JP2013082780A - CURING METHOD OF CURABLE COMPOSITION CONTAINING FLUORINE-CONTAINING (α-SUBSTITUTED) ACRYLIC COMPOUND - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing method of a curable composition containing a fluorine-containing (α-substituted) acrylic compound which can form a coating film having an excellent surface characteristic.SOLUTION: The curing method of a curable composition containing a fluorine-containing (α-substituted) acrylic compound includes the steps of: (ii) heating the composition at a temperature of 50 degree or more; and (iv) applying ultraviolet rays to cure the composition in an inert gas atmosphere.

Description

The present invention relates to a method for curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound.

Various fluorine-containing (α-substituted) acrylic compounds that are curable by irradiation with light such as ultraviolet rays and have excellent properties of fluorine compounds and excellent compatibility with non-fluorine organic compounds are known. When the fluorine-containing (α-substituted) acrylic compound is mixed with an ultraviolet curable non-fluorine hard coat composition and applied to a substrate, the fluorine group moves to the surface side due to the difference in surface free energy. As a result, a cured film having the characteristics of a fluorine group on the outermost surface of the film is obtained. In addition to high hardness, wear resistance, durability, etc. derived from hard coats, this film has functions such as anti-stain, wiping, slipping, and anti-fogging properties derived from fluorine groups. It is useful as a hard coat agent imparted with properties.

In order to further improve the compatibility of fluorine-containing (α-substituted) acrylic compounds and non-fluorinated organic solvents, the fluorine-containing (α-substituted) acrylic with a non-fluorinated segment made bulky or a perfluoropolyether chain length shortened There are compounds and fluorine-containing (α-substituted) acrylic compounds in which the number of crosslinking groups is increased in order to improve ultraviolet curability (Patent Documents 1 to 3).

JP 2010-138112 A JP 2010-053114 A JP 2010-285501 A

  However, the fluorine-containing (α-substituted) acrylic compounds as described in Patent Documents 1 to 3 are highly compatible with non-fluorine ultraviolet curable compounds, but the fluorine groups hardly migrate to the substrate surface. Have the problem of becoming. Therefore, it is difficult to obtain sufficient water repellency / oil repellency, slipperiness and the like for the cured film. Accordingly, the present invention is a method for curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound, and an object thereof is to provide a curing method capable of forming a coating film having excellent surface characteristics. .

As a result of intensive efforts by the inventors, when curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound, the composition is heated at a temperature of 50 ° C. or higher before the step of irradiating with ultraviolet rays. It has been found that the above object can be achieved by performing the heating and the step of irradiating ultraviolet rays in an inert gas atmosphere.

That is, the present invention provides a method for curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound,
(Ii) a method comprising heating the composition at a temperature of 50 ° C. or higher, and (iv) curing the composition by irradiating with ultraviolet rays in an inert gas atmosphere.

  According to the curing method of the present invention, a curable composition containing a fluorine-containing (α-substituted) acrylic compound can be cured satisfactorily, and a cured film having sufficient water repellency / oil repellency, slipperiness, and the like can be obtained. Can be formed.

  The present invention is a method for performing a step of irradiating ultraviolet rays to cure the composition in an inert gas atmosphere, and heating the composition at a temperature of 50 ° C. or higher before the step of irradiating the composition with ultraviolet rays. It is the method characterized by including the process to do. The method of the present invention may include a step of (i) applying the composition to a substrate before the step (ii), and is suitably used as a method of forming a cured film on the substrate. can do. In the present invention, the kind of the inert gas is not particularly limited, but nitrogen gas is preferable from the viewpoint of availability. The heating temperature is 50 ° C. or higher and 160 ° C. or lower, preferably 60 ° C. or higher and 120 ° C. or lower. When heating temperature is less than the said lower limit, a fluorine group may not fully transfer to the substrate surface, and sufficient antifouling property may not be obtained. On the other hand, when the heating temperature exceeds the above upper limit value, the compound in the composition is thermally decomposed, partially thermoset, or the base material itself is thermally deformed depending on the base material used. A cured film may not be obtained.

  The heating method is not particularly limited, and for example, a batch type or conveyor type hot air drying furnace, a far infrared drying furnace, a near infrared drying furnace, an oven, or the like can be used. The heating time is not particularly limited, but is usually about 10 seconds to 10 minutes, preferably 30 seconds to 3 minutes. If the heating time is shorter than the above range, there is a possibility that the fluorine group does not sufficiently migrate to the substrate surface due to insufficient heating, and sufficient antifouling properties may not be obtained. There is a possibility that heat curing occurs and a uniform cured film cannot be obtained.

The method of irradiating the composition with ultraviolet rays may follow a conventionally known method. As the ultraviolet light source, a known light source such as a high-pressure mercury lamp, a metal halide lamp, an LED, or a laser can be used. The amount of ultraviolet irradiation is not particularly limited as long as it is sufficient to cure the curable composition and does not deteriorate the cured product layer or the substrate, but usually 100 mJ / cm ^{2 to} 3000 mJ / cm ² , particularly preferably ^{200mJ / cm 2 ~2000mJ / cm 2} . When the irradiation dose of ultraviolet rays exceeds the upper limit, the resulting cured film may be yellowed, and when the irradiation dose is less than the lower limit, curing may be insufficient.

The present invention further provides a method comprising the step of (iii) setting the temperature of the composition to less than 50 ° C. under an inert gas atmosphere after the step (ii) and before the step (iv). The said process assumes the case where ultraviolet irradiation is not performed immediately after heating, for example. When a curable composition containing a fluorine-containing (α-substituted) acrylic compound is heated and then stored or cooled in the air, the composition can be sufficiently cured even when irradiated with ultraviolet rays in a state where the temperature is lowered. Can not. However, by heating the composition and placing it in an inert gas atmosphere, the composition can be cured well even when irradiated with ultraviolet rays in a state where the temperature of the composition is lowered. Therefore, according to the method of the present invention, a film having excellent surface characteristics can be provided without being heated again even if the composition is not cured immediately after being heated.

