JP6674146B2 - Lipophilic hyperbranched polymer and polymerizable composition containing the same - Google Patents

Description

  The present invention relates to a lipophilic hyperbranched polymer, a polymerizable composition containing the same, a cured film obtained from the polymerizable composition, and a laminate containing the same as a hard coat layer. Specifically, the present invention relates to a polymerizable composition capable of forming a lipophilic hard coat layer that exhibits higher slipperiness.

  Polymer materials have been increasingly used in many fields in recent years. Along with this, the properties of the surface and interface as well as the polymer properties of the matrix have become important according to the respective fields. For example, by using a fluorine compound having a low surface free energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peeling properties, mold release properties, slip properties, abrasion resistance, and antireflection properties are obtained. Improvements in characteristics related to interface control such as chemical resistance are expected, and various proposals have been made.

  A water- and oil-repellent active energy ray-curable coating composition using a surface modifier made of a fluorine-based polymer and a silicone-based compound is used for various displays such as LCD (liquid crystal display), PDP (plasma display), and touch panel. It has been widely studied as various plastic films having a coating layer for preventing scratches. These repel water and oil components contained in fingerprints, exhibiting an effect of preventing fingerprint adhesion, and have the advantage of facilitating wiping of fingerprints. However, on the other hand, the adhering water / oil component forms fine droplets having a large contact angle, scatters light to give a cloudy appearance, and the fingerprint is rather conspicuous.

  On the other hand, an active energy ray-curable coating composition which gives a so-called lipophilic surface, which makes a fingerprint or a sebum component dirty to make the stain less noticeable (Patent Documents 1 and 2).

  By the way, the touch panel display of many smartphones employs a multi-touch function, and a pinch operation for enlarging (pinch-out) or reducing (pinch-in) the screen using a plurality of fingers, and a flick operation for swiping a finger in a certain direction on the screen. And a swipe operation. In order to obtain a smooth tactile sensation without being caught by the movement of the finger, there is a demand for slipperiness when the display surface is touched with a finger.

International Publication WO2012 / 128214 pamphlet JP 2011-42795 A

  As described above, various studies have been made on lipophilic materials, but these lipophilic surfaces have a higher coefficient of friction than water- and oil-repellent surfaces using fluoropolymers or silicone compounds, and have been contacted with fingers. The problem was that the tactile sensation was poor. That is, there has been a demand for a lipophilic hard coat layer that exhibits higher slipperiness.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, in a so-called highly fragmented polymer incorporating an initiator fragment, a lipophilic monomer having an aliphatic hydrocarbon group having 6 to 30 carbon atoms in the molecule. By adopting a lipophilic hyperbranched polymer occupying a larger proportion of the derived structure, as a resin surface modifier, it was found that a lipophilic cured film having good surface slipperiness could be formed, and the present invention was completed. Was.

That is, the present invention provides, as a first aspect, (a) 100 parts by mass of an active energy ray-polymerizable polyfunctional monomer, (b) 0.001 to 20 parts by mass of a lipophilic hyperbranched polymer, and (c) an active energy ray. A polymerizable composition comprising 1 to 20 parts by mass of a radical-generating polymerization initiator, wherein the (b) lipophilic hyperbranched polymer has a monomer A having two or more radically polymerizable double bonds in a molecule. And at least a monomer B having an aliphatic hydrocarbon group having 6 to 30 carbon atoms and at least one radical polymerizable double bond in a molecule, and the amount of the monomer B is based on the number of moles of the monomer A. A parent compound obtained by polymerizing a polymerizable compound in an amount of 400 to 1500 mol% with respect to the number of moles of the monomer A in the presence of a polymerization initiator C in an amount of 5 to 200 mol%. A sexual hyperbranched polymers, to the polymerizable composition.
As a second aspect, the monomer A is a divinyl compound or a di (meth) acrylate compound, the monomer B is a compound represented by the formula [2], and the polymerization initiator C is an azo-based polymerization initiator. The polymerizable composition according to the first aspect,
(Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms, L ² represents an alkylene group having 2 to 6 carbon atoms, and m represents Represents an integer of 0 to 30.)
As a third aspect, the present invention relates to the polymerizable composition according to the first aspect or the second aspect, wherein the polymerizable compound further includes a monomer D represented by the formula [3].
(Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, L ³ represents an alkylene group having 2 to 6 carbon atoms, and k is Represents an integer of 1 to 30)
As a fourth aspect, the (a) polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound, according to the first to third aspects. It relates to the polymerizable composition described in any one of the above.
As a fifth aspect, the present invention relates to the polymerizable composition according to any one of the first to fourth aspects, wherein the (c) polymerization initiator is an alkylphenone compound.
As a sixth aspect, the present invention relates to the polymerizable composition according to any one of the first to fifth aspects, further including (d) a solvent.
As a seventh aspect, the present invention relates to a cured film obtained from the polymerizable composition according to any one of the first to sixth aspects.
As an eighth aspect, a laminate comprising a hard coat layer on at least one surface of the substrate, wherein the hard coat layer is a polymerizable composition according to any one of the first to sixth aspects. To a laminate, which is formed by a method including a step of coating a coating on a base material to form a coating film, and a step of irradiating the coating film with ultraviolet rays to cure the coating film.
As a ninth aspect, the present invention relates to the laminate according to the eighth aspect, wherein the hard coat layer has a thickness of 1 to 30 μm.
As a tenth aspect, a monomer A having two or more radically polymerizable double bonds in the molecule, an aliphatic hydrocarbon group having 6 to 30 carbon atoms in the molecule and at least one radically polymerizable double bond A polymerizable compound containing at least a monomer B having the following formula: wherein the amount of the monomer B is 400 to 1500 mol% based on the number of moles of the monomer A; The present invention relates to a lipophilic hyperbranched polymer obtained by polymerizing in the presence of a polymerization initiator C.
As an eleventh aspect, the present invention relates to the lipophilic hyperbranched polymer according to the tenth aspect, wherein the monomer A is a compound having at least one of a vinyl group and a (meth) acryl group.
As a twelfth aspect, the present invention relates to the lipophilic hyperbranched polymer according to the eleventh aspect, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.
As a thirteenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to the twelfth aspect, wherein the monomer A is a compound represented by the formula [1].
(Wherein, R ¹ and R ² each independently represent 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 n represents 1 Represents an integer of from 30 to 30)
As a fourteenth aspect, the high lipophilicity according to any one of the tenth to thirteenth aspects, wherein the monomer B is a compound having at least one of a vinyl group and a (meth) acryl group. Related to branched polymers.
As a fifteenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to the fourteenth aspect, wherein the monomer B is a compound represented by the formula [2].
(Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms, L ² represents an alkylene group having 2 to 6 carbon atoms, and m represents Represents an integer of 0 to 30.)
As a sixteenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to the fifteenth aspect, wherein m is 0.
As a seventeenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to any one of the tenth to sixteenth aspects, wherein the polymerization initiator C is an azo-based polymerization initiator.
As an eighteenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to any one of the tenth to seventeenth aspects, wherein the polymerizable compound further includes a monomer D represented by the formula [3].
(Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, L ³ represents an alkylene group having 2 to 6 carbon atoms, and k is Represents an integer of 1 to 30)
As a nineteenth aspect, the present invention relates to the lipophilic hyperbranched polymer according to the eighteenth aspect, which is obtained by using the monomer D in an amount of 5 to 500 mol% based on the number of moles of the monomer A.
As a twentieth aspect, the present invention relates to a varnish containing the lipophilic hyperbranched polymer according to any one of the tenth to nineteenth aspects.

