JP6224414B2 - Curable composition and substrate - Google Patents

Description

  The present invention relates to a curable composition and a substrate surface-treated with the curable composition.

  Conventionally, a hard coat treatment has been widely used as a means for protecting the surface of a resin molded body or the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded body to make it difficult to be damaged. As a material constituting the hard coat layer, a thermosetting resin, an ultraviolet ray or electron beam curable resin, and a resin having both functions are often used.

  On the other hand, with the expansion of the application field of resin moldings and the trend toward higher added value, there is an increasing demand for higher functionality for the hard coat layer, and one of these is the need to impart antifouling properties to the hard coat layer. ing. This imparts water repellency, oil repellency and the like to the surface of the hard coat layer so that it is difficult to stain or can be easily removed even when soiled.

  As a method of imparting antifouling properties to the hard coat layer, a method of applying and fixing a fluorine-containing antifouling agent to the surface of the hard coat layer once formed is widely used, but the fluorine-containing curable component is cured. A method of simultaneously forming a hard coat layer and imparting antifouling properties by adding it to the previous curable resin composition and coating and curing it has also been studied. For example, Patent Document 1 discloses a means for forming a hard coat layer imparted with an antifouling property by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition. The present inventors have been developing various fluorine compounds that can impart antifouling properties to such curable resin compositions, and have proposed photocurable fluorine compounds (Patent Documents 2 to 5).

  These fluorine compounds for imparting antifouling properties are dissolved in the non-fluorinated hard coat composition (curing component), which is the main component during coating, and float and cure on the surface during coating and drying. To form a fluorine component film. However, a fluorine compound that improves the ease of floating on the surface and enhances the antifouling property has a high fluorine content and a low solubility in a non-fluorinated hard coat composition. There was a drawback. Therefore, there has been a demand for a method capable of enhancing the antifouling ability of the fluorine compound and maintaining the solubility in the non-fluorinated hard coat composition.

JP-A-6-221945 JP 2010-053114 A JP 2010-138112 A JP 2010-285501 A JP 2011-241190 A

  The present invention has been made in view of the above circumstances, and a cured resin layer having excellent compatibility between the curable component of the non-fluorinated hard coat composition and the fluorine compound, and excellent antifouling properties and scratch resistance. It aims at providing the curable composition which can be formed. Moreover, it aims at providing the base material surface-treated with this curable composition.

（式中、Ｒｆは炭素数１〜３のパーフルオロアルキル基と酸素原子によって構成される分子量４００〜２０，０００の１価又は２価のパーフルオロポリエーテル基であり、Ｑはａ＋１個以上のケイ素原子を含むａ＋１価の連結基であり、Ｚ^１は炭素数１〜２０で酸素原子、窒素原子、及びケイ素原子を含んでいてもよい２価の炭化水素基であり、環状構造を含んでいてもよい。Ｚ^２は炭素数１〜３０で酸素原子及び窒素原子を含んでいてもよい２価の炭化水素基であり、環状構造を含んでいてもよい。Ｚ^３は炭素数１〜２０で酸素原子及び窒素原子を含んでいてもよいｂ＋１価の炭化水素基であり、環状構造を含んでいてもよい。Ｒ^１は水素原子又は炭素数１〜６の炭化水素基であり、環状構造を含んでいてもよく、Ｒ^２及びＲ^３は水素原子又はフッ素原子であり、Ｒ^４は水素原子、フッ素原子、炭素数１〜６の炭化水素基のいずれかであり、環状構造を含んでいてもよい。ａは１〜１０の整数であり、ｂは１〜５の整数であり、ｃは１又は２である。）
（Ｂ）下記一般式（２）で示される化合物、

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ^２、Ｚ^３、及びｂは前記と同様である。）
を含有する硬化性組成物を提供する。 In order to solve the above problems, in the present invention,
(A) a fluorine-containing acrylate compound represented by the following general formula (1), and