In this invention, the temperature of the curable composition at the time of ultraviolet irradiation may be 0-160 degreeC, Preferably it may be 10-120 degreeC. When UV irradiation is performed at a temperature exceeding the upper limit, the compound in the composition is thermally decomposed or the cured film is yellowed accordingly, and a cured film having a uniform and good appearance is obtained. There is no possibility. Moreover, at the temperature below the lower limit value, a good cured film may not be obtained due to a decrease in curability.

  In the present invention, the substrate is not particularly limited, and examples thereof include substrates used in optical applications such as exterior plastic films, glass, plates, or substrates for liquid crystal display elements and organic EL elements. . For example, ABS resin, acrylic resin, polyethersulfone resin, polycarbonate resin, polyarylate resin, polyester resin, polyolefin resin, epoxy resin, polyimide resin, polyvinyl alcohol resin, polystyrene resin, etc., polyester, polytetrafluoro Examples include films such as ethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, and polyvinyl chloride, and glass.

In the present invention, as a method for coating the composition on a substrate, for example, conventional coating methods such as roll coating, gravure coating, dip coating, spray coating, spin coating, bar coating, and screen printing can be used. . At this time, the film thickness of the coating film to be formed is usually several nm to 100 μm, preferably several nm to 30 μm. When the obtained film thickness is less than the lower limit, sufficient surface hardness cannot be obtained, and when it exceeds the upper limit, the mechanical strength of the hard coat film is lowered and cracks are easily generated. In addition, when a curable composition contains a solvent, after apply | coating a composition to a base material, the process of drying this composition and removing a solvent may be included.

Moreover, the method of this invention can also be used for the method of hardening a composition and forming a molded article. An embodiment in which the composition is cured by the method of the present invention to form a molded article may be performed using a conventionally known apparatus, mold or the like. The thickness of the composition in the use mode is not particularly limited, but typically the upper limit is about 5 to 10 mm. Exceeding the upper limit is not preferable because it may cause insufficient curing.

  The curable composition cured by the method of the present invention is any resin composition that contains a fluorine-containing (α-substituted) acrylic compound in the composition and is curable with active energy rays such as ultraviolet rays and electron beams. Can also be used. The fluorine-containing (α-substituted) acrylic compound is preferably a compound having excellent characteristics of a fluorine compound and excellent compatibility with a non-fluorine organic compound. For example, fluorine-containing (α-substituted) acrylic compounds as disclosed in JP 2010-138112 A, JP 2010-53114 A, and JP 2010-285501 A can be used. The curable composition may be obtained by adding a fluorine-containing (α-substituted) acrylic compound to a commercially available hard coat agent. In particular, a composition containing (A) a fluorine-containing (α-substituted) acrylic compound, (B) an ultraviolet curable compound not containing fluorine, and (C) a photopolymerization initiator is included. Hereinafter, each component will be described in detail.

(A) Fluorine-containing (α-substituted) acrylic compound The fluorine-containing (α-substituted) acrylic compound has at least one acryl group, methacryl group, and α-fluoroacryl group at the terminal, and a fluoroalkyl group in the molecule. Or what has a fluoro polyether group is good. Among these, a compound having a unit in which at least one of units represented by the following formula is repeated twice or more is preferable.

式中、ａは１〜５の整数であり、ｂ、ｃ、及びｄはそれぞれ０〜５の整数であり、但しｃ＋ｄは０ではなく、ｅは０または１であり、Ｒｆはｅが０のときは１価の、ｅが１のときは２価の、フルオロアルキル基、またはフルオロアルキルエーテル基を有する基であり、Ｑは酸素原子、窒素原子、またはケイ素原子を有していてよいａ＋ｂ＋１価の有機基であり、Ｑ’は酸素原子、窒素原子、またはケイ素原子を有していてよいｃ＋ｄ＋１価の有機基であり、Ｒ^１はアクリル基、メタクリル基、およびα−フルオロアクリル基の少なくとも１を含む１価の有機基であり、Ｒ^２はアクリル基、メタクリル基、およびα−フルオロアクリル基のいずれも含まない１価の有機基である。

式中、ａ、ｂ、ｃ、ｄ、Ｒ^１、Ｒ^２、Ｒｆ、Ｑ、Ｑ’は上記と同じであり、ｖは１〜５の整数であり、Ｑ”は酸素原子、窒素原子、またはケイ素原子を有していてよいｃ’＋ｄ’＋２価の有機基であり、ｃ’、及びｄ’はそれぞれ０〜５の整数であり、但しｃ’＋ｄ’は０ではない。 The fluorine-containing (α-substituted) acrylic compound of the present invention can be represented by the following formula (1) or (2).

In the formula, a is an integer of 1 to 5, b, c, and d are each an integer of 0 to 5, provided that c + d is not 0, e is 0 or 1, and Rf is 0 in e. Is a monovalent group, and when e is 1, it is a divalent group having a fluoroalkyl group or a fluoroalkyl ether group, and Q is an a + b + 1 valent group that may have an oxygen atom, a nitrogen atom, or a silicon atom Q ′ is a c + d + 1 valent organic group which may have an oxygen atom, a nitrogen atom, or a silicon atom, and R ¹ is at least one of an acrylic group, a methacrylic group, and an α-fluoroacrylic group R ² is a monovalent organic group that does not contain any of an acryl group, a methacryl group, and an α-fluoroacryl group.

