JP6288542B2 - Curable composition containing silicon-containing polymer - Google Patents

Description

  The present invention relates to an active energy ray-curable coating composition containing a silicon-containing polymer and a hard coat layer having water slidability obtained by applying them.

  Plastic materials such as acrylic resin, polycarbonate resin, and ABS (acrylonitrile-butadiene-styrene copolymer) resin have well-balanced mechanical properties and are excellent in moldability, light weight, and transparency. It is widely used as a housing for electronic devices and cosmetics. In order to improve the surface hardness, barrier properties, chemical resistance, flame retardancy, heat resistance, etc. of these plastic materials, a technique by 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 the headlamps of automobiles, organic resin lenses for back monitor cameras, shields for motorcycle helmets, etc. Yes. In recent years, as such surface performance, not only “water repellency”, which has been conventionally evaluated by measuring contact angle as a property of repelling water droplets, but also “sliding water” (so-called “water repellency”) evaluated by water droplet falling behavior on inclined surfaces. Dynamic wettability ") is drawing attention.
A film having water repellency and water slidability on glass has been formed by reacting a silane compound having a perfluoroalkyl structure and a silane compound having a silicone structure with a silanol group on a glass substrate. Things have been proposed. However, a silane compound can form a film through a chemical bond on a substrate having a hydroxy group on the surface, such as glass and ceramics, but the above-mentioned acrylic resin, polycarbonate resin, ABS resin, etc. Since the plastic material does not have a hydroxy group, it is a substrate that is not suitable for coating (film formation) using a silane compound.

  On the other hand, as one of the methods for suppressing the adhesion of water droplets, a water-repellent and water-slidable hard coat formed by UV irradiation by using a silicone material as a surface modifier and added to an active energy ray polyfunctional acrylate A method for imparting water slidability to the hard coat layer surface has been proposed (Patent Document 1).

JP 2000-248200 A

  However, conventional proposals using silicone-based materials in surface modification of plastic materials can give a certain level of water repellency to the hard coat surface, but the lubricity is still not sufficient. It was.

  As a result of intensive investigations to achieve the above object, the present inventors have added a silicon-containing polymer having a specific structure to the active energy ray-curable coating liquid, thereby enabling not only water repellency but also water slidability. It has been found that an excellent hard coat can be formed, and the present invention has been completed.

（式中、Ｒ^１乃至Ｒ^３はそれぞれ独立して炭素原子数１乃至６のアルキル基を表し、Ｒ^４は水素原子又は炭素原子数１乃至６のアルキル基を表し、ｎは１乃至３の整数を表す。）
第３観点として、前記（ａ）含ケイ素ポリマーが式［２］で表される繰り返し単位構造を有する、第２観点に記載の硬化性組成物に関する。

（式中、Ｒ^１乃至Ｒ^４及びｎは前記と同じ意味を表し、Ｒ^５は水素原子又はメチル基を表し、Ｌ^１は２価の有機基を表す。）
第４観点として、前記（ａ）含ケイ素ポリマーが式［３］で表される繰り返し単位構造を有する、第３観点に記載の硬化性組成物に関する。

（式中、Ｒ^４、Ｒ^５、Ｌ^１及びｎは前記と同じ意味を表す。）
第５観点として、前記（ａ）含ケイ素ポリマーが式［４］で表される繰り返し単位構造を有する、第３観点に記載の硬化性組成物に関する。

（式中、Ｒ^１乃至Ｒ^３、Ｒ^５及びＬ^１は前記と同じ意味を表す。）
第６観点として、前記Ｌ^１が式［５］で表される２価の有機基を表す、第３観点乃至第５観点のうち何れか一項に記載の硬化性組成物に関する。

（式中、Ｌ^２は単結合又は炭素原子数１乃至６のアルキレン基を表し、＊は繰り返し単位構造における主鎖の炭素原子への結合端を表す。）
第７観点として、前記Ｌ^１がフェニレン基を表す、第３観点乃至第５観点のうち何れか
一項に記載の硬化性組成物に関する。
第８観点として、前記含ケイ素ポリマーが、さらに炭素原子数３乃至３０の脂環式基を有する繰り返し単位構造を含む、第１観点乃至第７観点のうち何れか１項に記載の硬化性組成物。
第９観点として、前記炭素原子数３乃至３０の脂環式基を有する繰り返し単位構造が、シクロヘキサン環、ノルボルナン環、アダマンタン環及びトリシクロ［５．２．１．０^２，６］デカン環からなる群から選ばれる少なくとも１つの脂環構造を有する、第８観点に記載の硬化性組成物。
第１０観点として、前記炭素原子数３乃至３０の脂環式基を有する繰り返し単位構造が、式［６］で表される、第８観点又は第９観点に記載の硬化性組成物。

