JP6261247B2 - Active energy ray-curable resin composition, coating agent composition using the same, and cured coating film - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition, a coating agent composition, and a cured coating film. More specifically, the present invention relates to antifouling performance (contamination resistance, fingerprint wiping property and durability thereof), cured coating. The present invention relates to an active energy ray-curable resin composition capable of obtaining a coating layer having excellent film characteristics (appearance, hardness, scratch resistance).

  If dirt such as fingerprints adheres to the screen of devices such as displays, monitors, and touch panels, and electrical appliances such as mobile phones, the transparency of the screen and the clarity of the screen may deteriorate, or the aesthetics may be impaired. I will. Therefore, various methods for wiping off dirt have been studied, and a method for overcoating a coating agent has been studied in order to improve the adhesion prevention and dirt removal performance of dirt.

  As a method for improving the antifouling property (dirt adhesion preventing property and dirt removing property) of the coating layer, a fluorine structure or silicone is used as a coating agent for the purpose of improving the water / oil repellency of the coating layer. A method of introducing a structure is known, and Patent Document 1 discloses a polysiloxane structure in which a silicone structure is introduced as a coating agent using a urethane acrylate compound widely used as a coating agent for hard coat applications. An active energy ray-curable resin composition obtained by blending a reactive fluorine-containing compound having a specific structure with a containing urethane (meth) acrylate compound is described.

Japanese Unexamined Patent Publication No. 2012-3260

  However, in the technique disclosed in Patent Document 1, an excellent antifouling performance is obtained by synergistically exhibiting the antifouling performance due to the polysiloxane structure and the antifouling performance of the fluorine-containing compound. Although the appearance at the time of blending the composition and the appearance of the cured coating film are also excellent, if the wiping of fingerprints etc. is repeated for a long time after forming the coating layer, the antifouling performance tends to decrease, When used in fields where higher fingerprint wiping properties are required, there is still room for improvement, and further improvement in antifouling performance has been demanded.

  Therefore, in the present invention, under such a background, the antifouling performance such as the antifouling property (water repellency, oil repellency) and the soil removability (fingerprint wiping property) is excellent, and the cured coating film has An object of the present invention is to provide an active energy ray-curable resin composition that is excellent in properties (coating appearance, coating hardness, scratch resistance), and useful for forming a coating layer that maintains antifouling performance. Furthermore, it aims at providing the coating agent composition and cured film which use it.

  However, as a result of intensive studies in view of such circumstances, the present inventors have made a polysiloxane structure-containing urethane (meth) acrylate compound having a certain antifouling performance into a monomer having a specific structure, particularly 4 or more ( An active energy ray-curable resin composition obtained by blending a reactive fluorine-containing compound obtained by polymerizing a fluorine monomer containing a (meth) acryloyl group has excellent antifouling properties such as oil repellency and fingerprint wiping properties Furthermore, the present inventors have found that the antifouling performance is sustained and have completed the present invention.

〔一般式（Ｉ）中、
Ｒ¹は、単結合、または炭素原子数１〜５のアルキレン基
Ｒ²は、２個以上の（メタ）アクリロイル基を有する一価の有機基
Ｘ₁は、炭素原子数１〜５のペルフルオロ基
ｍ＋ｎは、５〜５０の整数
である。〕

〔一般式（ＩＩ）中、
Ｒ ³ は、炭素原子数が１〜５０の二価の飽和脂肪族炭化水素基を含有する二価の有機基であり、ハロゲン原子によって置換されていてもよい。
Ｒ ⁴ は、水素原子またはメチル基である。
Ｘ ₂ は、下記の一般式（３）または（４）で示される基である。〕

〔一般式（３）および（４）中、＊は結合部位を示す。〕

〔一般式（ＩＩＩ）中、
Ｒ ⁵ は、炭素原子数が１〜１００の二価の飽和脂肪族炭化水素基を含有する二価の有機基であり、ハロゲン原子によって置換されていてもよく、該飽和脂肪族炭化水素基にはエーテル結合、エステル結合、アミド結合またはアリール基を有していてもよい。
Ｒ ⁶ は、水素原子またはメチル基である。〕