(In the formula, Rf is a monovalent or divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkyl group having 1 to 3 carbon atoms and an oxygen atom, and Q is a + 1 or more. A + 1 linking group containing a silicon atom, Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing an oxygen atom, a nitrogen atom and a silicon atom, and containing a cyclic structure Z ² is a divalent hydrocarbon group having 1 to 30 carbon atoms and optionally containing an oxygen atom and a nitrogen atom, and may contain a cyclic structure, and Z ³ has 1 to 20 carbon atoms. A b + 1 valent hydrocarbon group which may contain an oxygen atom and a nitrogen atom, and may contain a cyclic structure, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a cyclic structure; may comprise, ^{R 2} and ^{R 3} are hydrogen Komata is a fluorine atom, R ⁴ is a hydrogen atom, a fluorine atom, is either a hydrocarbon group having 1 to 6 carbon atoms, which may contain a cyclic structure .a is an integer of from 1 to 10, b is an integer of 1 to 5, and c is 1 or 2.)
(B) a compound represented by the following general formula (2),

(Wherein R ¹ , R ² , R ³ , R ⁴ , Z ² , Z ³ , and b are the same as described above.)
The curable composition containing this is provided.

  With such a curable composition, the compatibility between the curable component of the non-fluorinated hard coat composition and the fluorine compound is good, and a cured resin layer excellent in antifouling property and scratch resistance is formed. It becomes the curable composition which can be obtained.

  Moreover, it is preferable at this time that the said curable composition contains active energy ray-curable components other than the said (A) component and the said (B) component as (C) component.

  By containing such (C) component, it becomes a curable composition hardened | cured with an active energy ray.

  Moreover, at this time, it is preferable that the said curable composition contains a photoinitiator as (D) component and hardens | cures with an ultraviolet-ray.

  By containing such (D) component, it becomes a curable composition hardened | cured with an ultraviolet-ray.

  Furthermore, in this invention, the base material which apply | coated and hardened the said curable composition on the surface is provided.

  If it is such a base material, it will become a base material in which the cured resin layer which was transparent and smooth on the surface, and was excellent in antifouling property and abrasion resistance was formed.

  As described above, the curable composition of the present invention has good compatibility between the curable component of the non-fluorinated hard coat composition and the fluorine compound, and can be cured by active energy rays such as ultraviolet rays. It becomes a curable composition which can form the cured resin layer excellent in antifouling property and abrasion resistance. In addition, by applying and curing such a curable composition on the surface of the substrate, a substrate having a cured resin layer that is transparent and smooth on the surface and excellent in antifouling property and scratch resistance is obtained. Can do.

  As described above, there is an increasing demand for higher functionality for the hard coat layer, and development of an antifouling property imparting ability of the fluorine compound and development of the ability to maintain solubility in the non-fluorinated hard coat composition. It was sought after.

  As a result of intensive studies on the above problems, the present inventor has added a fluorine compound as the component (A) to the non-fluorinated hard coat composition, so that the cured film has water repellency, oil repellency, that is, antifouling property. It is found that the compatibility of the curable component of the non-fluorinated hard coat composition and the fluorine compound of the component (A) can be improved by including the compound of the component (B). Was completed.

（式中、Ｒｆは炭素数１〜３のパーフルオロアルキル基と酸素原子によって構成される分子量４００〜２０，０００の１価又は２価のパーフルオロポリエーテル基であり、Ｑはａ＋１個以上のケイ素原子を含むａ＋１価の連結基であり、Ｚ^１は炭素数１〜２０で酸素原子、窒素原子、及びケイ素原子を含んでいてもよい２価の炭化水素基であり、環状構造を含んでいてもよい。Ｚ^２は炭素数１〜３０で酸素原子及び窒素原子を含んでいてもよい２価の炭化水素基であり、環状構造を含んでいてもよい。Ｚ^３は炭素数１〜２０で酸素原子及び窒素原子を含んでいてもよいｂ＋１価の炭化水素基であり、環状構造を含んでいてもよい。Ｒ^１は水素原子又は炭素数１〜６の炭化水素基であり、環状構造を含んでいてもよく、Ｒ^２及びＲ^３は水素原子又はフッ素原子であり、Ｒ^４は水素原子、フッ素原子、炭素数１〜６の炭化水素基のいずれかであり、環状構造を含んでいてもよい。ａは１〜１０の整数であり、ｂは１〜５の整数であり、ｃは１又は２である。）
（Ｂ）下記一般式（２）で示される化合物、

