JP4285238B2 - Fluorine-containing unsaturated compound, fluorine-containing polymer, and curable composition using them - Google Patents

Description

  The present invention relates to a novel fluorine-containing unsaturated compound having a long-chain fluorine-containing polyether chain, a novel fluorine-containing polymer having a long-chain fluorine-containing polyether chain in the side chain, and a novel fluorine-containing unsaturated compound. The present invention relates to a photopolymerizable composition comprising a compound and an active energy ray curing initiator.

  Along with the development of multimedia, it is becoming increasingly important to improve the visibility of various display devices (because of less reflection when viewed from an angle, also called “visibility”). Even in a large display device, it is required to make it easier to see, and this characteristic is a technical problem.

  In order to improve the visibility of a display device, an antireflection film made of a low refractive index material is coated on the substrate of the display device.

  In addition, display devices for portable terminals that are often used outdoors are required to additionally impart water repellency and antifouling performance against oil components such as fingerprints and sebum.

  Conventionally, as a method of forming an antireflection film, for example, a method of forming a thin film of a fluorine compound by vapor deposition is known. However, in the vapor deposition method, it is difficult to form a film on a large-screen substrate, and a vacuum apparatus is required, which increases the cost.

  Under these circumstances, a method of forming an antireflection film by preparing a liquid composition in which a fluorine-containing polymer having a low refractive index is dissolved in an organic solvent and applying it to the surface of a substrate (for example, Patent Document 1) ), Photocurable acrylic monomers such as fluorine-containing acrylic monomers (with fluoroalkyl groups), fluorine-containing polyfunctional acrylic compounds (with fluoroalkyl groups) in addition to low refractive index fluorine-containing polymers After coating the composition containing the mixture, a method of photocuring the acrylic monomer (Patent Document 2, Patent Document 3, Patent Document 4, etc.), photoreactivity (polymerizability) on the side chain of the fluoropolymer ) And a method of photocuring a mixture of an acrylic monomer and a polyfunctional acrylic compound mixed with those having a functional group introduced therein (Patent Documents 5 and 6).

  However, coatings (such as photocured films) obtained from these materials have insufficient antifouling performance, for example, antifouling performance against oil components such as fingerprints and sebum even when a good water repellency is obtained. There is a low problem.

  As compounds capable of imparting water repellency, fluorine-containing acrylics having the above-described fluoroalkyl groups, acrylates having a perfluoropolyether chain (Polymer 42 (2001) 2299-2305, Patent Document 7), and the like have been proposed. However, even if a film made of these compounds has a good water repellency, it has insufficient antifouling properties against oil components such as fingerprints and sebum.

In addition, the silane compound having a perfluoropolyether chain of F- (CF ₂ CF ₂ CF ₂ O) _n — (Patent Document 8) has an antifouling property itself, but has adhesion to a resin-made substrate. Even if it is included in the coating film, it is easy to fall off and the durability is insufficient due to lack of photopolymerization and lack of photopolymerizability with other acrylic compounds.

Japanese Patent Application Laid-Open No. 6-1115023 JP-A-7-126552 Japanese Unexamined Patent Publication No. 7-188588 JP-A-8-48935 Japanese Patent No. 2527186 Japanese Patent No. 2543903 Japanese Patent Laid-Open No. 10-287719 WO97 / 07155

  An object of the present invention is to provide a photopolymerizable composition that can achieve high hardness in a coating film by photocuring while maintaining a low refractive index and can impart the antifouling performance.

  Furthermore, an object is to provide an antireflection film with improved antifouling properties while maintaining the antireflection effect, scratch resistance, and abrasion resistance, and an antireflection article coated with such an antireflection film. To do.

  In addition, these fluorine-containing polyether chain compounds are used in combination with other acrylic compounds (such as curing agents) and are exemplified by photopolymerization (or photocuring) properties, in combination with low refractive index compounds. The use as an antireflection material is not described.

  An object of the present invention is to achieve high hardness in a film by photopolymerization (photocuring) while maintaining antifouling properties, and to provide a fluorine-containing unsaturated compound therefor and a photopolymerizable composition containing the same. There is.

  Furthermore, it is an object to provide an antireflection film having an antireflection effect and improved scratch resistance and wear resistance while maintaining antifouling performance, and an antireflection article coated with such an antireflection film. And

  As a result of intensive research aimed at achieving such an object, the present inventors have found a novel fluorine-containing compound having a carbon-carbon double bond and a specific polyether structure, and when these are used, low refractive index properties and It has been found that antifouling performance can be imparted without reducing the hardness.

  Furthermore, the present inventors have found that a photopolymerized (photoeffect) product of a composition containing a specific fluorine-containing compound is useful as an antireflection film having both low reflection, high hardness, and antifouling properties.

  Based on this knowledge, the present inventors have completed the following present invention.

（式中、Ｘ¹およびＸ²は同じかまたは異なり、ＨまたはＦ；Ｘ³はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ⁴およびＸ⁵は同じかまたは異なり、Ｈ、Ｆ、またはＣＦ₃；ａ、ｂ、及びｃは同じかまたは異なり０または１；ｄは１〜４の整数；Ｒｆは炭素数１８〜２００のエーテル結合を含む含フッ素アルキル基）であって、
Ｒｆ基中に式（１）：

（式中、Ｘ⁶はＦまたはＨ）で示される繰り返し単位を６個以上有することを特徴とする含フッ素不飽和化合物（請求項１）に関する。 The present invention is directed to a general formula (M):

Wherein X ¹ and X ² are the same or different and H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and H, F, or CF ₃ A, b and c are the same or different 0 or 1; d is an integer of 1 to 4; Rf is a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms;
Formula (1) in the Rf group:

The present invention relates to a fluorine-containing unsaturated compound (Claim 1) having 6 or more repeating units represented by the formula (X ⁶ is F or H).

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｒｆ、ｂ、及びｄは式（Ｍ）と同じ）であることが好ましい（請求項２）。 Moreover, said Formula (M) is General formula (M-1):

(Wherein, X ¹ , X ² , X ³ , Rf, b, and d are the same as those in formula (M)).

（式中、Ｘ³およびＲｆ、ｄは式（Ｍ）と同じ）であることが好ましい（請求項３）。 Moreover, said formula (M-1) is general formula (M-2):

(Wherein X ³ and Rf, d are the same as those in formula (M)) (Claim 3).

（式中、Ｒｆ、ｄは式（Ｍ）と同じ）であることが好ましい（請求項４）。 Further, the above formula (M-2) is represented by the general formula (M-3):

(Wherein Rf and d are the same as those in formula (M)) (Claim 4).

（式中、ｎは６〜６６の整数）で示されるパーフルオロアルキル基を有することが好ましい（請求項５）。 In the above formulas (M), (M-1), (M-2) and (M-3), the formula (2):

It is preferable to have a perfluoroalkyl group represented by (wherein n is an integer of 6 to 66).

（式中、ｎは６〜６６の整数）で示されるパーフルオロアルキル基およびｄが１であることが好ましい（請求項６）。 In the above formulas (M), (M-1), (M-2) and (M-3), the Rf group is represented by formula (3):

(Wherein n is an integer of 6 to 66) and d is preferably 1 (claim 6).

（式中、構造単位Ｍは請求項１〜６のいずれかに記載の含フッ素不飽和化合物においてｄが１である含フッ素単量体に由来する構造単位、構造単位Ａは構造単位Ｍを構成する含フッ素単量体と共重合可能な単量体に由来する構造単位である。）で示され、構造単位Ｍを０．０１〜１００モル％および単位構造Ａを０〜９９．９９モル％含み、平均重合度が５〜１００００の含フッ素重合体（請求項７）に関する。 Further, the present invention provides the formula (4):

(In the formula, the structural unit M is a structural unit derived from a fluorine-containing monomer in which d is 1 in the fluorine-containing unsaturated compound according to any one of claims 1 to 6, and the structural unit A constitutes the structural unit M. The structural unit is derived from a monomer copolymerizable with the fluorine-containing monomer, and the structural unit M is 0.01 to 100 mol% and the unit structure A is 0 to 99.99 mol%. And a fluorine-containing polymer having an average degree of polymerization of 5 to 10,000 (claim 7).

  In the fluorine-containing polymer of the present invention, the structural unit M is a structural unit derived from a fluorine-containing monomer in which d is 1 in the fluorine-containing unsaturated compound according to any one of claims 3 to 6. (Claim 8).

In the fluorine-containing polymer of the present invention, the structural unit A is represented by the formula (A):
^{Rf 1 -O (O = C)} -CX 6 = CH 2
(Wherein X ⁶ is selected from H, F, CH ₃ and CF ₃ , Rf ¹ is a fluorine-containing alkyl group which may contain an ether bond having 2 to 20 carbon atoms) It is preferable that the structural unit M contains 0.01 to 99 mol% of the structural unit M and 1 to 99.99 mol% of the unit structure A (claim 9).

The present invention also relates to a photopolymerizable composition (claim 10) comprising (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6 and (b) an active energy ray initiator.

Furthermore, the present invention provides (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6,
The present invention relates to a photopolymerizable composition comprising (b) an active energy ray initiator and (c) a curing agent.

  In the photopolymerization composition containing the above curing agent, (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6 is a fluorine-containing acrylate compound, a fluorine-containing methacrylate compound, or a fluorine-containing α-fluoroacrylate. It is preferably at least one selected from the group consisting of compounds (claim 12).

  Furthermore, in the above-mentioned photosynthesis composition, the curing agent (c) is a polyhydric alcohol having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond. A polyfunctional acrylate in which two or more hydroxyl groups are replaced by an acrylate group, a polyhydric alcohol having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond Polyhydric alcohol having polyfunctional methacrylate in which two or more hydroxyl groups are replaced with methacrylate group and fluorine-containing alkyl group which may have ether bond or fluorine-containing alkylene group which may have ether bond A polyfunctional α- in which two or more hydroxyl groups are replaced with α-fluoroacrylate groups It is preferably at least one selected from the group consisting of fluoroacrylates.

  Moreover, this invention relates to the hardened | cured material (claim 14) obtained by photocuring the photopolymerizable composition in any one of Claims 10-13.