〔一般式（ＩＶ）中、
Ｒ ⁷ は、水素原子またはハロゲン原子によって置換されていてもよい炭素原子数１〜５０の一価の有機基である。
Ｒ ⁸ は、水素原子またはメチル基である。〕

〔一般式（Ｖ）中、
Ｒ ⁹ は、炭素原子数が２〜１０の二価または三価の飽和脂肪族炭化水素基であり、該飽和脂肪族炭化水素基はエーテル結合を有していてもよい。
Ｒ ¹⁰ は、水素原子またはメチル基である。
ｐは１または２の整数である。〕
That is, the gist of the present invention containing polysiloxane structure-containing urethane (meth) acrylate compound (A), and reactivity fluorine-containing compound (B),
An isocyanate represented by the following general formula (V) is obtained by copolymerizing the reactive fluorine-containing compound (B) with a polymerization component containing monomers represented by the general formulas (I) to (IV). The present invention relates to an active energy ray-curable resin composition, which is a reactive fluorine-containing compound obtained by reacting a group-containing (meth) acrylate , and further uses such an active energy ray-curable resin composition. And a cured coating film.

[In general formula (I),
R ¹ is a single bond or a C 1-5 alkylene group R ² is a monovalent organic group X ₁ having 2 or more (meth) acryloyl groups is a C 1-5 perfluoro group m + n is an integer of 5-50. ]

[In general formula (II),
R ³ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms, and may be substituted with a halogen atom.
R ⁴ is a hydrogen atom or a methyl group.
X ₂ is a group represented by the following general formula (3) or (4). ]

[In General Formulas (3) and (4), * indicates a binding site. ]

[In general formula (III),
R ⁵ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a halogen atom, and the saturated aliphatic hydrocarbon group includes May have an ether bond, an ester bond, an amide bond or an aryl group.
R ⁶ is a hydrogen atom or a methyl group. ]

[In general formula (IV),
R ⁷ is a monovalent organic group having 1 to 50 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
R ⁸ is a hydrogen atom or a methyl group. ]

[In general formula (V),
R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, and the saturated aliphatic hydrocarbon group may have an ether bond.
R ¹⁰ is a hydrogen atom or a methyl group.
p is an integer of 1 or 2. ]

The active energy ray-curable resin composition of the present invention is obtained by copolymerizing a polysiloxane structure-containing urethane (meth) acrylate compound and a polymerization component containing the monomers represented by the above general formulas (I) to (IV). Since the copolymer contains a reactive fluorine-containing compound obtained by reacting an isocyanate group-containing (meth) acrylate represented by the following general formula (V), the coating is cured by irradiation with active energy rays. When used as a layer, it is excellent in antifouling performance such as antifouling property and dirt removability, and in particular, the antifouling performance is excellent in the sustainability of the fingerprint wiping effect.
Further, polysiloxane structure-containing urethane (meth) acrylate compound and, is excellent in the above reactivity fluorine-containing compatibility with the compound having a specific structure, but also excellent in appearance when used as a blending time of appearance and the cured coating film It is.

The present invention is described in detail below.
The active energy ray-curable resin composition of the present invention has a reactivity obtained by polymerizing a polysiloxane structure-containing urethane (meth) acrylate compound (A) and a polymerization component containing the monomer represented by the general formula (I). It contains the fluorine-containing compound (B) as an essential component.
First, the polysiloxane structure-containing urethane (meth) acrylate compound (A) (hereinafter sometimes referred to as “urethane (meth) acrylate compound (A)”) will be described.

The polysiloxane structure-containing urethane (meth) acrylate compound (A) only needs to contain a polysiloxane structure in its structure, and in particular, as a component of the urethane (meth) acrylate compound, the following general formula It is a urethane (meth) acrylate compound obtained by using a polysiloxane compound having hydroxyl groups at both ends represented by (1) and a polysiloxane compound having hydroxyl groups at one end represented by the following general formula (2). It is preferable.
In addition, the said urethane (meth) acrylate type compound (A) may have a structure site | part derived from both general formula (1) and (2).

