitrogen-containing vinyl compound:
Dialylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide, etc. (A6) -containing silicon vinyl compounds:
Didimethyldivinylsilane, divinyl (methyl) (phenyl)silane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3- Fluorovinyl-based compounds containing (A7) such as tetraphenyldisilazane and dietokidivinylsilane:
1,4-Divinylperfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinylperfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-divinylperfluorooctane, 1,8-divinyl Hexadecafluorooctane, etc.

Of these, preferred are aromatic vinyl hydrocarbons in the group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones in the group (A2), and (meth) acrylics in the group (A3). It is an acid ester, a vinyl-based compound having a polyalkylene glycol chain of the (A4) group, and a nitrogen-containing vinyl-based compound of the (A5) group. Particularly preferred are ethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate from the viewpoint of solvent solubility and resin dispersibility.

[Monomer B having at least one hydrophilic site and two or more radically polymerizable double bonds in the molecule]
In the present invention, the monomer B having at least one hydrophilic moiety and two or more radically polymerizable double bonds in the molecule has at least one hydrophilic moiety and a vinyl group or a (meth) acryloyl group. A compound having either one or both of the above is preferable, and a divinyl compound or a di (meth) acrylate compound having at least one of the hydrophilic sites is particularly preferable.

Among them, the monomer B is preferably a compound having a phosphoric acid structure as the hydrophilic moiety, and in particular, bis (2- (meth) acryloyloxyethyl) = hydrogen = phosphate or 1,3-bis ((()). Meta) acryloyloxy) propyl-2-yl = dihydrogen = phosphate is preferred.

When the monomer B is used in combination with the monomer A, it is preferable to use the monomer A in a ratio of 50 to 300 parts by mass with respect to 100 parts by mass of the monomer B.

（式中、Ｒ²は水素原子又はメチル基を表し、Ｒ³乃至Ｒ⁵はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ²は炭素原子数２乃至１２のアルキレン基を表し、Ｘ^-は対アニオンを表し、ｋは１乃至３０の整数を表す。）

（式中、Ｒ⁶は水素原子又はメチル基を表し、Ｒ⁷及びＲ⁸はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ³は炭素原子数２乃至１２のアルキレン基を表し、Ｌ⁴はヒドロキシ基で置換されていてもよい炭素原子数１乃至１２のアルキレン基を表し、Ｚ^-はＣＯＯ^-基又はＳＯ₃ ^-基を表し、ｍは１乃至３０の整数を表す。）

（式中、Ｒ⁹は水素原子又はメチル基を表し、Ｒ¹⁰乃至Ｒ¹²はそれぞれ独立してヒドロキシ基で置換されていてもよい炭素原子数１乃至６のアルキル基を表し、Ｌ⁵及びＬ⁶はそれぞれ独立して炭素原子数２乃至１２のアルキレン基を表し、ｎは１乃至３０の整数を表す。）[Monomer C having at least one hydrophilic site and one radically polymerizable double bond in the molecule]
In the present invention, the monomer C having at least one hydrophilic moiety and one radically polymerizable double bond is preferably at least one of the hydrophilic moieties and either a vinyl group or a (meth) acryloyl group. It is preferably a compound having one of them, and particularly preferably at least one compound selected from the compound group represented by the following formulas [2] to [4].

(In the formula, R ² represents a hydrogen atom or a methyl group, R ^{3 to} R ⁵ represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ² represents a carbon. represents an alkylene group of atoms having 2 to 12, X ^- represents a counter anion, k is an integer of 1 to 30).

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ³ represents a carbon. represents an alkylene group of atoms having 2 to 12, L ⁴ represents an alkylene group which optionally may 1 to 12 carbon atoms be substituted with a hydroxy group, Z ^- is COO ^- group or a SO ₃ ^- represents a group, m Represents an integer from 1 to 30.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, and R ^{10 to} R ¹² represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, respectively, and L ⁵ and L ⁶ independently represents an alkylene group having 2 to 12 carbon atoms, and n represents an integer of 1 to 30.)

Carbon atoms that may be substituted with hydroxy groups in ^{R 3 to} R ⁵ in the above formula [2], R ⁷ and R ^{8 in} the formula [3], and R ^{10 to} R ^{12 in the formula [4].} Examples of the alkyl group of numbers 1 to 6 include methyl group, ethyl group, 2-hydroxyethyl group, n-propyl group, isopropyl group, 3-hydroxypropyl group, n-butyl group, isobutyl group, sec-butyl group, and the like. Examples thereof include a tert-butyl group, a 4-hydroxybutyl group, an n-hexyl group and a cyclohexyl group.

L ² in the formula [2], the alkylene group of the formula [3] in L ^3, and equation [4] L ⁵ and 2 to 12 carbon atoms in L ⁶ in an ethylene group, trimethylene group, methyl Examples include ethylene group, tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, decamethylene group, dodecamethylene group and the like. Be done.
Among these, from the viewpoint of the surface modification effect, L ² , L ³ , L ⁵ and L ⁶ are preferably ethylene groups.

^{Examples of the alkylene group having 1 to 12 carbon atoms which may be substituted with the hydroxy group in L 4} in the formula [3] include a methylene group, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group and a methylethylene group. Examples thereof include tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, decamethylene group and dodecamethylene group.
^{Among these, L 4} is preferably a methylene group from the viewpoint of surface modification effect.