Moreover, this invention is (a) at least 1 sort (s) of fluorine-containing unsaturated compound of Claims 1-6,
The present invention relates to a coating composition comprising (b) an active energy ray curing initiator and (d) a solvent (claim 15).

Furthermore, the present invention provides (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6,
(B) an active energy ray curing initiator,
The present invention also relates to a coating composition (c) comprising (c) a curing agent and (d) a solvent.

  In the coating composition containing the curing agent, (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6 is a fluorine-containing acrylate compound, a fluorine-containing methacrylate compound, and a fluorine-containing α-fluoroacrylate compound. Preferably, it is at least one selected from the group consisting of: (Claim 17).

  Further, in the coating composition, the curing agent (c) is a polyhydric alcohol having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond. Polyfunctional acrylates in which two or more hydroxyl groups are replaced with acrylate groups, polyhydric alcohols having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond A polyfunctional methacrylate having at least one hydroxyl group replaced with a methacrylate group and a polyhydric alcohol having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond. More than two hydroxyl groups replaced with α-fluoroacrylate groups Is preferably at least one selected from the group consisting ability α- fluoroacrylate (claim 18).

  The present invention also relates to a cured film (claim 19) obtained by photocuring a film formed by applying the coating composition according to claims 15-18.

  Moreover, this invention relates to the laminated body (Claim 20) which coat | covers the said cured film on a base material (e).

  In the laminate, the material of the substrate (e) is preferably one selected from the group consisting of acrylic resin, polycarbonate, polyethylene terephthalate, polyolefin, triacetyl cellulose, and glass (claim 21). .

  The present invention also relates to an antireflection article (claim 22) using the laminate according to claim 20 or 21.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorine-containing unsaturated compound which can implement | achieve high hardness in a film by photopolymerization (photocuring), and a photopolymerizable composition containing the same can be provided.

  Furthermore, it is possible to provide an antireflection film imparted with an antireflection effect and improved in scratch resistance and wear resistance while maintaining antifouling performance, and an antireflection article coated with such an antireflection film. .

  The first of the present invention relates to a novel fluorine-containing unsaturated compound having a fluorine-containing polyether chain.

（式中、Ｘ¹およびＸ²は同じかまたは異なり、ＨまたはＦ；Ｘ³はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ⁴およびＸ⁵は同じかまたは異なり、Ｈ、Ｆ、またはＣＦ₃；ａ、ｂ、及びｃは同じかまたは異なり０または１；ｄは１〜４の整数；Ｒｆは炭素数１８〜２００のエーテル結合を含む含フッ素アルキル基）であって、Ｒｆ基中に式（１）：

（式中、Ｘ⁶はＦまたはＨ）で示される繰り返し単位を６個以上有することを特徴とする含フッ素不飽和化合物である。これら長鎖の含フッ素ポリエーテルを含むことにより、重合体や硬化物に低屈折率性と防汚性および気体透過性を与えることができる。特に指紋や皮脂などの油成分に対する防汚性が付与できる点で好ましい。 The fluorine-containing unsaturated compound of the present invention has the general formula (M):

Wherein X ¹ and X ² are the same or different and H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and H, F, or CF ₃ A, b, and c are the same or different 0 or 1; d is an integer of 1 to 4; Rf is a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms, (1):

A fluorine-containing unsaturated compound having 6 or more repeating units represented by (wherein X ⁶ is F or H). By including these long-chain fluorine-containing polyethers, it is possible to impart low refractive index properties, antifouling properties and gas permeability to polymers and cured products. It is particularly preferable in terms of imparting antifouling properties against oil components such as fingerprints and sebum.

  That is, the fluorine-containing unsaturated compound of the general formula (M) is a compound containing a polymerizable ethylenic carbon-carbon double bond and a fluorine-containing polyether structure of the formula (1), and is a carbon-carbon double bond. May include at least one and up to four, and may be bonded to the terminal of the Rf group or may be bonded in the middle of the chain.

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｒｆ、ｂ及びｄは式（Ｍ）と同じ）
で示される含フッ素化合物である。 In detail, the fluorine-containing unsaturated compound of the general formula (M) is represented by the formula (M-1):

(Wherein X ¹ , X ² , X ³ , Rf, b and d are the same as those in formula (M))
It is a fluorine-containing compound shown by these.

  These are preferable in terms of good reactivity and polymerizability, and good copolymerizability with acrylic monomers and fluorine-containing ethylenic monomers.

（式中、Ｘ³およびＲｆ、ｄは式（Ｍ）と同じ）
で示される含フッ素化合物であり、これはアクリル系の炭素−炭素二重結合を有するもので、光重合性組成物に使用して、それ自体単独重合性、アクリル系単量体、多官能アクリル化合物との共重合性が良好な点で好ましい。 In more detail, the fluorine-containing unsaturated compound of the general formula (M) is represented by the formula (M-2):

(Wherein X ³ and Rf, d are the same as in formula (M))
This is a fluorine-containing compound having an acrylic carbon-carbon double bond, and is used in a photopolymerizable composition as a homopolymer, acrylic monomer, polyfunctional acrylic. It is preferable in terms of good copolymerizability with the compound.

（式中、Ｒｆ、ｄは式（Ｍ）と同じ）で示される含フッ素不飽和化合物がさらに重合（硬化）反応性が特に高く効率よく硬化物を得ることができる点で好ましい。また、得られる重合体（硬化物）の屈折率を低くできる点で好ましい。またさらに重合体が酸素などの気体透過性に優れる点でも好ましい。 In particular, among the fluorine-containing compounds of the formula (M-2), the formula (M-3):

A fluorine-containing unsaturated compound represented by the formula (wherein Rf and d are the same as those in the formula (M)) is further preferred because it has a particularly high polymerization (curing) reactivity and can efficiently obtain a cured product. Moreover, it is preferable at the point which can make the refractive index of the polymer (hardened | cured material) obtained low. Furthermore, the polymer is also preferable in that it has excellent gas permeability such as oxygen.

（式中、Ｒｆ、ｄは式（Ｍ）と同じ）
で示される含フッ素不飽和化合物が、含フッ素エチレン性単量体との共重合性が良好で、得られる重合体の透明性が特に高く、屈折率を低くできる点で好ましく、またさらに酸素などの気体透過性に優れる点でも好ましい。 In addition, the fluorine-containing compound of the formula (M) is represented by the formula (M-4):

(Where Rf and d are the same as in formula (M))
The fluorine-containing unsaturated compound represented by the formula is preferable in that it has good copolymerizability with the fluorine-containing ethylenic monomer, the transparency of the resulting polymer is particularly high, and the refractive index can be lowered. It is also preferable because of its excellent gas permeability.

（式中、Ｒｆ、ｄは式（Ｍ）と同じ）
で示される含フッ素不飽和化合物が、それ自体の単独重合性や、含フッ素エチレン性単量体との共重合性が良好で、得られる重合体の透明性が高く、屈折率を低くできる点で好ましい。またさらに酸素などの気体透過性に優れる点でも好ましい。 Further, the formula (M-5):

(Where Rf and d are the same as in formula (M))
The fluorine-containing unsaturated compound represented by is excellent in homopolymerization itself and copolymerization with a fluorine-containing ethylenic monomer, and the resulting polymer has high transparency and a low refractive index. Is preferable. Further, it is also preferable from the viewpoint of excellent gas permeability such as oxygen.

などがあげられる。 In addition to the above, preferred specific examples of the ethylenic carbon-carbon double bond contained in the fluorine-containing unsaturated compound of the formula (M) of the present invention include:

Etc.

などがあげられる。 As a preferable specific example of the ethylenic carbon-carbon double bond contained in the fluorine-containing unsaturated compound of the formula (M-1),

Etc.

などがあげられる。 As a preferable specific example of the ethylenic carbon-carbon double bond contained in the fluorine-containing unsaturated compound of the formula (M-2),

Etc.

などの構造を有する含フッ素不飽和化合物が具体的に好ましくあげられる。 In the case of a fluorine-containing compound containing two or more carbon-carbon double bonds,

Fluorine-containing unsaturated compounds having a structure such as

Among these, those having a structure of —O (C═O) CF═CH ₂ are preferable in that the refractive index can be lowered, the polymerization (curing) reactivity is particularly high, and a cured product can be obtained efficiently. .

（式中、Ｘ⁶はＦまたはＨ）で示される含フッ素エーテル鎖の繰り返し単位を６個以上必須成分として有することを特徴とし、炭素数１８〜２００の含フッ素有機基である。 In the fluorine-containing unsaturated compound of the present invention, the Rf group has the formula (1) in the chain:

It is a fluorine-containing organic group having 18 to 200 carbon atoms, characterized by having 6 or more repeating units of a fluorine-containing ether chain represented by the formula (wherein X ⁶ is F or H).

  It is important that the fluorine-containing polyether chain of the formula (1) is contained in Rf in the number of 6 or more as a repeating unit, thereby imparting antifouling property.

  In more detail, when used as a specific fluoropolymer structural unit, photopolymerizable composition and coating composition described later, those containing 6 or more repeating units of a fluoropolyether chain are included. However, when used in the form of a mixture, in the distribution of the fluorine-containing unsaturated compound having less than 6 repeating units and 6 or more fluorine-containing unsaturated compounds, the repeating unit of the polyether chain is 6 A mixture having the highest abundance ratio of at least one fluorine-containing unsaturated compound is preferable.

  The fluorine-containing polyether chain of the formula (1) preferably has 6.5 to 8, more preferably 10 or more, and 18 to 22, more preferably 20 or more repeating units. In addition, it is preferable in terms of improving the antifouling property, in particular, the removability with respect to the soil containing an oil component. Moreover, gas permeability is preferable at the point which can be provided much more effectively. Further, the fluorine-containing polyether chain may be present at the end of the Rf group or in the middle of the chain.

のパーフルオロポリエーテルであることが防汚性能、透明性と低屈折性と気体透過性の面でより好ましい。 Further, the fluorine-containing polyether chain of the formula (1) is

The perfluoropolyether is more preferable in terms of antifouling performance, transparency, low refraction, and gas permeability.