〔式中、Ｒ¹、Ｒ³は炭化水素基又はヘテロ原子を含む有機基を示し、Ｒ²はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、ａは１以上の整数であり、ｂ、ｃは１〜３の整数である。〕

[Wherein R ¹ and R ³ represent a hydrocarbon group or an organic group containing a hetero atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more, b and c are integers of 1 to 3. ]

〔式中、Ｒ¹はアルキル基を示し、Ｒ²はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、Ｒ³は炭化水素基又はヘテロ原子を含む有機基を示す。ａは１以上の整数であり、ｂは１〜３の整数である。〕

[Wherein, R ¹ represents an alkyl group, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and R ³ represents a hydrocarbon group or an organic group containing a hetero atom. a is an integer of 1 or more, and b is an integer of 1 to 3. ]

  First, a urethane (meth) acrylate compound (A1) (hereinafter referred to as “urethane (meth) acrylate compound (A1)) obtained by using a polysiloxane compound having hydroxyl groups at both ends represented by the general formula (1). ").) Is explained.

  The urethane (meth) acrylate compound (A1) is a polysiloxane compound (x1) having a hydroxyl group at both ends represented by the general formula (1) (hereinafter referred to as “polysiloxane compound (x1)”). ), A polyvalent isocyanate compound (x2), a hydroxyl group-containing (meth) acrylate compound (x3), and, if necessary, a polyol compound (x4).

In the polysiloxane compound (x1), R ¹ and R ³ in the general formula (1) are a hydrocarbon group or an organic group containing a hetero atom.
As a hydrocarbon group, it is C1-C30 normally, Preferably it is C1-C20, and a bivalent or trivalent hydrocarbon group is mentioned.
Examples of the divalent hydrocarbon group include an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
Examples of the organic group containing a hetero atom include an oxyalkylene group, a polyoxyalkylene group, a polycaprolactone group, and an amino group.

R ² in the general formula (1) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.
As carbon number of a cycloalkyl group, it is C3-C10 normally, Preferably it is 5-8, for example, a cyclopentyl group, a cyclohexyl group, norbornyl group etc. are mentioned.

The alkyl group, cycloalkyl group, and phenyl group may have a substituent. Examples of the substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. In addition, when the substituent has a carbon atom, the carbon atom is not included in the number of carbons defined in the description of R ² above.

  A in general formula (1) is an integer greater than or equal to 1, Preferably it is 5-200, Most preferably, it is an integer of 5-120. b is an integer of 1 to 3, preferably an integer of 1 to 2.

  The weight average molecular weight of the polysiloxane compound (x1) is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. If the weight average molecular weight is too low, the antifouling performance tends to decrease, and if it is too high, the transparency and scratch resistance tend to decrease.

  Specific examples of the polysiloxane compound (x1) represented by the general formula (3) include, for example, “X-22-160AS”, “KF-6001”, “KF-6002”, “ "KF-6003", "Silaplane FM-4411", "Silaplane FM-4421", "Silaplane FM-4425" manufactured by JNC, "XF42-B0970" manufactured by Momentive Performance Materials Japan, "BY 16-004" and "SF 8427" manufactured by Toray Dow Corning, "Macromonomer HK-20" manufactured by Toagosei, "DMS-C21", "DMS-C23" and "DBL" manufactured by GELEST -C31 "," DMS-CA21 "and other products.

  Examples of the polyvalent isocyanate compound (x2) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aromatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanate Alicyclic polyisocyanates such as natomethyl) cyclohexane, trimer compounds or multimer compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.). These can be used alone or in combination of two or more.

  Among these, it is an isocyanate compound having 3 or more isocyanate groups in one molecule, in particular, a polyisocyanate trimer or multimer compound, and the film hardness, scratch resistance, solvent resistance, and bleed. It is more preferable in that the amount of unreacted low molecular weight components that cause the above can be reduced.