（式中、Ｒ^６は水素原子又はメチル基を表し、Ｌ^３は単結合又は炭素原子数１乃至６のアルキレン基を表し、Ｍは前記炭素原子数３乃至３０の脂環式基を表す。）
第１１観点として、前記（ｂ）多官能モノマーが、多官能（メタ）アクリレート化合物及び多官能ウレタン（メタ）アクリレート化合物からなる群から選ばれる少なくとも１つである、第１観点乃至第１０観点のうち何れか一項に記載の硬化性組成物に関する。
第１２観点として、前記（ｃ）重合開始剤がアルキルフェノン化合物である、第１観点乃至第１１観点のうち何れか一項に記載の硬化性組成物に関する。
第１３観点として、さらに（ｄ）溶媒を含む、第１観点乃至第１２観点のうち何れか一項に記載の硬化性組成物に関する。
第１４観点として、第１観点乃至第１３観点のうち何れか一項に記載の硬化性組成物より得られる硬化膜に関する。
第１５観点として、基材の少なくとも一方の面にハードコート層を備える積層体であって、該ハードコート層が、第１観点乃至第１３観点のうち何れか一項に記載の硬化性組成物を前記基材上に塗布し塗膜を形成する工程、及び塗膜に活性エネルギー線を照射し硬化する工程を含む方法により形成されている、積層体に関する。
第１６観点として、前記ハードコート層が１ｎｍ〜１ｍｍの膜厚を有する、第１５観点に記載の積層体に関する。 That is, the present invention provides the first aspect as follows:
(A) 0.01-20 parts by mass of a silicon-containing polymer containing a repeating unit structure having a structure in which a trialkylsilyl group is bonded to a carbon atom,
(B) Active energy ray-curable polyfunctional monomer 100 parts by mass, and (c) 0.1-20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
The present invention relates to a curable composition comprising
As a second aspect, the (a) silicon-containing polymer relates to the curable composition according to the first aspect, in which the repeating unit structure has a group represented by the formula [1].

(Wherein R ^{1 to} R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents 1 to 3 carbon atoms) Represents an integer.)
As a 3rd viewpoint, the said (a) silicon-containing polymer is related with the curable composition as described in a 2nd viewpoint which has a repeating unit structure represented by Formula [2].

(Wherein R ^{1 to} R ⁴ and n represent the same meaning as described above, R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents a divalent organic group.)
As a fourth aspect, the present invention relates to the curable composition according to the third aspect, wherein the (a) silicon-containing polymer has a repeating unit structure represented by the formula [3].

(Wherein R ⁴ , R ⁵ , L ¹ and n represent the same meaning as described above.)
As a fifth aspect, the present invention relates to the curable composition according to the third aspect, wherein the (a) silicon-containing polymer has a repeating unit structure represented by the formula [4].

(Wherein R ^{1 to} R ³ , R ⁵ and L ¹ represent the same meaning as described above.)
As a sixth aspect, the present invention relates to the curable composition according to any one of the third aspect to the fifth aspect, in which L ¹ represents a divalent organic group represented by the formula [5].

(In the formula, L ² represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a bonding end to a carbon atom of the main chain in the repeating unit structure.)
As a seventh aspect, the present invention relates to the curable composition according to any one of the third aspect to the fifth aspect, in which L ¹ represents a phenylene group.
As an eighth aspect, the curable composition according to any one of the first aspect to the seventh aspect, in which the silicon-containing polymer further includes a repeating unit structure having an alicyclic group having 3 to 30 carbon atoms. object.
As a ninth aspect, the repeating unit structure having an alicyclic group having 3 to 30 carbon atoms comprises a cyclohexane ring, a norbornane ring, an adamantane ring, and a tricyclo [5.2.1.0 ^2,6 ] decane ring. The curable composition according to the eighth aspect, having at least one alicyclic structure selected from the group.
As a tenth aspect, the curable composition according to the eighth aspect or the ninth aspect, in which the repeating unit structure having an alicyclic group having 3 to 30 carbon atoms is represented by the formula [6].

(Wherein R ⁶ represents a hydrogen atom or a methyl group, L ³ represents a single bond or an alkylene group having 1 to 6 carbon atoms, and M represents the alicyclic group having 3 to 30 carbon atoms). )
As an eleventh aspect, in the first aspect to the tenth aspect, the (b) polyfunctional monomer is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of them.
As a twelfth aspect, the present invention relates to the curable composition according to any one of the first aspect to the eleventh aspect, in which the polymerization initiator (c) is an alkylphenone compound.
As a thirteenth aspect, the present invention relates to the curable composition according to any one of the first aspect to the twelfth aspect, further including (d) a solvent.
As a 14th viewpoint, it is related with the cured film obtained from the curable composition as described in any one of a 1st viewpoint thru | or a 13th viewpoint.
As a fifteenth aspect, a laminate comprising a hard coat layer on at least one surface of a substrate, wherein the hard coat layer is the curable composition according to any one of the first aspect to the thirteenth aspect. It is related with the laminated body currently formed by the method of apply | coating on the said base material and forming the coating film, and the method including the process of irradiating an active energy ray to a coating film and hardening.
As a 16th viewpoint, it is related with the laminated body as described in a 15th viewpoint that the said hard-coat layer has a film thickness of 1 nm-1 mm.

  The curable composition of the present invention can form a hard coat having excellent water repellency as well as water slidability on the surface of a plastic material.

1 is a diagram showing a ¹ H NMR spectrum of a silicon-containing monomer (SiCSt) obtained in Synthesis Example 1. FIG. FIG. 2 is a diagram showing a ¹ H NMR spectrum of the silicon-containing monomer (SiCMA) obtained in Synthesis Example 2. FIG. 3 is a diagram illustrating a conceptual diagram of sliding angle measurement in the embodiment.

<Curable composition>
The curable composition of the present invention contains (a) a silicon-containing polymer, (b) an active energy ray-curable polyfunctional monomer, and (c) a polymerization initiator that generates radicals by active energy rays,
If desired, (d) further comprises a solvent.
The components (a) to (d) will be described in detail below.