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ^２、Ｚ^３、及びｂは前記と同様である。）
を含有する硬化性組成物である。 That is, the present invention
(A) a fluorine-containing acrylate compound represented by the following general formula (1), and

(In the formula, Rf is a monovalent or divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkyl group having 1 to 3 carbon atoms and an oxygen atom, and Q is a + 1 or more. A + 1 linking group containing a silicon atom, Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing an oxygen atom, a nitrogen atom and a silicon atom, and containing a cyclic structure Z ² is a divalent hydrocarbon group having 1 to 30 carbon atoms and optionally containing an oxygen atom and a nitrogen atom, and may contain a cyclic structure, and Z ³ has 1 to 20 carbon atoms. A b + 1 valent hydrocarbon group which may contain an oxygen atom and a nitrogen atom, and may contain a cyclic structure, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a cyclic structure; may comprise, ^{R 2} and ^{R 3} are hydrogen Komata is a fluorine atom, R ⁴ is a hydrogen atom, a fluorine atom, is either a hydrocarbon group having 1 to 6 carbon atoms, which may contain a cyclic structure .a is an integer of from 1 to 10, b is an integer of 1 to 5, and c is 1 or 2.)
(B) a compound represented by the following general formula (2),

(Wherein R ¹ , R ² , R ³ , R ⁴ , Z ² , Z ³ , and b are the same as described above.)
Is a curable composition containing

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A) component]
Component (A) in the curable composition of the present invention imparts antifouling performance to the cured resin layer, and is a fluorine-containing acrylate compound represented by the following general formula (1).

In the general formula (1), Rf is a monovalent or divalent molecule having a molecular weight of 400 to 20,000, preferably 1,000 to 10,000, composed of a perfluoroalkyl group having 1 to 3 carbon atoms and an oxygen atom. A perfluoropolyether group having particularly the following structure as a repeating unit is preferred.

Rf may be any one of these structures, or a random or block polymer composed of a plurality of structures. As Rf having such a structure, for example, the following structures can be given as particularly preferred examples.
Incidentally, bonds of Rf are all bound to ^{Z 1.}

In the general formula (1), Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing an oxygen atom, a nitrogen atom, and a silicon atom, and may contain a cyclic structure.
Examples of particularly preferred structures for Z ¹ include the following.

In the general formula (1), Z ² is a divalent hydrocarbon group having 1 to 30 carbon atoms and optionally containing an oxygen atom and a nitrogen atom, and may contain a cyclic structure.
Examples of particularly preferred structures for Z ² include the following.

In the above general formula (1), Z ³ is a b + 1 valent hydrocarbon group having 1 to 20 carbon atoms and optionally containing an oxygen atom and a nitrogen atom, and may contain a cyclic structure. In addition, b is an integer of 1-5, and 1 or 2 is particularly preferable.
The following can be raised as a particularly preferable structure for Z ³ .

ここで、Ｔはａ＋１価の連結基であり、ａは上記と同様であり、ｄは１〜５であり、破線は結合手を示す。Ｔの例としては、例えば以下のものが例示される。

In the general formula (1), Q is an a + 1 valent linking group containing a + 1 or more silicon atoms and may have a cyclic structure. Preferred examples of such Q include an a + 1 valent linking group comprising a siloxane structure having a + 1 silicon atoms, a halogen-substituted or unsubstituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. It is done. Specifically, the following structures are specifically shown as preferable structures. However, a is an integer of 1-10 independently, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-4.

Here, T is an a + 1 valent linking group, a is the same as described above, d is 1 to 5, and a broken line indicates a bond. Examples of T include the following.

In the general formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and may include a cyclic structure. Particularly preferred as R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are a hydrogen atom or a fluorine atom. R ⁴ is any one of a hydrogen atom, a fluorine atom, and a hydrocarbon group having 1 to 6 carbon atoms, and may include a cyclic structure, and a hydrogen atom or a fluorine atom is particularly preferable.

  In said general formula (1), a is an integer of 1-10 independently, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-4. b is an integer of 1 to 5, and 1 or 2 is particularly preferable. c is 1 or 2.