In the formula, a, b, c, d, R ¹ , R ² , Rf, Q, and Q ′ are the same as above, v is an integer of 1 to 5, and Q ″ is an oxygen atom, a nitrogen atom, or C ′ + d ′ + a divalent organic group which may have a silicon atom, c ′ and d ′ are each an integer of 0 to 5, provided that c ′ + d ′ is not 0.

式中、Ｒ^４は、互いに独立に、水素原子、フッ素原子、メチル基、又はトリフルオロメチル基であり、Ｒ^５は炭素数１〜１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の有機基であり、ｎは１又は２の整数である。Ｒ^５はエチレン基であるのが特に好ましい。 In the formulas (1) and (2), R ¹ is a monovalent organic group containing at least one of an acryl group, a methacryl group, and an α-fluoroacryl group, preferably the following formula (3) or (4) Is a group represented by

In the formula, R ⁴ is independently of each other a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁵ may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent organic group, and n is an integer of 1 or 2. R ⁵ is particularly preferably an ethylene group.

Examples of R ¹ include the groups shown below.

式中、ｆ、ｇ、ｈ、及びｉはＲ^２の分子量が３０〜６００、好ましくは６０〜３００となる範囲において、それぞれ独立に０〜２０の整数、好ましくは１〜１０の整数である。各繰り返し単位の配列はランダムであってもよい。Ｒ^３は炭素数１〜１０、好ましくは炭素数１〜６の、飽和もしくは不飽和の炭化水素基であり、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、シクロヘキシル基、フェニル基、ベンジル基等があげられる。特に好ましくはメチル基、及びエチル基である。 In the formulas (1) and (2), R ² is a monovalent organic group that does not contain any of an acryl group, a methacryl group, and an α-fluoroacryl group, and is preferably represented by the following formula (5). It is a group.

In the formula, f, g, h, and i are each independently an integer of 0-20, preferably an integer of 1-10, in the range where the molecular weight of R ² is 30-600, preferably 60-300. The arrangement of each repeating unit may be random. R ³ is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, Examples include 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group and the like. Particularly preferred are a methyl group and an ethyl group.

ｈ、ｇは０〜２０の整数、好ましくは１〜１０の整数であり、ｈ＋ｇは１〜４０、好ましくは１〜２０であり、式中のプロピレン基は分岐していてもよく、各繰り返し単位はランダムに結合されていてもよい。 Such R ² is preferably a group represented by the following formula.

h and g are integers of 0 to 20, preferably 1 to 10, h + g is 1 to 40, preferably 1 to 20, and the propylene group in the formula may be branched, and each repeating unit. May be combined randomly.

In the formulas (1) and (2), Q and Q ′ are independently an a + b + 1 valent organic group which may have an oxygen atom, a nitrogen atom, or a silicon atom. a is an integer of 1 to 5, and b is an integer of 0 to 5. c and d are each an integer of 0 to 5, provided that c + d = 0 is not satisfied. Therefore, Q and Q 'are 2 to 11 valent organic groups, preferably 2 to 6 valent organic groups. Q and Q ′ may include a hydroxyl group, an ether bond, an ester bond, an amide bond, and a urethane bond, and may include a cyclic structure or a branch on the way. Q and Q ′ may be the same or different.

One embodiment of Q and Q ′ is a divalent organic group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, which may have an oxygen atom, a nitrogen atom, or a silicon atom. And the like groups.

式中Ｑ^２は、互いに独立に、エーテル結合、エステル結合、アミド結合、ウレタン結合を含んでいてもよい炭素数３〜２０の２価の有機基であり、途中環状構造や分岐を含んでいてもよく、それぞれ同一でも異なっていてもよい。Ｑ^２は、上記Ｑ及びＱ’の一態様として記載した基であってよく、好ましくは以下に示される基である。

（式中、右端の炭素原子がＮ原子に結合する） Moreover, as another aspect of Q and Q ', the group shown below is mentioned.

Wherein Q ² each independently, an ether bond, an ester bond, an amide bond, a divalent organic radical of 3 to 20 carbon atoms which may contain a urethane bond, include an intermediate ring structure or branch They may be the same or different. Q ² may be a group described as one embodiment of Q and Q ′ above, and is preferably a group shown below.

(In the formula, the rightmost carbon atom is bonded to the N atom)

式中、ａ’は１〜４の整数、ｂ’及びｂ”は０〜４の整数であり、ａ’＋ｂ’＋ｂ”は２、３または４であり、各繰返し単位の配列はランダムであってよい。Ｑ^１は、互いに独立に、炭素数３〜２０のエーテル結合、エステル結合、アミド結合、ウレタン結合を含んでいてもよい２価の連結基であり、途中環状構造や分岐を含んでいてもよく、それぞれ同一でも異なっていてもよい。Ｚは、酸素原子、窒素原子、またはケイ素原子を有していてよい２価の連結基であり、Ｚが式（１）及び（２）中のＲｆに結合する。 Moreover, as another aspect of Q and Q ', group shown by following formula (6) is mentioned.

In the formula, a ′ is an integer of 1 to 4, b ′ and b ″ are integers of 0 to 4, a ′ + b ′ + b ″ is 2, 3 or 4, and the sequence of each repeating unit is random. It's okay. Q ¹ is a divalent linking group that may include an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, independently of each other, and may include a cyclic structure or a branch in the middle. These may be the same or different. Z is a divalent linking group that may have an oxygen atom, a nitrogen atom, or a silicon atom, and Z is bonded to Rf in the formulas (1) and (2).