The X in the formula [2] ^- The represented counter anion, e.g., chloride, bromide, halide ions such as iodide ions; benzenesulfonate anion, p- toluenesulfonate anion, methanesulfonate anion, trifluoromethane Sulfonate anions such as sulfonate anions; perclorate anions; borate anions such as tetrafluoroborate anions and tetraphenylborate anions; hexafluorophosphate anions; acetate anions and the like can be mentioned.

Examples of the monomer C include aminoalkyl (meth) acrylates such as 2- (N, N-dimethylamino) ethyl (meth) acrylate and 2- (N-tert-butylamino) ethyl (meth) acrylate; Meta) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N- Methylol (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- (2-dimethylaminoethyl) (meth) acrylamide, N- Acrylamides such as (3-dimethylaminopropyl) (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholin; N- (2- (meth) acryloyloxy Ethyl) -N, N, N-trimethylammonium = chloride, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium = bromide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium = iodide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium = methanesulfonate, N- (2- (meth) acryloyloxyethyl)- N, N-diethyl-N-methylammonium = methanesulfonate, N- (2- (meth) acryloyloxyethyl) -N-butyl-N, N-dimethylammonium = iodide, N- (2- (meth) acryloyloxyethyl) (Meta) acryloyl group-containing quaternary ammonium salts such as propyl) -N, N-diethyl-N-methylammonium = chloride; 2-((2- (meth) acryloyloxyethyl) dimethylammonio) acetate (N-( 2- (Meta) acryloyloxyethyl) -N, also called N-dimethylglycine), 3-((2- (meth) acryloyloxyethyl) dimethylammonio) propanoate, 4-((2- (meth) acryloyloxy) Carboxybetaines such as ethyl) dimethylammonio) butanoate, 5-((2- (meth) acryloyloxyethyl) dimethylammonio) pentanoate; ((2- (meth) acryloyl) Luoxyethyl) dimethylammonio) methanesulfonate, 2-((2- (meth) acryloyloxyethyl) dimethylammonio) ethanesulfonate, 3-((2- (meth) acryloyloxyethyl) dimethylammonio) propan-1- Sulfobetaines such as sulfonate, 4-((2- (meth) acryloyloxyethyl) dimethylammonio) butane-1-sulfonate; 2- (meth) acryloyloxyethyl = dividrogen = phosphate, 4- (meth) acryloyloxy Examples include (meth) acryloyl group-containing phosphoric acid esters such as butyl = dividrogen = phosphate; phosphorylcholines such as (2- (meth) acryloyloxyethyl) phosphorylcholine and (4- (meth) acryloyloxybutyl) phosphorylcholine.

Among the above-mentioned monomer Cs, N- (2-hydroxyethyl) acrylamide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium = chloride, N- (2- (meth) acryloyloxyethyl) Ethyl) -N, N-dimethylglycine, 3-((2- (meth) acryloyloxyethyl) dimethylammonio) propan-1-sulfonate, 2- (meth) acryloyloxyethyl = dividrogen = phosphate, (2-( Meta) acryloyloxyethyl) phosphorylcholine is preferred, especially N- (2-hydroxyethyl) acrylamide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium = chloride, N- (2-). (Meta) acryloyloxyethyl) -N, N-dimethylglycine, 2- (meth) acryloyloxyethyl = dividrogen = phosphate are preferred.

In the present invention, the amount of the monomer C used is 50 to 1,200 mol% with respect to the total number of moles of the monomer A and the monomer B from the viewpoint of solvent solubility, resin dispersibility and surface modification effect. More preferably, it is used in an amount of 100 to 1,000 mol%.

（式中、Ｒ¹³は水素原子又はメチル基を表し、Ｒ¹⁴は炭素原子数１乃至１２のフルオロアルキル基を表す。）
中でも、前記モノマーＤは下記式［６］で表される化合物であることが好ましい。

（式中、Ｒ¹³は前記式［５］における定義と同じ意味を表し、Ｇは水素原子又はフッ素原子を表し、ｐは１又は２を表し、ｑは０乃至５の整数を表す。）[Monomer D having the fluoroalkyl group and at least one radically polymerizable double bond in the molecule]
In the present invention, the monomer D having a fluoroalkyl group and at least one radically polymerizable double bond in the molecule preferably has a fluoroalkyl group in the molecule and either a vinyl group or a (meth) acryloyl group. A compound having at least one is preferable, and a compound represented by the following formula [5] is particularly preferable.

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a fluoroalkyl group having 1 to 12 carbon atoms.)
Above all, the monomer D is preferably a compound represented by the following formula [6].

(In the formula, R ¹³ has the same meaning as the definition in the above formula [5], G represents a hydrogen atom or a fluorine atom, p represents 1 or 2, and q represents an integer of 0 to 5.)

Examples of such monomer D include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl. (Meta) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-) 3-Methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H- Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate , 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-per Fluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3-( Examples thereof include perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate and 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate.
Among these, 2,2,2-trifluoroethyl (meth) acrylate is most preferable from the viewpoint of hydrophilicity and surface modification effect.

In the present invention, the amount of the monomer D used is 50 to 300 mol%, more preferably 50, based on the total number of moles of the monomer A and the monomer B from the viewpoint of hydrophilicity and surface modification effect. It is preferably used in an amount of ~ 150 mol%.