Since the lipophilic hyperbranched polymer of the present invention actively introduces a branched structure, entanglement between molecules is smaller than that of a linear polymer and shows a fine particle-like behavior. High dispersibility. For this reason, in the resin which is the matrix, the aggregation of the highly branched polymer is prevented, and it is easy to move to the surface, and it is easy to give an activity (eg, lipophilicity) to the resin surface. Therefore, by adding the lipophilic hyperbranched polymer of the present invention to the polymerizable composition, the surface of the cured film obtained from the composition can be hardened without impairing the original hardness of the hard coat and excellent scratch resistance. And surface modification properties such as lipophilicity (fingerprint resistance) can be easily provided.
In short, the polymerizable composition of the present invention has an effect that it has an excellent slidability and can form a lipophilic cured film (hard coat layer) in which fingerprints and sebum components are not conspicuous. By adding the lipophilic hyperbranched polymer to the polymerizable composition, there is an effect that a slip property and a lipophilic property can be imparted to the surface of a cured film formed from the composition.

<< polymerizable composition >>
<(A) Active energy ray polymerizable polyfunctional monomer>
As the above-mentioned component (a) active energy ray polymerizable polyfunctional monomer (hereinafter, also simply referred to as component (a) polyfunctional monomer), a polymerizable site which is polymerized by the action of a component (c) polymerization initiator described later, There is no particular limitation as long as the compound has two or more in the molecule. Examples thereof include polyfunctional monomers containing two or more (meth) acryl groups such as urethane acrylic, epoxy acrylic, and various (meth) acrylates. Can be
Preferably, the component (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. 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-added pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) Acrylate, tricyclo [5.2.1.0 ^2,6 ] decane dimethanol di (meth) acrylate, Lis (hydroxyethyl) isocyanurate di (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, ditrimethylolpropanetetra ( (Meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, tris ((meth) acryloyloxyethyl) phosphate, modified ε-caprolactone tri (meth) acrylate, propylene oxide Additional glycerin tris (meth) acrylate, glycerol tri (meth) acrylate, dioxane glycol di (meth) acryle G, 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 and the like can be mentioned.
These compounds may be used alone or as a mixture of two or more as necessary.
Among these examples, compounds containing three or more (meth) acryl groups such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable, and pentaerythritol tetra (meth) acrylate, dipenta Compounds containing four or more (meth) acryl groups, such as erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, are more preferred.

  Examples of the polyfunctional urethane (meth) acrylate compound include urethane compounds having two or more (meth) acryl groups having an ethylenically unsaturated bond site. The polyfunctional urethane (meth) acrylate compound suitably used in the present invention may be either an aliphatic urethane (meth) acrylate or an aromatic urethane (meth) acrylate. These compounds may be used alone or as a mixture of two or more as necessary.

The polyfunctional urethane (meth) acrylate compound suitably 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-naphthalene diisocyanate, and 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 Among 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. Isocyanate group-containing compounds such as divalent or trivalent diisocyanate compounds or polyisocyanate compounds, and multimeric polyisocyanate compounds obtained by multiplying these compounds.
Examples of the (meth) acrylic monomer having active hydrogen include, for example, 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, Praxel (registered trademark) FA series and FM series manufactured by Daicel Corporation) can also be used. Also, dipentaerythritol poly (meth) acrylate (for example, “DPHA” manufactured by Daicel Ornex Co., Ltd.) can be used.

  Specific examples of commercially available products of these polyfunctional urethane (meth) acrylate compounds include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF manufactured by Kyoeisha Chemical Co., Ltd. -8001G, DAUA-167, etc .; manufactured by Daicel Ornex Co., Ltd .: EBECRYL (registered trademark) 204, 205, 210, 215, 220, 6202, 230, 244, 245, 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, RM8200, KRM8200AE, KRM7735, KRM8296, KRM8452; manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Shikko (registered trademark) UV-1700B, UV-6300B, UV-7550B, UV7600B, UV-7605B, UV-7610B , UV-7620E, UV-7620EA, UV-7630B, UV-7640B, UV-7650B and the like.

