JP5649183B2 - Curing method for curable composition containing fluorine-containing (α-substituted) acrylic compound - Google Patents

Description

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

  Acrylic compounds can be easily cured by irradiation with ultraviolet rays, and can be applied to the surface of various articles typified by plastic resin and cured to provide a wide range of hard coat materials that protect the surface and provide new functions. Used for applications.

  These hard coats, in addition to the conventionally required hardness, wear resistance, chemical resistance, durability, etc., according to the spread of their applications, antifouling properties, weather resistance, slip properties, antistatic properties, antifogging properties There are demands for further high functions such as property, indifference, antireflection, and the like. Among them, attention has been focused on improving dirt prevention, dirt wiping, especially fingerprint resistance and fingerprint wiping.

  As a method for imparting antifouling properties to hard coats, attempts have been widely made to create a fluorine-based compound layer on the surface and improve water and oil repellency to repel dirt components containing water and oil. As a typical technique, there is widely known a method in which a polymerizable monomer having a perfluoroalkyl group in the side chain, for example, a polymer obtained from a fluorine-containing alkyl ester of acrylic acid or a fluorine-containing alkyl ester of methacrylic acid is added to the composition. It has been. In recent years, a fluorine-containing (α-substituted) acrylic compound having a fluoropolyether group has been studied for more advanced characteristics (Patent Documents 1 to 3). These fluorine-containing (α-substituted) acrylic compounds are added to the hard coat and applied to the substrate. The surface free energy causes fluorine groups to emerge on the surface of the film, forming a layer with a high fluorine content on the outermost surface layer. It has been tried.

  However, the fluorine-containing (α-substituted) acrylic compound has a large inhibition of curing by oxygen. Therefore, if the hard coat containing a fluorine-containing (α-substituted) acrylic compound is cured in air, the fluorine-containing (α-substituted) acrylic compound will be insufficiently cured, causing damage to the film surface and residual stains. The intended hard coat surface cannot be obtained. Therefore, in order to obtain a hard coat surface that fully exhibits the effect of the fluorine-containing (α-substituted) acrylic compound, ultraviolet irradiation must be performed in an inert gas atmosphere such as nitrogen gas or argon, which is expensive. There was a drawback. In addition, when the hard coat to which the fluorine-containing (α-substituted) acrylic compound is added is not cured immediately after being applied to the substrate, for example, when the substrate is cured after being stored once, the surface state of the obtained film is There was also the problem of getting worse.

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

  The present invention can form a coating film with excellent surface characteristics even when irradiated with ultraviolet rays in the air, and when the substrate coated with the curable composition is once irradiated with ultraviolet rays after storage Even so, it is an object of the present invention to provide a curing method capable of forming a coating film having excellent surface characteristics. As a result of intensive efforts, the inventors of the present invention, when curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound, irradiating the composition with ultraviolet rays after setting the temperature of the composition to 50 ° C. or higher. It discovered that the said objective can be achieved by hardening a thing.

That is, the present invention
It is a method of curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound,
(I) a step of applying the composition to a substrate;
(Ii) after the step (i), drying the composition;
(Iii) After the step (ii), the step of setting the temperature of the composition to less than 50 ° C., and (iv) After the step (iii), the temperature of the composition is set to 50 ° C. or higher and then irradiated with ultraviolet rays. Providing a method comprising curing the composition.

  The curing method of the present invention can form a film having an excellent surface state even when irradiated with ultraviolet rays in air. Moreover, even if it is a case where ultraviolet rays are irradiated after storing the base material which coated the curable composition, the coating film excellent in the surface characteristic can be formed.