In Formula (2), v is an integer of 1-5. Q ″ is a c ′ + d ′ + divalent organic group that may have an oxygen atom, a nitrogen atom, or a silicon atom. C ′ and d ′ are each an integer of 0 to 5, provided that c ′ + d ′. = 0. Accordingly, Q ″ is a 3 to 12 valent organic group, preferably a 3 to 5 valent organic group. Q ″ may include a hydroxyl group, an ether bond, an ester bond, an amide bond, and a urethane bond, and may include a cyclic structure or a branch on the way.

式中、ｃ”、ｄ”及びｂ'''は０〜３の整数であり、但し、ｃ”＋ｄ”＋ｂ'''は１、２、３のいずれかの値であり、各繰返し単位の配列はランダムであってよい。Ｑ^１は、互いに独立に、炭素数３〜２０のエーテル結合、エステル結合、アミド結合、ウレタン結合を含んでいてもよい２価の連結基であり、途中環状構造や分岐を含んでいてもよく、それぞれ同一でも異なっていてもよい。Ｚは、酸素原子、窒素原子、またはケイ素原子を有していてよい２価の連結基であり、Ｚが式（２）中のＲｆに夫々結合する Q ″ is preferably a group represented by the following formula (7).

In the formula, c ″, d ″ and b ′ ″ are integers of 0 to 3, provided that c ″ + d ″ + b ′ ″ is any one of 1, 2, and 3 and The sequence may be random. Q ¹ is a divalent linking group that may include an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, independently of each other, and may include a cyclic structure or a branch in the middle. These may be the same or different. Z is a divalent linking group which may have an oxygen atom, a nitrogen atom, or a silicon atom, and Z is bonded to Rf in the formula (2), respectively.

In formulas (6) and (7), Q ¹ is preferably a group represented by the following formula.

In the formulas (6) and (7), Z is preferably a group represented by the following formula.

Among these, a group represented by the following formula is preferable.

In particular, a group represented by the following formula is preferred.

In the formulas (1) and (2), Rf is a monovalent or divalent fluoroalkyl group or a group having a fluoroalkyl ether group. The fluoroalkyl group should have 2 to 20 carbon atoms, preferably 4 to 8 carbon atoms. The group having a fluoroalkyl ether group preferably has a unit in which at least one of units represented by the following formula is repeated twice or more.

式中、ｊ、ｋ、ｌ及びｍは、Ｒｆの分子量が２００〜６０００、好ましくは４００〜２０００となる範囲において、それぞれ独立に０〜１００、好ましくは１〜５０、さらに好ましくは２〜１５の整数である。また、各繰り返し単位の配列はランダムであってよい。上記式中、ｐは１〜６の整数、Ｘは互い独立に、フッ素原子またはＣＦ_３基である。 A group having a monovalent fluoroalkyl ether group can be represented by the following formula.

In the formula, j, k, l and m are each independently 0 to 100, preferably 1 to 50, more preferably 2 to 15 in the range where the molecular weight of Rf is 200 to 6000, preferably 400 to 2000. It is an integer. Further, the arrangement of each repeating unit may be random. In the above formula, p is an integer of 1 to 6, and X is independently a fluorine atom or a CF ₃ group.

Preferred examples of the monovalent Rf include the following groups.

式中、ｐは１〜６の整数、ｎは２〜２００の整数である

式中、Ｘはフッ素原子又はＣＦ_３基、ｐは１〜６の整数、ｑ、ｎはそれぞれ０〜２００の整数、但し、ｑ＋ｎは２〜２００である。各繰り返し単位はランダムに結合されていてよい。

式中、Ｘはフッ素原子又はＣＦ_３基、ｐ^１及びｐ^２は互いに独立に１〜６の整数、ｎ、ｑ^１及びｑ^２は互いに独立に０〜２００の整数であり、ｎ＋ｑ^１＋ｑ^２は２〜２００である。各繰り返し単位はランダムに結合されていてよい。 A group having a divalent fluoroalkyl ether group can be represented by the following formula.

In the formula, p is an integer of 1 to 6, and n is an integer of 2 to 200.

In the formula, X is a fluorine atom or CF ₃ group, p is an integer of 1 to 6, q and n are each an integer of 0 to 200, provided that q + n is 2 to 200. Each repeating unit may be bonded at random.

In the formula, X is a fluorine atom or CF ₃ group, p ¹ and p ² are each independently an integer of 1 to 6, n, q ¹ and q ² are each independently an integer of 0 to 200, and n + q ¹ + q ² Is 2 to 200. Each repeating unit may be bonded at random.

式中、ｑ^１＋ｑ^２は２〜２００である。各繰り返し単位はランダムに結合されていてよい。 Preferred examples of the divalent Rf include the following groups.

In the formula, q ¹ + q ² is 2 to 200. Each repeating unit may be bonded at random.

式中、Ｒｆ^１は上述した１価のフルオロアルキル基またはフルオロアルキルエーテル基を有する基である。 Examples of the compound represented by the above formula (1) and having a monovalent Rf include the following compounds.

In the formula, Rf ¹ is a group having the above-described monovalent fluoroalkyl group or fluoroalkyl ether group.

式中、ａ’、ｂ’、ｈは上述の通りである。

式中、ａ’は上述の通りである。Ｒｆ^１は上述した１価のフルオロアルキル基またはフルオロアルキルエーテル基を有する基である Moreover, the compound shown below can be mentioned.

In the formula, a ′, b ′, and h are as described above.

In the formula, a ′ is as described above. Rf ¹ is a group having the monovalent fluoroalkyl group or fluoroalkyl ether group described above.

式中、Ｒｆ^２は上述した２価のフルオロアルキル基またはフルオロアルキルエーテル基を有する基である。 Examples of the compound represented by the above formula (1) and having a divalent Rf include the following compounds.

