WO2016125865A1 - Hydrophilic fluorine-containing hyperbranched polymer and polymerizable composition containing same - Google Patents

Abstract

[Problem] To provide a hydrophilic hyperbranched polymer useful as a surface modifier for improving the hydrophilicity of a surface and making it possible to form a hard coating layer capable of actualizing high hardness by multifunctional hard coating. [Solution] A hydrophilic hyperbranched polymer having at least one hydrophilic site and a fluoroalkyl group in the molecule, said hydrophilic hyperbranched polymer being obtained by polymerizing a polymerizable compound in the presence of a polymerization initiator; the polymerizable compound including at least a hydrophilic monomer and a monomer D that has a fluoroalkyl group and at least one radical polymerizable double bond in the molecule; the hydrophilic monomer comprising at least two monomers selected from the group consisting of a monomer A that has two or more radical polymerizable double bonds in the molecule, a monomer B that has at least one hydrophilic site and two or more radical polymerizable double bonds in the molecule, and a monomer C that has at least one hydrophilic site and one radical polymerizable double bond in the molecule, or the hydrophilic monomer alternatively comprising the monomer B; the polymerization initiator E being present in a specific amount relative to the total number of moles of monomer A and monomer B.

Description

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

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, lightness, and transparency. As widely used. In order to improve the surface hardness, barrier properties, chemical resistance, flame retardancy, heat resistance, etc. of these plastic materials, a technique using a hard coat 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 makes it difficult for water droplets to adhere to rain when exposed to organic resin lenses such as automotive headlamps, back monitor cameras, and motorcycle helmet shields that are made of plastic. ing. However, in a product or member having a transparent function, there is a problem in that light reflection occurs due to adhesion of water droplets and the light transmittance is hindered.
As a solution to such surface performance problems, attention has been paid not only to the water-repellent property “water repellency” hitherto evaluated by contact angle measurement, but also to the property “hydrophilicity” that spreads even when a water droplet adheres.

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

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

As described above, various photocatalysts using titanium oxide and methods for producing a hydrophilic surface using a coating composition have been proposed, but the problem is that the use environment is limited and the hydrophilicity is not sufficient. Moreover, in order to provide the durability of a plastic surface, it was a subject that film | membrane hardness was insufficient.
Thus, 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 intensive studies to achieve the above object, the present inventors have adopted a hydrophilic hyperbranched polymer obtained by introducing a hydrophilic site and a fluorine functional group as a resin surface modifier. The present inventors have found that a hard coat layer capable of improving the hydrophilicity of the surface and exhibiting high hardness by a polyfunctional hard coat can be formed, and the present invention has been completed.

That is, the present invention provides, as a first aspect, a hydrophilic highly branched structure having at least one hydrophilic site selected from the group consisting of an amino group, an amide structure, an ammonium group, and a phosphate structure in the molecule and a fluoroalkyl group. A polymer having a monomer A having two or more radical polymerizable double bonds in the molecule, the at least one hydrophilic site and two or more radical polymerizable double bonds in the molecule; At least two types selected from the group consisting of the monomer B and the monomer C having at least one hydrophilic site and one radical polymerizable double bond in the molecule, or the hydrophilic monomer consisting of the monomer B , A polymerizable compound containing at least the monomer D having the fluoroalkyl group and at least one radical polymerizable double bond in the molecule Relates to hydrophilic, highly branched polymer is a polymer of a polymerization initiator E of 5 ~ 200 mol% weight relative to the total moles of the monomers A and the monomers B.
As a second aspect, the polymerizable compound includes a monomer F having an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may include an ether bond and one radical polymerizable double bond in the molecule. It further relates to the hydrophilic hyperbranched polymer according to the first aspect.
As a third aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the first aspect or the second aspect, wherein each of the radical polymerizable double bonds is independently a vinyl group or a (meth) acryloyl group.
As a fourth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the third aspect, wherein the monomer B is a divinyl compound or a di (meth) acrylate compound.
As a fifth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to any one of the first aspect to the fourth aspect, wherein the monomer B is a compound having a phosphoric acid structure.
As a sixth aspect, the monomer B is bis (2- (meth) acryloyloxyethyl) = hydrogen = phosphate or 1,3-bis ((meth) acryloyloxy) propyl-2-yl = dihydrogen = phosphate. And the hydrophilic hyperbranched polymer described in the fifth aspect.
As a seventh aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the third aspect, in which the monomer A is a divinyl compound or a di (meth) acrylate compound.
As an eighth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the seventh aspect, in which the monomer A is a compound represented by the formula [1].