[(A) Silicon-containing polymer]
The (a) silicon-containing polymer is a polymer containing a repeating unit structure having a structure in which a trialkylsilyl group is bonded to a carbon atom as an essential unit structure (hereinafter, also simply referred to as (a) a silicon-containing polymer). Here, in the silicon-containing polymer, the repeating unit structure having a trialkylsilyl group may consist of only one repeating unit structure having a trialkylsilyl group, or two or more different having a trialkylsilyl group. It may contain a repeating unit structure. When two or more types of repeating unit structures are included, the bonds may be random bonds, block bonds, or combinations thereof.

上記式［１］中、Ｒ^１乃至Ｒ^３はそれぞれ独立して炭素原子数１乃至６のアルキル基を表し、Ｒ^４は水素原子又は炭素原子数１乃至６のアルキル基を表し、ｎは１乃至３の整数を表す。 Preferably, (a) the silicon-containing polymer is a polymer including a repeating unit structure having a group represented by the following formula [1].

In the above formula [1], R ^{1 to} R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is 1 Represents an integer of 3 to 3.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{1 to} R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group and the like. Among these, a methyl group is preferable.
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Here, the alkyl group having 1 to 6 carbon atoms includes 1 to 6 carbon atoms exemplified for the aforementioned R ^{1 to} R ^3. The same group as the alkyl group of is mentioned. Among these, R ⁴ is preferably a hydrogen atom.
N is preferably 1.

上記式［２］中、Ｒ^１乃至Ｒ^４及びｎは前記と同じ意味を表し、Ｒ^５は水素原子又はメチル基を表し、Ｌ^１は２価の有機基を表す。 In addition, the (a) silicon-containing polymer preferably has a repeating unit structure represented by the following formula [2].

In the above formula [2], R ^{1 to} R ⁴ and n represent the same meaning as described above, R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents a divalent organic group.

上記式［３］又は式［４］中、Ｒ^４、Ｒ^５、Ｌ^１及びｎは前記と同じ意味を表す。 Among the repeating unit structures represented by the above formula [2], a repeating unit structure represented by the following formula [3] or a repeating unit structure represented by the following formula [4] is particularly preferable.

In the above formula [3] or [4], R ⁴ , R ⁵ , L ¹ and n represent the same meaning as described above.

上記式［５］中、Ｌ^２は単結合又は炭素原子数１乃至６のアルキレン基を表し、＊は繰り返し単位構造における主鎖の炭素原子への結合端を表す。 The divalent organic group represented by L ¹ is preferably a divalent organic group represented by the following formula [5] or a phenylene group.

In the above formula [5], L ² represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a bond end to the carbon atom of the main chain in the repeating unit structure.

Examples of the alkylene group having 1 to 6 carbon atoms represented by L ² include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethyl group. A chain or branched alkylene group such as a methylene group or a hexamethylene group; a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclobutane-1,3-diyl group, a cyclopentane-1, And cyclic alkylene groups such as 2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, and the like. .
Among these, L ² is preferably a methylene group or an ethylene group.

The (a) silicon-containing polymer in the present invention may be a polymer composed only of a repeating unit structure having a trialkylsilyl group bonded to the carbon atom, but as long as the effects of the present invention are not impaired, Other repeating unit structures such as a repeating unit structure derived from (meth) acrylic acid and its derivatives not having a trialkylsilyl group, and a repeating unit structure derived from a vinyl compound and its derivatives. It may further have a structure.
The bond between such other repeating unit structure and the above-described repeating unit structure having a trialkylsilyl group may be a random bond, a block bond, or a combination thereof.

上記式［６］中、Ｒ^６は水素原子又はメチル基を表し、Ｌ^３は単結合又は炭素原子数１乃至６のアルキレン基を表し、Ｍは前記炭素原子数３乃至３０の脂環式基を表す。
ここで炭素原子数１乃至６のアルキレン基は上述のＬ^２における基と同様の基が挙げられ、炭素原子数３乃至３０の脂環式基としては、好ましくはシクロヘキサン環、ノルボルナン環、アダマンタン環及びトリシクロ［５．２．１．０^２，６］デカン環から選択される基が望ましい。 Suitable examples of the other repeating unit structure include a repeating unit structure having an alicyclic group having 3 to 30 carbon atoms. Among them, the repeating unit structure having an alicyclic group having 3 to 30 carbon atoms is selected from the group consisting of a cyclohexane ring, a norbornane ring, an adamantane ring, and a tricyclo [5.2.1.0 ^2,6 ] decane ring. It is preferable to have at least one alicyclic structure.
The repeating unit structure having an alicyclic group having 3 to 30 carbon atoms preferably has a structure derived from (meth) acrylic acid, that is, a structure represented by the following formula [6].

In the above formula [6], R ⁶ represents a hydrogen atom or a methyl group, L ³ represents a single bond or an alkylene group having 1 to 6 carbon atoms, and M represents the alicyclic group having 3 to 30 carbon atoms. Represents.
Here, examples of the alkylene group having 1 to 6 carbon atoms include the same groups as those in L ² described above, and the alicyclic group having 3 to 30 carbon atoms is preferably a cyclohexane ring, a norbornane ring or an adamantane ring. And a group selected from a tricyclo [5.2.1.0 ^2,6 ] decane ring is desirable.

  The structural ratio (molar ratio) between the repeating unit structure having a trialkylsilyl group bonded to a carbon atom and the repeating unit structure having an alicyclic group having 3 to 30 carbon atoms in the silicon-containing polymer used in the present invention is: For example, it can be 10: 1 to 1:10.