[Polymerization initiator E]
As the polymerization initiator E, an azo-based polymerization initiator is preferably used. Examples of the azo-based polymerization initiator include the compounds shown in the following (1) to (5).
(1) Azonitrile compound:
2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (2,4-dimethylvaleronitrile) 1-cyclohexanecarbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, etc .;
(2) Azoamide compound:
2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N- [2-( 1-Hydroxybutyl)] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N- (2-propenyl) -2- Methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), etc .;
(3) Cyclic azoamidine compound:
2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrolate, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl)) Propane], 2,2'-azobis (1-imimino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc.;
(4) Azoamidine compound:
2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] tetrahydrate, etc.;
(5) Others:
2,2'-Azobisisobutyrate dimethyl, 4,4'-azobis (4-cyanovalerate), 2,2'-azobis (2,4,4-trimethylpentane), 1,1'-azobis (1-acetoxy-) 1-phenylethane), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate), bis (2- (perfluoromethyl) ethyl) 4,4'-azobis (4-cyanovalerate), bis (2- (Perfluorobutyl) ethyl) 4,4'-azobis (4-cyanovalerate), bis (2- (perfluorohexyl) ethyl) 4,4'-azobis (4-cyanovalerate) and the like.

Among the above azo-based polymerization initiators, 2,2'-azobis (2-methyl) from the viewpoint of dispersibility of the hydrophilic highly branched polymer in the active energy ray-polymerizable polyfunctional monomer in the polymerizable composition described later. Butyronitrile) is preferred.

The polymerization initiator E is used in an amount of 5 to 200 mol%, preferably 20 to 200 mol%, more preferably 20 to 100, based on the total number of moles of the monomer A and the monomer B. Used in molar% amount.

[Monomer F having an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond in the molecule and one radically polymerizable double bond]
In the present invention, in addition to the monomers A to D, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and a monomer F having one radically polymerizable double bond are provided. Further may be included. By adding the monomer F, it is possible to suppress the formation of fine particles that impair the surface uniformity at the time of forming the cured film (hard coat layer) described later, and to further improve the surface uniformity of the cured film.
The monomer F is preferably a compound having an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and either a vinyl group or a (meth) acryloyl group. preferable.

Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain the ether bond include a linear alkyl group having 1 to 30 carbon atoms and a branched alkyl group having 1 to 30 carbon atoms. , A cyclic alkyl group having 3 to 30 carbon atoms or an alkyl group having 30 or less carbon atoms consisting of a chain or a combination of these chains, and at least a part of these alkyl groups is interrupted by an ether bond (-O-). Groups are mentioned, preferably linear alkyl groups having 1 to 30 carbon atoms.
Specifically, the following linear, branched or cyclic methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecil group, icosyl group, etc. In addition, groups in which at least a part of these are interrupted by an ether bond can be mentioned.

Among them, preferable monomer F in the present invention includes butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate and the like.

In the present invention, the amount of the monomer F used is 50 to 500 mol% with respect to the total number of moles of the monomer A and the monomer B from the viewpoint of improving the reactivity and the surface uniformity, and more preferably. It is preferably used in an amount of 50-200 mol%.

[Other monomers]
In the present invention, the monomer A, the monomer B, the monomer C, the monomer D and other monomers not belonging to the monomer F may be copolymerized, and in that case, the other monomer has one radical polymerizable property in the molecule. The monomer having a double bond is not particularly limited, but a vinyl compound or a (meth) acrylate compound is preferable.
In the present invention, the amount of the other monomer used is preferably 5 to 300 mol% with respect to the total number of moles of the monomer A and the monomer B.

[Manufacturing method of hydrophilic highly branched polymer]
The hydrophilic hyperbranched polymer of the present invention is a polymerizable compound containing at least two of the above-mentioned monomers A to C, or a hydrophilic monomer composed of monomer B, monomer D, and optionally monomer F. , It is obtained by polymerizing in the presence of a predetermined amount of the polymerization initiator E with respect to the total number of moles of the monomer A and the monomer B. Examples of the polymerization method include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and massive polymerization, and among them, solution polymerization or precipitation polymerization is preferable. In particular, from the viewpoint of controlling the molecular weight, it is preferable to carry out the reaction by solution polymerization in an organic solvent.

Examples of the organic solvent used at this time include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetraline; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane; Halogens such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl Esters or ester ethers such as cellosolve acetate and propylene glycol monomethyl ether acetate; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, etc. Alcohols; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; sulfoxides such as dimethylsulfoxide, and mixed solvents of two or more of these.