(In the formula, each 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 represents an integer of 1 to 30. Represents.)
As a ninth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the eighth aspect, wherein L ¹ is an ethylene group.
As a tenth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the eighth aspect or the ninth aspect, wherein a is an integer of 1 to 10.
As an eleventh aspect, any one of the first aspect to the tenth aspect can be obtained 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 hydrophilic hyperbranched polymer described in 1.
As a twelfth aspect, the hydrophilic hyperbranch according to the third to eleventh aspects, wherein the monomer C is at least one compound selected from the group of compounds represented by formula [2] to formula [4]. Relates to polymers.

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

(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, and L ³ represents carbon 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 an SO ₃ ⁻ group, m Represents an integer of 1 to 30.)

(Wherein R ⁹ represents a hydrogen atom or a methyl group, R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, 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 aspect, according to any one of the first aspect to the twelfth aspect, obtained 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. It relates to a hydrophilic hyperbranched polymer.
As a fourteenth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to the third aspect to the thirteenth aspect, in which 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.)
As a fifteenth aspect, the present invention relates to the hydrophilic hyperbranched polymer according to any one of the first aspect to the fourteenth aspect, in which the polymerization initiator E is an azo polymerization initiator.
As a sixteenth aspect, (a) 100 parts by mass of an active energy ray polymerizable polyfunctional monomer, (b) 0.001 to 20 mass of the hydrophilic hyperbranched polymer according to any one of the first aspect to the fifteenth aspect And (c) a polymerizable composition containing 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.
As a seventeenth aspect, the present invention relates to the polymerizable composition according to the sixteenth aspect, in which the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
As an eighteenth aspect, the present invention relates to the polymerizable composition according to the sixteenth aspect or the seventeenth aspect, wherein the (c) polymerization initiator is an alkylphenone compound.
As a nineteenth aspect, the present invention relates to a cured film obtained from the polymerizable composition according to any one of the sixteenth aspect to the eighteenth aspect.
As a twentieth aspect, a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is polymerizable according to any one of the sixteenth aspect to the eighteenth aspect. The present invention relates to a hard coat film which is an ultraviolet curable film of the composition.
A twenty-first aspect relates to the hard coat film according to the twentieth aspect, wherein the hard coat layer has a thickness of 1 to 30 μm.
As a twenty-second aspect, there is provided a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the polymerizable composition according to any one of the sixteenth aspect to the eighteenth aspect is used. The present invention relates to a method for producing a hard coat film, which includes a step of coating a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays and curing.

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

<Hydrophilic highly branched polymer>
In the present invention, an amino group (such as —NH ₂ ), an amide structure (such as —C (═O) —NH—), an ammonium group (such as —N (CH ₃ ) ₃ ⁺ ) and a phosphate structure (— It is intended for a hydrophilic hyperbranched polymer having at least one hydrophilic part selected from the group consisting of O—P (═O) (OH) —O— and the like and a fluoroalkyl group.
Specifically, the present invention relates to a monomer A having two or more radical polymerizable double bonds in the molecule, the at least one hydrophilic portion and two or more radical polymerizable double bonds in the molecule. At least two types selected from the group consisting of monomer B and monomer C having at least one hydrophilic site and one radical polymerizable double bond in the molecule, or a hydrophilic monomer consisting of monomer B; Monomer D having the fluoroalkyl group and at least one radical-polymerizable double bond in the molecule, and optionally 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 radical polymerizable double bond, 5 to 20 with respect to the total number of moles of the monomer A and the monomer B It relates hydrophilic hyperbranched polymer obtained by polymerizing in the presence of mol% of the polymerization initiator E.
Further, the hydrophilic hyperbranched polymer needs other monomers that do not belong to the monomer A, the monomer B, the monomer C, the monomer D, and the monomer F, as long as the effects of the present invention are not impaired. It may be copolymerized accordingly.
The hydrophilic hyperbranched polymer is a so-called initiator fragment incorporation (IFIRP) type hyperbranched polymer, and has a fragment of the polymerization initiator E used for polymerization at the terminal.

[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 one or both of a vinyl group and a (meth) acryloyl group, and particularly a divinyl compound or A di (meth) acrylate compound is preferred. 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.