Examples of such a (a) silicon-containing polymer include poly (2- (trimethylsilyl) ethyl (meth) acrylate), poly (3- (trimethylsilyl) propyl (meth) acrylate), poly (2,2-bis ( Trimethylsilyl) ethyl (meth) acrylate), poly (2,2,2-tris (trimethylsilyl) ethyl (meth) acrylate), poly (4-((trimethylsilyl) methyl) styrene), poly (4- (bis (trimethylsilyl)) Methyl) styrene), poly (4- (tris (trimethylsilyl) methyl) styrene), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (methyl (meth) acrylate)), poly ((2- (Trimethylsilyl) ethyl (meth) acrylate) -co- (tert-butyl) (Meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (stearyl (meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (Cyclohexyl (meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (4-tert-butylcyclohexyl (meth) acrylate)), poly ((2- (trimethylsilyl) ethyl ( (Meth) acrylate) -co- (tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (1-adamantyl) (Meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) ) Acrylate) -co- (2-methyladamantan-2-yl (meth) acrylate)), poly ((2- (trimethylsilyl) ethyl (meth) acrylate) -co- (isobornyl (meth) acrylate)), etc. Can be mentioned.
These silicon-containing polymers may be used alone or as a mixture of two or more if necessary.

  The weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography of the (a) silicon-containing polymer used in the curable composition of the present invention is 1,000 to 500,000, preferably 2,000 to 100,000.

[(B) Active energy ray-curable polyfunctional monomer]
The (b) active energy ray-curable polyfunctional monomer (hereinafter, also simply referred to as (b) polyfunctional monomer) includes (meth) acrylic groups such as urethane acrylic, epoxy acrylic, and various (meth) acrylates. Examples thereof include polyfunctional monomers containing two or more.
Preferably, at least one monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound is desirable. 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 such active energy ray-curable polyfunctional monomers, examples of polyfunctional (meth) acrylate compounds include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. ,
Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate , Pentaerythritol di (meth) acrylate monostearate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pen Erythritol ethylene glycol adduct tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A ethylene glycol adduct (meth) acrylate Bisphenol F ethylene glycol adduct (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate, trishydroxyethyl isocyanurate di (meth) acrylate, trishydroxyethyl isocyanurate Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, dito Limethylolpropane tetra (meth) acrylate, trimethylolpropane ethylene glycol adduct tri (meth) acrylate, trimethylolpropane propylene glycol adduct tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, modified ε-caprolactone tri ( (Meth) acrylate, glycerin propylene glycol adduct tris (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, undec Noxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1, Examples thereof include 3-adamantane dimethanol di (meth) acrylate.
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 3 or more (meth) acrylic 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) acryl groups such as erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate is more preferable.

  Moreover, as a polyfunctional urethane (meth) acrylate compound, the urethane compound which has 2 or more of the (meth) acryl groups which have the site | part of an ethylenically unsaturated bond is mentioned. 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 -Diisocyanate compounds obtained by hydrogenating aromatic isocyanates among these diisocyanate compounds (for example, hydrogenated xylylene diisocyanate, water, trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or dicyclomethane diisocyanate) Diisocyanate compounds such as diphenylmethane diisocyanate), triphenylmethane triisocyanate Over DOO, divalent or trivalent diisocyanate compounds such as dimethylene triphenyl triisocyanate or a polyisocyanate compound and an isocyanate group-containing compounds such as these by multimerization multimeric polyisocyanate compounds obtained can be mentioned.
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, etc. 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 include 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: 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, KRM 200, KRM8200AE, KRM7735, KRM8296, KRM8452; manufactured by Nippon Synthetic Chemical Co., Ltd .: Purple light (registered trademark) UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7605B, UV- 7610B, UV-7620E, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, and the like.

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

[(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-based 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-methylphenyl ) 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-aminodipropane) hydrochloride, 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-imida) Rin-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 include 4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, 1-diazo-4-N, N-diethylaminobenzeneborofluoride.

Examples of the o-quinonediazide compounds include 1,2-naphthoquinone-diazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinone-diazide (2) -5-sulfonic acid ester, 1,2- Examples thereof include naphthoquinone-diazide (2) -4-sulfonyl chloride.

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

  Examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 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 -A benzoyl diphenyl ether, benzyl, etc. can be mentioned.

  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 (cyclopenta Dienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,5) 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bi (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 can be mentioned.

  Among the above (c) polymerization initiators, an alkylphenone compound is particularly preferable. Commercially available photopolymerization initiators can be used as the alkylphenone-based photopolymerization initiator, for example, manufactured by BASF: IRGACURE (registered trademark) 651, 184, 2959, 127, 907, 369, 379EG, DAROCUR (registered trademark) 1173, MBF, and the like.

[(D) Solvent]
The curable composition of the present invention may further include (d) a solvent to form a varnish.
The solvent used at this time may be any solvent that dissolves or disperses the components (a) to (c) and other components described below. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin. Aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene Halides such as orthodichlorobenzene; ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, γ-butyrolactone, methyl pyruvate, ethyl pyruvate, ethyl hydroxyacetate, ethyl lactate, butyl lactate, 2-hydroxy 2-methyl ethyl propionate, -Methyl hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Esters or ester ethers such as glycol monomethyl ether acetate (PGMEA) and propylene glycol monopropyl ether acetate; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol Ethers such as monoethyl ether and propylene glycol monomethyl ether (PGME); Ketones such as seton, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclopentanone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol , Tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol and other alcohols; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-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.