In the formula, Rf ² is a group having the above-described divalent fluoroalkyl group or fluoroalkyl ether group.

式中、Ｒｆ^２は上述した２価のフルオロアルキル基またはフルオロアルキルエーテル基を有する基である。 Moreover, the compound shown below can be mentioned.

In the formula, Rf ² is a group having the above-described divalent fluoroalkyl group or fluoroalkyl ether group.

Further, as the fluorine-containing (α-substituted) acrylic compound used in the present invention, a copolymer obtained by polymerizing the above-mentioned fluorine-containing (α-substituted) acrylic compound and a non-fluorine-containing (α-substituted) acrylic compound having a reactive group. A copolymer obtained by further reacting a compound having a (meth) acrylic group and a reactive group with the coalescence can be used. The copolymer includes the above fluorine-containing acrylate compound, acrylics having a hydroxyl group such as 2-hydroxyethyl acrylate, acrylates having an isocyanate group such as 2-isocyanatoethyl acrylate, and epoxy such as glycidyl methacrylate. It can be obtained by copolymerizing a group-containing acrylate and the like, and further reacting with a (meth) acrylic compound having a group reactive to the functional group of the obtained copolymer. For example, an acrylate having an isocyanate group may be reacted with a hydroxyl group, an acrylate having a hydroxyl group with an isocyanate group, and acrylic acid with an epoxy group.

（式中、Ｘ^１はフッ素原子、水素原子、塩素原子、またはエーテル結合を含んでいてよく、水素原子の一部または全てがフッ素化されていてよい、炭素数１〜４のアルキル基であり、Ｘ^２およびＸ^３は、互いに独立に、フッ素原子、水素原子、または塩素原子である）
と、以下の繰り返し単位（ｂ）

（但し、Ｙは水酸基、又は、エーテル結合またはエステル結合を１以上有していても良い、少なくとも１の水酸基を有する、炭素数１〜１０の１価の有機基であり、Ｒ^１は水素原子または炭素数１〜６のアルキル基である）とを有する含フッ素共重合体（Ｄ）に、
（メタ）アクリル基を有するイソシアネート化合物（Ｅ）を反応させて得られる含フッ素（α置換）アクリル化合物を使用する事ができる。 Further, as the fluorine-containing (α-substituted) acrylic compound used in the present invention, the following repeating unit (a)

(In the formula, X ¹ is a C 1-4 alkyl group which may contain a fluorine atom, a hydrogen atom, a chlorine atom, or an ether bond, and part or all of the hydrogen atoms may be fluorinated. , X ² and X ³ are each independently a fluorine atom, a hydrogen atom or a chlorine atom)
And the following repeating unit (b)

(However, Y is a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms, which may have one or more ether bonds or ester bonds, and R ¹ is a hydrogen atom. Or a fluorine-containing copolymer (D) having a C 1-6 alkyl group)
A fluorine-containing (α-substituted) acrylic compound obtained by reacting an isocyanate compound (E) having a (meth) acryl group can be used.

In the repeating unit (a), X ¹ , X ² and X ³ are preferably fluorine atoms or chlorine atoms, and in particular, the unit (a) is tetrafluoroethylene and / or chlorotrifluoroethylene. Is preferred. The repeating units (a) and (b) may be used alone or in combination of two or more. The fluorine-containing copolymer (D) has at least one hydroxyl group in order to react with the isocyanate compound (E). In the above repeating unit (b), the group represented by Y includes —OCH ₂ CH ₂ OH, —OCH ₂ CH ₂ CH ₂ CH ₂ OH, —OCH ₂ CH ₂ OCH ₂ CH ₂ OH, —COOCH ₂ CH _2. OH, and _{-COOCH 2 CH 2 CH 2 CH 2} OH, it can be cited. Of _{these, -OCH 2 CH 2 CH 2 CH} 2 OH, and -COOCH ₂ CH ₂ OH is preferred. R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group.

  The fluorine-containing copolymer (D) has a weight average molecular weight of 500 to 50000, preferably 1000 to 20000, and 2 to 200, preferably 4 to 100, repeating units (a) in one molecule. The repeating unit (b) should contain 2 to 200, preferably 4 to 100.

  The fluorine-containing copolymer (D) can be produced by copolymerizing the raw material compound of the unit (a) and the compound of the unit (b) by a conventionally known method. Examples of the raw material for the unit (a) include fluoroolefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, pentafluoropropylene, and hexafluoropropylene. Examples of the raw material for the unit (b) include hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, glycidyl vinyl ether, glycidyl allyl ether, hydroxyethyl allyl ether, hydroxyethyl methacrylate, methacrylic acid, 10-undecenoic acid, and alkoxyvinylsilane. The fluorine-containing copolymer (D) may contain polymerized units other than the unit (a) and the unit (b).

  A fluorine-containing (α-substituted) acrylic compound can be obtained by reacting the fluorine-containing copolymer (D) with an isocyanate compound (E) having an acrylic group and / or a methacrylic group. In order to easily obtain the above compounds, commercially available products such as “Lumiflon” (Asahi Glass Co., Ltd.), “Fluonate” (DIC Corporation), “Zeffle” (Daikin Industries Co., Ltd.), “Ceraful Coat” (Central Glass) A method of reacting a fluorine-containing polymer having a hydroxyl group with an isocyanate compound having an acrylic group and / or a methacrylic group, such as “Zaflon” (Toagosei Co., Ltd.), is preferable.