Of these, aromatic hydrocarbons, halides, esters, ester ethers, ethers, ketones, alcohols, amides and the like are preferable, and benzene, toluene, xylene and o are particularly preferable. -Dichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, 2-propanol, n-butanol , Isobutyl alcohol, tert-butyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

When the polymerization reaction is carried out in the presence of an organic solvent, the mass of the organic solvent with respect to a total of 1 part by mass of the monomer A and the monomer B is usually 5 to 120 parts by mass, preferably 10 to 110 parts by mass. ..
The polymerization reaction is carried out under normal pressure, pressure sealing, or reduced pressure, and is preferably carried out under normal pressure because of the simplicity of the apparatus and operation. Further, it is preferable to carry out the operation in an atmosphere of an inert gas such as _{N 2.}
The polymerization temperature is arbitrary as long as it is equal to or lower than the boiling point of the reaction mixture, but is preferably 50 to 200 ° C., more preferably 80 to 150 ° C., and 80 to 130 ° C. from the viewpoint of polymerization efficiency and molecular weight adjustment. More preferred.
The reaction time cannot be unconditionally specified because it varies depending on the reaction temperature, the type and ratio of the monomer A, the monomer B, the monomer C, the monomer D, the polymerization initiator E, and optionally the type and the ratio of the monomer F, the type of the polymerization solvent, and the like. However, it is preferably 30 to 720 minutes, more preferably 40 to 540 minutes.
After completion of the polymerization reaction, the obtained hydrophilic highly branched polymer is recovered by an arbitrary method, and if necessary, post-treatment such as washing is performed. Examples of the method for recovering the polymer from the reaction solution include a method such as reprecipitation.

The weight average molecular weight (Mw) of the hydrophilic highly branched polymer measured by gel permeation chromatography in terms of polystyrene is 1,000 to 400,000, preferably 1,000 to 200,000, more preferably 1,000. ~ 50,000.

<Polymerizable composition>
The present invention relates to a polymerizable composition containing the hydrophilic hyperbranched polymer, specifically, (a) 100 parts by mass of an active energy ray-polymerizable polyfunctional monomer, and (b) the hydrophilic hyperbranched polymer 0.001 to 20. Polymerizable compositions containing 1 to 20 parts by mass of a polymerization initiator and (c) a polymerization initiator that generates radicals by active energy rays are also included.

[(A) Active energy ray-polymerizable polyfunctional monomer]
As the above-mentioned (a) active energy ray-polymerizable polyfunctional monomer (hereinafter, also simply referred to as (a) polyfunctional monomer), a polymerizable site that polymerizes by the action of a component (c) polymerization initiator described later is included in the molecule. The compound having two or more of them is not particularly limited, and examples thereof include polyfunctional monomers containing two or more (meth) acryloyl groups such as urethane acrylic type, epoxy acrylic type, and various (meth) acrylate type compounds.
Preferably, the (a) polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.

Among such active energy ray-curable polyfunctional monomers, examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate ) Acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, dipenta Erislitol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, tricyclo [5 2.1.0 ^2,6 ] Decandimethanol di (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, ε-caprolactone-modified tris (2- (Meta) acryloyloxyethyl) isocyanurate, trimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate Meta) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, propylene oxide-modified glycerin tri (meth) acrylate, glycerol tri (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydride Loxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene , Bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantandiol di (meth) acrylate, 1,3-adamantan dimethanoldi (meth) Acryloyl and the like can be mentioned.
One of these compounds may be used alone, or two or more of these compounds may be mixed and used as required.
Among these examples, compounds containing three or more (meth) acryloyl groups such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable, and pentaerythritol tetra (meth) acrylate and dipenta are further preferable. Compounds containing four or more (meth) acryloyl groups, such as erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, are more preferable.

Examples of the polyfunctional urethane (meth) acrylate compound include urethane compounds having two or more (meth) acryloyl groups having an ethylenically unsaturated bond site. The polyfunctional urethane (meth) acrylate compound preferably used in the present invention may be either an aliphatic urethane (meth) acrylate or an aromatic urethane (meth) acrylate. One of these compounds may be used alone, or two or more of these compounds may be mixed and used as required.

The polyfunctional urethane (meth) acrylate compound preferably used in the present invention is obtained, for example, by reacting a polyisocyanate compound with a (meth) acrylic monomer having active hydrogen.
Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalenedi isocyanate, and m-. Phenylene diisocyanate, p-phenylenedi isocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dicyclomethane diisocyanate, or diisocyanate compounds obtained by hydrogenating aromatic isocyanates among these diisocyanate compounds (for example, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane) Diisocyanate compounds such as diisocyanate), divalent or trivalent diisocyanate compounds or polyisocyanate compounds such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, etc. Examples thereof include isocyanate group-containing compounds such as.
Examples of the (meth) acrylic monomer having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and ethylene glycol mono (meth) acrylate. , Propropylene glycol mono (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide and the like. These lactone adducts (for example, Praxel (registered trademark) FA series, FM series, etc. manufactured by Daicel Co., Ltd.) can also be used. Further, dipentaerythritol poly (meth) acrylate (for example, "DPHA" manufactured by Daicel Cytec Co., Ltd.) can also be used.

Specific examples of commercially available products of these polyfunctional urethane (meth) acrylates are manufactured by Kyoeisha Chemical Co., Ltd .: AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF- 8001G, DAUA-167, etc .; manufactured by Daicel Cytec Co., Ltd .: EBECRYL (registered trademark) 204, 205, 210, 215, 220, 6202, 230, 244, 245, 264, same 265, 270, 280/15 IB, 1259, 5129, 8210, 8301, 8307, 8411, 8804, 8807, 9227EA, 9260, 284, 285, 294/25 HD , 4820, 4858, 8402, 8405, 9270, 8311, 8701, KRM8200, KRM8200AE, KRM7735, KRM8286, KRM8452, etc .; manufactured by Nippon Synthetic Chemical Co., Ltd .: Shikou (registered trademark) UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620E, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, etc. Can be mentioned.

Further, (a) the polyfunctional monomer may be used by mixing the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate.