Among the monomers A, a compound represented by the following formula [1] is particularly preferable.

(In the formula, each 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 represents 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 a hydroxy group represented by L ¹ include, for example, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, a methylethylene group, Tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, decamethylene group, dodecamethylene group, etc. Among these, an ethylene group or a hexamethylene group is preferable from the viewpoint of the surface modification effect.
In the formula [1], a is preferably an integer of 1 to 10.

As said monomer A, the organic compound shown to the following (A1) thru | or (A7) is mentioned, for example.
(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 (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc. (A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, tri Vinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones:
(A2-1) vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (A2-2) allyl ester; diallyl maleate, diallyl phthalate, Diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc. (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl Tons, 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, trimethylol Propane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxy titanium tri (meth) acrylate, dioxane glycol di (meth) acrylate, tricyclo [5.2.1.0 ^{2 , 6} ] decane dimethanol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, 9,9-bis [4- (2- (meta ) Acryloxyoxy Si) 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 and the like (A4) Vinyl compound having a polyalkylene glycol chain:
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 compounds:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide, etc. (A6) silicon-containing vinyl compounds:
Dimethyldivinylsilane, divinyl (methyl) (phenyl) silane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3- Tetraphenyldisilazane, dietodivinylsilane, etc. (A7) Fluorine-containing vinyl compounds:
1,4-divinylperfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinylperfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-divinylperfluorooctane, 1,8-divinyl Hexadecafluorooctane etc.

Among these, preferred are the above-mentioned aromatic vinyl hydrocarbons of the group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), (meth) acrylic of the group (A3). An acid ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (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 portion and two or more radical polymerizable double bonds in the molecule]
In the present invention, the monomer B having at least one hydrophilic portion and two or more radical polymerizable double bonds in the molecule includes at least one of the hydrophilic portions and a vinyl group or a (meth) acryloyl group. It is preferable that it is a compound which has any one or both of these, and it is especially preferable that it is a divinyl compound or di (meth) acrylate compound which has at least 1 sort (s) of the said hydrophilic part.

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

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

[Monomer C having at least one hydrophilic portion and one radical polymerizable double bond in the molecule]
In the present invention, the monomer C having at least one hydrophilic portion and one radical polymerizable double bond is preferably at least one of the hydrophilic portion and either a vinyl group or a (meth) acryloyl group. It is preferable that it is a compound which has these, and it is especially preferable that it is at least 1 sort (s) of compounds selected from the compound group represented by following formula [2] thru | or formula [4].

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

(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, and L ³ represents carbon 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 an SO ₃ ⁻ group, m Represents an integer of 1 to 30.)

(Wherein R ⁹ represents a hydrogen atom or a methyl group, R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, 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.)

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] that may be substituted with a hydroxy group Examples of the alkyl group of formula 1 to 6 include a methyl group, an ethyl group, a 2-hydroxyethyl group, an n-propyl group, an isopropyl group, a 3-hydroxypropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, 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, etc. It is 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 a hydroxy group in L ⁴ in the formula [3] include a methylene group, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, a methylethylene group, Examples 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 these, from the viewpoint of the surface modification effect, L ⁴ is preferably a methylene group.

Examples of the counter anion represented by X ⁻ in formula [2] include halide ions such as chloride ion, bromide ion and iodide ion; benzenesulfonate anion, p-toluenesulfonate anion, methanesulfonate anion, trifluoromethane Examples include sulfonate anions such as sulfonate anions; perchlorate anions; borate anions such as tetrafluoroborate anions and tetraphenylborate anions; hexafluorophosphate anions; acetate anions.