  The reaction of the hydroxyl group of the fluorine-containing copolymer (D) and the isocyanate compound (E) can be allowed to proceed by mixing both under mild conditions of 0 to 70 ° C. The rate of the reaction is determined by a suitable catalyst system such as stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate. A tin derivative, an iron derivative such as iron acetylacetonate, a titanium alcoholate such as titanium tetraisopropylate, a tertiary amine such as triethylamine, or N-methylmorpholine is added to the total reactant weight. It can be increased by adding from 001 to 2% by weight, preferably from 0.001 to 0.5% by weight. Moreover, you may dilute with various solvents as needed, and may react.

(B) UV curable compound containing no fluorine The UV curable compound containing no fluorine is not particularly limited as long as it can be mixed with the above fluorine-containing (α-substituted) acrylic compound and can be cured. In particular, acrylates are preferable. For example, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) Acrylate, isocyanuric acid EO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropante 2-6 functional (meth) acrylic such as la (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate Compounds, ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resins, and side chains of acrylic ester copolymers ( Examples include those containing a copolymer into which a (meth) acryloyl group has been introduced.

  Also, urethane acrylates, those obtained by reacting polyisocyanate with (meth) acrylate having hydroxyl group, those obtained by reacting polyisocyanate and terminal diol polyester with hydroxyl group (meth) acrylate, excess in polyol It is also possible to use a polyisocyanate obtained by reacting with a diisocyanate obtained by reacting a (meth) acrylate having a hydroxyl group. Among them, (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diene Urethane acrylates obtained by reacting isocyanate and polyisocyanate selected from diphenylmethane diisocyanate are preferred. The above compounds may be used alone or in combination of two or more. Moreover, you may mix | blend monofunctional acrylates for the physical property adjustment of a composition.

(C) Photopolymerization initiator
A photoinitiator will not be restrict | limited especially if an acrylic compound can be hardened by ultraviolet irradiation. Preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1.2-octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone-1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) -Propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and the like, and may be used alone or in combination of two or more.

The blending amount of the fluorine-containing (α-substituted) acrylic compound in the curable composition may be appropriately adjusted according to the desired oil repellency, solubility of the composition, and curing conditions. The mixing ratio of the component (A), the component (B), and the component (C) is not particularly limited, but the component (A) is 0.01 to 30 parts by mass, preferably 100 to 30 parts by mass, preferably 0.05 to 5 parts by mass, component (C) is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass. When the blending amount of the fluorine-containing (α-substituted) acrylic compound exceeds the above upper limit, the fluorine-containing acrylate component layer becomes thick and the performance as a hard coat agent may be impaired. If the amount is less than the lower limit, the fluorine group cannot sufficiently cover the surface of the hard coat layer, and sufficient water / oil repellency and slipperiness may not be obtained. Moreover, when the compounding quantity of a component (C) exceeds the said upper limit, the film after hardening yellows and there exists a possibility of causing deterioration of an external appearance. Moreover, if it is less than the said lower limit, hardening may become inadequate and the performance as a hard-coat agent may be impaired.

  The ultraviolet curable composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, as other components, as long as the performance is not impaired depending on the application. You may mix | blend an agent, antioxidant, surfactant, a coloring agent, a filler, etc. Examples of organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, t-butanol, diacetone alcohol; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, butyl acetate, cyclohexyl acetate, etc. And the like. The said solvent may be individual 1 type or may mix 2 or more types. Although the usage-amount of a solvent is not restrict | limited in particular, 50-10000 mass parts with respect to a total of 100 mass parts of a component (A), a component (B), and a component (C), Especially 100-1000 mass parts and Preferably, the amount is such that

Various hard coat agents containing the components (B) and (C) are commercially available from various companies. The curable composition of the present invention may be one obtained by adding the above fluorine-containing (α-substituted) acrylic compound to the commercially available hard coat agent. Examples of commercially available hard coat agents include Arakawa Chemical Industries, Ltd. “Beam Set”, Ohashi Chemical Industries, Ltd. “Ubic”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd., “Cashew UV” JSR Co., Ltd. “Desolite”, Dainichi Seika Kogyo Co., Ltd. “Seika Beam”, Nippon Synthetic Chemical Co., Ltd. “Shikou”, Fujikura Kasei Co., Ltd. “Fuji Hard”, Mitsubishi Rayon Co., Ltd. “Diabeam”, Musashi Paint "Ultravine" etc. are mentioned. The hard coat agent further includes an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, and a colorant depending on the purpose. , And fillers can also be blended.

The cured film obtained from the present invention gives the coated surface excellent water repellency, oil repellency and fingerprint resistance, so that the coated surface is difficult to be stained by human fat such as fingerprints, sebum, sweat, cosmetics, etc. Even if it adheres, the hard coat surface excellent in wiping off is given. For this reason, for example, it is used for the purpose of protecting the surface of an article that may be touched by a human body and contaminated with human fat, cosmetics, or the like. Such articles include, for example, magneto-optical discs, optical discs such as CD / LD / DVD / Blu-ray discs, optical recording media represented by hologram recording, etc .; glasses lenses, prisms, lens sheets, pellicle films, polarizing plates, Optical components, optical devices such as optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes (VFDs), fields Various screen display devices such as emissive projection display and toner display, especially PCs, mobile phones, personal digital assistants, game machines, digital cameras, digital video cameras, automatic cash withdrawal and deposit devices, automatic cash payments , Navigation devices for automobiles, image display devices such as security system terminals, and touch panel (touch sensors, touch screen) type image display input devices that also operate; mobile phones, portable information terminals, portable music players, Input devices such as portable game machines, remote controllers, controllers, keyboards, panel switches for in-vehicle devices; mobile phone, portable information terminals, cameras, portable music players, portable game consoles, etc .; automobile exteriors, pianos, High-quality furniture, painting and surfaces of marble, etc .; protective glass for art exhibits, show windows, showcases, advertising covers, covers for photo stands, watches, windshields for automobiles, window glass for trains, aircraft, etc., automotive headlights Transparent glass such as tail lamps Or transparent plastic (acrylic, polycarbonate, etc.) member, various mirrors member, and the like.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

上記式（１０）において、Ｒｆ^１は−ＣＦ_２（ＯＣＦ_２ＣＦ_２）_ｘ１（ＯＣＦ_２）_ｙ１ＯＣＦ_２−であり、ｘ１／ｙ１は０．９、ｘ１＋ｙ１≒４５である。 [Preparation Example 1]
(A1) Preparation of fluorinated acrylate compound 1 A compound represented by the following formula (10) was obtained according to the method of Example 2 described in paragraphs 0052 to 0061 of JP2010-285501A.