[(B) Hydrophilic hyperbranched polymer]
In the polymerizable composition of the present invention, a hydrophilic highly branched polymer is used as the component (b). In the polymerizable composition, the hydrophilic hyperbranched polymer has a role as a surface modifier for imparting hydrophilicity.
The hydrophilic hyperbranched polymer of the component (b) is in an amount of 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the active energy ray-polymerizable polyfunctional monomer of the component (a). It is preferable to use it in the amount of parts by mass.

[(C) Polymerization initiator that generates radicals by active energy rays]
The above-mentioned (c) polymerization initiator that generates radicals by active energy rays (hereinafter, also simply referred to as (c) polymerization initiator) is a compound (light) that generates active radicals when irradiated with active energy rays such as ultraviolet rays (light). Any radical polymerization initiator) can be used without particular limitation.
Examples of such photoradical polymerization initiators include benzoin compounds, alkylphenone compounds, thioxanthone compounds, azide compounds, diazo compounds, o-quinone diazide compounds, acylphosphine oxide compounds, and oxime ester compounds. , Benzophenones, biscumarin, bisimidazole compounds, organic peroxides, titanosen compounds, thiol compounds, halogenated hydrocarbon compounds, trichloromethyltriazine compounds, or onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used. ..
These polymerization initiators may be used alone or in combination of two or more, if necessary.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and the like.

Examples of the alkylphenone-based compound include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl = phenyl = ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1. -On, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1-(4- (4- (2-hydroxy-2-methyl) Propionyl) benzyl) phenyl) -2-methylpropan-1-one, methyl phenylglycoxylate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2- (dimethylamino) -2-((4-methylphenyl) methyl) -1- (4-morpholinophenyl) butane-1-one And so on.

Examples of the thioxanthone-based compound include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like. Can be done.

Examples of the azide compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazide chalcone, and 4,4'-diazidodiphenyl sulfide. , 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidosylben and the like.

Examples of the diazo compound include 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis (N- (2-). Carboxyethyl) -2-methylpropion amidine), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-methyl-N- (2- (1-hydroxy)) Buty)) propionamide), 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2'-azobis (2- (5-methyl-2-imidazolin-2-) Il) Propane) dihydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl)) Propane) dihydrochloride disulfate, 2,2'-azobis (2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane) dihydrochloride, 2,2'-azobis (2-( 1- (2-Hydroxyethyl) -2-imidazolin-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl) propane), 1-diazo-2, 5-diethoxy-4-p-trillmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, 1-diazo-4-N, N-diethylaminobenzeneborofluoride and the like can be mentioned. it can.

Examples of the o-quinone diazide compound include 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester, and 1,2-naphthoquinone-. Examples thereof include 2-diazide-4-sulfonyl chloride and the like.

Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] esterone and the like can be mentioned.

Examples of the benzophenones include benzophenone, 4,4'-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacrydone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4 -Benzoyl diphenyl ether, benzyl and the like can be mentioned.

The bisquemarin is, for example, commercially available as 3,3'-carbonylbis (7- (diethylamino) -2H-chromen-2-one) (BC (CAS [63226-13-1]) manufactured by Midori Kagaku Co., Ltd.). ) Etc. can be mentioned.

Examples of the bisimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-bi. Examples thereof include imidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Examples of the organic peroxide include acetyl peroxide, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide and the like.

Examples of the titanosen compound include bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) diphenyltitanium, and bis (cyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl). ) Titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4,6-trifluorophenyl) titanium, bis (cyclo) Pentazienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5 , 6-Pentafluorophenyl) Titanium, Bis (Methylcyclopentadienyl) Bis (2,3,5,6-Tetrafluorophenyl) Titanium, Bis (2,6-difluorophenyl) Bis (Methylcyclopentadienyl) Titanium, bis (cyclopentadienyl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like can be mentioned.

Among the above-mentioned (c) polymerization initiators, alkylphenone compounds are particularly preferable. A commercially available photopolymerization initiator can be used as the alkylphenone-based photopolymerization initiator. For example, BASF Japan Ltd .: IRGACURE (registered trademark) 651, 184, 2959, 127, 907, 907. 369, 379EG, DAROCUR (registered trademark) 1173, MBF and the like can be mentioned.

The polymerization initiator of the component (c) is preferably used in an amount of 1 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer of the component (a).

Additives generally added to the polymerizable composition of the present invention as needed, such as a photosensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, as long as the effects of the present invention are not impaired. Surfactants, adhesion-imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately blended.

<Cured film>
The polymerizable composition of the present invention can be coated on a base material and photopolymerized (cured) to form a molded product such as a cured film or a laminate. The cured film thus obtained is also an object of the present invention.
Examples of the base material include plastic materials [polycarbonate, poly (meth) acrylate, polystyrene, polyester (polyethylene terephthalate (PET), etc.), polyolefin, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer). Material (ABS) resin, acrylonitrile-styrene copolymer (AS) resin, norbornene-based resin, etc.], metal, wood, paper, glass, silicon dioxide, slate, etc. can be mentioned, and among them, a plastic material is preferable. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The polymerizable composition of the present invention is preferably dissolved or dispersed in a solvent to form a varnish (film forming material), and the varnish is applied onto a substrate by a cast coating method, a spin coating method, a blade coating method, a dip coating method, or the like. A roll coating method, a bar coating method, a die coating method, a spray coating method, a curtain coating method, an inkjet method, a printing method (convex, intaglio, lithographic printing, screen printing, etc.), etc. are appropriately selected and applied, and then a hot plate or an oven is used. It can be dried and formed into a film.
Among these coating methods, it is desirable to use the spin coating method because it can be applied in a short time, so that even a highly volatile solution can be used, and the spin coating method can be easily and uniformly applied. In addition, the roll coating method, bar coating method, die coating method, and spray coating method are used because they can be easily applied and a smooth coating film can be formed over a large area without uneven coating. Is desirable.