（式中、Ｒｆ、Ｚ^１、Ｑ、ａ、及びｃは上記と同様であり、［ ］で括られたａ個の水素原子はすべて連結基Ｑ中のケイ素原子と結合している。）

（式中、Ｒ^１及びＺ^２は上記と同様である。）

（式中、Ｒｆ、Ｚ^１、Ｚ^２、Ｑ、Ｒ^１、ａ、及びｃは上記と同様である。） The component (A) is not particularly limited in its synthesis method. For example, a fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (3) (hereinafter referred to as fluoropolyether) Compound (3)) and an alcohol represented by the following general formula (4) (hereinafter referred to as alcohol (4)) are bonded by a hydrosilylation (addition) reaction, and an a × c valence represented by the following general formula (5) is obtained. A fluorine-containing alcohol (hereinafter, fluorine-containing alcohol (5)) is synthesized.

(In the formula, Rf, Z ¹ , Q, a, and c are the same as described above, and all a hydrogen atoms enclosed in [] are bonded to the silicon atom in the linking group Q.)

(In the formula, R ¹ and Z ² are the same as above.)

(In the formula, Rf, Z ¹ , Z ² , Q, R ¹ , a, and c are the same as above.)

  In the addition reaction, the fluoropolyether compound (3) and the alcohol (4) are mixed, and the reaction is carried out at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. in the presence of a platinum group metal-based addition reaction catalyst. Desirably, it is desirable to react 0.9-5.0 mole times of alcohol (4) with respect to the a hydrogen atoms enclosed by [] in the fluoropolyether compound (3). With such an amount, the progress of the dehydrogenation reaction by the hydrogen atom in the fluoropolyether compound (3) and the hydroxyl group in the alcohol (4) can be suppressed.

  The above addition reaction can be carried out without a solvent, but may be diluted with a solvent as necessary. At this time, a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluent solvent. However, the boiling point is higher than the target reaction temperature and does not inhibit the reaction, and the fluorine-containing product generated after the reaction. The alcohol (5) is preferably soluble at the reaction temperature. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable. Hexafluoride is preferred.

  As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferable, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum or the like supported on activated carbon can be suitably used. The compounding amount of the catalyst is preferably such that the amount of metal contained is 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 ppm by mass with respect to compound (3).

（式中、Ｚ^３、Ｒ^２、Ｒ^３、Ｒ^４、及びｂは上記と同様である。） Next, by forming a urethane bond with the fluorine-containing alcohol (5) thus obtained and the isocyanate compound represented by the following general formula (6) (hereinafter, isocyanate compound (6)), the component (A) A fluorine-containing acrylate compound can be synthesized.

(In the formula, Z ³ , R ² , R ³ , R ⁴ , and b are the same as above.)

The reaction of the fluorinated alcohol (5) and the isocyanate compound (6) is carried out in a dry atmosphere in air or an inert gas (N ₂ , Ar, etc.) at a reaction temperature of 0 to 120 ° C., preferably 20 to 100 ° C. The reaction can be carried out by mixing both under the conditions of 0.5 to 48 hours, preferably 1 to 4 hours. Moreover, reaction of a fluorine-containing alcohol (5) and an isocyanate compound (6) can also be performed by 1 type, respectively, and can also be performed combining two or more.

  The reaction ratio of the fluorinated alcohol (5) and the isocyanate compound (6) is such that all the hydroxyl groups in the fluorinated alcohol (5) are reacted with the isocyanate groups in the isocyanate compound (6). It is preferable to use the isocyanate compound (6) so that the amount of the isocyanate group is equal to or more than the number of moles of the hydroxyl group. Therefore, when the amount of hydroxyl groups in the fluorinated alcohol (5) contained in the reaction system is 1 mol, the amount of isocyanate groups in the isocyanate compound (6) is 1.0 to 3.0 mol, particularly 1.0 to 3.0 mol. It is preferable to carry out the reaction at a ratio of 2.0 mol. When the unreacted isocyanate compound (6) remains, it may be removed by a known method such as distillation under reduced pressure.