  The present invention relates to a method for curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound, wherein the temperature of the composition is set to 50 ° C. or higher during ultraviolet irradiation. Prior to the step (iv), the method of the present invention may include (i) a step of applying the composition to a substrate, and is suitably used as a method for forming a cured film on the substrate. can do. By raising the temperature of the composition at the time of ultraviolet irradiation, the fluorine groups in the composition are unevenly distributed on the surface of the film, resulting in a film having excellent antifouling properties and water / oil repellency. In addition, since the fluorine-containing (α-substituted) acrylic compound that is susceptible to inhibition of curing by oxygen is likely to undergo molecular motion by heating, it can be sufficiently cured even by ultraviolet irradiation in air. Among these, it is preferable that the temperature of the composition is 50 ° C. or higher and 160 ° C. or lower, preferably 60 ° C. or higher and 120 ° C. or lower, and then the ultraviolet ray is irradiated to cure the composition. Less than the lower limit is not preferable because sufficient curability cannot be obtained. If the value exceeds the upper limit, the resin or film serving as the substrate and the acrylic compound itself in the composition may be decomposed, which is not preferable.

  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.

  In the present invention, an apparatus that raises the temperature of the composition applied to the substrate to 50 ° C. or higher can raise the composition to a target temperature and can maintain the temperature until ultraviolet irradiation. There is no particular limitation. For example, a batch type or conveyor type hot air drying furnace, a far infrared drying furnace, a near infrared drying furnace, or the like can be used. The process can be performed in air. The heating time is not particularly limited, but usually about 10 seconds to 10 minutes is preferable. If the heating time is too long, partial thermal curing occurs and the cured state becomes non-uniform. Moreover, when a base material is a resin molding and a film, deterioration of a base material may occur. On the other hand, if the heating time is too short, the entire coated composition may not reach the above temperature. In addition, when the said method includes the process of drying a composition, the process of drying a composition and the process of setting a composition as the said temperature can be made into the same process, and a separate process may be sufficient as it.

The method of irradiating the composition with ultraviolet rays may follow a conventionally known method. In the present invention, ultraviolet irradiation can be performed in air. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, an LED, or the like can be used. The ultraviolet irradiation amount and the irradiation time are not particularly limited as long as they are sufficient to cure the curable composition and do not deteriorate the cured product layer or the substrate. Usually, the amount of UV irradiation ^{100mJ / cm 2 ~3000mJ / cm 2} , in particular at ^{200mJ / cm 2 ~2000mJ / cm 2} .

  The present invention further includes a step of (ii) drying the composition after step (i) and before step (iv), and (iii) a step of setting the temperature of the composition to less than 50 ° C. A method of including is provided. This method corresponds to a curing method in the case where ultraviolet rays are not immediately irradiated after the composition is applied to a substrate. The purpose of the step (ii) of drying the composition is to volatilize the solvent in the composition. The drying step may be performed according to a conventionally known method. For example, it can carry out by heating in the range of 50-120 degreeC for 10 second-10 minutes in a hot air dryer. In the step (iii) of setting the temperature of the composition to less than 50 ° C., for example, after the composition is coated on the substrate and dried, the substrate is temporarily stored under a temperature condition of less than 50 ° C. In general, it is in the range of 0 to 40 ° C., more preferably in the range of 10 to 30 ° C. The storage period may be appropriately selected. In the present invention, step (iii) can be performed in air. According to the method of the present invention, the composition is not cured immediately after the composition is applied to the substrate and dried. For example, when the composition is cured after a long time, such as when wound on a roll and stored. However, a film having excellent surface characteristics can be provided.

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, and the like. 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 compounds such as la (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, these (meth) acrylic compounds Ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resins, and co-polymers with (meth) acryloyl groups introduced into the side chains of acrylic ester copolymers The thing containing coalescence etc. is mentioned.

  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 with respect to 100 parts by mass of the component (B), 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. The composition 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, a colorant, depending on the purpose. And a filler etc. can also be mix | blended.

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 (A) 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.

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

  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 repellency, oil repellency and antifouling properties to the surface of an acrylic hard coat. As a result, it is possible to impart a hard coat surface with excellent wiping properties to the substrate, which makes it difficult for dirt due to human fat such as fingerprints, sebum, sweat, and cosmetics to adhere. 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.