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

<(B) Lipophilic highly branched polymer>
Component (b) is a lipophilic hyperbranched polymer comprising a monomer A having two or more radically polymerizable double bonds in the molecule, an aliphatic hydrocarbon group having 6 to 30 carbon atoms in the molecule, and at least one A polymerizable compound containing at least a monomer B having a radical polymerizable double bond, wherein the amount of the monomer B is 400 to 1500 mol% based on the number of moles of the monomer A, By polymerization in the presence of a polymerization initiator C in an amount of 5 to 200 mol%.
The lipophilic hyperbranched polymer is a so-called initiator fragment incorporation (IFIRP) type hyperbranched polymer, and has a fragment of the polymerization initiator C used for polymerization at its terminal.

[Polymerizable compound]
[Monomer A]
In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has at least one of a vinyl group and a (meth) acryl group, and particularly a divinyl compound or a di ( It is preferably a 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.

  Among the monomers A, compounds represented by the following formula [1] are particularly preferable.

In the above formula [1], R ¹ and R ² each independently represent 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, n represents an integer of 1 to 30.

Examples of the alkylene group having 2 to 12 carbon atoms which may be substituted with the hydroxy group represented by L ¹ include an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, a methylethylene group, a tetramethylene group, Methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, decamethylene group, dodecamethylene group, (tricyclo [5.2.1.0 ^{2 , 6} ] decane-2,5-diyl) bismethylene group and the like.
Among these, an ethylene group and a hexamethylene group are preferable from the viewpoint of the surface modification effect.

  From the viewpoint of the surface modification effect, n in the formula [1] is preferably an integer of 1 to 10.

  Examples of such a monomer A include the following compounds (A1) to (A5).

(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, cyclooctadiene, norbornadiene and the like.
(A1-3) Aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine and the like.

(A2) Vinyl ester, allyl ester, vinyl ether, allyl ether and vinyl ketone:
(A2-1) Vinyl esters; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate and the like.
(A2-2) Allyl esters: diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth) acrylate and the like.
(A2-3) Vinyl ethers: divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like.
(A2-4) Allyl ether; diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane and the like.
(A2-5) Vinyl ketone; divinyl ketone, diallyl ketone and the like.

(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, trimethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10 Decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (Meth) acryloyloxypropane, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dioxane glycol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) ) Acrylate, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluoro Len, bis [2- (meth) acryloylthioethyl] sulfide, bis [4- (meth) acryloylthiophenyl] sulfide, alkoxytitanium tri (meth) acrylate, isophorone urethane di (meth) acrylate, aliphatic urethane di (meth) Acrylate, aromatic 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, ethylene oxide-added polypropylene glycol (molecular weight: 700, etc.) di (meth) acrylate and the like.

(A5) Nitrogen-containing vinyl compound:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylene bis (meth) acrylamide, bismaleimide and the like.

  These monomers A may be used alone or in combination of two or more.

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), and (meth) acrylic groups of the group (A3). Acid esters, vinyl compounds having a polyalkylene glycol chain of the group (A4), and nitrogen-containing vinyl compounds of the group (A5), more preferably (meth) acrylate esters of the group (A3). Particularly preferred are ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) from the viewpoints of lipophilicity and resin dispersibility. ) Acrylate and tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate. Among them, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate are more preferable.

[Monomer B]
In the present invention, the monomer B having an aliphatic hydrocarbon group having 6 to 30 carbon atoms and at least one radical polymerizable double bond in the molecule has at least one of a vinyl group and a (meth) acryl group. It is preferable to have one, and particularly preferable is a compound represented by the following formula [2].

In the above formula [2], R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms, and L ² represents an alkylene group having 2 to 6 carbon atoms. , M represents an integer of 0 to 30.

Examples of the aliphatic hydrocarbon group having 6 to 30 carbon atoms represented by R ⁴ include a hexyl group, an ethylhexyl group, a 3,5,5-trimethylhexyl group, a heptyl group, an octyl group, a 2-octyl group, and an isooctyl group. , Nonyl, decyl, isodecyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), hexadecyl (palmityl), octadecyl (stearyl), isostearyl, aralkyl Linear or branched alkyl groups such as behenyl group, lignoceryl group, serotoyl group, montanyl group, merissyl group; cyclohexyl group, 4-tert-butylcyclohexyl group, isobornyl group, norbornenyl group, menthyl group, adamantyl group, tricyclo [5.2.1.0 ^2,6] decanyl group, etc. Such alicyclic group.
Among these, an aliphatic hydrocarbon group having 8 to 20 carbon atoms is preferable from the viewpoint of lipophilicity and slipperiness, and for example, a lauryl group and an isostearyl group are preferable.

The alkylene group of 2 to 6 carbon atoms L ² represents, for example, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyl trimethylene And a hexamethylene group.
Among these, an ethylene group is preferable from the viewpoint of the surface modification effect.

  From the viewpoint of the surface modification effect, m in the formula [2] is preferably 0.