（式中、Ｘ⁶は式（１）と同じ、Ｒ¹は水素原子、ハロゲン原子またはアルキル基、含フッ素アルキル基、エーテル結合を含むアルキル基およびエーテル結合を含む含フッ素アルキル基から選ばれる少なくとも１種、Ｒ²は二価以上の有機基、ｎは６〜６６の整数、ｅは０または１）の構造であることが好ましい。 Specifically, the Rf group is represented by the formula (5):

(Wherein X ⁶ is the same as in formula (1), R ¹ is at least selected from a hydrogen atom, a halogen atom or an alkyl group, a fluorine-containing alkyl group, an alkyl group containing an ether bond and a fluorine-containing alkyl group containing an ether bond) One type, R ² is preferably a divalent or higher-valent organic group, n is an integer of 6 to 66, and e is 0 or 1).

That is, it is a fluorine-containing organic group that is bonded to a reactive carbon-carbon double bond via a divalent or higher-valent organic group R ² and further has R ¹ at the terminal.

（ｌ：１〜１０、ｍ：１〜１０、ｎ：０〜５）
なかでもエーテル結合を含む含フッ素アルキレン基が好ましく、具体的には、

（Ｘ⁹、Ｘ^9'はＦまたはＣＦ₃；Ｘ^10'はＨまたはＦ；ｏ＋ｐは１〜３０；ｑは０または１；ｒ、ｓは０または１）
などが、例示される。 R ² may be any organic group that can bind the fluorine-containing polyether chain of the formula (1) to a reactive carbon-carbon double bond, and examples thereof include an alkylene group and a fluorine-containing alkylene group. , Selected from an alkylene group containing an ether bond and a fluorine-containing alkylene group containing an ether bond, among which a fluorine-containing alkylene group and a fluorine-containing alkylene group containing an ether bond are preferable in terms of transparency and low refractive index. ,In particular,

(L: 1 to 10, m: 1 to 10, n: 0 to 5)
Of these, a fluorine-containing alkylene group containing an ether bond is preferred. Specifically,

(X ⁹ and X ^{9 ′} are F or CF ₃ ; X ^{10 ′} is H or F; o + p is 1 to 30; q is 0 or 1; r, s is 0 or 1)
Etc. are exemplified.

（Ｘ⁹はＦまたはＣＦ₃；ｎは０または１〜１０；ｍは１〜１０）
等も利用できる。 In addition, R ² is

(X ⁹ is F or CF ₃ ; n is 0 or 1 to 10; m is 1 to 10)
Etc. can also be used.

In the Rf group of the formula (5), R ¹ is present at the terminal and is selected from hydrogen, a halogen atom, a fluorine-containing alkyl group, an alkyl group containing an ether bond, and a fluorine-containing alkyl group containing an ether bond, However, it is preferably a fluorine atom, a fluorine-containing alkyl group having 1 to 30 carbon atoms, or a fluorine-containing alkyl group containing an ether bond having 1 to 30 carbon atoms in terms of transparency, low refractive index and antifouling property, In particular, a fluorine atom, a perfluoroalkyl group having 1 to 30 carbon atoms, and a perfluoroalkyl group containing an ether bond having 1 to 30 carbon atoms are preferable.

（ｌ：１〜１０、ｍ：１〜１０、ｎ：０〜５）
なかでもエーテル結合を含む含フッ素アルキレン基が好ましく、具体的には、

（Ｘ⁹、Ｘ^9'はＦまたはＣＦ₃；Ｘ^10'はＨまたはＦ；ｏ＋ｐは１〜３０；ｑは０または１；ｒ、ｓは０または１）
などが好ましく上げられる。 In particular,

(L: 1 to 10, m: 1 to 10, n: 0 to 5)
Of these, a fluorine-containing alkylene group containing an ether bond is preferred. Specifically,

(X ⁹ and X ^{9 ′} are F or CF ₃ ; X ^{10 ′} is H or F; o + p is 1 to 30; q is 0 or 1; r, s is 0 or 1)
Etc. are preferably raised.

（式中、ｎは６〜６６の整数）で示されるパーフルオロアルキル基を有するもの（式（５）においてＲ¹、Ｘ⁶がいずれもＦ）であり、
さらに、Ｒｆ基のより好ましい具体例は式（３）：

（式中、ｎは６〜６６の整数）で示されるパーフルオロアルキル基（ただしｄは１）である。 Of these, more preferred is the formula (2) at the end:

(Wherein, n is an integer of 6 to 66) having a perfluoroalkyl group (in formula (5), R ¹ and X ⁶ are both F),
Furthermore, a more preferred specific example of the Rf group is represented by the formula (3):

(Wherein, n is an integer of 6 to 66) (where d is 1).

  Those having an Rf group are preferable in that they are excellent in transparency, low refractive index property and antifouling property, and further excellent in gas permeability.

などがあげられる。 Therefore, preferred specific examples of the fluorine-containing unsaturated compound of the present invention are:

Etc.

  The second of the present invention relates to a fluorine-containing polymer obtained by polymerizing the fluorine-containing unsaturated compound of the present invention.

（式中、構造単位Ｍは前記式（Ｍ）に記載の含フッ素不飽和化合物においてｄが１である含フッ素単量体に由来する構造単位、構造単位Ａは構造単位Ｍを構成する含フッ素単量体と共重合可能な単量体に由来する構造単位である）で示され、構造単位Ｍを０．０１〜１００モル％および単位構造Ａを０〜９９．９９モル％含み、平均重合度が５〜１００００の含フッ素重合体である。 The polymer of the present invention has the formula (4):

(In the formula, the structural unit M is a structural unit derived from a fluorinated monomer in which d is 1 in the fluorinated unsaturated compound described in the formula (M), and the structural unit A is a fluorinated component constituting the structural unit M. A structural unit derived from a monomer copolymerizable with the monomer), containing 0.01 to 100 mol% of the structural unit M and 0 to 99.99 mol% of the unit structure A, and having an average polymerization It is a fluorine-containing polymer having a degree of 5 to 10,000.

（式中、Ｘ¹およびＸ²は同じかまたは異なり、ＨまたはＦ；Ｘ³はＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ⁴およびＸ⁵は同じかまたは異なり、Ｈ、Ｆ、またはＣＦ₃；ａ、ｂ、及びｃは同じかまたは異なり０または１；Ｒｆは炭素数１８〜２００のエーテル結合を含む含フッ素アルキル基）であって、Ｒｆ基中に式（１）：

（式中、Ｘ⁶はＦまたはＨ）で示される繰り返し単位を６個以上有する構造単位であり、好ましくは一般式（Ｍ−７）：

（式中、Ｘ¹、Ｘ²、Ｘ³、Ｒｆおよびｂは式（Ｍ−６）と同じ）で示される構造単位、
一般式（Ｍ−８）：

（式中Ｘ³およびＲｆは式（Ｍ−６）と同じ）で示される構造単位、
より好ましくは、一般式（Ｍ−９）：

（式中、Ｒｆは式（Ｍ−６）と同じ）で示される構造単位である。 Specifically, the general formula (M-6):

Wherein X ¹ and X ² are the same or different and H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and H, F, or CF ₃ A, b, and c are the same or different 0 or 1; Rf is a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms, and the Rf group has the formula (1):

(Wherein X ⁶ is F or H), which is a structural unit having 6 or more repeating units, preferably represented by formula (M-7):

(Wherein X ¹ , X ² , X ³ , Rf and b are the same as those in formula (M-6)),
General formula (M-8):

(Wherein X ³ and Rf are the same as those in formula (M-6)),
More preferably, the general formula (M-9):

(Wherein Rf is the same as in formula (M-6)).

  That is, it is a homopolymer of the aforementioned fluorine-containing unsaturated compound or a copolymer with a copolymerizable monomer.

  As the monomer constituting the structural unit-(M)-, those having the d of 1 among the above-mentioned novel fluorine-containing unsaturated compounds of the present invention can be used, and the above-mentioned fluorine-containing unsaturated compounds are the same. It can be used as a preferred example.

  In the fluoropolymer of the present invention, the structural unit A is an optional component, and the monomer constituting the structural unit M, that is, the above-mentioned fluorine-containing unsaturated compound formulas (M), (M-1), (M-2) ) And (M-3) are not particularly limited as long as they are monomers capable of copolymerization with (M-3), and may be appropriately selected according to the intended use of the polymer, required characteristics, and the like.

  For example, the following structural units can be exemplified.

(1) Structural unit derived from fluorine-containing ethylenic monomer (A1)
These can maintain the refractive index of the fluorine-containing polymer low, and the monomer can be used to adjust the mechanical properties and glass transition point of the polymer. Can be increased, which is preferable.

（式中、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁸はＨまたはＦ、Ｘ¹⁷はＨ、ＦまたはＣＦ₃、ｈ１、ｉ１、ｊは０または１、Ｚ²はＨ、ＦまたはＣｌ、Ｒｆ⁵は炭素数１〜２０の含フッ素アルキレン基、炭素数２〜１００のエーテル結合を含む含フッ素アルキレン基）で示されるものが好ましい。 As a structural unit derived from a fluorine-containing ethylenic monomer, the general formula (A1):

(Wherein X ¹⁵ , X ¹⁶ and X ¹⁸ are H or F, X ¹⁷ is H, F or CF ₃ , h1, i1, j is 0 or 1, Z ² is H, F or Cl, and Rf ⁵ is carbon. A fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group containing an ether bond having 2 to 100 carbon atoms is preferable.

などの単量体から誘導される構造単位が好ましくあげられる。 As a specific example,

Preferred are structural units derived from monomers such as

  These monomers of the formula (A1) are also preferable because they have good copolymerizability with the monomers represented by the formulas (M-4) and (M-5).

(2) Structural unit derived from fluorine-containing acrylic monomer (A2)
These are preferable in terms of good copolymerizability with the fluorine-containing unsaturated compound of (M-2) and (M-3) of the present invention, and the refractive index of the obtained fluorine-containing copolymer can be kept low. Further, by selecting a monomer, the mechanical properties of the polymer, the glass transition point, etc. can be adjusted. Particularly, the copolymerization with the structural unit M can increase the glass transition point, which is preferable.