In the above formula (10), Rf ¹ is —CF ₂ (OCF ₂ CF ₂ ) _x1 (OCF ₂ ) _y1 OCF ₂ —, and x1 / y1 is 0.9 and x1 + y1≈45.

[Preparation Example 2]
(A2) Preparation of fluorinated acrylate compound 2 Except for using 1,1- (bisacryloyloxymethyl) ethyl isocyanate instead of acryloyloxyethyl isocyanate described in paragraph 0057 of JP2010-285501A A compound represented by the following formula (11) was obtained in the same manner as in Example 1 described in paragraphs 0052 to 0057 of JP2010-285501A.

上記式（１１）において、Ｒｆ^１は−ＣＦ_２（ＯＣＦ_２ＣＦ_２）_ｘ１（ＯＣＦ_２）_ｙ１ＯＣＦ_２−であり、ｘ１／ｙ１は０．９、ｘ１＋ｙ１≒４５である。

In the above formula (11), Rf ¹ is —CF ₂ (OCF ₂ CF ₂ ) _x1 (OCF ₂ ) _y1 OCF ₂ —, and x1 / y1 is 0.9 and x1 + y1≈45.

で示される化合物を用いた以外は特開２０１０−２８５５０１号公報の段落００５２〜段落００５７に記載されている実施例１と同様の方法で、下記式（１３）で表される化合物を得た。 [Preparation Example 3]
(A3) Preparation of fluorinated acrylate compound 3 Instead of the compound represented by formula (16) described in paragraph 0053 of JP2010-285501A, the following formula (12)

A compound represented by the following formula (13) was obtained in the same manner as in Example 1 described in paragraphs 0052 to 0057 of JP 2010-285501 A except that the compound represented by formula (1) was used.

上記式（１３）において、Ｒｆ^２は上述の通り。

In the above formula (13), Rf ² is as described above.

Preparation of curable composition The ingredients shown in Table 1 were mixed, mixed and stirred, and then filtered through a 0.45 micron hydrophobic PTFE filter to obtain compositions 1 to 3. .

Preparation of cured film [Examples 1, 2 and 3]
Compositions 1 to 3 were placed on a polycarbonate substrate with No. 7 was applied with a wire bar (wet film thickness 16.0 μm), heated in an oven at 80 ° C. for 1 minute, and then cooled to near room temperature in nitrogen. Thereafter, in a nitrogen atmosphere, a cured film was prepared by irradiating 1.6 J / cm ² of ultraviolet rays for 6 seconds with a conveyor type ultraviolet irradiation device (manufactured by Panasonic Electric Works Co., Ltd.).

[Comparative Examples 1, 2, and 3]
Compositions 1 to 3 were placed on a polycarbonate substrate with No. 1 7 (wet film thickness 16.0 μm), cooled to near room temperature in nitrogen, and 1.6 J / cm ^{2 in a} nitrogen atmosphere with a conveyor type ultraviolet irradiation device (manufactured by Panasonic Electric Works Co., Ltd.). Were cured for 6 seconds to produce a cured film.

[Comparative Example 4]
Composition 1 was prepared on a polycarbonate substrate with No. 1 7 was applied with a wire bar (wet film thickness 16.0 μm), heated in an oven at 80 ° C. for 1 minute, and then cooled to near room temperature in an air atmosphere. Thereafter, the composition was not cured when irradiated with ultraviolet rays of 1.6 J / cm ² for 6 seconds with a conveyor type ultraviolet irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) in an air atmosphere. did.

Evaluation of antifouling performance of cured film Each cured film was evaluated as follows. The results are shown in Table 2.

[Contact angle measurement]
The water contact angle, oleic acid contact angle, and oleic acid tumbling angle of each cured film were measured using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

[Dynamic friction coefficient]
The dynamic friction coefficient for Bencott (trade name, manufactured by Asahi Kasei Co., Ltd.) was measured with a surface property tester (manufactured by Shinto Kagaku Co.).

[Magic ink repellency]
A line was drawn on the film with an oil marker (trade name, manufactured by Zebra Corporation) and Himackey (trade name, manufactured by Zebra Corporation), and the degree of ink repelling was visually observed. The evaluation was performed using the following indicators.
○: Repels well △: Some parts do not repel ×: Does not repel at all

  As shown in Table 2, the cured film obtained by the method of the present invention has water and oil repellency compared to the cured film obtained by the methods of Comparative Examples 1 to 3 in which the composition was not heated before ultraviolet irradiation. In addition, the slipperiness is excellent. In addition, a cured film having excellent surface characteristics was obtained by the method of the present invention, although it was not possible to obtain a cured film by the method of Comparative Example 4 which was applied to the substrate and then cooled in air. be able to.

  According to the curing method of the present invention, a film having excellent surface characteristics can be formed. In particular, it is useful for imparting water / oil repellency and antifouling properties to the surface of an acrylic hard coat. Therefore, the method of the present invention is useful as a method for forming a paint film or a protective film on the surface of an article that may be touched by a human body and contaminated with human fat, cosmetics, or the like.