Examples of such a monomer B include hexyl (meth) acrylate, ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-octyl. (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, palmityl (meth) ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl Meth) acrylate, isobornyl (meth) acrylate, norbornene (meth) acrylate, menthyl (meth) acrylate, adamantane (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decane (meth) acrylate, 2- ( Hexyloxy) ethyl (meth) acrylate, 2- (lauryloxy) ethyl (meth) acrylate, 2- (stearyloxy) ethyl (meth) acrylate, 2- (isostearyloxy) ethyl (meth) acrylate, 2- (cyclohexyl) Oxy) ethyl (meth) acrylate, trimethylene glycol = monolauryl ether = (meth) acrylate, tetramethylene glycol = monolauryl ether = (meth) acrylate, hexamethylene glycol = monolauryl ether = (Meth) acrylate, diethylene glycol = monostearyl ether = (meth) acrylate, triethylene glycol = monostearyl ether = (meth) acrylate, tetraethylene glycol = monolauryl ether = (meth) acrylate, tetraethylene glycol = monostearyl ether = (Meth) acrylate, tetraethylene glycol = monoisostearyl ether = (meth) acrylate, hexaethylene glycol = monostearyl ether = (meth) acrylate, and the like.
These monomers B may be used alone or in combination of two or more.

  From the viewpoint of the reactivity (polymerizability) of the polymerizable compound and the surface modification effect of the highly branched polymer obtained by polymerization, the monomer B is used in an amount of 400 to 1500 mol% based on the number of moles of the monomer A, and is preferably used. Is used in an amount of 400 to 1000 mol%, more preferably 500 to 700 mol%.

[Monomer D]
The polymerizable compound used in the present invention may include a compound represented by the following formula [3] as monomer D in addition to the monomers A and B.

In the above formula [3], R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L ³ represents an alkylene group having 2 to 6 carbon atoms. , K represents an integer of 1 to 30.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, Examples include an n-pentyl group, an isoamyl group, a neopentyl group, a tert-amyl group, a sec-isoamyl group, and a cyclopentyl group.

Examples of the alkylene group having 2 to 6 carbon atoms represented by L ³ include the same groups as those exemplified as L ² in the above formula [2].
Among these, an ethylene group and a methylethylene group are preferable from the viewpoint of the surface modification effect.

  From the viewpoint of the surface modification effect, k in the formula [3] is preferably an integer of 1 to 10.

Examples of such a monomer D include 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and polyethylene glycol mono ( (Meth) acrylate (the number of ethylene glycol units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) , 23), polyethylene glycol = monomethyl ether = (meth) acrylate (number of ethylene glycol units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16) , 17, 18, 19, 20, 21, 22, 23), polyethylene glycol = monoethyl ether = (meth ) Acrylate (the number of ethylene glycol units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 22) 23, etc.), polyethylene glycol = monobutyl ether = (meth) acrylate (the number of ethylene glycol units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 16 17, 18, 19, 20, 21, 22, 23), propylene glycol = monomethyl ether = (meth) acrylate, propylene glycol = monoethyl ether = (meth) acrylate, propylene glycol = monobutyl ether = (meth) acrylate, Polypropylene glycol = monomethyl ether = (meth) acrylate (propylene glycol Number of units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, etc.), 4 -Hydroxybutyl (meth) acrylate and the like.
These monomers D may be used alone or in combination of two or more.

  Of these, preferred are 2-methoxyethyl (meth) acrylate and polyethylene glycol mono (meth) acrylate (the number of ethylene glycol units: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12). , 13, 14, 15, 15, 16, 17, 18, 19, 20, 21, 22, 23, etc.), polyethylene glycol = monomethyl ether = (meth) acrylate (the number of ethylene glycol units: 2, 3, 4, 5, 6) , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, etc.). Among these, tetraethylene glycol = monomethyl ether = (meth) acrylate and nonaethylene glycol = monomethyl ether = (meth) acrylate are more preferable.

[Other monomers]
The polymerizable compound used in the present invention may include other monomers that do not belong to the monomers A, B and D as long as the effects of the present invention are not impaired.
The other monomer is not particularly limited as long as it has one radical polymerizable double bond in the molecule, but is preferably a vinyl compound or a (meth) acrylate compound.
Examples of such a monomer include the following compounds (1) and (2).

(1) Fluorine-containing monomer:
2- (trifluoromethyl) acrylic acid, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3- Pentafluoropropyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) ) Acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, and the like.

(2) Silicon-containing monomer:
3- (triethoxysilyl) propyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (dimethoxy (methyl) silyl) propyl (meth) acrylate, trimethoxy (vinyl) silane, triethoxy (vinyl) ) Silane, tris (2-methoxyethoxy) (vinyl) silane, dimethoxy (methyl) (vinyl) silane, 4- (trimethoxysilyl) styrene and the like.

[Polymerization initiator C]
In the present invention, as the polymerization initiator C, an azo-based polymerization initiator is preferably used. Examples of the azo-based polymerization initiator include the following compounds (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 and the like.

(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (N- (2-carboxyethyl) -2-methylpropionamidine) tetrahydrate and the like.

(5) Others:
2,2′-azobis (methyl isobutyrate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis ( 1-acetoxy-1-phenylethane), 1,1′-azobis (methyl 1-cyclohexanecarboxylate), 4,4′-azobis (2- (perfluoromethyl) ethyl 4-cyanopentanoate), 4,4 '-Azobis (2- (perfluorobutyl) ethyl 4-cyanopentanoate), 4,4'-azobis (2- (perfluorohexyl) ethyl 4-cyanopentanoate) and the like.

  Among these, 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobis ( 2,4-dimethylvaleronitrile) is preferred.

  The polymerization initiator C is used in an amount of 5 to 200 mol%, preferably 20 to 200 mol%, more preferably 20 to 100 mol%, based on the number of moles of the monomer A.

[Method for producing lipophilic hyperbranched polymer]
The lipophilic hyperbranched polymer of the present invention is obtained by polymerizing the above-mentioned monomer A and monomer B and optionally monomer D in the presence of a predetermined amount of polymerization initiator C with respect to monomer A. Examples of the polymerization method include known methods, for example, solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization. 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 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 celloso And ethers such as propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol and tert. Alcohols such as -butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol and ethylene glycol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide And a mixed solvent of two or more of these.