（式中、Ｘ¹、Ｘ²は同じかまたは異なりＨまたはＦ；Ｘ³は同じかまたは異なりＨ、Ｃｌ、ＣＨ₃、ＦまたはＣＦ₃；Ｒｆ¹は炭素数１〜２０の炭化水素基、炭素数１〜２０の含フッ素アルキル基、炭素数２〜１００のエーテル結合を有する含フッ素アルキル基または炭素数３〜２０の含フッ素アリール基であって、Ｘ¹、Ｘ²、Ｘ³、Ｒｆ¹のいずれかにフッ素原子を含む）で示されるものが好ましい。 The structural unit derived from the fluorinated acrylic monomer is represented by the general formula (A2):

Wherein X ¹ and X ² are the same or different H or F; X ³ is the same or different H, Cl, CH ₃ , F or CF ₃ ; Rf ¹ is a hydrocarbon group having 1 to 20 carbon atoms, A fluorine-containing alkyl group having 1 to 20 carbon atoms, a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms, or a fluorine-containing aryl group having 3 to 20 carbon atoms, wherein X ¹ , X ² , X ³ , Rf ¹ includes a fluorine atom).

などが好ましくあげられる。 In formula (A2), —Rf ¹ is specifically

Etc. are preferred.

（Ｚ⁴、Ｚ⁵：Ｈ、Ｆ、Ｃｌ、ｎ：１〜１０） In particular,

^{(Z 4, Z 5: H} , F, Cl, n: 1~10)

(3) Acrylic or methacrylic monomers not containing fluorine:
Examples include acrylic acid, methacrylic acid, acrylic esters and methacrylic esters, as well as maleic anhydride, maleic acid, maleic esters, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.

  By introducing a structural unit derived from these, solubility in a solvent, adhesion to a substrate, compatibility with a photoinitiator and other additives can be improved, which is preferable.

  Moreover, these monomers are also preferable in terms of good copolymerizability with the fluorine-containing unsaturated compound represented by the formulas (M-2) and (M-3).

（式中、Ｘ¹¹、Ｘ¹²、Ｘ¹³はＨまたはＦ、Ｘ¹⁴はＨ、Ｆ、ＣＦ₃、ｈは０〜２、ｉは０または１、Ｒｆ⁴は炭素数１〜４０の含フッ素アルキレン基、炭素数２〜１００のエーテル結合を有する含フッ素アルキレン基、Ｚ¹は−ＯＨ、−ＣＨ₂ＯＨ、−ＣＯＯＨ、カルボン酸誘導体、−ＳＯ₃Ｈ、スルホン酸誘導体、エポキシ基、シアノ基から選ばれるもの）で示される構造単位であり、なかでも式（Ａ３−１）：

（式中、Ｒｆ⁴、Ｚ¹は式（Ａ３）と同じ）
で示される構造単位が好ましい。 (4) Structural unit derived from a fluorine-containing ethylenic monomer having a functional group (A3)
These are preferable in that they can provide adhesion to a substrate and solubility in a solvent, particularly a general-purpose solvent while maintaining the refractive index of the curable fluorine-containing polymer and its cured product low, and other than that Y is involved. It is preferable at the point which can provide functions, such as crosslinking | crosslinked property. The structural unit derived from a preferred fluorine-containing ethylenic monomer having a functional group has the general formula (A3):

(In the formula, X ¹¹ , X ¹² and X ¹³ are H or F, X ¹⁴ is H, F, CF ₃ , h is 0 to 2, i is 0 or 1, and Rf ⁴ is fluorine containing 1 to 40 carbon atoms. An alkylene group, a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, Z ¹ is —OH, —CH ₂ OH, —COOH, carboxylic acid derivative, —SO ₃ H, sulfonic acid derivative, epoxy group, cyano group A structural unit represented by formula (A3-1):

(Wherein Rf ⁴ and Z ¹ are the same as those in formula (A3))
Is preferred.

などの含フッ素エチレン性単量体から誘導される構造単位が好ましくあげられる。 More specifically,

A structural unit derived from a fluorine-containing ethylenic monomer such as is preferred.

（式中、Ｒｆ⁴、Ｚ¹は式（Ａ３）と同じ）
で示される構造単位も好ましく例示でき、より具体的には、

などの単量体から誘導される構造単位があげられる。 Formula (A3-2):

(Wherein Rf ⁴ and Z ¹ are the same as those in formula (A3))
The structural unit represented by can also be preferably exemplified, and more specifically,

And structural units derived from monomers such as

などがあげられる。 In addition, as the functional group-containing fluorine-containing ethylenic monomer,
_{CF 2 = CFCF 2 -O-Rf} 4 -Z 1, CF 2 = CF-Rf 4 -Z 1,
^{_{CH 2 = CH-Rf 4 -Z}} 1, CH 2 = CHO-Rf 4 -Z 1
(Rf ⁴ is the same as Rf ⁴ of formula (A3))
And more specifically,

Etc.

Among them, the functional group Z ¹ in the formula (A3) is preferably —OH, —CH ₂ OH, —COOH, or a carboxylic acid ester group. Further, these monomers of the formula (A3) have good copolymerizability with the monomers represented by the formulas (M-4) and (M-5) and the monomer represented by the formula (A1). Is preferable.

(5) Aliphatic cyclic structural unit having fluorine (A4)
When these structural units are introduced, the transparency can be increased, the refractive index can be further lowered, and a curable fluorine-containing polymer having a high glass transition point can be obtained, and the cured product can be expected to have higher hardness. This is preferable.

（式中、Ｘ¹⁹、Ｘ²⁰、Ｘ²³、Ｘ²⁴、Ｘ²⁵、Ｘ²⁶は同じかまたは異なりＨまたはＦ；Ｘ²¹、Ｘ²²は同じかまたは異なりＨ、Ｆ、ＣｌまたはＣＦ₃；Ｒｆ⁶は炭素数１〜１０の含フッ素アルキレン基または炭素数２〜１０のエーテル結合を有する含フッ素アルキレン基；ｎ２は０〜３の整数；ｎ１、ｎ３、ｎ４、ｎ５は同じかまたは異なり０または１の整数）で示されるものが好ましい。 As the fluorine-containing aliphatic cyclic structural unit, the formula (A4):

Wherein X ¹⁹ , X ²⁰ , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ are the same or different H or F; X ²¹ , X ²² are the same or different H, F, Cl or CF ₃ ; Rf ⁶ is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms; n2 is an integer of 0 to 3; n1, n3, n4 and n5 are the same or different and 0 or An integer of 1 is preferable.

（式中、Ｒｆ⁶、Ｘ²¹、Ｘ²²は前記と同じ）で示される構造単位があげられる。 For example,

(Wherein Rf ⁶ , X ²¹ and X ²² are the same as those described above).

などがあげられる。 In particular,

Etc.

(6) Structural unit derived from an ethylenic monomer containing no fluorine Introducing a structural unit derived from an ethylenic monomer containing no fluorine within a range that does not deteriorate the refractive index (higher refractive index) Also good.

  Thereby, the solubility in a general-purpose solvent is improved, and the compatibility with an additive such as a photocatalyst or a curing agent added as necessary is preferable.

Specific examples of non-fluorinated ethylenic monomers include
α-olefins:
Vinyl ether or vinyl ester monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride:
Allyl monomers such as CH ₂ = CHOR, CH ₂ = CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms):
CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH,
Allyl ether monomers such as CH ₂ = CHCH ₂ COOH and CH ₂ = CHCH ₂ Br:

(7) Structural unit derived from alicyclic monomer As a copolymerization component of structural unit M (particularly M-4 and M-5 monomers) or structural unit M (particularly M-4, M-) 5) and the structural unit of the aforementioned fluorine-containing ethylenic monomer (described above (1)) or the non-fluorine ethylenic monomer (described above (6)), in addition to fat as a third component A cyclic monomer structural unit may be introduced, which is preferable because it can achieve a high glass transition point and a high hardness.

（ｍ：０〜３、Ａ、Ｂ、Ｃ、Ｄは、Ｈ、Ｆ、Ｃｌ、ＣＯＯＨ、ＣＨ₂ＯＨ、炭素数１〜５のパーフルオロアルキルなど）で示されるノルボルネン誘導体、

などの脂環式単量体や、これらに置換基を導入した誘導体などがあげられる。 Specific examples of alicyclic monomers include

A norbornene derivative represented by (m: 0 to 3, A, B, C, D is H, F, Cl, COOH, CH ₂ OH, C 1-5 perfluoroalkyl, etc.),

And alicyclic monomers such as these, and derivatives obtained by introducing substituents into these.

  In the fluoropolymer of the present invention, the combination and composition ratio of the structural unit M (M-6, M-7, M-8, M-9) and A are the intended use and physical properties (particularly from the above examples). The glass transition point, melt processability, solvent solubility, etc.), functions (transparency, refractive index, surface properties), etc. can be selected in various ways.

  The fluoropolymer of the present invention contains the structural unit M (M-6, M-7, M-8, M-9) as an essential component, and the structural unit M itself maintains a low refractive index. In addition, it has a feature of having a function of imparting transparency and a function of imparting water repellency, antifouling property and solvent resistance.

  Furthermore, in the case of a copolymer comprising the structural unit M of the present invention and the structural unit A of a monomer that can be copolymerized, by selecting the structural unit A from the above-mentioned examples, mechanical properties (high Tg, etc.) ) And a lower refractive index polymer. Further, the copolymerization of the structural unit A can improve solvent solubility, melt molding processability, film formability, compatibility with additives and the like. Moreover, when it uses for lamination | stacking, adhesiveness with a base material can also be improved by copolymerization.

  In the fluoropolymer according to the present invention, the surface function of water repellency and antifouling properties is effective even when the composition contains only a very small amount of structural unit M (for example, 0.01 to 5 mol%). I found that it can be improved. At the same time, lubricity and slipperiness can be imparted.

  It has also been found that the fluoropolymer of the present invention can have a particularly low refractive index, for example, 1.35 or less, and depending on the composition ratio, it can be 1.32 or less, and even 1.30 or less.

  Further, the present inventors have shown that a specific fluorine-containing polymer having a specific fluorine-containing polyether structure in the side chain as in the present invention is excellent in gas permeability (specifically, oxygen permeability coefficient, oxygen selective permeability, etc.). I found out.