Examples of the hydroxyl group-containing (meth) acrylate compound (x3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned. These can be used alone or in combination of two or more.
Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable in that a coating film having high hardness can be obtained.

  Furthermore, you may use a polyol type compound (x4) in the range which does not impair the effect of this invention. Examples of the polyol compound (x4) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, and the like.

  Examples of polyether polyols include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.

  Examples of the polyester-based polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And reactants.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, and the like.
Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  As a weight average molecular weight of a polyol type compound (x4), 50-8,000 are preferable, Especially preferably, it is 50-5,000, More preferably, it is 600-3,000. If the weight average molecular weight of the polyol (x4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if too small, curing shrinkage tends to increase and stability tends to decrease.

The urethane (meth) acrylate compound (A1) preferably has 2 or more ethylenically unsaturated groups, and has 4 or more ethylenically unsaturated groups in terms of hardness of the cured coating film. It is particularly preferable that it has 6 or more ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (A1) contains is 30 normally, Preferably it is 25 or less.

As a manufacturing method of a urethane (meth) acrylate type compound (A1), it is not specifically limited, for example,
(I): Polysiloxane compound (x1), polyvalent isocyanate compound (x2) (polyisocyanate compound (x2) reacted in advance with polyol compound (x4) if necessary), hydroxyl group-containing A method in which the (meth) acrylate compound (x3) is charged and reacted at once;
(B): A polysiloxane compound (x1) and a polyvalent isocyanate compound (x2) (if necessary, a polyvalent isocyanate compound (y2) previously reacted with a polyol compound (x4)) are reacted. And then reacting the hydroxyl group-containing (meth) acrylate compound (x3),
(C): Polyvalent isocyanate compound (x2) (polyisocyanate compound (x2) previously reacted with polyol compound (x4) if necessary) and hydroxyl group-containing (meth) acrylate compound (x3 ), And then reacting the polysiloxane compound (x1),
(D): Polyvalent isocyanate compound (x2) (polyisocyanate compound (x2) previously reacted with polyol compound (y4) if necessary) and hydroxyl group-containing (meth) acrylate compound (x3) ), After reacting a part of the polysiloxane compound (x1), and further reacting the remaining hydroxyl group-containing (meth) acrylate compound (x3),
Among these, the method (b) or (d) is preferable and the method (2) is particularly preferable from the viewpoint of stability of reaction control and compatibility.

  In addition, what is necessary is just to follow the manufacture example of a well-known general urethane type polyol, when making a polyol type compound (x4) and a polyvalent isocyanate type compound (x2) react previously, for example.

  In the method (b), after reacting the hydroxyl group of the polysiloxane compound (x1) with the isocyanate group of the polyvalent isocyanate compound (x2) under the condition that the isocyanate group remains, the polyvalent isocyanate compound is then reacted. The residual isocyanate group of the compound (x2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (x3).

  The reaction molar ratio between the polysiloxane compound (x1) and the polyvalent isocyanate compound (x2) is, for example, that the polysiloxane compound (x1) has two hydroxyl groups and the polyisocyanate compound (x2) has an isocyanate group. Is two polysiloxane compounds (x1): polyisocyanate compounds (x2) 1: 1.1 to 2.2, and the polysiloxane compounds (x1) have two hydroxyl groups. When the polyisocyanate compound (x2) has three isocyanate groups, the polysiloxane compound (x1): polyisocyanate compound (x2) may be about 0.5 to 2.2. .

  In the addition reaction between the reactive organism and the hydroxyl group-containing (meth) acrylate compound (x3), the reaction is terminated when the residual isocyanate group in the reaction system becomes 0.5% by weight or less. ) An acrylate compound (A1) is obtained.

  Moreover, the weight of the structural part derived from the polysiloxane compound (x1) contained in 100 parts by weight of the urethane (meth) acrylate compound (A1) is 0.1 to 80 parts by weight within the above molar ratio range. Preferably there is.

  In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include the same ones as described above.

  In such a reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene An organic solvent such as can be used.