  Among these, preferred are aromatic hydrocarbons, halides, esters, ester ethers, ethers, ketones, alcohols, amides and the like, 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, isopropyl alcohol, 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 performed in the presence of an organic solvent, the mass of the organic solvent is usually 3 to 100 parts by mass, and preferably 5 to 50 parts by mass with respect to 1 part by mass of the monomer A.

The polymerization reaction is carried out at normal pressure, under pressure or under reduced pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, it is preferable to perform the treatment under an atmosphere of an inert gas such as N ₂ .
The polymerization temperature is optional as long as it is equal to or lower than the boiling point of the reaction mixture, but is preferably from 50 to 200 ° C, more preferably from 80 to 150 ° C, and from 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 polymerization initiator C and, if desired, the type and ratio of the monomer D, the type of the polymerization solvent, etc., but cannot be unconditionally specified, but is preferably 30 to 720 minutes, more preferably 40 to 540 minutes.
After completion of the polymerization reaction, the obtained lipophilic hyperbranched polymer is recovered by an optional 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 weight average molecular weight (Mw) of the lipophilic hyperbranched polymer measured in terms of polystyrene by gel permeation chromatography is 1,000 to 400,000, preferably 1,000 to 200,000, more preferably 1,000. ~ 50,000.

In the polymerizable composition of the present invention, the component (b) the lipophilic hyperbranched polymer serves as a surface modifier for imparting lipophilicity and slipperiness to the surface of a cured film or hard coat obtained from the polymerizable composition. Is provided.
The component (b) lipophilic hyperbranched polymer is used in an amount of 0.001 to 20 parts by mass, for example 0.01 to 10 parts by mass, based on 100 parts by mass of the component (a) active energy ray-polymerizable polyfunctional monomer. Is preferred.
In addition, the component (b) lipophilic hyperbranched polymer can be blended with the polymerizable composition in the form of a varnish dissolved or dispersed in a solvent capable of dissolving or dispersing the polymerizable composition shown below.

<(C) Polymerization initiator generating radical by active energy ray>
The component (c) a polymerization initiator that generates a radical by an active energy ray (hereinafter, also simply referred to as a component (c) a polymerization initiator) is, for example, a compound that generates an active radical upon irradiation with an active energy ray such as ultraviolet light (light). Any (photoradical polymerization initiator) can be used without particular limitation.
Such photo-radical polymerization initiators include, for example, 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 may be used as a mixture of two or more as needed.

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

  Examples of the alkylphenone-based compound include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl = phenyl = ketone, 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-methylphenyl ) Methyl) -1- (4-morpholinophenyl) can be given butan-1-one and the like.

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

  Examples of the azide compound include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, and 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-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), and 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-imida) Phosphorus-2-yl) propane) hydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) hydrochloride, 2,2′-azobis (2- (2-imidazoline-2-) Yl) propane) sulfate, 2,2′-azobis (2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane) hydrochloride, 2,2′-azobis (2- (1- ( 2-hydroxyethyl) -2-imidazolin-2-yl) propane) hydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane), 1-diazo-2,5-diethoxy- Examples thereof include 4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzenechloride, 1-diazo-4-N, N-diethylaminobenzeneborofluoride and the like.

  Examples of the o-quinonediazide compound include 1,2-naphthoquinonediazide- (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide- (2) -5-sulfonic acid ester, and 1,2-naphthoquinonediazide- (2) -5-sulfonic acid ester. Naphthoquinonediazide- (2) -4-sulfonyl chloride and the like can be mentioned.

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

  Examples of the oxime ester-based compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9 -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, -Benzoyldiphenyl ether, benzyl and the like.

  As the above biscoumarin, for example, commercially available as 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) (BC (CAS [63226-13-1] by Midori Kagaku)) And the like).

  Examples of the bisimidazole compound include, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-bi 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, di-tert-butyl peroxide, and the like.

  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 (methylcyclopentadienyl) ) Bis (2,3,5,6-tetrafluorophenyl) titanium, bis (2,6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (cyclopentadienyl) bis (2,6-difluoro -3- (1H-pyrrol-1-yl) phenyl) titanium and the like.

  Among the component (c) polymerization initiators, an alkylphenone compound is particularly preferred. As the alkylphenone-based photopolymerization initiator, a commercially available photopolymerization initiator can be used. For example, BASF Japan K.K .: IRGACURE (registered trademark) 651, 184, 959, 127, 907, and 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, based on 100 parts by mass of the component (a) polyfunctional monomer.

  In the polymerizable composition of the present invention, as long as the effects of the present invention are not impaired, additives generally added as necessary, for example, a photosensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, Surfactants, adhesion promoters, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, and the like may be appropriately blended.

<(D) Solvent>
The polymerizable composition of the present invention can be dissolved or dispersed in a solvent to form a varnish (film-forming material).
The solvent used in the form of the varnish may be any solvent capable of dissolving or dispersing the components (a) to (c) and other components. For example, aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin may be used. 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; -Hydroxy-2-methylpropionic acid Tyl, methyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl cellosolve acetate, ethyl cellosolve Ester or ester ether 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 and propylene glycol monomethyl ether (PGME) Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone and cyclohexanone; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol , Sec-butyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, and other alcohols; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl- Organic solvents such as amides such as 2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO). These organic solvents may be used alone or in a combination of two or more.
The concentration at which the above components (a) to (c) and other components are dissolved or dispersed in a solvent is arbitrary, but the components (a) to (c) and other components (solid content) and the total mass of the solvent (total) (Mass), 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.
The varnish thus obtained may be one that has been previously filtered using a filter having a pore size of about 0.2 μm.