  For the purpose of improving water repellency and antifouling property, in the copolymer of the structural unit M and the structural unit A, the content ratio of the structural unit M is 0 with respect to all monomers constituting the fluoropolymer. It may be 0.01 mol% or more, preferably 0.1 mol% or more, and more preferably 1 mol% or more.

  Since the fluoropolymer of the present invention has both antifouling properties and low refractive index properties, it is particularly preferable for use in antireflection coatings.

  Furthermore, when transparency is required, such as for use in an antireflection film, the polymer is preferably a fluorine-containing polymer having a combination and composition in which the combination of the structural unit M and the structural unit A can be amorphous.

  The molecular weight of the fluoropolymer of the present invention is, for example, a fluoropolymer having an average degree of polymerization of 5 to 10,000. Although it varies depending on the average molecular weight of the structural unit M alone (the number of repeating units of the fluorinated polyether), the number average molecular weight can be selected from the range of 5000 to 20000000, but is preferably selected from the range of 10,000 to 5000000, particularly 10,000 to 1000000. Are preferred. If the molecular weight is too low, the mechanical properties are likely to be insufficient, and the strength is fragile and the strength tends to be insufficient. If the molecular weight is too high, the solvent solubility tends to be poor, and the film formability and leveling properties tend to be poor, particularly when forming a thin film.

  When the fluoropolymer of the present invention is used for an antireflection agent, it can be variously determined depending on the type and content of the structural unit M, and the type of the copolymer structural unit A used as necessary. The refractive index is preferably 1.45 or less, more preferably 1.40 or less, and particularly preferably 1.38 or less.

  More preferred fluoropolymers of the present invention are homopolymers or copolymers composed of the above-mentioned structural units (M-8) and (M-9), particularly heavy polymers composed of structural units (M-9). The coalescence is preferable in terms of heat resistance, transparency, and low refractive index.

In the case of the copolymer composed of the structural units (M-8) and (M-9), the copolymer component is represented by the formula (A):
^{Rf 1 -O (O = C)} -CX 6 = CH 2 (A)
(Wherein X ⁶ is selected from H, F, CH ₃ and CF ₃ , Rf ¹ is a fluorine-containing alkyl group which may contain an ether bond having 2 to 20 carbon atoms) The structural unit is preferably. It is a fluorine-containing polymer comprising the structural units (M-8) and (M-9) in an amount of 0.01 to 99 mol% and the structural unit (A) in an amount of 1 to 99.99 mol%.

  The fluorine-containing polymer of the present invention comprises a monomer (M) having a fluorine-containing polyether chain corresponding to each structural unit, and a monomer (A) as a copolymerization component when used in a known manner (copolymerization). ) Obtained by polymerization. As the polymerization method, a radical polymerization method, an anionic polymerization method, a cationic polymerization method or the like can be used. Among these, the monomers exemplified for obtaining the polymer having a hydroxyl group of the present invention have good radical polymerizability, and are easy to control the quality such as composition and molecular weight, and are easy to industrialize. Legal methods are preferably used.

  In order to start radical polymerization, the means is not limited as long as it proceeds radically, but for example, it is started by organic or inorganic radical polymerization initiator, heat, light, or ionizing radiation. As the polymerization mode, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like can be used. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, the temperature, and the like. The copolymer composition can be controlled by the monomer composition of the charged monomers.

  The third of the present invention is a photopolymerizable (curable) composition using the above-mentioned fluorine-containing unsaturated compound having a fluorine-containing polyether chain.

One of the compositions of the present invention is
It is a photopolymerizable composition comprising (a) a fluorine-containing unsaturated compound having a fluorine-containing polyether chain, and (b) an active energy ray curing initiator.

  The fluorine-containing unsaturated compound (a) having a fluorine-containing polyether chain in the composition of the present invention is the above-mentioned fluorine-containing unsaturated compound having a carbon-carbon double bond and a fluorine-containing polyether chain. The same as described above can be preferably used.

  The active energy ray curing initiator (b), for example, generates radicals and cations only when irradiated with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X rays, γ rays, etc., and is curable. It functions as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the fluorine-containing polymer, and usually one that generates radicals or cations with ultraviolet light, particularly one that generates radicals.

  According to this curable fluorine-containing resin composition, polymerization (curing) reaction can be easily started by the active energy ray, and there is no need for heating at high temperature, and curing reaction is possible at relatively low temperature. It is preferable in that it can be applied to a base material that is low in temperature and easily deforms, decomposes, or colors with heat, such as a transparent resin base material.

  The active energy ray curing initiator (b) in the composition of the present invention is the type of carbon-carbon double bond (radical reactive or cationic reactive) in the fluorine-containing unsaturated compound (a), the activity used. Fluorine-containing unsaturated compound (a) having a radical-reactive carbon-carbon double bond generally using an active energy ray in the ultraviolet region, although it is appropriately selected depending on the type of energy ray (wavelength range, etc.) and irradiation intensity. Examples of the initiator that cures can include the following.

Acetophenone acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropan-1-one, etc.

Benzoin benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

Benzophenone benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.

Thioxanthones Thioxanthone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc.

Other benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

  Depending on the type of the fluorine-containing polymer and the type of the active energy ray initiator described above, the compatibility may be lost, and the coating composition itself or the coated film may become cloudy, resulting in transparency and curing reactivity. May decrease.

  The present inventors have found that compatibility with a fluorine-containing polymer can be improved by introducing a fluorine atom or a fluorine-containing organic group into the active energy ray initiator itself.

  Specifically, it is preferable that the initiator contains a fluorine-containing alkyl group, a fluorine-containing alkylene group, a fluorine-containing alkyl group having an ether bond, or a fluorine-containing alkylene group having an ether bond, for example, an initiator having an OH group. One having a structure in which a fluorine-containing carboxylic acid having a fluorine-containing organic group (polyvalent carboxylic acid) or the like is introduced by an ester bond (for example, the formula (b) in Example 16), a fluorine-containing carboxyl in an initiator having an amino group Examples include a structure in which an acid (polycarboxylic acid) is introduced through an amide bond.

  Introducing a fluorine-containing organic group into the initiator is preferable in that the fluorine-containing polymer having a high fluorination rate has good compatibility and can improve the polymerization (curing) reactivity and the transparency of the film.

  Moreover, you may add photoinitiator adjuvants, such as amines, sulfones, and sulfines, as needed.

  Moreover, the following can be illustrated as an initiator which hardens the fluorine-containing unsaturated compound (a) which has a cation reactive carbon-carbon double bond.

Onium salt Iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt, etc.

Sulfone compounds β-ketoester, β-sulfonylsulfone and their α-diazo compounds, etc.

Sulfonic acid esters Alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc.

Other Sulfonimide compounds, diazomethane compounds, etc.

  Also in these cation-reactive active energy ray initiators, compatibility with the fluorine-containing polymer can be improved in the same manner as described above by introducing a fluorine atom or a fluorine-containing organic group.

  You may add a hardening | curing agent (c) further to the fluorine-containing unsaturated compound (a) and active energy ray hardening initiator (b) of this invention as needed.

  The curing agent (c) is preferably one having at least one carbon-carbon unsaturated bond and capable of being polymerized with a radical or an acid. Specifically, a radical polymerizable monomer such as an acrylic monomer, a vinyl ether type And cationically polymerizable monomers such as monomers. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.

  These so-called curing agents having a carbon-carbon unsaturated bond react with radicals and cations generated by the reaction of the active energy ray curing initiator (b) in the composition of the present invention with active energy rays such as light, The fluorine-containing unsaturated compound (a) in the composition of the present invention can be crosslinked by copolymerization with a carbon-carbon double bond.

  Monofunctional acrylic monomers include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, α-fluoroacrylic acid, α-fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid In addition to esters, (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.

（ＸはＨ、ＣＨ₃またはＦ、Ｒｆは炭素数２〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基）で表わされる化合物が好ましい。 Among them, in order to keep the refractive index of the cured product low, an acrylate monomer having a fluoroalkyl group is preferable.

A compound represented by (X is H, CH ₃ or F, and Rf is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms) is preferable.

などがあげられる。 In particular,

Etc.

  As polyfunctional acrylic monomers, compounds in which the hydroxyl groups of polyhydric alcohols such as diols, triols, and tetraols are replaced with acrylate groups, methacrylate groups, or α-fluoroacrylate groups are generally known. .

  Specifically, each of 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include compounds in which two or more hydroxyl groups of polyhydric alcohols are replaced with any one of an acrylate group, a methacrylate group, and an α-fluoroacrylate group.

  Further, two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group, a fluorine-containing alkyl group containing an ether bond, a fluorine-containing alkylene group or a fluorine-containing alkylene group containing an ether bond are converted into an acrylate group, a methacrylate group, α A polyfunctional acrylic monomer substituted with a fluoroacrylate group can also be used, and is particularly preferable in that the refractive index of the cured product can be kept low.

（Ｒｆは炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキル基、ＲはＨまたは炭素数１〜３のアルキル基）、

（Ｒｆ’は炭素数１〜４０の含フッ素アルキレン基またはエーテル結合を含む含フッ素アルキレン基、ＲはＨまたは炭素数１〜３のアルキル基）
などの一般式で示される含フッ素多価アルコール類の２個以上のヒドロキシル基をアクリレート基、メタアクリレート基またはα−フルオロアクリレート基に置き換えた構造のものが好ましくあげられる。 As a specific example

(Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group containing an ether bond, R is H or an alkyl group having 1 to 3 carbon atoms),

(Rf ′ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group containing an ether bond, R is H or an alkyl group having 1 to 3 carbon atoms)
Preferred are those having a structure in which two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by the general formulas such as are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

  In addition, when these exemplified monofunctional and polyfunctional acrylic monomers are used in the composition of the present invention as a curing agent, an α-fluoroacrylate compound is particularly preferable in terms of good curing reactivity.

  In the composition of the present invention, the amount of the active energy ray curing initiator (b) added is the type and content of the carbon-carbon double bond in the fluorine-containing unsaturated compound (a), and whether or not the curing agent is used. Depending on the amount of the curing agent used, the initiator used, the type of active energy ray, and the amount of irradiation energy (strength and time, etc.), the fluorine-containing unsaturated compound (a) and the curing agent (c ) To 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and most preferably 0.1 to 10 parts by weight.