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; (Meth) 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- (3-dimethylaminopropyl) (meta Acrylamides such as acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine; N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethyl Ammonium 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) acryloylo (Meth) acryloyl group-containing 4 such as (ethyl) -N-butyl-N, N-dimethylammonium iodide, N- (2- (meth) acryloyloxypropyl) -N, N-diethyl-N-methylammonium chloride 4 Secondary ammonium salts; 2-((2- (meth) acryloyloxyethyl) dimethylammonio) acetate (also referred to as N- (2- (meth) acryloyloxyethyl) -N, N-dimethylglycine), 3-(( 2- (meth) acryloyloxyethyl) dimethylammonio) propanoate, 4-((2- (meth) acryloyloxyethyl) dimethylammonio) butanoate, 5-((2- (meth) acryloyloxyethyl) dimethylammonio ) Carboxybetaines such as pentanoate; ((2- (meth) acrylo) Yloxyethyl) dimethylammonio) methanesulfonate, 2-((2- (meth) acryloyloxyethyl) dimethylammonio) ethanesulfonate, 3-((2- (meth) acryloyloxyethyl) dimethylammonio) propane- Sulfobetaines such as 1-sulfonate, 4-((2- (meth) acryloyloxyethyl) dimethylammonio) butane-1-sulfonate; 2- (meth) acryloyloxyethyl = dividrogen phosphate, 4- (meth) (Meth) acryloyl group-containing phosphate esters such as acryloyloxybutyl = dividrogen = phosphate; phosphorylcholines such as (2- (meth) acryloyloxyethyl) phosphorylcholine and (4- (meth) acryloyloxybutyl) phosphorylcholine And the like.

Among the above monomers C, N- (2-hydroxyethyl) acrylamide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2- (meth) acryloyloxy Ethyl) -N, N-dimethylglycine, 3-((2- (meth) acryloyloxyethyl) dimethylammonio) propane-1-sulfonate, 2- (meth) acryloyloxyethyl = dibidogen = phosphate, (2- ( (Meth) acryloyloxyethyl) phosphorylcholine is preferred, particularly N- (2-hydroxyethyl) acrylamide, N- (2- (meth) acryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2- (Meth) acryloyloxyethyl) -N, N-dimethyl group Shin, 2- (meth) acryloyloxyethyl = Jibidorogen = phosphate is preferred.

In the present invention, the monomer C is used in an amount of 50 to 1,200 mol% based on 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%.

[Monomer D having the fluoroalkyl group and at least one radical polymerizable double bond in the molecule]
In the present invention, the monomer D having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule preferably has a fluoroalkyl group and either a vinyl group or a (meth) acryloyl group in the molecule. 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.)
Especially, it is preferable that the said monomer D is a compound represented by following formula [6].

(In the formula, R ¹³ represents the same meaning as defined in 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 a monomer D include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl. (Meth) 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-octaful Lopentyl (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-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluoro Octyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) Accel Relay 3- (perfluoro-7-methyl-octyl) -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 monomer D is used in an amount of 50 to 300 mol% with respect to the total number of moles of the monomer A and the monomer B, more preferably 50% 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 polymerization initiator is preferably used. Examples of the azo polymerization initiator include 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 ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
(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) and the like;
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 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-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc .;
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc .;
(5) Other:
Dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid), 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 polymerization initiators, 2,2′-azobis (2-methyl) is preferable from the viewpoint of dispersibility of the hydrophilic hyperbranched 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 mol based on the total number of moles of the monomer A and the monomer B. Used in an amount of mol%.

[Monomer F having an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond and one radical polymerizable double bond in the molecule]
In the present invention, in addition to the monomer A to monomer D, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may contain an ether bond, and a monomer F having one radical polymerizable double bond Further, it may be included. By adding the monomer F, when forming a cured film (hard coat layer), which will be described later, it is possible to suppress the generation of fine particles that impair the surface uniformity, 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 an 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 composed of a combination of these chains or rings, and at least a part of these alkyl groups is interrupted by an ether bond (—O—). Group, preferably a linear alkyl group 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), nonadecyl group, icosyl group, etc. And groups in which at least a part of these are interrupted by an ether bond.

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

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

[Method for producing hydrophilic hyperbranched polymer]
The hydrophilic hyperbranched polymer of the present invention is a polymerizable compound comprising a hydrophilic monomer selected from at least two of the aforementioned monomers A to C or a monomer B, a monomer D, and optionally a monomer F. The polymerization is performed in the presence of a predetermined amount of a 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 bulk polymerization. Among these, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.

Examples of the organic solvent used at this time include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Halides 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; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cello Ethers such as rube and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol and other alcohols; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides; dimethyl sulfoxide, etc. Examples thereof include sulfoxides and a mixed solvent of two or more of these.