Claims (19)

In a method of curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound,
(Ii) a method comprising heating the composition at a temperature of 50 ° C. or higher, and (iv) irradiating the composition with an ultraviolet ray in an inert gas atmosphere to cure the composition.   The method according to claim 1, wherein the method comprises the step of (iii) bringing the temperature of the composition to less than 50 ° C. under an inert gas atmosphere after step (ii) and before step (iv). Method.   The method of Claim 1 or 2 which heats this composition at 50 degreeC or more and 160 degrees C or less.   The curable composition contains (A) a fluorine-containing (α-substituted) acrylic compound, (B) an ultraviolet curable compound not containing fluorine, and (C) a photopolymerization initiator. 2. The method according to item 1.   The fluorine-containing (α-substituted) acrylic compound has at least one acryl group, methacryl group, and α-fluoroacryl group at the terminal, and has a fluoroalkyl group or a fluoropolyether group in the molecule. The method according to any one of claims 1 to 4. The fluorine-containing (α-substituted) acrylic compound has the following general formula (1)

(In the formula, a is an integer of 1 to 5, b, c, and d are each an integer of 0 to 5, provided that c + d is not 0, e is 0 or 1, and Rf is 0 in e. Is a monovalent group, and when e is 1, it is a divalent group having a fluoroalkyl group or a fluoroalkyl ether group, and Q may have an oxygen atom, a nitrogen atom, or a silicon atom a + b + 1 Q ′ is a c + d + 1 valent organic group which may have an oxygen atom, a nitrogen atom, or a silicon atom, and R ¹ is at least ^one of an acrylic group, a methacryl group, and an α-fluoroacryl group. 1 is a monovalent organic group, and R ² is a monovalent organic group that does not contain any of an acryl group, a methacryl group, and an α-fluoroacryl group)
Or the following general formula (2)

(Wherein a, b, c, d, R ¹ , R ² , Rf, Q, Q ′ are the same as above, v is an integer of 1 to 5, Q ″ is an oxygen atom, a nitrogen atom, Or c ′ + d ′ + divalent organic group which may have a silicon atom, c ′ and d ′ are each an integer of 0 to 5, provided that c ′ + d ′ is not 0)
The method of claim 5, wherein: The method according to claim 6, wherein Rf has a unit in which at least one of units represented by the following formula is repeated twice or more.

The method according to claim 6 or 7, wherein R ¹ is a group represented by the following formula (3) or (4).

(In the formula, R ⁴ is, independently of each other, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁵ may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. A good divalent or trivalent organic group, and n is an integer of 1 or 2) The method according to any one of claims 6 to 8, wherein R ² is a group represented by the following formula (5).

In the formula, f, g, h, and i are each independently an integer of 0 to 20 in the range where the molecular weight of R ² is 30 to 600. The arrangement of each repeating unit may be random. R ³ is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms) The method according to any one of claims 6 to 9, wherein Q and / or Q 'is a group represented by the following formula (6).

(Wherein, a ′ is an integer of 1 to 4, b ′ and b ″ are integers of 0 to 4, a ′ + b ′ + b ″ is 2, 3 or 4, and the arrangement of each repeating unit is random. Q ¹ is a divalent linking group which may contain an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, independently of each other, and includes a cyclic structure or a branch in the middle. Z may be the same or different, and Z is a divalent linking group which may have an oxygen atom, a nitrogen atom, or a silicon atom, and in formula (1) or (2) Binds to Rf) The method according to claim 6, wherein Q ″ is a group represented by the following formula (7).

(Where c ″, d ″ and b ′ ″ are integers of 0 to 3, provided that c ″ + d ″ + b ′ ″ is any one of 1, 2, 3 and each repeating unit. Q ¹ is a divalent linking group which may contain an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms and is cyclic in the middle. And may be the same or different, and Z is a divalent linking group which may have an oxygen atom, a nitrogen atom, or a silicon atom, in the formula (2) To each Rf) The method according to claim 10 or 11, wherein Q ¹ is any of the following groups.

The method according to claim 10 or 11, wherein Z is any of the following groups.

  The fluorine-containing (α-substituted) acrylic compound is a fluorine-containing (α-substituted) acrylic compound described in any one of claims 6 to 13, and a non-fluorine-containing (α-substituted) acrylic compound having a reactive group The method according to any one of claims 1 to 4, which is a copolymer obtained by further reacting a copolymer having a (meth) acrylic group and a reactive group with a copolymer obtained by polymerizing the above. . The fluorine-containing (α-substituted) acrylic compound has the following repeating unit (a)

(In the formula, X ¹ is a C 1-4 alkyl group which may contain a fluorine atom, a hydrogen atom, a chlorine atom, or an ether bond, and part or all of the hydrogen atoms may be fluorinated. , X ² and X ³ are each independently a fluorine atom, a hydrogen atom or a chlorine atom)
And the following repeating unit (b)

(However, Y is a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms, which may have one or more ether bonds or ester bonds, and R ¹ is a hydrogen atom. Or a fluorine-containing copolymer (D) having a C 1-6 alkyl group)
The method of any one of Claims 1-4 which is a fluorine-containing ((alpha) substituted) acrylic compound obtained by making the isocyanate compound (E) which has a (meth) acryl group react.   The method according to any one of claims 1 to 15, wherein the method comprises the step of (i) applying the composition to a substrate before the step (ii).   The method of Claim 16 that a base material is a resin molding, a film, or glass.   An article provided with a cured film obtained by the method according to claim 16 or 17.   A molded product obtained by curing the curable composition by the method according to claim 1.