  Specifically, with respect to the total number of moles of the carbon-carbon double bond content (number of moles) contained in the fluorine-containing unsaturated compound (a) and the number of moles of the carbon-carbon unsaturated bond of the curing agent (c). 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably 0.5 to 10 mol%.

  In the photopolymerizable composition of the present invention, the content of the fluorine-containing unsaturated compound (a) can be appropriately selected depending on the purpose and use of the composition and the cured product, but in the case of imparting water repellency and antifouling property to the cured product. It is effective only by mixing a small amount with respect to the curing agent (c) and other additives that can be a binder. For example, 0.01% with respect to 100 parts by weight of a cured product (total of resin components that can be a curing agent and a binder) The effect appears when the amount is at least part by weight, preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight. Cured products obtained by photopolymerization (curing) of these compositions are preferred in that the fluorine-containing unsaturated compound (a) exhibits water repellency and antifouling effects, and further, the durability of the effects is good. . Further, the fluorine-containing unsaturated compound (a) itself is suitable for optical applications such as antireflection applications because it has a high effect of reducing the refractive index.

  Another embodiment of the composition of the present invention is an embodiment using a solvent, which can be coated on various substrates by dissolving or dispersing in a solvent to form a coating film. It is preferable in that it can be efficiently cured by irradiation with a line or the like, and a cured film can be obtained.

That is, the coating composition of the present invention is
A composition comprising (a) a fluorine-containing unsaturated compound having a fluorine-containing polyether chain, (b) an active energy ray curing initiator, and (d) a solvent, or (a) a fluorine-containing unsaturated having a fluorine-containing polyether chain. Compound (b) active energy ray curing initiator,
(C) A composition comprising a curing agent and (d) a solvent.

  As the fluorine-containing unsaturated compound (a), the active energy ray curing initiator (b), and the curing agent (c), the same compounds as those described above can be preferably used.

  The solvent (d) includes a curable fluorine-containing polymer (a), an active energy ray curing initiator (b) and a curing agent (c) to be added as necessary, a binder component (such as a resin), a leveling agent, a light There is no particular limitation as long as the additive such as a stabilizer can be dissolved or dispersed uniformly, but those that dissolve the entire composition uniformly are particularly preferable. The mode of using this solvent is particularly preferable in the field where a thin layer coating (around 0.1 μm) is required, such as an antireflection coating, and is highly transparent so that a uniform coating can be obtained with high productivity.

  Examples of the solvent (d) include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate , Ester solvents such as amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol solvents such as rubacetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol, ethanol, propanol, isopropanol, butanol, etc. Examples of the alcohol solvent include aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

  Furthermore, in order to improve the solubility of the fluorine-containing unsaturated compound (a) and the curing agent (c) containing a fluorine atom, a fluorine-based solvent may be used as necessary.

などのフッ素系アルコール類、
ベンゾトリフルオライド、パーフルオロベンゼン、パーフルオロ（トリブチルアミン）、ＣｌＣＦ₂ＣＦＣｌＣＦ₂ＣＦＣｌ₂などがあげられる。 Examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). , Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene,

Fluorine alcohols such as
Examples thereof include benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl _{2 and the} like.

  These fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents.

  Of these, ketone solvents, acetate solvents, alcohol solvents, aromatic solvents, and the like are preferable in terms of paintability and coating productivity.

  The present inventors have also found that the leveling property of the polymer film after coating and drying on the base material can be improved by mixing a fluorine-containing alcohol solvent together with these general-purpose solvents.

  This leveling improvement effect is high for resin base materials, particularly acrylic resins, cellulosic resins, polyethylene terephthalate, polycarbonate, and polyolefin, and particularly remarkable for polyethylene terephthalate base materials.

  The fluorine-containing alcohol to be added may be one having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher, and capable of dissolving the fluorine-containing unsaturated compound (a) and the curing agent (c).

などが好ましい具体例である。 For example,

Etc. are preferable specific examples.

  The fluorinated alcohol may be used as a solvent by itself, but it is also effective when used in addition to general-purpose solvents such as the above-mentioned ketone solvents, acetate ester solvents, non-fluorine alcohol solvents, and aromatic solvents. It is.

  When used in combination, the addition amount is 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 10 to 30% by weight, based on the whole solvent.

  As content of the solvent (d) in the fluorine-containing resin composition for coating of the present invention, the type of solid content to be dissolved, the presence or absence and use ratio of a curing agent, the type of substrate to be applied, and the target film thickness It is preferably selected so that the total solid content in the composition is 0.1 to 70% by weight, preferably 1 to 50% by weight.

  The composition of the present invention may contain various additives as necessary in addition to the above-mentioned compounds.

  Examples of such additives include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, and reinforcing agents.

  The composition of the present invention can also contain inorganic compound fine particles for the purpose of increasing the hardness of the cured product.

  The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable. Specifically, magnesium fluoride (refractive index 1.38), silicon oxide (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. . The particle diameter of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 50 nm or less.

  When using inorganic compound fine particles, it should be used in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the composition and the adhesion in the low refractive index material. Is desirable. Furthermore, in order to improve the dispersion stability of the inorganic compound fine particles and the adhesion in the low refractive index material in the composition, the surface of the inorganic fine particle compound may be modified in advance using various coupling agents. it can. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

  As the coating method, a known coating method can be adopted as long as the film thickness can be controlled.

  For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected considering the controllability and controllability of the film thickness.

  A photopolymerizable (curable) composition comprising the fluorine-containing unsaturated compound (a) of the present invention and an active energy ray curing initiator (b) and / or a curing agent (c), and the coating of the present invention by the method described above The coating obtained by applying the fluororesin composition for use to a substrate and drying it can be photocured by irradiating it with active energy rays such as ultraviolet rays, electron beams or radiation.

The irradiation amount of the active energy ray is, for example, 100 mJ / cm ² U or more, preferably 500 mJ / cm ² U, more preferably 1000 mJ / cm ² U in the case of ultraviolet irradiation with a high-pressure mercury lamp.

  When cured, the carbon-carbon double bonds of the fluorine-containing unsaturated compound (a) and the curing agent (c) of the present invention are polymerized between molecules, and the carbon-carbon double bonds in the polymer are reduced or eliminated. As a result, the film hardness is increased, the mechanical strength is improved, the wear resistance, the scratch resistance is improved, and further, not only becomes insoluble in the solvent dissolved before curing, It becomes insoluble in many other types of solvents.

  Even after light irradiation, excellent water repellency and antifouling property of the fluorine-containing unsaturated compound (a) can be imparted, and the durability of the effect is improved by light irradiation.

  That is, the present invention also relates to a cured film thus obtained by photocuring.

  The present invention also relates to a laminate obtained by coating the substrate (e) with the obtained photocured film. As the base material (e), as described above, acrylic resin, polycarbonate, polyethylene terephthalate, polyolefin, triacetyl cellulose, glass, and the like are preferable.

  As described above, the present invention further provides an antireflection coating with improved antireflection effect, scratch resistance, abrasion resistance, and antifouling property, and a substrate made of such an antireflection film. The present invention also relates to an antireflection article using the coated laminate, for example, various large or portable display devices.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Example 1 (Synthesis of fluorine-containing unsaturated compound n≈20)
In a 500 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, perfluoropolyether alcohol having an average molecular weight of 3686:
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CH ₂ OH
(N ≒ 20)
18.4 g, triethylamine 1.1 g, 1,1,1,3,3,3-hexafluorometaxylene 125 g were charged and cooled to 5 ° C. or lower with ice.

While stirring under a nitrogen stream, further α-fluoroacrylic acid fluoride:
CH ₂ = CFCOF
A solution prepared by dissolving 0.84 g of the above in 5 ml of 1,1,1,3,3,3-hexafluorometaxylene was added dropwise over about 10 minutes. After completion of dropping, the temperature was raised to room temperature and stirring was continued for 4 hours.

  The ether solution after the reaction was put into a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, dried over anhydrous magnesium sulfate, and then separated by filtration. After the solvent was distilled off from the filtrate by an evaporator, it was further dried for 6 hours in a vacuum while being heated to 70 ° C. to obtain 16.9 g of a colorless and transparent liquid having a high viscosity.

であった。 The obtained product was examined by ¹ H-NMR analysis, ¹⁹ F-NMR analysis and IR analysis.

Met.

Example 2 (Synthesis of fluorine-containing unsaturated compound n≈7)
Instead of perfluoropolyether alcohol having an average molecular weight of 3686 in Example 1, perfluoropolyether alcohol having an average molecular weight of 1460:
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CH ₂ OH
(N ≒ 7)
A reaction with α-fluoroacrylic acid fluoride and an isolation operation were performed in the same manner as in Example 1 except that 7.3 g was used. 6.7 g of a colorless and transparent liquid having a high viscosity was obtained.

であった。 The obtained product was examined by ¹ H-NMR analysis, ¹⁹ F-NMR analysis and IR analysis.

Met.

Synthesis Example 1 (Synthesis of fluorine-containing unsaturated compound n≈4.5)
Instead of perfluoropolyether alcohol having an average molecular weight of 3686 in Example 1, perfluoropolyether alcohol having an average molecular weight of 1063:
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CH ₂ OH
(N ≒ 4.5)
A reaction with α-fluoroacrylic acid fluoride and an isolation operation were performed in the same manner as in Example 1 except that 5.3 g was used. 4.8 g of a colorless and transparent liquid having a high viscosity was obtained.

であった。 The obtained product was examined by ¹ H-NMR analysis, ¹⁹ F-NMR analysis and IR analysis.

Met.