<Curing film>
The polymerizable composition of the present invention or a varnish obtained by dissolving or dispersing the composition in a solvent is coated on a substrate and photopolymerized (cured) to form a molded product such as a cured film or a laminate. Can be. 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, polyamide, polyimide, polyamideimide, epoxy resin, melamine resin, triacetyl cellulose, ABS (acrylonitrile-butadiene-styrene copolymer) resin, AS (acrylonitrile-styrene copolymer) resin, norbornene resin, etc., FRP (fiber reinforced plastic), metal, wood, paper, glass, silicon dioxide, slate, etc. Among them, a plastic material is preferable. The shape of these substrates may be plate-like, film-like, or three-dimensionally formed.

The polymerizable composition of the present invention, preferably a varnish-form polymerizable composition, is cast-coated on a substrate, spin-coated, blade-coated, dip-coated, roll-coated, bar-coated, die-coated, Spray coat method, curtain coat method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) can be appropriately selected and applied, and then dried on a hot plate or oven to form a film. it can.
Among these coating methods, it is desirable to use a spin coating method because of the advantage that a solution having high volatility can be used because it can be applied in a short time and that uniform coating can be easily performed. In addition, the roll coating method, the bar coating method, the die coating method, and the spray coating method are used because they can be easily applied and can form a smooth coating film without coating unevenness on a large area. Is desirable.

After the coating, preferably, the coating is preliminarily dried (prebaked) on a hot plate or an oven, and then is irradiated with active energy rays such as ultraviolet rays to be photocured. Examples of the active energy ray include an ultraviolet ray, an electron beam, and an X-ray. As a light source used for ultraviolet irradiation, a solar ray, 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.
Thereafter, by performing post-baking, specifically by heating using a hot plate, an oven or the like, the polymerization can be finally completed.
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.

<Laminate with hard coat layer>
In addition, the present invention is formed by applying the polymerizable composition, preferably in the form of a varnish, to a film substrate, forming a coating film, and irradiating the coating film with ultraviolet rays to cure the coating film. A hard coat film provided with a hard coat layer on at least one surface of a film substrate as described above is also an object.
The substrate, the coating method, and the irradiation of energy rays such as ultraviolet rays used herein are the same as those of the above-described <cured film>, the coating method, and the active energy ray irradiation.
In the hard coat film of the present invention, the thickness of the hard coat layer is preferably from 1 to 30 μm, more preferably from 1 to 10 μm.

  According to the present invention, a polymerizable composition capable of forming a cured film having lipophilicity and slipperiness on its surface can be obtained. The polymerizable composition of the present invention is suitably used as a material for a lipophilic hard coat layer on the surface of various displays such as LCDs, PDPs, and touch panels.

Hereinafter, the present invention will be described more specifically 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 physical property analysis are as follows.

(1) Gel permeation chromatography (GPC)
Apparatus: Tosoh Corporation HLC-8220GPC
Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko KK
Column temperature: 40 ° C
Eluent: tetrahydrofuran Detector: RI
(2) Bar coating device: PM-9050MC manufactured by SMT Co., Ltd.
Bar: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., maximum thickness 22 μm (corresponding to wire bar # 9)
Coating speed: 4.0 m / min (3) Oven equipment: Advantech Toyo Co., Ltd. dust-free dryer DRC433FA
(4) UV irradiation 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) Dynamic friction coefficient μ _k measurement device: Shinto Kagaku Co., Ltd. Load fluctuation type friction and wear test system TRIBOGEAR HHS2000
Probe: 0.6mmR Sapphire pin Load: 50g
Measurement speed: 1 mm / sec Scanning distance: 1 cm

The abbreviations have the following meanings.
HDDM: 1,6-hexanediol dimethacrylate [NK ester HD-N manufactured by Shin-Nakamura Chemical Co., Ltd.]
4EDM: tetraethylene glycol dimethacrylate [Blenmer (registered trademark) PDE-200 manufactured by NOF Corporation]
9EDM: Nonaethylene glycol dimethacrylate [Blenmer (registered trademark) PDE-400 manufactured by NOF Corporation]
LA: lauryl acrylate [LA manufactured by Osaka Organic Chemical Industry Co., Ltd.]
ISTA: Isostearyl acrylate [ISTA manufactured by Osaka Organic Chemical Industry Co., Ltd.]
4ELA: tetraethylene glycol = monolauryl ether = acrylate [Blenmer (registered trademark) ALE-200 manufactured by NOF Corporation]
4EMM: tetraethylene glycol = monomethyl ether = methacrylate [Blenmer (registered trademark) PME-200 manufactured by NOF Corporation]
9EMM: nonaethylene glycol = monomethyl ether = methacrylate [Blenmer (registered trademark) PME-400 manufactured by NOF Corporation]
AMBN: 2,2'-azobis (2-methylbutyronitrile) [V-59, manufactured by Wako Pure Chemical Industries, Ltd.]
UV7600: 6-functional urethane acrylate [Shinko (registered trademark) UV7600B 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

[Example 1] Production of lipophilic hyperbranched polymer HBP1 A 50 mL reaction flask was charged with 13 g of MIBK, and nitrogen was poured for 5 minutes with stirring, and the mixture was heated until the internal solution was refluxed (about 116 ° C).
In another 30 mL reaction flask, 1.3 g (5 mmol) of HDDM as monomer A, 6.0 g of LA as monomer B (25 mmol, 500 mol% based on monomer A), 0.5 g of AMBN as initiator C (2.5 mmol, And 50 g of MIBK), and 13 g of MIBK. The mixture was purged with nitrogen by flowing nitrogen for 5 minutes with stirring, and cooled to 0 ° C. in an ice bath.
The content was dropped into the refluxing MIBK in the 50 mL reaction flask from the 30 mL reaction flask charged with HDDM, LA, and AMBN using a dropping pump over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour.
The reaction mixture was cooled to room temperature (about 25 ° C.) to obtain 33.1 g of a target hyperbranched polymer (HBP1) as a MIBK solution having a polymer concentration of 23% by mass.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured in terms of polystyrene by GPC was 6,900, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.2.