  In the urethane bond formation reaction, an appropriate catalyst may be added to increase the reaction rate. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate, tin compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and other titanates or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxy Monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate) Over G), although zirconium tetraacetyl acetonate, zirconium chelate compound and the like, these are not limited to one type thereof may be used as a mixture of two or more kinds. The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.

  Moreover, you may dilute with a suitable solvent as needed and may react. As such a solvent, any solvent that does not react with an isocyanate group or a hydroxyl group can be used without particular limitation. Specifically, ethers such as tetrahydrofuran, diisopropyl ether, and dibutyl ether, acetone, methyl ethyl ketone, and methyl butyl ketone. And ketones such as methyl isobutyl ketone and cyclohexanone.

ここで、上記一般式（２）中のＺ^２、Ｚ^３、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びｂは、上述の一般式（１）のものと同様である。 [Component (B)]
The component (B) in the curable composition of the present invention is a phase between the fluorinated acrylate compound as the component (A) described above and the curable component of the non-fluorinated hard coat composition such as the component (C) described later. It is a compound which improves solubility and is represented by the following general formula (2).

Here, Z ² , Z ³ , R ¹ , R ² , R ³ , R ⁴ , and b in the general formula (2) are the same as those in the general formula (1).

Examples of the component (B) include the following.

The component (B) is not particularly limited in its synthesis method. For example, the alcohol represented by the following general formula (4) used in the synthesis of the above component (A) and the following general formula (6) ) To form a urethane bond with an isocyanate compound.

  The synthesis method is the same as the reaction of the fluorinated alcohol (5) and the isocyanate compound (6) at the time of synthesizing the component (A). For example, in the synthesis of the fluorinated alcohol (5) While the surplus alcohol (4) present is present, an isocyanate compound (6) appropriately added to the amount of alcoholic hydroxyl group contained in the alcohol (4) and the fluorinated alcohol (5) is added, and the components (A) and (B ) Component may be synthesized, and the alcohol (4) used in the synthesis of the component (A), the alcohol (4) having a structure other than the isocyanate compound (6), and the isocyanate compound (6) are used ( A composition comprising the component B) may be used. The combination of these components (A) and (B) may be a single compound or a combination of a plurality of compounds.

[Component (C)]
Moreover, the curable composition of this invention contains the curable composition hardened | cured by an active energy ray by containing active energy ray-curable components other than (A) component and (B) component as (C) component, can do.
The active energy ray curable component of the component (C) used as appropriate in the present invention is a curable component of the non-fluorinated hard coat composition, and corresponds to the structure of the component (A) and component (B) described above. It is something that does not.

  As such component (C), any component can be used as long as it can be mixed with component (A) and component (B) and can be cured, but acrylates are particularly preferred. Preferably, 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) acryloyloxime ) Ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) ) 2-6 functional (meth) acrylic compounds such as acrylates, epoxy acrylates obtained by adding these (meth) acrylic compounds to ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, and acrylic resins. And those containing a copolymer having a (meth) acryloyl group introduced into the side chain of the acrylate copolymer.

  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 diisocyanate And urethane acrylates obtained by reacting 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.

[(D) component]
Moreover, the curable composition of this invention can be made into the curable composition hardened | cured by an ultraviolet-ray by containing a photoinitiator as (D) component.
(D) component in this invention is a photoinitiator, and if it can harden an acrylic compound by ultraviolet irradiation, it will not specifically limit. The structure of the ultraviolet curable compound containing no fluorine is not particularly limited, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl- Phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -One, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2 -(Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butano 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- (O-acetyloxime), 2-hydroxy-1 -{4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and the like may be mentioned alone or in combination of two or more.

  In the curable composition of the present invention, the blending amount of each component may be appropriately determined according to the desired water repellency, oil repellency, solubility of the composition, curing conditions, and the like. (A) Component, (B) The mixing ratio of the component, the component (C), and the component (D) is not particularly limited. For example, the component (B) is preferably 0.0001 to 0.5 parts by mass with respect to 1 part by mass of the component (A), More preferably, it is 0.01-0.1 mass part. When the component (C) is included, the amount of the component (C) is preferably 1 to 10,000 parts by weight, more preferably 5 to 1,000 parts by weight with respect to 1 part by weight of the component (A). The amount is particularly preferably 10 to 200 parts by mass. Furthermore, when using (D) component, the compounding quantity of (D) component is 0.1 when the total amount of (A) component, (B) component, and (C) component is 100 mass parts. -10 mass parts is preferable, Most preferably, it is 0.5-5 mass parts.