The solvent used in the form of the varnish may be any solvent that dissolves or disperses the above-mentioned components (a) to (c) and other components, and for example, aromatic carbonization of benzene, toluene, xylene, ethylbenzene, tetraline and the like. Hydrogens; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloro Halogens such as ethylene and o-dichlorobenzene; ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, γ-butyrolactone, methyl pyruvate, ethyl pyruvate, ethyl hydroxyacetate, ethyl lactate, butyl lactate, 2 Ethyl-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Esters or ester ethers such as ethyl, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl ether acetate; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve , Ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME) and other ethers; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone. , Cyclohexanone and other ketones; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, 2-butanol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol and the like. Alcohols; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP); organic solvents such as sulfoxides such as dimethylsulfoxide (DMSO). Be done. One of these organic solvents may be used alone, or two or more kinds of organic solvents may be mixed and used.
The concentration at which the above-mentioned components (a) to (c) and other components are dissolved or dispersed in the solvent is arbitrary, but the total mass (total) of the above-mentioned components (a) to (c), other components (solid content) and the solvent. The solid content concentration is 0.5 to 80% by mass, preferably 1 to 70% by mass, and more preferably 1 to 60% by mass with respect to the mass).
The varnish thus obtained may be subjected to coating after being filtered in advance using a filter having a pore size of about 0.2 μm or the like.

After the above coating, preferably, it is pre-dried on a hot plate or an oven, and then irradiated with active energy rays such as ultraviolet rays to be photo-cured. Examples of the active energy ray include ultraviolet rays, electron beams, X-rays and the like. As the light source used for ultraviolet irradiation, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.
Then, if necessary, it may be heated using a post-bake, specifically, a hot plate, an oven, or the like.
The thickness of the film formed by the coating is usually 0.01 to 50 μm, preferably 0.05 to 50 μm after drying and curing.

<Hard coat film with hard coat layer>
Further, the present invention is formed by a step of applying the above-mentioned polymerizable composition, preferably in the form of a varnish, the above-mentioned polymerizable composition on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays to cure the coating film. Hard-coated films having a hard-coat layer on at least one surface of the film substrate are also included.
The base material, coating method, and energy ray irradiation such as ultraviolet rays used here are the same as those of the base material, coating method, and active energy ray irradiation in the above-mentioned <cured film>.
In the hard coat film of the present invention, the film thickness of the hard coat layer is preferably 1 to 30 μm, more preferably 1 to 10 μm.

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

(1) Gel Permeation Chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex® OHpak SB-803HQ, OHpak SB-804HQ
Column temperature: 40 ° C
Eluent: N, N-dimethylformamide (29.6 mM phosphoric acid and 29.6 mM lithium bromide added)
Detector: RI
(2) Bar coat application device: PM-9050MC manufactured by SMT Co., Ltd.
Bar: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., maximum film thickness 22 μm (equivalent to wire bar # 9)
Coating speed: 6.7 m / min (3) Oven device: Dust-free dryer manufactured by Advantech Toyo Co., Ltd. DRC433FA
(4) UV irradiation device Device: H02-L41 manufactured by Eye Graphics Co., Ltd.
(5) Contact angle measuring device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C
(6) HAZE
Equipment: Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

The abbreviations have the following meanings.
9DMA: Nonaethylene glycol dimethacrylate [Blemmer (registered trademark) PDE-400 manufactured by NOF CORPORATION]
DMA: Ethylene glycol dimethacrylate [1G manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
HDN: 1,6-Hexanediol dimethacrylate [HD-N manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
PDMA: Bis (2-methacryloyloxyethyl) = hydrogen = phosphate [Light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.]
ACA: N- (2-acryloyloxyethyl) -N, N, N-trimethylammonium = chloride [DMAMC manufactured by Osaka Organic Chemical Industry Co., Ltd.]
BTM: N- (2-methacryloyloxyethyl) -N, N-dimethylglycine [GLBT manufactured by Osaka Organic Chemical Industry Co., Ltd.]
HAA: N- (2-hydroxyethyl) acrylamide [HEAA® manufactured by KJ Chemicals Co., Ltd.]
PMA: 2-methacryloyloxyethyl = dihydrogen = phosphate [Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.]
C1FA: 2,2,2-trifluoroethyl acrylate [Viscoat 3F manufactured by Osaka Organic Chemical Industry Co., Ltd.]
C1FM: 2,2,2-trifluoroethyl methacrylate [Light Ester M-3F manufactured by Kyoeisha Chemical Co., Ltd.]
AMBN: 2,2'-azobis (2-methylbutyronitrile) [V-59 manufactured by Wako Pure Chemical Industries, Ltd.]
BA: Butyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
LA: Lauryl acrylate [NOF Corporation Blemmer (registered trademark) LA]
UV7600: 6-functional urethane acrylate [Shikou (registered trademark) UV-7600B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.]
I184: 1-Hydroxycyclohexyl = Phenyl = Ketone [IRGACURE (registered trademark) 184 manufactured by BASF Japan Ltd.]
MIBK: Methyl Isobutyl Ketone PGME: Propylene Glycol Monomethyl Ether