[Example 2] Production of lipophilic hyperbranched polymer HBP2 Example 2 was repeated except that the amount of LA was changed to 8.4 g (35 mmol, 700 mol% based on monomer A), and the amount of MIBK was changed to 19 g. By operating in the same manner as in Example 1, 48.3 g of the desired hyperbranched polymer (HBP2) was obtained as a MIBK solution having a polymer concentration of 21% by mass.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured in terms of polystyrene by GPC was 5,600, and the degree of dispersion: Mw / Mn was 3.3.

[Example 3] Production of lipophilic hyperbranched polymer HBP3 Example 1 except that the amount of LA was changed to 12.0 g (50 mmol, 1000 mol% based on monomer A) and the amount of MIBK was changed to 19 g each. By operating in the same manner as in Example 1, 51.9 g of the desired hyperbranched polymer (HBP3) was obtained as a MIBK solution having a polymer concentration of 26% by mass.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 6,600, and the degree of dispersion: Mw / Mn was 3.0.

[Example 4] Production of lipophilic hyperbranched polymer HBP4 The same operation as in Example 1 was performed except that monomer A was changed to 1.7 g (5 mmol) of 4EDM and the amount of MIBK was changed to 10 g, respectively. 27.9 g of a highly branched polymer (HBP4) was obtained as a MIBK solution having a polymer concentration of 29% by mass.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 6,300, and the degree of dispersion: Mw / Mn was 2.8.

[Example 5] Production of lipophilic hyperbranched polymer HBP5 The same operation as in Example 1 was carried out except that monomer A was changed to 2.8 g (5 mmol) of 9 EDM and the amount of MIBK was changed to 17 g, respectively. 42.2 g of a highly branched polymer (HBP5) was obtained as a MIBK solution having a polymer concentration of 22% by mass.
The weight-average molecular weight Mw of the obtained hyperbranched polymer measured in terms of polystyrene by GPC was 8,800, and the degree of dispersion: Mw / Mn was 4.2.

[Example 6] Production of lipophilic hyperbranched polymer HBP6 Monomer B was used in 8.1 g (25 mmol, 500 mol% based on monomer A) of AMSTA and 0.6 g (3 mmol, 60 mol% based on monomer A) of AMBN was used. ), The same operation as in Example 1 was carried out except that the amount of MIBK used was changed to 8 g each, to obtain 25.1 g of the desired hyperbranched polymer (HBP6) as a MIBK solution having a polymer concentration of 39% by mass. Was.
The weight-average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 4,500, and the degree of dispersion: Mw / Mn was 2.5.

[Example 7] Production of lipophilic hyperbranched polymer HBP7 Monomer B was used in 10.4 g (25 mmol, 500 mol% based on monomer A) of 4ELA and 0.6 g (3 mmol, 60 mol% based on monomer A) of AMBN was used. ), The operation was performed in the same manner as in Example 1 except that the amount of MIBK used was changed to 8 g each, to obtain 27.4 g of the desired hyperbranched polymer (HBP7) as a MIBK solution having a polymer concentration of 45% by mass. Was.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 9,900, and the degree of dispersion: Mw / Mn was 3.0.

[Example 8] Production of lipophilic hyperbranched polymer HBP8 13 g of MIBK was charged into a 50 mL reaction flask, and nitrogen was poured thereinto for 5 minutes while stirring, and the mixture was heated until the internal solution was refluxed (about 116 ° C).
In another 30 mL reaction flask, 1.3 g (5 mmol) of HDDM as monomer A, 6.0 g (25 mmol, 500 mol% based on monomer A) of monomer B, and 0.3 g (0.5 mmol, based on monomer A) of 9 EMM as monomer D 10 mol%), 0.6 g of AMBN (3 mmol, 60 mol% based on monomer A) as initiator C, and 13 g of MIBK were charged, nitrogen was introduced for 5 minutes while stirring, nitrogen replacement was performed, and the mixture was cooled to 0 ° C. in an ice bath. did.
The contents were dropped into the refluxing MIBK in the 50 mL reaction flask from the 30 mL reaction flask charged with HDDM, LA, 9 EMM, and AMBN using a dropping pump over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour.
The reaction mixture was cooled to room temperature (about 25 ° C.) to obtain 33.4 g of the objective hyperbranched polymer (HBP8) as a MIBK solution having a polymer concentration of 24% by mass.
The weight-average molecular weight Mw of the obtained hyperbranched polymer measured in terms of polystyrene by GPC was 6,400, and the degree of dispersion: Mw / Mn was 3.0.

[Example 9] Production of lipophilic hyperbranched polymer HBP9 The amount of LA used was 12.0 g (50 mmol, 1000 mol% based on monomer A), and the amount of monomer D was 4.1 g (15 mmol, 300 mol% based on monomer A). ), The same operation as in Example 8 was carried out, except that each was changed, to obtain 43.3 g of the desired hyperbranched polymer (HBP9) as a MIBK solution having a polymer concentration of 41% by mass.
The weight-average molecular weight Mw of the obtained hyperbranched polymer measured in terms of polystyrene by GPC was 9,600, and the degree of dispersion: Mw / Mn was 3.4.

[Production Example 1] Production of lipophilic hyperbranched polymer HBP10 Example 1 except that the amount of LA used was changed to 1.2 g (5 mmol, 100 mol% based on monomer A) and the amount of MIBK used was changed to 8 g each. By operating in the same manner as in Example 1, 18.0 g of the desired hyperbranched polymer (HBP10) was obtained as a MIBK solution having a polymer concentration of 16% by mass.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 8,200, and the degree of dispersion: Mw / Mn was 4.3.