In the curable composition of the present invention, the above components (a) to (c) are used in an amount of 0.01 to 20 parts by mass, preferably 0.0. 1 to 10 parts by mass, (c) 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass of a polymerization initiator.
Moreover, when (d) a solvent is included, the density | concentration (solid content concentration) of the total mass of (a)-(c) component with respect to the total mass (total mass) of all the components (a)-(d). It is 0.5-80 mass%, Preferably it is 1-70 mass%, More preferably, it is preferable to set it as 1-60 mass%. Here, the solid content is obtained by removing the solvent component from all the components of the curable composition.

[Other additives]
Furthermore, additives that are generally added to the curable composition of the present invention as needed, such as photosensitizers, polymerization inhibitors, polymerization initiators, and leveling, unless the effects of the present invention are impaired. 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 said curable composition of this invention can comprise molded articles, such as a cured film and a laminated body, by coating on a base material and making it photopolymerize (harden | cure). 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, ABS (acrylonitrile-butadiene-styrene). Copolymer) resin, AS (acrylonitrile-styrene copolymer) 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 coating method of the curable composition of the present invention includes a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, a spray coating method, a curtain coating method, an inkjet method, A printing method (engraving, intaglio, lithographic, screen printing, etc.) can be selected as appropriate. In particular, since it can be applied in a short time, even a highly volatile solution can be used, and uniform application can be easily performed. It is desirable to use a spin coating method because of the advantage that it can be used. 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 curable composition used here can be suitably used in the form of the aforementioned varnish. It is preferable that the curable composition is filtered in advance using a filter having a pore diameter of about 0.2 μm in advance and then used for coating.

After coating, preferably followed by preliminary drying with a hot plate or oven, etc., and then 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, or the like can be used.
In addition, the thickness of the film | membrane by coating is 1 nm-50 micrometers normally after drying and hardening, Preferably it is 1 nm-20 micrometers.

<Laminated body with hard coat layer>
In addition, it is formed by a method comprising a step of applying the curable composition of the present invention on the substrate to form a coating film, and a step of irradiating the coating film with an active energy ray such as ultraviolet rays and curing. A laminate comprising a hard coat layer on at least a part of the surface of the substrate is also an object of the present invention.
The substrate, coating method, and energy ray irradiation such as ultraviolet rays used here are the same as the substrate, coating method, and ultraviolet irradiation in the aforementioned <cured film>.
Moreover, it is preferable that the base material in the said laminated body is poly (meth) acrylate resin or polyester (polyethylene terephthalate (PET) resin).
In the laminate, the hard coat layer preferably has a thickness of 1 nm to 1 mm, more preferably 1 nm to 50 μm, and particularly preferably 1 nm to 20 μm.

As described above, the curable composition of the present invention forms a hard coat having excellent water repellency and water slidability on the surface of the plastic material by adding the silicon-containing polymer (a) as a surface modifier. can do.
In the present specification, the term “sliding water” does not merely evaluate the stability (falling angle) of a droplet with respect to an inclined surface, but refers to the surface performance evaluated by the falling behavior of the water droplet on the inclined surface. It means the water drop removal performance and the behavior at that time. Therefore, the water slidability can be evaluated, for example, by measuring the speed (acceleration) at which a droplet of a certain weight moves (falls) at a predetermined inclination angle and its acceleration, and by observing the shape change and internal flow of the droplet during movement. it can.
In the present invention, when the sample substrate on which a droplet having a constant weight is placed is inclined from the horizontal position, the lowest point of the portion where the surface of the droplet contacts the inclined surface (sample substrate) is the inclined surface. The inclination angle of the sample substrate with respect to the horizontal position when displaced downward is defined as a sliding angle, and is measured and evaluated as an index of water slidability.

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) ¹ H NMR spectrum instrument: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: CDCl ₃
Criteria: CDCl ₃ (7.24 ppm)
(2) Gel permeation chromatography (GPC)
Device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(3) Glass transition temperature (Tg) measurement Device: DSC204 F1 Phoenix (registered trademark) manufactured by NETZSCH
Measurement conditions: Under nitrogen atmosphere Temperature increase rate: 5 ° C / min (25-200 ° C)
(4) 5% weight loss temperature (Td _5% ) measurement device: TG8120 manufactured by Rigaku Corporation
Measurement conditions: Under air atmosphere Temperature rising rate: 10 ° C / min (25-400 ° C)
(5) Wire bar coater device: PM-9050MC manufactured by SMT Co., Ltd.
Wire bar: No. 9
Application speed: 4 m / min (6) Spin coater Device: MS-A100 manufactured by Mikasa Co., Ltd.
(7) Oven device: DRC433FA manufactured by Advantech Toyo Co., Ltd.
(8) UV irradiation device Device: H02-L41 manufactured by Eye Graphics Co., Ltd.
(9) Contact angle and sliding angle measurement device: DM-501, DM-SA01 (sliding method kit) manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C
Inclination speed (sliding angle measurement): 2 degrees / second