The cured film formed by the method of the present invention is a casing of various devices carried by human hands such as tablet computers, notebook PCs, mobile phones, portable (communication) information terminals, digital media players, electronic book readers, liquid crystals, Surfaces of display devices such as plasma, organic EL and other flat panel displays and TV screens, automobile exteriors, glossy surfaces of pianos and furniture, surface of building stones such as marble, toilets, baths, bathrooms, etc. Building materials, protective glass for art exhibitions, show windows, showcases, photo frame covers, watches, windshields for automobiles, window glass for trains, aircraft, etc., made of transparent glass or transparent plastic such as automobile headlights, tail lamps, etc. (Acrylic, polycarbonate, etc.) coating of members, various mirror members, etc. It is useful as a film and a surface protective film.

In particular, various devices having a display input device that performs operations on the screen with a human finger or palm such as a touch panel display, such as a tablet computer, notebook PC, mobile phone, portable (communication) information terminal, digital media player, electronic book Readers, digital photo frames, game machines, digital cameras, digital video cameras, automobile navigation systems, automatic cash withdrawal and deposit devices, cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS It is useful as a surface protective film for various controllers such as terminals and remote controllers, and display input devices such as panel switches for in-vehicle devices.

Further, the cured film formed by the method of the present invention is an optical recording medium such as a magneto-optical disk or optical disk; glasses lens, prism, lens sheet, pellicle film, polarizing plate, optical filter, lenticular lens, Fresnel lens, antireflection film. It is also useful as a surface protective film for optical components and optical devices such as optical fibers and optical couplers.

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

（式中、Ｒｆは−ＣＦ_２（ＯＣＦ_２ＣＦ_２）_ｌ（ＯＣＦ_２）_ｍＯＣＦ_２−であり、ｌ／ｍ＝０．９、ｌ＋ｍ≒４５（平均値）である）
で示される両末端にα―不飽和結合を有するパーフルオロポリエーテル５００ｇと、ｍ−キシレンヘキサフロライド７００ｇ、及びテトラメチルシクロテトラシロキサン３６１ｇを投入し、攪拌しながら９０℃まで加熱した。ここに塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．４４２ｇ（Ｐｔ単体として１．１×１０^−６モルを含有）を仕込み投入し、内温を９０℃以上に維持したまま４時間攪拌を継続した。^１Ｈ−ＮＭＲで原料のアリル基が消失したのを確認した後、溶剤や過剰のテトラメチルシクロテトラシロキサンを減圧留去し、活性炭処理を行い、下記式（９）で示す無色透明の液体パーフルオロポリエーテル含有化合物４９８ｇを得た。

[Preparation Example 1]
(A) Preparation of fluorinated acrylate compound Under a dry nitrogen atmosphere, a 2000 ml three-necked flask equipped with a reflux apparatus and a stirring apparatus was charged with

(In the formula, Rf is —CF ₂ (OCF ₂ CF ₂ ) ₁ (OCF ₂ ) _m OCF ₂ —, and 1 / m = 0.9, l + m≈45 (average value))
500 g of perfluoropolyether having an α-unsaturated bond at both ends, 700 g of m-xylene hexafluoride and 361 g of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. Here, 0.442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was charged and stirring was continued for 4 hours while maintaining the internal temperature at 90 ° C. or higher. did. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure, the activated carbon treatment was performed, and a colorless and transparent liquid pars represented by the following formula (9) was obtained. 498 g of a fluoropolyether-containing compound was obtained.