[Production Example 2] Production of lipophilic hyperbranched polymer HBP11 The used amount of LA was 3.6 g (15 mmol, 300 mol% based on monomer A), and the used amount of AMBN was 0.6 g (3 mmol, based on monomer A). 60 mol%) and the amount of MIBK used was changed to 8 g each, and the same operation as in Example 1 was carried out to obtain the desired hyperbranched polymer (HBP11) as a MIBK solution having a polymer concentration of 26% by mass. 6 g were obtained.
The weight average molecular weight Mw of the obtained hyperbranched polymer measured by GPC in terms of polystyrene was 7,000, and the degree of dispersion: Mw / Mn was 3.3.

  In the hyperbranched polymers HBP1 to HBP11 obtained in Examples 1 to 9 and Production Examples 1 and 2, the composition and the amount of the monomer and the initiator, the weight average molecular weight Mw, the dispersity: Mw / Mn, the polymer concentration [% by mass] ] Are also shown in Table 1.

[Examples 10 to 18 and Comparative Examples 1 to 3]
The following components were mixed to prepare a polymerizable composition having a nonvolatile content of 40% by mass.
(1) Polyfunctional monomer: 100 parts by mass of UV7600 (2) Surface modifier: 1 part by mass of surface modifier described in Table 2 (as a highly branched polymer)
(3) Polymerization initiator: I184 6 parts by mass (4) Solvent: MIBK Amount shown in Table 2 A4 size PET film [Cosmoshine (registered trademark) A4100, manufactured by Toyobo Co., Ltd., thickness] (125 μm) (by applying an easy-adhesion treatment) to form 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 having an exposure amount of 300 mJ / cm ^{2 in} an air atmosphere to expose a hard coat film having a hard coat layer having a thickness of about 5 to 6 μm.

The resulting hard coat layer, the contact angle of water and oleic acid were evaluated dynamic friction coefficient mu _k. The procedure of each evaluation is shown below. The results are also shown in Table 2.
[Contact angle]
1 μL of the probe liquid (water or oleic acid) was attached to the surface of the hard coat layer, and the contact angle was measured 5 times after 10 seconds (water) or 60 seconds (oleic acid), and the average value was defined as the contact angle.
[Dynamic friction coefficient]
The dynamic friction coefficients at five locations on the surface of the hard coat layer were measured, and the average value was defined as the dynamic friction coefficient. The smaller the value of the dynamic friction coefficient is, the smaller the friction with the probe to be used is. The coefficient of dynamic friction required for the hard coat layer applied to the surface of a display element such as a touch panel is desirably, for example, 0.1 or less.

As shown in Table 2, the hard coat layer containing the lipophilic hyperbranched polymer (HBP1 to HBP9) of the present invention as a surface modifier was compared with the hard coat layer not using the surface modifier (Comparative Example 1). In the layers (Examples 10 to 18), the results were that the contact angle of oleic acid was small and the dynamic friction coefficient was a small value of 0.1 or less. That is, the lipophilic hyperbranched polymer of the present invention was able to impart lipophilicity to the surface of the hard coat with a small amount of addition, and obtained a surface having excellent slipperiness.
On the other hand, in the hard coat layers to which HBP10 and HBP11 were added (Comparative Examples 2 and 3), the dynamic friction coefficient was extremely large as compared with the above-mentioned examples, and the hyperbranched polymer imparted sufficient slipperiness to the hard coat layer surface. It turned out to be impossible.

Claims (8)

(A) 100 parts by mass of an active energy ray polymerizable polyfunctional monomer,
A polymerizable composition comprising (b) 0.001 to 20 parts by mass of a lipophilic hyperbranched polymer, and (c) 1 to 20 parts by mass of a polymerization initiator that generates a radical by an active energy ray,
(A) the active energy ray-polymerizable polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound;
(B) The lipophilic hyperbranched polymer comprises a monomer A having two or more radically polymerizable double bonds in the molecule, an aliphatic hydrocarbon group having 6 to 30 carbon atoms in the molecule, and at least one at least and a monomer B having a radical polymerizable double bond, a polymerizable compound is 400～1500Mol% weight amounts of the monomer B is relative to the number of moles of the monomers a, relative to the number of moles of the monomer a A polymerizable composition which is a lipophilic hyperbranched polymer obtained by polymerizing a polymerization initiator C in an amount of from 5 to 200 mol%. The monomer A is a divinyl compound or a di (meth) acrylate compound, the monomer B is a compound represented by the formula [2], and the polymerization initiator C is an azo-based polymerization initiator. 2. The polymerizable composition according to 1.

(Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms, L ² represents an alkylene group having 2 to 6 carbon atoms, and m represents Represents an integer of 0 to 30.) The polymerizable composition according to claim 1, wherein the polymerizable compound further includes a monomer D represented by Formula [3].

(Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, L ³ represents an alkylene group having 2 to 6 carbon atoms, and k is Represents an integer of 1 to 30) The polymerizable composition according to any one of claims 1 to 3 , wherein the polymerization initiator (c) is an alkylphenone compound. The polymerizable composition according to any one of claims 1 to 4 , further comprising (d) a solvent. A cured film obtained from the polymerizable composition according to any one of claims 1 to 5 . A method for producing a laminate comprising a hard coat layer on at least one surface of a substrate, by applying the polymerizable composition according to the substrate in any one of 請 Motomeko 1 to claim 5 forming a coating film, and by irradiating ultraviolet radiation curing the coating film, step a including forming the hard coat layer, the manufacturing method of the laminate. The method according to claim 7 , wherein the hard coat layer has a thickness of 1 to 30 μm.