Among these, preferred are aromatic hydrocarbons, halides, esters, ester ethers, ethers, ketones, alcohols, amides, etc., and particularly preferred are benzene, toluene, xylene, o -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 relative 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, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2.
The polymerization temperature is arbitrary as long as it is not higher than the boiling point of the reaction mixture, but is preferably 50 to 200 ° C., more preferably 80 to 150 ° C., more preferably 80 to 130 ° C. from the viewpoint of polymerization efficiency and molecular weight control. More preferred.
The reaction time varies depending on the reaction temperature, the monomer A, the monomer B, the monomer C, the monomer D, the polymerization initiator E, and the type and ratio of the monomer F, the polymerization solvent type, 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 hyperbranched polymer is collected by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

The hydrophilic hyperbranched polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography in terms of polystyrene of 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, (b) the hydrophilic hyperbranched polymer 0.001 to 20 A polymerizable composition containing 1 part by mass and 1 to 20 parts by mass of a polymerization initiator that generates a radical by active energy rays is also an object.

[(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 is polymerized by the action of a component (c) polymerization initiator described later, There is no particular limitation as long as it is a compound having two or more, and examples thereof include polyfunctional monomers containing two or more (meth) acryloyl groups such as urethane acrylic, epoxy acrylic and various (meth) acrylates.
Preferably, (a) the 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- Candiol di (meth) 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, dipentaerythritol 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 ] decanedimethanol di (meth) acrylate, Tris (Hydroxyethyl) isocyanurate di (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, ε-caprolactone modified tris (2- (meth) acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) Acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, propylene oxide modified Glycerin tri (meth) acrylate, glycerol tri (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy 1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, etc. Can be mentioned.
These compounds may be used individually by 1 type, and may mix and use 2 or more types as needed.
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 A compound containing four or more (meth) acryloyl groups such as erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate is more preferable.

Also, examples of the polyfunctional urethane (meth) acrylate compound include a urethane compound having two or more (meth) acryloyl groups having an ethylenically unsaturated bond site. The polyfunctional urethane (meth) acrylate compound suitably used in the present invention may be either aliphatic urethane (meth) acrylate or aromatic urethane (meth) acrylate. These compounds may be used individually by 1 type, and may mix and use 2 or more types as needed.

The polyfunctional urethane (meth) acrylate compound suitably used in the present invention is obtained, for example, by a reaction between a polyisocyanate compound and 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-naphthalene diisocyanate, m- Phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dicyclomethane diisocyanate or Of these diisocyanate compounds, diisocyanate compounds obtained by hydrogenating aromatic isocyanates (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate), triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, etc. And an isocyanate group-containing compound such as a divalent or trivalent diisocyanate compound or a polyisocyanate compound, and a multivalent polyisocyanate compound obtained by multiplying them.
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. Propylene 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, Plaxel (registered trademark) FA series and FM series manufactured by Daicel Corporation) 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 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, 264 265, 270, 280 / 15IB, 1259, 5129, 8210, 8301, 8307, 8411, 8804, 8807, 9227EA, 9260, 284, 285, 294 / 25HD 4820, 4858, 8402, 8405, 9270, 8311, 8701, KR 8200, KRM8200AE, KRM7735, KRM8296, KRM8452, etc .; Nippon Synthetic Chemical Co., Ltd .: Purple light (registered trademark) UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7605B -7610B, UV-7620E, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, and the like.

(A) The polyfunctional monomer may be used by mixing the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate.

[(B) Hydrophilic highly branched polymer]
In the polymerizable composition of the present invention, a hydrophilic hyperbranched polymer is used as the component (b). In the polymerizable composition, the hydrophilic hyperbranched polymer serves as a surface modifier that imparts hydrophilicity.
The hydrophilic hyperbranched polymer of the component (b) is preferably 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight per 100 parts by weight of the component (a) active energy ray polymerizable polyfunctional monomer. It is preferably used in an amount of parts by mass.

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

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

Examples of the alkylphenone compounds include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl = phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, 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 phenylglyoxylate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2-((4-methyl Phenyl) methyl) -1- (4-morpholinophenyl) can be given butan-1-one and the like.

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

Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide. 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidostilbene, and the like.

Examples of the diazo compound include 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (N- (2- Carboxyethyl) -2-methylpropionamidine), 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) Butyl)) propionamide), 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propionamide), 2,2′-azobis (2- (5-methyl-2-y) Dazolin-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride, 2,2'-azobis (2- (2-imidazoline- 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-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, 1-diazo-4-N, N-diethylaminobenzeneborofluoride, etc. Raised Rukoto can.