[Example 1] Production of hydrophilic hyperbranched polymer (HBP1) having a fluoroalkyl group 13 g of PGME (4 parts by mass with respect to the amount of monomer B used) was charged into a 100 mL reaction flask, and nitrogen was poured for 5 minutes with stirring. , Heated until the internal solution refluxed (approximately 120 ° C.).
In another 50 mL reaction flask, PDMA 3.2 g (10 mmol) as monomer B, C1FM 1.7 g (10 mmol, 1 molar equivalent to monomer B) as monomer D, and AMBN 1.0 g (5 mmol, monomer B) as polymerization initiator E. (0.5 molar equivalent) and 13 g of PGME (4 parts by mass with respect to the amount of monomer B used) were charged, nitrogen was poured for 5 minutes with stirring to perform nitrogen substitution, and the mixture was cooled to 0 ° C. in an ice bath.
The contents were added dropwise from the above-mentioned 50 mL reaction flask in which PDMA, C1FM, and AMBN were charged into the refluxed PGME in the above-mentioned 100 mL reaction flask over 1 hour using a dropping pump. After completion of the dropping, the mixture was further stirred for 1 hour.
The reaction mixture was cooled to room temperature (approximately 25 ° C.) to obtain 31.5 g of the desired highly branched polymer (HBP1) as a PGME solution having a polymer concentration of 18% by mass.
The weight average molecular weight of the obtained highly branched polymer measured by GPC in terms of polystyrene was 4,900, and the dispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 5.9.

[Examples 2 to 7] Production of Hydrophilic Highly Branched Polymers (HBP2 to HBP7) Having Fluoroalkyl Groups Each highly branched polymer was produced in the same manner as in Example 1 according to the description in Table 1. The monomer A, the monomer C, and the monomer F were mixed and charged together with the monomer B, the monomer D, and the initiator E.
Further, in Table 1, [molar equivalents] in monomer C, monomer D, monomer F and polymerization initiator E indicate molar equivalents with respect to the total number of moles of monomer A and monomer B, respectively, and [parts by mass] in PGME. , 1 part by mass of Monomer A and Monomer B in total. The description of X + Y (for example, 10 + 10) in PGME means that X parts by mass is used as the amount of PGME to be refluxed in advance, and Y parts by mass is used as the amount of PGME to be mixed with each monomer or the like.
Table 1 also shows the polymer concentration of the obtained highly branched polymer PGME solution, the weight average molecular weight measured by GPC in terms of polystyrene: Mw, and the dispersity: Mw / Mn.

[Production Example 1] Production of Hydrophilic Highly Branched Polymer (HBP8) Not Having a Fluoroalkyl Group A highly branched polymer was produced in the same manner as in Example 1 according to the description in Table 1. Table 1 also shows the polymer concentration of the obtained highly branched polymer PGME solution, the weight average molecular weight measured by GPC in terms of polystyrene: Mw, and the dispersity: Mw / Mn.

[Examples 8 to 15 and Comparative Examples 1 and 2]
The following components were mixed to prepare a curable composition having a non-volatile content concentration of 40% by mass.
(1) Polyfunctional monomer: UV7600 100 parts by mass (2) Surface modifier: Surface modifier shown in Table 2 Amount shown in Table 2 (as a highly branched polymer)
(3) Polymerization initiator: I184 6 parts by mass (4) Solvent: MIBK The amount shown in Table 2 This curable composition is applied to an A4 size PET film [Cosmo Shine (registered trademark) A4100 manufactured by Toyobo Co., Ltd., thickness. A coating film was obtained by applying a solvent coat on the top (125 μm] (on the side of the easily adhesive-treated surface). The coating was dried in an oven at 100 ° C. for 3 minutes to remove the solvent. The obtained film was exposed to UV light having an exposure amount of 300 mJ / cm ^{2 in} an air atmosphere to prepare a hard coat film having a hard coat layer having a thickness of about 5 to 6 μm.

The contact angles of water and oleic acid, HAZE, and surface uniformity of the obtained hard coat layer were evaluated. As for the contact angle, 1 μL of the probe liquid (water or oleic acid) was adhered to the surface of the hard coat layer, and the contact angle was measured 5 times after 10 seconds, and the average value was taken as the contact angle value. The surface uniformity was evaluated by visually confirming the state of the surface of the hard coat layer and according to the following criteria. The results are also shown in Table 2.
[Surface uniformity evaluation criteria]
A: Fine particles are not observed over the entire surface and smooth B: Fine particles are observed on a part of the surface C: Fine particles are scattered

As shown in Table 2, the hydrophilic high-branched polymer (HBP1 to HBP7) having a fluoroalkyl group of the present invention is used as a surface modifier as compared with the hard coat layer (Comparative Example 1) in which no surface modifier is used. In the hard coat layer (Examples 8 to 15) added as, the result was obtained that the contact angle of water was small. That is, it was obtained that the hydrophilic hyperbranched polymer having a fluoroalkyl group of the present invention can impart hydrophilicity to the hard coat surface with a small amount of addition.
Further, it was obtained that the surface uniformity of the obtained hard coat layer could be further improved by adding the monomer F.
On the other hand, in the hard coat layer (Comparative Example 2) using the hydrophilic highly branched polymer (HPB8) containing no fluoroalkyl group, the contact angle of water was extremely large as compared with the above-mentioned example, and the highly branched polymer was obtained. The result is that almost no hydrophilicity can be imparted to the surface of the hard coat layer.