で示される化合物１１．９ｇ、ｍ−キシレンヘキサフロライド５０．０ｇ、及び、ビニルシロキサン変性塩化白金酸のトルエン溶液０．０４４２ｇ（Ｐｔ単体として１．１×１０^−７モルを含有）を混合し、１００℃で４時間攪拌した。^１Ｈ−ＮＭＲ及びＩＲでＳｉ−Ｈ基が消失したのを確認した後、減圧溜去し、活性炭処理を行い、淡黄色透明の液体パーフルオロポリエーテル含有化合物を得た。乾燥空気雰囲気下で、該生成物５０．０ｇに対して、ＴＨＦ５０．０ｇとアクリロイルオキシエチルイソシアネート７．０５を混合し、５０℃に加熱した。そこにジオクチル錫ラウレート０．０５ｇを添加し、５０℃下２４時間攪拌した。加熱終了後、８０℃、２Ｔｏｒｒで減圧留去を行い、淡黄色のペースト状物質５６．１ｇを得た。^１Ｈ−ＮＭＲの結果から下記式（１１）に示す化合物であることを確認した。

（式中、Ｒｆは−ＣＦ_２（ＯＣＦ_２ＣＦ_２）_ｌ（ＯＣＦ_２）_ｍＯＣＦ_２−であり、ｌ／ｍ＝０．９、ｌ＋ｍ≒４５（平均値）である） Under a dry air atmosphere, 50.0 g of the compound represented by the above formula (9), the following formula (10)

11.9 g of the compound represented by the formula, 50.0 g of m-xylene hexafluoride, and 0.0442 g of a toluene solution of vinylsiloxane-modified chloroplatinic acid (containing 1.1 × 10 ⁻⁷ mol as a simple substance of Pt) , And stirred at 100 ° C. for 4 hours. After confirming the disappearance of the Si-H group by ¹ H-NMR and IR, it was distilled off under reduced pressure and treated with activated carbon to obtain a light yellow transparent liquid perfluoropolyether-containing compound. Under a dry air atmosphere, 50.0 g of THF and acryloyloxyethyl isocyanate 7.05 were mixed with 50.0 g of the product, and heated to 50 ° C. Dioctyltin laurate 0.05g was added there, and it stirred at 50 degreeC for 24 hours. After completion of the heating, vacuum distillation was performed at 80 ° C. and 2 Torr to obtain 56.1 g of a pale yellow pasty substance. It confirmed that it was a compound shown to following formula (11) from the result of < ¹ > H-NMR.

(In the formula, Rf is —CF ₂ (OCF ₂ CF ₂ ) ₁ (OCF ₂ ) _m OCF ₂ —, and 1 / m = 0.9, l + m≈45 (average value))

[Preparation Example 2]
Preparation of Curable Composition 1 part by mass of the compound of the above formula (11), 100 parts by mass of dipentaerythritol hexaacrylate (NK ester A9550: manufactured by Shin-Nakamura Chemical), 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (Irgacure 127: manufactured by Ciba Japan Co., Ltd.) and 150 parts by mass of 2-propanol were blended. After mixing and stirring, filtration was performed with a 0.45 micron hydrophobic PTFE filter (hereinafter referred to as composition 1).

（式中、Ｒｆは下記の基である

上記式において、ｊは繰返し単位の数を示し、５．２（平均値）である）
トルエン２０.０ｇを仕込み、攪拌しながら９０℃まで加熱した。ここに、下記式（１３）

（上記式において、ｈは繰返し単位の数を示し、４．５（平均値）である）
で表わされるポリオキシエチレンメチルアリルエーテル９．７５ｇとビニルシロキサン変性塩化白金酸のトルエン溶液０．０１１０ｇ（Ｐｔ単位として２．７３×１０^-８モルを含有）の混合溶液を１時間かけて滴下し、９０℃で１２時間攪拌した。当該反応溶液を室温まで冷却した。 [Adjustment Example 3]
Under a dry nitrogen atmosphere, in a 100 ml three-necked flask equipped with a reflux device and a stirrer, 50.0 g of a fluorine-containing cyclic siloxane represented by the following formula (12):

(In the formula, Rf is the following group:

(In the above formula, j represents the number of repeating units and is 5.2 (average value))
Toluene 20.0 g was charged and heated to 90 ° C. with stirring. Here, the following formula (13)

(In the above formula, h represents the number of repeating units and is 4.5 (average value))
A mixed solution of 9.75 g of polyoxyethylene methyl allyl ether and 0.0110 g of a toluene solution of vinylsiloxane-modified chloroplatinic acid (containing 2.73 × 10 ⁻⁸ mol as Pt unit) was added dropwise over 1 hour. , And stirred at 90 ° C. for 12 hours. The reaction solution was cooled to room temperature.