Examples of the o-quinonediazide compounds include 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester, 1,2-naphthoquinone- 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 compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9. And -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

Examples of the benzophenones include benzophenone, 4,4′-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4 -Benzoyl diphenyl ether, benzyl and the like.

Examples of the biscoumarin include 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) (commercially available from Midori Chemical Co., Ltd. as BC (CAS [63226-13-1]). For example).

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

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

Examples of the titanocene 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 Pentadienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5) , 6-Pentafluorophenyl) titanium, bis (methylcyclopentadiene) Bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (cyclopentadienyl) bis (2,6- And difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.

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

The component (c) polymerization initiator 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 component (a) polyfunctional monomer.

In the polymerizable composition of the present invention, unless the effects of the present invention are impaired, additives generally added as necessary, for example, photosensitizers, polymerization inhibitors, polymerization initiators, leveling agents, Surfactants, adhesion-imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, and the like may be appropriately blended.

<Curing film>
The polymerizable composition of the present invention can form a molded product such as a cured film or a laminate by coating on a substrate and photopolymerization (curing). The cured film thus obtained is also an object of the present invention.
Examples of the substrate include plastic materials [polycarbonate, poly (meth) acrylate, polystyrene, polyester (polyethylene terephthalate (PET), etc.), polyolefin, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer. (ABS resin, acrylonitrile-styrene copolymer (AS) resin, norbornene resin, etc.), metal, wood, paper, glass, silicon dioxide, slate, etc., among which plastic materials are preferred. 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 cast on a substrate, a spin coating method, a blade coating method, a dip coating method, Roll coating method, bar coating method, die coating method, spray coating method, curtain coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) are appropriately selected and applied, and then hot plate or oven Etc., and can be formed into a film.
Among these coating methods, it is desirable to use a spin coating method because it can be applied in a short time, so that even a highly volatile solution can be used, and uniform coating can be easily performed. In addition, the roll coating method, bar coating method, die coating method, and spray coating method should be used because of the advantage that it can be applied easily and a smooth coating film can be formed with no coating unevenness in a large area. Is desirable.

The solvent used in the form of the varnish only needs to dissolve or disperse the components (a) to (c) and other components. For example, aromatic carbonization such as benzene, toluene, xylene, ethylbenzene, and tetralin. 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 Halides 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 -Hydroxy-2-methylpropionic acid Chill, methyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl cellosolve acetate, ethyl cellosolve Esters or ester ethers such as 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 Ethers such as ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME) Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, cyclohexanone; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl Alcohols such as alcohol, 2-butanol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl- Examples include amides such as 2-pyrrolidone (NMP); and organic solvents such as sulfoxides such as dimethyl sulfoxide (DMSO). These organic solvents may be used individually by 1 type, and 2 or more types of organic solvents may be mixed and used for them.
The concentration of dissolving or dispersing the components (a) to (c) and other components in the solvent is arbitrary, but the total mass (total) of the components (a) to (c) and other components (solid content) The solid concentration is 0.5 to 80% by mass, preferably 1 to 70% by mass, and more preferably 1 to 60% by mass.
The varnish thus obtained may be subjected to coating after being filtered in advance using a filter having a pore diameter of about 0.2 μm.

After the above-mentioned coating, it is preferably followed by preliminary drying with a hot plate or oven, followed by photocuring by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
Then, you may heat using post-baking, specifically a hot plate, oven, etc. as needed.
The thickness of the film formed by 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>
In addition, the present invention is formed by a step of coating the polymerizable composition, preferably the polymerizable composition in the form of a varnish, on a film substrate to form a coating film, and a step of irradiating the coating film with ultraviolet rays and curing the coating film. A hard coat film provided with a hard coat layer on at least one surface of a film base material is also an object.
The substrate, coating method, and energy ray irradiation such as ultraviolet rays used here are the same as the substrate, coating method, and active energy ray irradiation in the aforementioned <cured film>.
In the hard coat film of the present invention, the thickness of the hard coat layer is preferably 1 to 30 μm, more preferably 1 to 10 μm.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