Example 3 (Homopolymerization of fluorine-containing unsaturated compound n≈20)
14.7 g of the fluorine-containing unsaturated compound (n≈20) obtained in Example 1 in a 300 ml glass four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 80 g and 2 of hexafluorometaxylene, After adding 65 mg of 2-azobisisobutyronitrile (AIBN) and 40 mg of isooctyl mercaptoacetate, the inside of the flask was purged with nitrogen. After stirring at 70 ° C. for 30 minutes, when the stirring was stopped and the mixture was allowed to stand, a gel-like solid precipitated. This gel-like solid was taken out and squeezed and filtered using a polyethylene mesh. The obtained solid was added to 200 ml of hexafluorometaxylene, washed with heating (reflux conditions), and the precipitated polymer after stationary cooling was again filtered and taken out. Then, it vacuum-dried at 150 degreeC for 5 hours, and obtained translucent raw rubber-like solid 6.2g. The obtained solid was subjected to IR analysis to confirm that the carbon-carbon double bond had disappeared.

Example 4 (Homopolymerization of fluorine-containing unsaturated compound n≈7)
The same flask as in Example 3 was reacted at 65 ° C. for 2.5 hours using 19 g of the fluorine-containing unsaturated compound (n≈7) obtained in Example 2, 80 g of hexafluorometaxylene, 18 mg of AIBN and 46 mg of mercaptoacetate isooctyl acetate. Except for the above, a polymerization reaction, washing of the polymer, and drying were performed in the same manner as in Example 3 to obtain 12.7 g of a translucent raw rubber-like solid. ^When examined by ¹⁹ F-NMR analysis and IR analysis, it was a homopolymer of a fluorine-containing unsaturated compound (n≈7).

Synthesis Example 2 (Homopolymerization of fluorine-containing unsaturated compound n≈4.5)
Reaction was performed at 60 ° C. for 7 hours using 12 g of the fluorine-containing unsaturated compound (n≈4.5) obtained in Synthesis Example 1, 80 g of hexafluorometaxylene, 18 mg of AIBN and 27 mg of mercaptoacetate isooctyl in the same flask as in Example 3. Except for the above, a polymerization reaction, washing of the polymer, and drying were carried out in the same manner as in Example 3 to obtain 12.7 g of a translucent rubber-like solid. ^When examined by ¹ H-NMR analysis, ¹⁹ F-NMR analysis and IR analysis, it was a homopolymer of a fluorine-containing unsaturated compound (n≈4.5).

Synthesis example 3 (homopolymerization of αF-acrylate)
In a glass 200 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 10 g of hexafluoroisopropyl αF-acrylate (HFIP-αF acrylate), 20 g of ethyl acetate, 11 mg of AIBN, and 54 mg of mercaptoacetate isooctyl acetate were placed. The mixture was stirred at 60 ° C. for 2.5 hours under a nitrogen stream. Thereafter, the reaction solution was poured into 800 ml of hexane to precipitate a polymer, and the obtained polymer was vacuum-dried at 50 ° C. for 15 hours to obtain 8.3 g of a white solid. NMR and IR analysis confirmed that the product was a homopolymer of hexafluoroisopropyl αF-acrylate.

Examples 5-6 and Comparative Examples 1-2 (Measurement of physical properties of homopolymer of fluorine-containing unsaturated compound)
Homopolymers of fluorine-containing unsaturated compounds obtained in Example 3 and Example 4 (corresponding to Examples 5 and 6 respectively), and fluorine-containing polymers obtained in Synthesis Examples 2 and 3 (respectively comparative examples) 1 and Comparative Example 2) were used to prepare films by the methods described below, and the refractive index and surface characteristics were measured by the methods described below using the obtained films. The results are shown in Table 1.

(1) Film production method A polymer is placed in a mold and compression-molded at 170 ° C. using a heat press apparatus to produce a film having a thickness of about 500 μm.

(2) The film produced in refractive index (n _D) of the measurement (1), measured for light having a wavelength of 590nm at 25 ° C. using an Abbe refractometer.

(3) Measurement of surface characteristics (i) Contact angle Using a contact angle meter, the contact angle of 3 μl of pure water and n-hexadecane is measured.
(Ii) Falling angle A film is placed on a glass test plate, a droplet of 15 μl of pure water is formed on the film, tilted with the test table, and when the droplet starts to move downward, the sample table becomes a horizontal surface. Let the angle be the falling angle. The falling angle is measured in the same manner for a 3 μl droplet of n-hexadecane.

Example 7 (copolymerization of fluorine-containing unsaturated compound n≈20 and αF-acrylate)
In the same flask as in Example 3, 2.44 g of the fluorine-containing unsaturated compound (n≈20) obtained in Example 1, 7.56 g of hexafluoroisopropyl α-fluoroacrylate (HFIP-αF acrylate), hexafluorometa After adding 40 g of xylene, 106 mg of AIBN, and 65.4 mg of isooctyl mercaptoacetate, the inside of the flask was purged with nitrogen. After stirring at 60 ° C. for 2.5 hours under a nitrogen stream, 150 ml of HCFC225 was added and dissolved. This solution was poured into 500 ml of hexane to precipitate a polymer. This polymer was taken out, put into a 200 ml beaker together with 50 g of perfluorohexane, stirred for 30 minutes and allowed to stand. The precipitated gel polymer was taken out and vacuum-dried at 80 ° C. for 10 hours to obtain 6.2 g of a white solid. It was a copolymer of fluorine-containing unsaturated compound (n≈20): HFIP-αF acrylate = 2: 98 mol% by ¹⁹ F-NMR analysis and IR analysis. A glass transition temperature derived from the main chain skeleton was observed at 92 ° C. by DSC analysis.

Example 8 (copolymerization of fluorine-containing unsaturated compound n≈20 and αF-acrylate)
In Example 7, using 3.4 g of fluorine-containing unsaturated compound (n≈20), 4.3 g of hexafluoroisopropyl α-fluoroacrylate (HFIP-αF acrylate), 124 mg of AIBN and 77 mg of mercaptoacetate isooctyl acetate, 4 at 65 ° C. Polymerization reaction, polymer washing and drying were carried out in the same manner as in Example 7 except that the reaction was carried out for 5 hours to obtain 5.6 g of a white solid. It was a copolymer of fluorine-containing unsaturated compound (n≈20): HFIP-αF acrylate = 4.5: 95.5 mol% by ¹⁹ F-NMR analysis and IR analysis. A glass transition temperature derived from the main chain skeleton was observed at 88 ° C. by DSC analysis.

Example 9 (copolymerization of fluorine-containing unsaturated compound n≈20 and αF-acrylate)
In Example 7, 6.8 g of a fluorine-containing unsaturated compound (n≈20), 1.3 g of hexafluoroisopropyl α-fluoroacrylate (HFIP-αF acrylate), 120 mg of AIBN and 70 mg of mercaptoacetate isooctyl acetate were used at 65 ° C. Polymerization reaction, polymer washing and drying were carried out in the same manner as in Example 7 except that the reaction was carried out for 5 hours to obtain 3.5 g of a white solid. It was a copolymer of fluorine-containing unsaturated compound (n≈20): HFIP-αF acrylate = 27.1: 72.9 mol% by ¹⁹ F-NMR analysis and IR analysis.

Example 10 (copolymerization of fluorine-containing unsaturated compound n≈7 and αF-acrylate)
6.8 g of fluorine-containing unsaturated compound (n≈7) instead of fluorine-containing unsaturated compound (n≈20) in Example 7, 3.2 g of hexafluoroisopropyl α-fluoroacrylate (HFIP-αF acrylate), A polymerization reaction, washing and drying of the polymer were carried out in the same manner as in Example 7 except that 60 mg of AIBN and 36 mg of isooctyl mercaptoacetate were used and reacted at 65 ° C. for 6 hours to obtain 4.8 g of a white solid. It was a copolymer of fluorine-containing unsaturated compound (n≈7): HFIP-αF acrylate = 29.3: 70.7 mol% by ¹⁹ F-NMR analysis and IR analysis.

Examples 11-15 and Comparative Examples 3-4 (Measurement of physical properties of copolymer of fluorine-containing unsaturated compound)
Homopolymers of fluorine-containing unsaturated compounds obtained in Examples 7 to 10 and Example 4 (corresponding to Examples 11 to 14 and Example 15 respectively), and fluorine-containing polymers obtained in Synthesis Examples 2 and 3 (Corresponding to Comparative Example 3 and Comparative Example 4, respectively), and a film was prepared by the method described below, and the obtained film was used for refractive index, surface characteristics, and gas (oxygen gas and nitrogen gas) permeability. Was measured by the method described below. The results are shown in Table 2.

(1) Production of Film A film was produced in the same manner as in Example 5.

(2) Measurement of refractive index (n _D ) Measurement was performed in the same manner as in Example 5.

(3) Measurement of surface characteristics (contact angle and sliding angle) Measurement was performed in the same manner as in Example 5.

(4) Measurement of gas (oxygen gas and nitrogen gas) permeability The measurement of oxygen and nitrogen permeation was performed by using a pressurized gas permeation measuring machine (Gasperm-100 manufactured by JASCO Corporation) as a schematic block diagram shown in FIG. ). The measurement was performed using a single gas of oxygen and nitrogen, applying a pressure of 0.02 to 0.2 MPa · G on the pressure side, and atmospheric pressure on the permeation side. In this apparatus, the gas permeation amount per time can be obtained by continuously observing the gas amount permeated by the measuring instrument. As a measurement sample, the sample film 1 obtained by cutting the film produced by the above method into a circle having a diameter of 5 cm is put in the sample cell 2, and oxygen gas and nitrogen gas whose pressure is adjusted by the pressure side pressure adjustment syringe 3 are applied to the sample film 1. The permeation amount per unit time is measured by the permeation amount measuring syringe 4 for each gas. Using the measured values of the gas permeation amount per unit time, the pressure on the permeation side, the measurement area of the sample, the membrane pressure, and the pressure on the pressurization side, the permeation coefficients (K ) Is calculated. In order to evaluate gas permeability selectivity, the selectivity (α) is expressed as oxygen gas permeability coefficient (K _O2 ) / nitrogen gas permeability coefficient (K _N2 ).

の化合物の０．２ｇ、硬化剤（ｃ）として式（ｃ）：

のテトラアクリレートの１．８ｇを溶剤（ｄ）としてのＨＣＦＣ−２２５の２００ｇに混合し、均一なコーテイング用組成物を調製した。 Example 16
Formula (b): 0.2 g of fluorine-containing unsaturated compound (n≈20) (a) obtained in Example 1 and active energy ray initiator (b):

0.2 g of the compound of formula (c) as the curing agent (c):

A uniform coating composition was prepared by mixing 1.8 g of the above tetraacrylate with 200 g of HCFC-225 as the solvent (d).