Abbreviations represent the following meanings.
DCP: tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate [manufactured by Hitachi Chemical Co., Ltd., FANCLIL (registered trademark) FA-513M]
IB: Isobornyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester IB-X]
STA: stearyl acrylate [Osaka Organic Chemical Co., Ltd. STA]
TB: tert-butyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester TB]
MAIB: 2,2′-azobis (methyl isobutyrate) [MAIB manufactured by Otsuka Chemical Co., Ltd.]
KRM8200: Hexafunctional aliphatic urethane acrylate [KRM8200, manufactured by Daicel-Cytec Co., Ltd.]
M403: 5-6 functional aliphatic acrylate [Aronix (registered trademark) M403 manufactured by Toagosei Co., Ltd.]
UV7600B: polyfunctional urethane acrylate [manufactured by Nippon Synthetic Chemical Co., Ltd., purple light (registered trademark) UV-7600B]
EB350: Dimethylsilicone diacrylate surface modifier [Daicel Cytec Co., Ltd. EBCRYL350]
FM0721: Dimethyl silicone acrylate surface modifier [Sailor Plain (registered trademark) FM-0721 manufactured by JNC Corporation]
UV3500: Polyether-modified dimethyl silicone acrylate surface modifier [BYK (registered trademark) -UV3500, manufactured by Big Chemie Japan Co., Ltd.]
Irg. 184: 1-hydroxycyclohexyl = phenyl = ketone [IRGACURE (registered trademark) 184 manufactured by BASF Japan Ltd.]
PET: Polyethylene terephthalate PMMA: Polymethyl methacrylate IPE: Diisopropyl ether MEK: Methyl ethyl ketone MIBK: Methyl isobutyl ketone THF: Tetrahydrofuran

[Synthesis Example 1] Synthesis of silicon-containing monomer (SiCSt) Magnesium [manufactured by Kanto Chemical Co., Ltd.] 5.09 g (0.21 mol) and THF 300 g were placed in a 1 L four-necked flask, and the atmosphere was replaced with nitrogen at 0 ° C. While stirring, 28.1 g (0.18 mol) of chlorotrimethylsilane [manufactured by Tokyo Chemical Industry Co., Ltd.] and 28.1 g (0.26 mol) of chloromethylstyrene [manufactured by AGC Seimi Chemical Co., Ltd.] were dissolved in 419 g of THF. The solution was added dropwise over 4 hours. After the dropping, the temperature was raised to room temperature (approximately 25 ° C.), and the reaction was allowed to proceed for 12 hours with stirring. The obtained reaction solution was dropped into an aqueous ammonium chloride solution, quenched, extracted with IPE, washed with brine, dried over magnesium sulfate, and the solvent was evaporated to obtain 36.7 g of a crude product. This crude product is purified by alumina column chromatography (developing solvent; hexane: toluene = 4: 1) to obtain the desired product (SiCSt) 33.
1 g (containing 30% by mass of toluene from ¹ H NMR spectrum measurement) was obtained (yield 89%).
FIG. 1 shows the ¹ H NMR spectrum of the obtained SiCSt.

[Synthesis Example 2] Synthesis of silicon-containing monomer (SiCMA) In a 100 mL four-necked flask, 2.37 g (20 mmol) of 2-trimethylsilylethanol [manufactured by Tokyo Chemical Industry Co., Ltd.], triethylamine [manufactured by Kanto Chemical Co., Inc.] 2.23 g (22 mmol) and 11 g of chloroform were charged. The inside of the flask was replaced with nitrogen and then cooled in an ice bath. Into this, a solution prepared by dissolving 2.30 g (22 mmol) of methacrylic acid chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] in 11 g of chloroform was dropped over 30 minutes. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature (approximately 25 ° C.) for 12 hours.
11 g of water was added to the reaction mixture, and the chloroform layer was separated. The remaining aqueous layer was extracted twice with 11 g of chloroform, and all the chloroform layers were combined and dried over magnesium sulfate. The chloroform layer was purified by silica gel column chromatography (developing solvent: hexane). The obtained solution was concentrated and dried under reduced pressure to obtain 1.50 g of oily target product (SiCMA) (yield 40%).
The ¹ H NMR spectrum of the obtained SiCMA is shown in FIG.

[Synthesis Example 3] Synthesis of silicon-containing polymer 1 (PSiCSt) In a 20 mL two-necked flask, 2.77 g of the 70 mass% SiCCS toluene solution obtained in Synthesis Example 1 (1.94 g (10 mmol) as SiCTS)), MAIB0 .16 g (0.7 mmol) and MIBK 2.9 g were charged. After replacing the inside of the flask with nitrogen, the mixture was stirred at 90 ° C. for 2 hours. To the reaction solution, 2.2 g of MIBK was added, and this was added to 70 g of methanol to precipitate the product. The obtained slurry was subjected to suction filtration to obtain 0.35 g of a white solid target product (PSiCSt) (yield 18%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained PSiCMA was 4,300, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.

[Synthesis Example 4] Synthesis of Silicon-Containing Polymer 2 (PSiCMMA) A 20 mL two-necked flask was charged with 2.63 g (14 mmol) of SiCMA manufactured according to Synthesis Example 2, 0.16 g (0.7 mmol) of MAIB, and 4 g of MIBK. After replacing the inside of the flask with nitrogen, the mixture was stirred at 80 ° C. for 3 hours. 15 g of MIBK was added to the reaction solution, and this was added to 143 g of a methanol-water mixed solution (mass ratio 1: 1) to precipitate the product. After removing the supernatant by decantation, the residue was dissolved in 20 g of acetone. The acetone solution was distilled off under reduced pressure and dried under reduced pressure to obtain 2.21 g of oily target product (PSiCMMA) (yield 84%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained PSiCMA was 21,100, and the degree of dispersion: Mw / Mn was 2.0.