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

Abbreviations represent the following meanings.
9DMA: Nonaethylene glycol dimethacrylate [Blenmer (registered trademark) PDE-400 manufactured by NOF Corporation]
DMA: ethylene glycol dimethacrylate [Shin Nakamura Chemical Co., Ltd. 1G]
HDN: 1,6-hexanediol dimethacrylate [HD-N manufactured by Shin-Nakamura Chemical Co., Ltd.]
PDMA: Bis (2-methacryloyloxyethyl) = hydrogen = phosphate [Kyoeisha Chemical Co., Ltd. light ester P-2M]
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 (registered trademark) manufactured by KJ Chemicals Co., Ltd.]
PMA: 2-methacryloyloxyethyl = dihydrogen = phosphate [Kyoeisha Chemical Co., Ltd. light ester P-1M]
C1FA: 2,2,2-trifluoroethyl acrylate [Biscoat 3F manufactured by Osaka Organic Chemical Industry Co., Ltd.]
C1FM: 2,2,2-trifluoroethyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester M-3F]
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 [Blenmer (registered trademark) LA manufactured by NOF Corporation]
UV7600: 6-functional urethane acrylate [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light (registered trademark) UV-7600B]
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 A 100 mL reaction flask was charged with 13 g of PGME (4 parts by mass with respect to the amount of monomer B used), and nitrogen was poured for 5 minutes while stirring. The inner solution was heated to reflux (approximately 120 ° C.).
In a separate 50 mL reaction flask, 3.2 g (10 mmol) of PDMA as monomer B, 1.7 g of C1FM (10 mmol, 1 molar equivalent to monomer B) as monomer D, 1.0 g of AMBN (5 mmol, monomer B as polymerization initiator E) 0.5 mole equivalent) and 13 g of PGME (4 parts by mass with respect to the amount of monomer B used) were charged, and nitrogen was introduced for 5 minutes while stirring, followed by nitrogen substitution and cooling to 0 ° C. in an ice bath.
The contents were added dropwise from the 50 mL reaction flask charged with PDMA, C1FM, and AMBN to the refluxed PGME in the 100 mL reaction flask using a dropping pump over 1 hour. After completion of 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 target hyperbranched polymer (HBP1) as a PGME solution having a polymer concentration of 18% by mass.
The obtained highly branched polymer had a weight average molecular weight Mw of 4,900 and a dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) of 5.9 as measured by GPC.

[Examples 2 to 7] Production of hydrophilic hyperbranched polymers having fluoroalkyl groups (HBP2 to HBP7) Each hyperbranched polymer was produced in the same manner as in Example 1 according to the description in Table 1. Monomer A, monomer C, and monomer F were mixed and charged together with monomer B, monomer D, and initiator E.
In Table 1, [molar equivalent] in monomer C, monomer D, monomer F and polymerization initiator E indicates the molar equivalent to the total number of moles of monomer A and monomer B, respectively, and [part by mass] in PGME. , Parts by mass relative to a total of 1 part by mass of monomer A and monomer B. In addition, 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 mixed with each monomer.
Table 1 also shows the polymer concentration of the obtained hyperbranched polymer PGME solution, the weight average molecular weight: Mw and the dispersity: Mw / Mn measured in terms of polystyrene by GPC.

[Production Example 1] Production of hydrophilic hyperbranched polymer having no fluoroalkyl group (HBP8) A hyperbranched 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 hyperbranched polymer PGME solution, the weight average molecular weight: Mw and the dispersity: Mw / Mn measured in terms of polystyrene by GPC.

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

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

As shown in Table 2, the hydrophilic hyperbranched polymer (HBP1 to HBP7) having a fluoroalkyl group of the present invention is compared with a hard coat layer (Comparative Example 1) that does not use a surface modifier. In the hard coat layers added as (Examples 8 to 15), the contact angle of water was small. That is, the hydrophilic hyperbranched polymer having a fluoroalkyl group according to the present invention was able to give the hard coat surface hydrophilicity with a small addition amount.
Moreover, the result that the surface uniformity of the obtained hard-coat layer can be improved more by adding the monomer F was obtained.
On the other hand, in the hard coat layer (Comparative Example 2) using the hydrophilic hyperbranched polymer (HPB8) that does not contain a fluoroalkyl group, the contact angle of water is extremely large as compared with the above example, and the hyperbranched polymer As a result, almost no hydrophilicity could be imparted to the hard coat layer surface.