[Other additives]
The curable composition of the present invention 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, and a surfactant depending on the purpose. Further, a colorant, a filler, and the like can be blended.
Moreover, various hard coat agents in which the component (B) and the component (C) are blended are commercially available from various companies. The curable composition of the present invention may be obtained by adding a fluorine-containing (α-substituted) acrylate compound as the component (A) to such a 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. Also, even when using commercially available hard coat agents, depending on the purpose, organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants An agent, a surfactant, a colorant, a filler, and the like can 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 used individually by 1 type, and 2 or more types may be mixed and used for it. Although the usage-amount of a solvent is not restrict | limited in particular, 50-10,000 mass parts are preferable with respect to a total of 100 mass parts of (A)-(D) component, and become 100-1,000 mass parts especially. Such an amount is preferred.

  In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited and may be known ones. Can be used.

  Although the hardening method of the curable composition of this invention is not specifically limited, For example, when (C) component is contained, it can be hardened by an active energy ray, and also contains the photoinitiator of (D) component. In the case, it can be cured by ultraviolet rays.

  As described above, the curable composition of the present invention has good compatibility between the curable component of the non-fluorinated hard coat composition and the fluorine compound, and can be cured by active energy rays such as ultraviolet rays. It becomes a curable composition which can form the cured resin layer excellent in antifouling property and abrasion resistance.

  Furthermore, in this invention, the base material which apply | coated and hardened the curable composition of this invention mentioned above on the surface is provided. As described above, when the curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of the substrate. 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 becomes difficult to adhere dirt due to human fat such as fingerprints, sebum, sweat, cosmetics, etc., and a hard coat surface excellent in wiping property can be given to the substrate. For this reason, the curable composition of this invention can provide the coating film or protective film with respect to the surface of the base material (article) which a human body may touch and may be polluted with human fat, cosmetics, etc.

  The cured film (cured resin layer) formed using the curable composition of the present invention is a tablet computer, notebook PC, mobile phone, portable (communication) information terminal, digital media player, electronic book reader, etc. Cases of various devices that can be carried around: various flat panel displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, CRTs, and toner-based displays And display operation equipment surfaces such as TV screens, car exteriors, glossy surfaces of pianos and furniture, surfaces of building stones such as marble, decorative building materials around water such as toilets, baths, and washrooms, protective glass for art displays , Show window, showcase Covers for photo frames, watches, glass for automobile windows, windows for trains, aircraft, etc., transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlights and tail lamps, and various mirror members 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 curable composition of the present invention includes optical recording media such as magneto-optical disks and optical disks; spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, It is also useful as a surface protection film for optical parts and optical devices such as antireflection films, optical fibers and optical couplers.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these.

（Ａ−２）成分

The structures of the component (A) and the component (B) blended in the compositions of Examples and Comparative Examples are shown below.
[(A) component]
(A-1) Component

(A-2) component

（Ｂ−２）成分

[Component (B)]
(B-1) Component

(B-2) Component

[Evaluation of compatibility between curable component of non-fluorinated hard coat composition and fluorine compound]
1,6-Hexanediol diacrylate (hereinafter referred to as (C-1) component) which is a non-fluorinated active energy ray-curable component as the (A) component, (B) component, and (C) component. Were mixed in the amounts shown in Table 1 below to prepare a curable composition. The results obtained by measuring the turbidity of each composition obtained with a turbidimeter (2100N manufactured by HACH) are also shown in Table 1.

  As shown in Table 1, in Example 1, Example 2 and Example 3 containing the component (B) in addition to the component (A) and the component (C-1), the comparison not containing the component (B) Turbidity was low compared with Example 1 and Comparative Example 2, and the compatibility of the component (A) and the component (C-1) was good.