[Synthesis Example 5] Synthesis of Silicon-containing Copolymer 1 (P (SiCMA-TB)) In a 50 mL two-necked flask, 1.86 g (10 mmol) of SiCMA prepared according to Synthesis Example 2, 1.42 g (10 mmol) of TB, and 0.92 g of MAIB (4 mmol) and 10 g of MEK were charged. After replacing the inside of the flask with nitrogen, the mixture was stirred at 80 ° C. for 2 hours. 3 g of MEK was added to the reaction solution, and this was added to 66 g of cold methanol to precipitate the product. The obtained slurry was subjected to suction filtration to obtain 2.91 g of the target product (P (SiCMA-TB)) as a white solid (yield 89%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained P (SiCMA-TB) was 4,900, and the degree of dispersion: Mw / Mn was 2.3. The unit structure composition (molar ratio) calculated from the ¹ H NMR spectrum was SiCMA unit: TB unit = 1: 1.

[Synthesis Example 6] Synthesis of Silicon-containing Copolymer 2 (P (SiCMA-ST)) In a 50 mL two-necked flask, 3.73 g (20 mmol) of SiCMA prepared according to Synthesis Example 2, 0.65 g (2 mmol) of STA, 1.01 g of MAIB (4.4 mmol) and 13 g of MEK were charged. After replacing the inside of the flask with nitrogen, the mixture was stirred at 80 ° C. for 2 hours. 4 g of MEK was added to the reaction solution, and this was added to 88 g of cold methanol to precipitate the product. The obtained slurry was subjected to suction filtration to obtain 3.96 g of a white solid target product (P (SiCMA-ST)) (yield 90%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained P (SiCMA-ST) was 8,400, and the degree of dispersion: Mw / Mn was 1.8. The unit structure composition (molar ratio) calculated from the ¹ H NMR spectrum was SiCMA unit: STA unit = 10: 1.

[Synthesis Example 7] Synthesis of Silicon-containing Copolymer 3 (P (SiCMA-DCP)) In a 50 mL two-necked flask, 1.86 g (10 mmol) of SiCMA prepared according to Synthesis Example 2, 2.21 g (10 mmol) of DCP, 0.92 g of MAIB (4 mmol) and 12 g of MEK were charged. After replacing the inside of the flask with nitrogen, the mixture was stirred at 80 ° C. for 2 hours. 4 g of MEK was added to the reaction solution, and this was added to 82 g of cold methanol to precipitate the product. The obtained slurry was subjected to suction filtration to obtain 3.55 g of the target product (P (SiCMA-DCP)) as a white solid (yield 87%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained P (SiCMA-DCP) was 11,000, and the degree of dispersion: Mw / Mn was 2.4. The unit structure composition (molar ratio) calculated from the ¹ H NMR spectrum was SiCMA unit: DCP unit = 1: 1.

[Synthesis Example 8] Synthesis of Silicon-containing Copolymer 4 (P (SiCMA-IB)) In a 50 mL two-necked flask, 1.86 g (10 mmol) of SiCMA prepared according to Synthesis Example 2; 4.45 g (20 mmol) of IB; 1.38 g of MAIB (6 mmol) and 19 g of MEK were charged. After replacing the inside of the flask with nitrogen, the mixture was stirred at 80 ° C. for 2 hours. 6 g of MEK was added to the reaction solution, and this was added to 126 g of cold methanol to precipitate the product. The obtained slurry was subjected to suction filtration to obtain 5.22 g of the target product (P (SiCMA-IB)) as a white solid (yield 83%).
The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained P (SiCMA-IB) was 5,700, and the degree of dispersion: Mw / Mn was 2.0. The unit structure composition (molar ratio) calculated from the ¹ H NMR spectrum was SiCMA unit: IB unit = 1: 2.

[Examples 1-2, Comparative Examples 1-4]
As a polyfunctional monomer, M403 60 parts by mass and KRM8200 40 parts by mass, polymerization initiator Irg. 184 5 parts by mass, and silicon-containing polymers 1 to 2 prepared in Synthesis Example 3 and Synthesis Example 4 described in Table 1 as surface modifiers, or 1 part by mass of a commercially available silicone-based surface modifier (Comparative Example 1 is (Without addition) was dissolved in 106 parts by mass of MIBK (105 parts by mass only in Comparative Example 1) to prepare a curable composition having a solid content concentration of 50% by mass.
This curable composition is applied to a PET film [Cosmo Shine (registered trademark) A4100 manufactured by Toyobo Co., Ltd.] using a wire bar (groove thickness of 20 μm) and coated with a bar coat (application speed: 4 m / min). Obtained. The obtained coating film was dried in an oven at 100 ° C. for 3 minutes to remove the solvent. A hard coat film was produced by irradiating this coating film with UV light having an integrated exposure amount of 400 mJ / cm ² .
The static contact angle of water (1 μL) and the sliding angle of 60 μL of water droplets were measured for each of the obtained hard coat films. Each measured value was calculated by arithmetically averaging measured values at three different points on the same film. The results are also shown in Table 1. The sliding angle was measured by the following procedure.