Claims (22)

1. A hydrophilic hyperbranched polymer having in the molecule at least one hydrophilic portion selected from the group consisting of an amino group, an amide structure, an ammonium group and a phosphoric acid structure and a fluoroalkyl group,
   The polymer is
   Monomer A having two or more radically polymerizable double bonds in the molecule, monomer B having at least one hydrophilic site and two or more radically polymerizable double bonds in the molecule, and at least the above in the molecule At least two types selected from the group consisting of monomers C having one hydrophilic part and one radical polymerizable double bond, or a hydrophilic monomer consisting of the monomer B;
   A polymerizable compound comprising at least the fluoroalkyl group and a monomer D having at least one radical polymerizable double bond in the molecule;
   A hydrophilic hyperbranched polymer which is a polymerized product with a polymerization initiator E in an amount of 5 to 200 mol% based on the total number of moles of the monomer A and the monomer B.
2. The polymerizable compound further includes a monomer F having an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may include an ether bond and one radical polymerizable double bond in the molecule. Item 2. The hydrophilic highly branched polymer according to Item 1.
3. The hydrophilic hyperbranched polymer according to claim 1 or 2, wherein the radical polymerizable double bond is independently a vinyl group or a (meth) acryloyl group.
4. The hydrophilic hyperbranched polymer according to claim 3, wherein the monomer B is a divinyl compound or a di (meth) acrylate compound.
5. The hydrophilic highly branched polymer according to any one of claims 1 to 4, wherein the monomer B is a compound having a phosphoric acid structure.
6. The monomer B is bis (2- (meth) acryloyloxyethyl) = hydrogen = phosphate or 1,3-bis ((meth) acryloyloxy) propyl-2-yl = dihydrogen = phosphate according to claim 5. The hydrophilic hyperbranched polymer described.
7. The hydrophilic highly branched polymer according to claim 3, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.
8. The hydrophilic highly branched polymer according to claim 7, wherein the monomer A is a compound represented by the formula [1].
   

   

   (In the formula, each 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 represents an integer of 1 to 30. Represents.)
9. The hydrophilic hyperbranched polymer according to claim 8, wherein L ¹ is an ethylene group.
10. The hydrophilic hyperbranched polymer according to claim 8 or 9, wherein a is an integer of 1 to 10.
11. The hydrophilicity according to any one of claims 1 to 10, obtained using the monomer C in an amount of 50 to 1,200 mol% based on the total number of moles of the monomer A and the monomer B. Hyperbranched polymer.
12. The hydrophilic highly branched polymer according to claim 3, wherein the monomer C is at least one compound selected from the group of compounds represented by formulas [2] to [4].
    

    

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

    

    (Wherein R ⁶ represents a hydrogen atom or a methyl group, R ^{7 and} R ⁸ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, and L ³ represents Represents an alkylene group having 2 to 12 carbon 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 an SO ₃ ⁻ group, m represents an integer of 1 to 30.)
    

    

    (Wherein R ⁹ represents a hydrogen atom or a methyl group, R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, 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.)
13. The hydrophilic hyperbranch according to any one of claims 1 to 12, obtained by using the monomer D in an amount of 50 to 300 mol% based on the total number of moles of the monomer A and the monomer B. polymer.
14. The hydrophilic highly branched polymer according to claim 3, 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.)
15. The hydrophilic hyperbranched polymer according to any one of claims 1 to 14, wherein the polymerization initiator E is an azo polymerization initiator.
16. (A) 100 parts by mass of an active energy ray polymerizable polyfunctional monomer,
    (B) 0.001 to 20 parts by mass of the hydrophilic hyperbranched polymer according to any one of claims 1 to 15, and (c) a polymerization initiator 1 to 20 that generates radicals by active energy rays. Polymeric composition containing a mass part.
17. The polymerizable composition according to claim 16, wherein the (a) polyfunctional monomer is a polyfunctional (meth) acrylate compound.
18. The polymerizable composition according to claim 16 or 17, wherein (c) the polymerization initiator is an alkylphenone compound.
19. A cured film obtained from the polymerizable composition according to any one of claims 16 to 18.
20. 19. A hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is UV-cured of the polymerizable composition according to claim 16. Hard coat film that is a film.
21. The hard coat film according to claim 20, wherein the hard coat layer has a thickness of 1 to 30 μm.
22. A method for producing a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the polymerizable composition according to any one of claims 16 to 18 is applied on the film substrate. The manufacturing method of a hard coat film including the process of apply | coating and forming a coating film, and the process of irradiating an ultraviolet-ray to a coating film and hardening.