（上記式において、Ｒｆは上記の通りであり、ｈ、ａ、及びｂはそれぞれ繰返し単位の数を示し、ｈは４．５（平均値）、ａ&shy;は１．５（平均値）、ｂは１．５（平均値）である）
［調製例４］
硬化性組成物の調製
上記式（１４）の化合物を１質量部、ジペンタエリスリトールヘキサアクリレート（ＮＫエステル Ａ９５５０：新中村化学製）１００質量部、２−ヒロドキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］フェニル｝−２−メチル−プロパン−１−オン（イルガキュアー１２７：チバ・ジャパン（株）製）３質量部、２−プロパノール１５０質量部を配合し、混合し攪拌した後に、０．４５ミクロンの疎水性ＰＴＦＥフィルターでろ過を行った（以下、組成物２と称す）。 In a 100 ml three-necked flask equipped with a reflux apparatus and a stirrer in a dry nitrogen atmosphere, 16.9 g of allyl alcohol was charged and heated to 90 ° C., and then the reaction solution was added dropwise over 3 hours, and then at 90 ° C. for 16 hours. Stir. The obtained reaction solution was distilled off under reduced pressure at 100 ° C. and 6 Torr for 2 hours to remove unreacted allyl alcohol. Under a dry air atmosphere, 7.01 g of 2-isocyanatoethyl acrylate and 0.010 g of dioctyltin laurate were added to 60.0 g of the obtained compound, mixed, and stirred at 25 ° C. for 12 hours. A compound represented by the formula (14) was obtained.

(In the above formula, Rf is as described above, h, a, and b each represent the number of repeating units, h is 4.5 (average value), a &shy; is 1.5 (average value), b Is 1.5 (average value))
[Preparation Example 4]
Preparation of curable composition 1 part by mass of the compound of the above formula (14), 100 parts by mass of dipentaerythritol hexaacrylate (NK ester A9550: manufactured by Shin-Nakamura Chemical), 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (Irgacure 127: manufactured by Ciba Japan) and 150 parts by mass of 2-propanol are blended. After mixing and stirring, the mixture was filtered through a 0.45 micron hydrophobic PTFE filter (hereinafter referred to as composition 2).

[Example 1]
Composition 1 was coated on a polycarbonate substrate with wire bar No. 7 (wet film thickness 16.0 μm). Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) equipped with a drying furnace just before the ultraviolet irradiation part, heating the coated surface at 105 ° C. for 1 minute in the air, and setting the temperature of the composition to 100 ° C. The composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds.

[Example 2]
Composition 1 was coated on a polycarbonate substrate with wire bar No. 7 (wet film thickness 16.0 μm). Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) equipped with a drying furnace just before the ultraviolet irradiation part, heating the coated surface at 74 ° C. for 1 minute in air, and setting the temperature of the composition to 70 ° C. The composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds.

[Example 3]
Composition 1 was coated on a polycarbonate substrate with wire bar No. 7 (wet film thickness 16.0 μm), and the coated surface was heated for 1 minute at 100 ° C. with a hot air dryer (Isuzu Seisakusho). The upper solvent was volatilized. Thereafter, the coated surface was once cooled to room temperature (25 ° C.). Cooling was done in air. Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) equipped with a drying furnace just before the ultraviolet irradiation part, heating the coated surface at 105 ° C. for 1 minute in the air, and setting the temperature of the composition to 100 ° C. The composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds.