  An acrylic board (MR-100 manufactured by Mitsubishi Rayon Co., Ltd.) that has been subjected to a single-sided hard coat treatment as a base material is immersed in the obtained coating composition for 10 seconds, and is pulled up at room temperature and dipped at a speed of 10 mm / sec. Coat and air dry at room temperature.

Subsequently, ultraviolet rays were irradiated with a high-pressure mercury lamp at an irradiation intensity of 1500 mJ / cm ² U at room temperature to cure the coating.

  About the obtained hardened film, pencil hardness and surface characteristics (contact angle and sliding angle) were measured. The results are shown in Table 3.

(Pencil hardness)
Measured according to JIS K5400.

(Contact angle)
The above acrylic plate is measured by the method described in Example 5.

(Tumble angle)
The above acrylic plate is measured by the method described in Example 5.

(Fingerprint adhesion)
A finger is pressed against the application surface of the acrylic plate, and the ease of fingerprint attachment is visually determined. Evaluation is based on the following criteria.
○: Fingerprints are not easily attached or fingerprints are not conspicuous even if attached.
(Triangle | delta): Although there is little adhesion of a fingerprint, the fingerprint can fully be confirmed.
X: A fingerprint adheres as clearly as the untreated acrylic plate.

(Fingerprint wiping)
After the above fingerprint adhesion test, the attached fingerprint is wiped once with Kimwipe (manufactured by Jujo Kimberley Co., Ltd.), and the ease of wiping the attached fingerprint is visually determined. Evaluation is based on the following criteria.
○: Fingerprints can be completely wiped off.
Δ: A fingerprint wiping trace remains.
X: The fingerprint wiping trace spreads and is difficult to remove.

Comparative Example 5
A coating composition was prepared, coated and cured in the same manner as in Example 16 except that the fluorine-containing unsaturated compound (n≈20) was not used. Various physical properties were obtained in the same manner as in Example 16. Was measured. The results are shown in Table 3.

Comparative Example 6
A coating composition was prepared in the same manner as in Example 16 except that the fluorine-containing unsaturated compound (n≈4.5) obtained in Synthesis Example 1 was used instead of the fluorine-containing unsaturated compound (n≈20). Then, various physical properties were measured in the same manner as in Example 16 for the coated and cured product. The results are shown in Table 3.

式（ｂ）：

式（ｃ）

Formula (b):

Formula (c)

Example 17 (synthesis of fluorine-containing unsaturated compound n≈7)
A 1 liter four-necked flask equipped with a dry ice cooler, a thermometer, and a stirrer was charged with 7.7 g of cesium fluoride, 50 ml of tetraglyme, and a perfluoropolyether compound having an average molecular weight of 1476:
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ COF
(N ≒ 7)
The reaction was carried out by adding hexafluoropropylene oxide from a bomb at a rate of refluxing with a dry ice cooler while maintaining the temperature in the flask at 10 ° C. with stirring. After 8 hours from the start of the reaction, the addition of hexafluoropropylene oxide was stopped, 50 ml of methanol was added while cooling with ice water, and the mixture was washed several times with water.

と
ＣＦ₃ＣＦ₂ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂ＣＦ₂Ｏ）_nＣＦ₂ＣＦ₂ＣＯＯＣＨ₃
（ｎ≒７）
との８５／１５モル％の混合物であった。 When the obtained reaction mixture was examined by ¹⁹ F-NMR and ¹ H-NMR,

And CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ COOCH ₃
(N ≒ 7)
And a 85/15 mol% mixture.

  Subsequently, the methyl ester was put into a 1-liter flask, and saponification reaction was performed using 5% by weight NaOH / methanol solution using phenolphthalein as a pH indicator. Methanol was distilled off under reduced pressure and vacuum dried to a constant weight to obtain a solid.

  The solid matter was put into a 500 ml flask, heated at 150 to 240 ° C. while circulating nitrogen gas, and washed repeatedly with water to obtain a colorless and transparent viscous liquid (yield 150 g).

When this liquid was examined by ¹⁹ F-NMR and ¹ H-NMR,
_{CF 3 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) n (CF 2) 3 OCF = CF 2
(N ≒ 7)
And CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n (CF ₂ ) ₃ OCHFHC ₃
(N ≒ 7)
And CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ H
(N ≒ 7)
And 82/11/7 mol% of the mixture.

It is a schematic block diagram of the pressurization type gas permeation measuring machine used for measurement of gas permeation amount.

Claims (22)

General formula (M):

Wherein X ¹ and X ² are the same or different and H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and H, F, or CF ₃ A, b and c are the same or different 0 or 1; d is an integer of 1 to 4; Rf is a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms;
Formula (1) in the Rf group:

A fluorine-containing unsaturated compound having 6 or more repeating units represented by (wherein X ⁶ is F or H). Formula (M) is General Formula (M-1):

The fluorine-containing unsaturated compound according to claim 1, wherein X ¹ , X ² , X ³ , Rf, b, and d are the same as those in formula (M). Formula (M-1) is General Formula (M-2):

The fluorine-containing unsaturated compound according to claim 2, wherein X ³ and Rf and d are the same as those in formula (M). Formula (M-2) is General Formula (M-3):

The fluorine-containing unsaturated compound according to claim 3, wherein Rf and d are the same as those in formula (M). At the end of the Rf group, the formula (2):

The fluorine-containing unsaturated compound according to any one of claims 1 to 4, which has a perfluoroalkyl group represented by the formula (wherein n is an integer of 6 to 66). The Rf group is represented by formula (3):

The fluorine-containing unsaturated compound according to any one of claims 1 to 4, wherein a perfluoroalkyl group represented by (wherein n is an integer of 6 to 66) and d is 1. Formula (4):

(In the formula, the structural unit M is a structural unit derived from a fluorine-containing monomer in which d is 1 in the fluorine-containing unsaturated compound according to any one of claims 1 to 6, and the structural unit A constitutes the structural unit M. The structural unit is derived from a monomer copolymerizable with the fluorine-containing monomer, and the structural unit M is 0.01 to 100 mol% and the unit structure A is 0 to 99.99 mol%. A fluorine-containing polymer having an average degree of polymerization of 5 to 10,000. The fluorine-containing polymer according to claim 7, wherein the structural unit M is a structural unit derived from a fluorine-containing monomer in which d is 1 in the fluorine-containing unsaturated compound according to any one of claims 3 to 6. The structural unit A is represented by the formula (A):
^{Rf 1 -O (O = C)} -CX 6 = CH 2
(Wherein X ⁶ is selected from H, F, CH ₃ and CF ₃ , Rf ¹ is a fluorine-containing alkyl group which may contain an ether bond having 2 to 20 carbon atoms) The fluorine-containing polymer according to claim 8, comprising 0.01 to 99 mol% of the structural unit M and 1 to 99.99 mol% of the unit structure A. A photopolymerizable composition comprising (a) at least one fluorine-containing unsaturated compound according to claims 1 to 6, and (b) an active energy ray initiator. (A) at least one fluorine-containing unsaturated compound according to claims 1 to 6,
A photopolymerizable composition comprising (b) an active energy ray initiator, and (c) a curing agent. (A) The at least one fluorine-containing unsaturated compound according to claim 1 , 2, 3, 5 or 6 is selected from the group consisting of a fluorine-containing acrylate compound, a fluorine-containing methacrylate compound and a fluorine-containing α-fluoroacrylate compound. The photopolymerizable composition according to claim 11, which is at least one kind. In the curing agent (c), two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond are converted into an acrylate group. Two or more hydroxyl groups of polyhydric alcohol having a substituted polyfunctional acrylate, a fluorine-containing alkyl group that may have an ether bond or a fluorine-containing alkylene group that may have an ether bond are used as a methacrylate group. Two or more hydroxyl groups of a polyhydric alcohol having a substituted polyfunctional methacrylate and a fluorine-containing alkyl group which may have an ether bond or a fluorine-containing alkylene group which may have an ether bond are α-fluoro Selected from the group consisting of polyfunctional α-fluoroacrylates substituted with acrylate groups The photopolymerizable composition according to claim 12, wherein the photopolymerizable composition is at least one kind. Hardened | cured material obtained by photocuring the photopolymerizable composition in any one of Claims 10-13. (A) at least one fluorine-containing unsaturated compound according to claims 1 to 6,
A coating composition comprising (b) an active energy ray curing initiator and (d) a solvent. (A) at least one fluorine-containing unsaturated compound according to claims 1 to 6,
(B) an active energy ray curing initiator,
(C) A coating composition comprising a curing agent and (d) a solvent. (A) The at least one fluorine-containing unsaturated compound according to claim 1 , 2, 3, 5 or 6 is selected from the group consisting of a fluorine-containing acrylate compound, a fluorine-containing methacrylate compound and a fluorine-containing α-fluoroacrylate compound. The coating composition according to claim 16, wherein the composition is at least one. In the curing agent (c), two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group optionally having an ether bond or a fluorine-containing alkylene group optionally having an ether bond are converted into an acrylate group. The substituted polyfunctional acrylate, the fluorine-containing alkyl group that may have an ether bond or the two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkylene group that may have an ether bond as a methacrylate group Two or more hydroxyl groups of a polyhydric alcohol having a substituted polyfunctional methacrylate and a fluorine-containing alkyl group optionally having an ether bond or a fluorine-containing alkylene group optionally having an ether bond are α-fluoro Selected from the group consisting of polyfunctional α-fluoroacrylates substituted with acrylate groups The coating composition according to claim 17, wherein the coating composition is at least one kind. The cured film obtained by photocuring the film formed by apply | coating the coating composition of Claims 15-18. A laminate obtained by coating the cured film according to claim 19 on a substrate (e). The laminate according to claim 20, wherein the material of the substrate (e) is one selected from the group consisting of acrylic resin, polycarbonate, polyethylene terephthalate, polyolefin, triacetyl cellulose, and glass. An antireflection article comprising the laminate according to claim 20 or 21.

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