Claims (14)

(A) 100 parts by mass of a polyfunctional monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound,
A polymerizable composition containing 0.001 to 20 parts by mass of a hydrophilic highly branched polymer and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
The hydrophilic hyperbranched polymer is a hydrophilic hyperbranched polymer having at least one hydrophilic moiety selected from the group consisting of an amino group, an amide structure, an ammonium group and a phosphoric acid structure and a fluoroalkyl group in the molecule. ,
The hydrophilic highly branched polymer is
Monomer A, which is a compound represented by the following formula [1], bis (2- (meth) acryloyloxyethyl) = hydrogen = phosphate, or 1,3-bis ((meth) acryloyloxy) propyl-2-yl = At least two types are selected from the group consisting of the monomer B having dihydrogen = phosphate and the monomer C which is at least one compound selected from the compound group represented by the following formulas [2] to [4], or the monomer. A hydrophilic monomer consisting of B and
A polymerizable compound containing at least monomer D, which is a compound represented by the following formula [6], and
A hydrophilic hyperbranched polymer which is a polymer of 5 to 200 mol% of the polymerization initiator E with respect to the total number of moles of the monomer A and the monomer B.
When the monomer B is used in combination with the monomer A, the ratio of the monomer A to 100 parts by mass of the monomer B is 50 to 300 parts by mass.
The amount of the monomer C used is 50 to 1,200 mol% with respect to the total number of moles of the monomer A and the monomer B.
The amount of the monomer D used is 50-300 mol% with respect to the total number of moles of the monomer A and the monomer B, and the hydrophilic hyperbranched polymer is a fragment of the polymerizable initiator E at the end. The hydrophilic hyperbranched polymer has a weight average molecular weight (Mw) of 1,000 to 50,000 as measured by gel permeation chromatography in terms of polystyrene.
Polymerizable composition.

(In the formula, R ¹ independently represents a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 2 to 12 carbon atoms which may be substituted with a hydroxy group, and a is an integer of 1 to 30. Represents.)

(In the formula, R ² represents a hydrogen atom or a methyl group, R ^{3 to} R ⁵ each represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ² represents a carbon. It represents an alkylene group having 2 to 12 atoms, X ⁻ represents a counter anion, and k represents an integer of 1 to 30.)

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ³ represents a carbon. It represents an alkylene group having 2 to 12 atoms, L ⁴ represents an alkylene group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, Z ⁻ represents a COO ⁻ group or a SO ₃ ⁻ group, and m Represents an integer from 1 to 30.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, and R ^{10 to} R ¹² each represent an alkyl group having 1 to 6 carbon atoms which may be independently substituted with a hydroxy group, and L ⁵ and L. ⁶ independently represents an alkylene group having 2 to 12 carbon atoms, and n represents an integer of 1 to 30.)

(In the formula, R ¹³ represents a hydrogen atom or a methyl group, G represents a hydrogen atom or a fluorine atom, p represents 1 or 2, and q represents an integer of 0 to 5.) The polymerizable compound further comprises, in the molecule, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond, and a monomer F having one radically polymerizable double bond. Item 2. The polymerizable composition according to Item 1. The polymerizable composition according to claim 2, wherein the radically polymerizable double bonds are independently vinyl groups or (meth) acryloyl groups. The polymerizable composition according to any one of claims 1 to 3 , wherein L ¹ is an ethylene group. The polymerizable composition according to any one of claims 1 to 4 , wherein a is an integer of 1 to 10. The polymerizable property according to any one of claims 1 to 5 , which is obtained by using the monomer C in an amount of 100 to 1,000 mol% with respect to the total number of moles of the monomer A and the monomer B. Composition. The polymerizable composition according to any one of claims 1 to 6 , which is obtained by using the monomer D in an amount of 50 to 150 mol% with respect to the total number of moles of the monomer A and the monomer B. .. The polymerizable composition according to any one of claims 1 to 7 , wherein the polymerization initiator E is an azo-based polymerization initiator. The polymerizable composition according to any one of claims 1 to 8 , wherein the polyfunctional monomer (a) is a polyfunctional (meth) acrylate compound. The polymerizable composition according to any one of claims 1 to 9 , wherein the polymerization initiator (c) is an alkylphenone compound. A cured film obtained from the polymerizable composition according to any one of claims 1 to 10. A hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is UV-curable of the polymerizable composition according to any one of claims 1 to 10. A hard coat film that is a film. The hard coat film according to claim 12 , wherein the hard coat layer has a film thickness of 1 to 30 μm. A method for producing a hard coat film having a hard coat layer on at least one surface of the film base material, wherein the polymerizable composition according to any one of claims 1 to 10 is placed on the film base material. A method for producing a hard coat film, which comprises a step of applying and forming a coating film and a step of irradiating the coating film with ultraviolet rays to cure the coating film.