[Example 4]
Composition 1 was coated on a polycarbonate substrate with wire bar No. 7 (wet film thickness 16.0 μm). Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) equipped with a drying furnace immediately before the ultraviolet irradiation part, heating the coated surface at 53 ° C. for 1 minute in the air and setting the temperature of the composition to 50 ° C. The composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds.

[Example 5]
Composition 2 was coated on a polycarbonate substrate with wire bar No. 7 (wet film thickness 16.0 μm). Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) equipped with a drying furnace just before the ultraviolet irradiation part, heating the coated surface at 105 ° C. for 1 minute in the air, and setting the temperature of the composition to 100 ° C. The composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds.

[Comparative Example 1]
Composition 1 was prepared on a polycarbonate substrate with No. 1 7 was coated with a wire bar (wet film thickness 16.0 μm) and heated in a hot air dryer at 100 ° C. for 1 minute to volatilize the solvent on the coating film. Thereafter, the coated surface was once cooled to room temperature (25 ° C.). Cooling was done in air. Using a conveyor type metal halide UV irradiation device, the composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1600 mJ / cm ² for 6 seconds in the air. The maximum temperature of the sample surface during irradiation was 42 ° C.

[Contact angle measurement]
The water contact angle, oleic acid contact angle, and oleic acid falling angle of the film on each substrate formed by the above method were measured using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

[Evaluation of magic repellency]
A 3 cm long line was drawn with Zebra's Himacky bold and the appearance was visually observed. Evaluation was performed using the following indicators. The results are shown in Table 1.
◎: Line cannot be formed and ink is repelled to form droplets ○: After the line is formed, ink is repelled and the lines disappear to form droplets △: Ink remains in the shape of the line X: The shape of the line remains without being played.

[Evaluation of fingerprint wiping property]
Five panelists evaluated the adhesion of fingerprints and the wipeability of fingerprints with tissue on each substrate. Evaluation was carried out using the following indices, and the average value was determined. The results are shown in Table 1.
4: Easy to wipe 3: Wipe 2: Hard to wipe 1: Not wipeable

  As shown in Table 1, after the composition was applied to a substrate, the substrate was once cooled in air and then irradiated with ultraviolet rays as it was, resulting in water / oil repellency and magic repellency. And the fingerprint wiping property was inferior (Comparative Example 1). On the other hand, the coating film obtained by the method of the present invention was excellent in water / oil repellency, magic repellency, and fingerprint wiping (Examples 1 to 5).

  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 repellency, 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 (18)

It is a method of curing a curable composition containing a fluorine-containing (α-substituted) acrylic compound,
(I) a step of applying the composition to a substrate;
(Ii) after the step (i), drying the composition;
(Iii) After the step (ii), the step of setting the temperature of the composition to less than 50 ° C., and (iv) After the step (iii), the temperature of the composition is set to 50 ° C. or higher and then irradiated with ultraviolet rays. And curing the composition.   The method according to claim 1, wherein the temperature of the composition is set to 50 ° C. or more and 160 ° C. or less, and then the composition is cured by irradiation with ultraviolet rays.   The method according to claim 1 or 2, wherein the ultraviolet irradiation is performed in air.   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 acrylic 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.
- _(CF 2 O) -
_{- (CF 2 CF 2 O)} -
_{- (CF 2 CF 2 CF 2} O) -
_{- (CF (CF 3) CF} 2 O) - 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.

A fluorine-containing (α-substituted) acrylic compound is a fluorine-containing (α-substituted) acrylic compound described in any one of claims 7 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 compound having a (meth) acrylic group and a reactive group with a copolymer obtained by polymerizing a polymer. . 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.   In the step (iii), after the step (ii), the substrate coated with the composition and dried is stored at a temperature lower than 50 ° C., and the temperature of the composition is lower than 50 ° C. Item 16. The method according to any one of Items 1 to 15.   The method according to any one of claims 1 to 16, wherein in the step (iii), the temperature of the composition is in the range of 0 to 40 ° C. The method of any one of Claims 1-17 whose base material is a resin molding, a film, or glass.