[Evaluation of antifouling properties]
Component (A), component (B), and tetrafunctional acrylate (EBECRYL 40, manufactured by Daicel Cytec Inc .; hereinafter referred to as component (C-2)) as component (C), and 1-hydroxy as component (D) Cyclohexyl phenyl ketone and 2-propanol as a solvent were mixed in the amounts shown in Table 2 below to prepare a curable composition.

Each of the prepared compositions was placed on a polycarbonate substrate with a 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, the coating surface is irradiated with ultraviolet rays with an integrated irradiation amount of 1,600 mJ / cm ² in a nitrogen atmosphere. The object was cured. The appearance, water contact angle, oleic acid contact angle, and magic repellent property of the obtained cured film were evaluated and measured.

(Evaluation and measurement method)
1) Appearance evaluation of cured film It evaluated by visual observation.
2) Water contact angle measurement Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.
3) Measurement of oleic acid contact angle Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 7 μL droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.
4) Evaluation of magic repellency A straight line was drawn on the surface of the cured film with a magic pen (Sebra Hi-Maky Bold), and the repellency was evaluated by visual observation.

As shown in Table 3, Example 4 and Example 5 containing the component (A) and the component (B) in addition to the component (C-2) are transparent and smooth, and have water repellency and oil repellency. That is, a cured film having excellent antifouling properties could be obtained.
On the other hand, in Comparative Example 3 and Comparative Example 4 that do not contain the component (B), the component (A) contains water repellency and oil repellency, but the compatibility between the component (A) and the component (C-2). When it was hardened, it became a cloudy yuzu skin-like cured film. Furthermore, in Comparative Example 5 containing neither component (A) nor component (B), a cured film having sufficient water repellency and oil repellency could not be obtained.

  As described above, the curable composition of the present invention has good compatibility between the curable component of the non-fluorinated hard coat composition and the fluorine compound, and can be cured by active energy rays such as ultraviolet rays. It became clear that it becomes a curable composition which can form the cured resin layer excellent in antifouling property.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (3)

(A) a fluorine-containing acrylate compound represented by the following general formula (1),

(In the formula, Rf is a monovalent or divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkyl group having 1 to 3 carbon atoms and an oxygen atom, and Q is a + 1 or more. A + 1 linking group containing a silicon atom, Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing an oxygen atom, a nitrogen atom and a silicon atom, and containing a cyclic structure Z ² is a divalent hydrocarbon group having 1 to 30 carbon atoms and optionally containing an oxygen atom and a nitrogen atom, and may contain a cyclic structure, and Z ³ has 1 to 20 carbon atoms. A b + 1 valent hydrocarbon group which may contain an oxygen atom and a nitrogen atom, and may contain a cyclic structure, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a cyclic structure; may comprise, ^{R 2} and ^{R 3} are hydrogen Komata is a fluorine atom, R ⁴ is a hydrogen atom, a fluorine atom, is either a hydrocarbon group having 1 to 6 carbon atoms, which may contain a cyclic structure .a is an integer of from 1 to 10, b is an integer of 1 to 5, and c is 1 or 2.)
(B) a compound represented by the following general formula (2), and

(Wherein R ¹ , R ² , R ³ , R ⁴ , Z ² , Z ³ , and b are the same as described above.)
(C) an active energy ray-curable component other than the component (A) and the component (B),
Containing
The component (C) is a curable component of the non-fluorinated hard coat composition , and the (meth) acryloyl is added to the side chain of the bifunctional to hexafunctional (meth) acrylic compound, epoxy acrylate, or acrylate copolymer. Group-introduced copolymer, urethane acrylate, reaction product of polyisocyanate and hydroxyl group-containing (meth) acrylate, polyisocyanate and terminal diol polyester and hydroxyl group-containing (meth) acrylate reaction product, polyol One or two or more non-fluorinated compounds selected from a reaction product of polyisocyanate, which is a reaction product of a diisocyanate with excess diisocyanate, and a (meth) acrylate having a hydroxyl group, and monofunctional acrylates A curable composition characterized by that.   The curable composition according to claim 1, wherein the curable composition contains a photopolymerization initiator as a component (D) and is cured by ultraviolet rays.   A substrate comprising the curable composition according to claim 1 or 2 applied to a surface and cured.