[Sliding angle measurement]
On the film to measure, 60 microliters of tap water was dripped using the micro syringe. The film was tilted at a rate of 2 degrees / second, and the tilt angle when the water droplet began to roll (displaced in the tilt direction) was taken as the sliding angle.
Specifically, as shown in FIG. 3, first, the film 2 on which the water droplet 1 is placed is gradually inclined from the horizontal plane X, and the lowest point A among the portions in contact with the film 2 on which the surface of the water droplet is inclined is determined. Observe. At point A, the tangent line Y of the water droplet 1 and the surface of the film 2 form an angle θa. And the angle (alpha) which inclined the film 2 from the horizontal surface X at the time of the point A moving toward the downward direction (arrow direction) of an inclined surface is measured as a sliding angle.

[Examples 3 to 6, Comparative Example 5]
100 parts by mass of UV7600B as a polyfunctional monomer and Irg. 184 parts by mass, and 1 part by mass of silicon-containing copolymers 1 to 4 prepared in Synthesis Examples 5 to 8 described in Table 1 as surface modifiers (without addition of Comparative Example 5), 428 parts by mass of toluene ( Example 3), dissolved in 161 parts by mass of MIBK (Examples 4 to 6) or 159 parts by mass of MIBK (Comparative Example 5) to prepare a curable composition having a solid content of 40% by mass (20% by mass only in Example 3). did.
This curable composition was spin-coated on a PMMA substrate (slope for 5 seconds, 1,500 rpm × 30 seconds, slope for 5 seconds), and heated and dried in an oven at 100 ° C. for 3 minutes to form a film. A hard coat was produced by irradiating the coating film with UV light having an integrated exposure amount of 400 mJ / cm ² .
For each of the obtained hard coat films, the static contact angle of water (1 μL) and the sliding angle of 60 μL of water droplets were measured according to the procedure described above. Each measured value was calculated by arithmetically averaging measured values at three different points on the same film. The results are also shown in Table 1.

As shown in Table 1, compared with the hard coats of Comparative Example 1 and Comparative Example 5 in which no surface modifier is used, the hard coats of Examples 1 to 6 have a large contact angle and a sliding angle. The result that it became small was obtained, ie, the result that both water repellency and water slidability improved was obtained.
On the other hand, in the hard coats of Comparative Example 2 to which a surface modifier known to impart water slidability is added, and Comparative Examples 3 and 4 to which a general-purpose silicone-based surface modifier is added, Although the water repellency was improved as compared with the hard coat of Comparative Example 1, the result that the sliding property was deteriorated (the sliding angle was increased) was obtained.

Claims (14)

(A) 0.01-20 parts by mass of a silicon-containing polymer containing a repeating unit structure having a structure in which a trialkylsilyl group is bonded to a carbon atom,
(B) Active energy ray-curable polyfunctional monomer 100 parts by mass, and (c) 0.1-20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
A curable composition comprising
The (a) silicon-containing polymer has a repeating unit structure represented by the formula [2],

(Wherein R ^{1 to} R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁵ represents a hydrogen atom or Represents a methyl group, L ¹ represents a divalent organic group, and n represents an integer of 1 to 3.)
The (b) polyfunctional monomer is selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound, and includes at least a polyfunctional urethane (meth) acrylate compound.
Curable composition. The curable composition according to claim 1, wherein the silicon-containing polymer (a) has a repeating unit structure represented by the formula [3].

(Wherein R ⁴ , R ⁵ , L ¹ and n represent the same meaning as described above.) The curable composition according to claim 1, wherein the (a) silicon-containing polymer has a repeating unit structure represented by the formula [4].

(Wherein R ^{1 to} R ³ , R ⁵ and L ¹ represent the same meaning as described above.) The curable composition according to any one of claims 1 to 3, wherein L ¹ represents a divalent organic group represented by the formula [5].

(In the formula, L ² represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a bonding end to a carbon atom of the main chain in the repeating unit structure.) The curable composition according to claim 1, wherein L ¹ represents a phenylene group. The curable composition according to any one of claims 1 to 5, wherein the silicon-containing polymer further comprises a repeating unit structure having an alicyclic group having 3 to 30 carbon atoms. The repeating unit structure having an alicyclic group having 3 to 30 carbon atoms is at least selected from the group consisting of a cyclohexane ring, a norbornane ring, an adamantane ring and a tricyclo [5.2.1.0 ^2,6 ] decane ring. The curable composition of Claim 6 which has one alicyclic structure. The curable composition according to claim 6 or 7, wherein the repeating unit structure having an alicyclic group having 3 to 30 carbon atoms is represented by the formula [6].

(Wherein R ⁶ represents a hydrogen atom or a methyl group, L ³ represents a single bond or an alkylene group having 1 to 6 carbon atoms, and M represents the alicyclic group having 3 to 30 carbon atoms). ) The curable composition according to any one of claims 1 to 8, wherein the polymerization initiator (c) is an alkylphenone compound. The curable composition according to any one of claims 1 to 9, further comprising (d) a solvent. The cured film obtained from the curable composition as described in any one of Claims 1 thru | or 10. A method for producing a laminate comprising a hard coat layer on at least one surface of a substrate, applying a curable composition according to on the substrate in any one of 請 Motomeko 1 to claim 10 forming a coating film by, and the coating film with an active energy ray irradiation and cured, comprising the step of forming a hard coat layer, the manufacturing method of the laminate. The manufacturing method of the laminated body of Claim 12 with which the said hard-coat layer has a film thickness of 1 nm-1 mm. It is a laminated body provided with a hard-coat layer in at least one surface of a base material, Comprising: This hard-coat layer consists of hardened | cured material of the curable composition as described in any one of Claim 1 thru | or 10. , Laminate.

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