  The reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

  The weight average molecular weight of the urethane (meth) acrylate compound (A1) thus obtained is usually preferably 500 to 50,000, and more preferably 500 to 30,000. When the weight average molecular weight is too small, the curing shrinkage tends to be large and the coating film properties tend to decrease. When the weight average molecular weight is too large, the viscosity becomes high and difficult to handle, and the hardness and scratch resistance of the cured coating film tend to decrease.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (high-performance liquid chromatography (the Showa Denko company make, "Shodex GPC system-11 type | mold")). Exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / book, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) 3 Measured by using this series.
Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described later is measured according to the above method.

The viscosity at 20 ° C. of the 40 wt% methyl isobutyl ketone solution of the urethane (meth) acrylate compound (A1) is preferably 5 to 5,000 mPa · s, more preferably 10 to 2,500 mPa · s, The pressure is preferably 15 to 1,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured using a B-type viscometer.

  As for the said urethane (meth) acrylate type compound (A1), only 1 type may be used independently and 2 or more types may be used together.

  Next, a urethane (meth) acrylate compound (A2) (hereinafter referred to as “urethane (meth) acrylate compound (A2) obtained by using a polysiloxane compound having a hydroxyl group at one end represented by the general formula (2)”. ) ").) Is explained.

  The urethane (meth) acrylate compound (A2) is a polysiloxane compound (y1) having a hydroxyl group at one end represented by the general formula (2) (hereinafter referred to as “polysiloxane compound (y1)”). ), A polyvalent isocyanate compound (y2), a hydroxyl group-containing (meth) acrylate compound (y3), and, if necessary, a polyol compound (y4).

With respect to the polysiloxane compound (y1), R ¹ in the general formula (2) is an alkyl group, and the alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.

R ² in the general formula (2) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.
As carbon number of a cycloalkyl group, it is C3-C10 normally, Preferably it is 5-8, for example, a cyclopentyl group, a cyclohexyl group, norbornyl group etc. are mentioned.

The alkyl group, cycloalkyl group, and phenyl group may have a substituent. Examples of the substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. In the case where the substituent has a carbon atom, said carbon atom shall not included in the number of carbon atoms is specified in the description of the R ^2.

R ³ in the general formula (2) is a hydrocarbon group or an organic group containing a hetero atom.
As a hydrocarbon group, it is C1-C30 normally, Preferably it is C1-C20, and a bivalent or trivalent hydrocarbon group is mentioned.
Examples of the divalent hydrocarbon group include an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
Examples of the organic group containing a hetero atom include an oxyalkylene group, a polyoxyalkylene group, a polycaprolactone group, and an amino group.

  A in general formula (2) is an integer greater than or equal to 1, Preferably it is 5-200, Most preferably, it is an integer of 5-120. b is an integer of 1 to 3, preferably an integer of 1 to 2.

  The weight average molecular weight of the polysiloxane compound (y2) used in the present invention is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. It is preferable. If the weight average molecular weight is too low, the antifouling performance tends to decrease, and if it is too high, the coating film hardness and scratch resistance tend to decrease.

  Specific examples of the polysiloxane compound (y1) represented by the general formula (2) include, for example, “X-22-170BX”, “X-22-170DX”, “X-22-2” manufactured by Shin-Etsu Chemical Co., Ltd. 176DX "," X-22-176F "," Silaplane FM-0411 "," Silaplane FM-0421 "," Silaplane FM-0425 "," Silaplane FM-DA11 "," Silaplane "manufactured by Chisso Corporation Products such as “FM-DA21”, “Silaplane FM-DA26”, and the like.

  Examples of the polyvalent isocyanate compound (y2) include those similar to those exemplified as the polyvalent isocyanate compound (x2) in the description of the urethane (meth) acrylate (A1).

  Examples of the hydroxyl group-containing (meth) acrylate compound (y3) are the same as those exemplified as the hydroxyl group-containing (meth) acrylate compound (x3) in the description of the urethane (meth) acrylate (A1). Is mentioned.

  Furthermore, a polyol compound (y4) may be used as long as the effects of the present invention are not impaired. For example, those exemplified as the polyol compound (x4) in the description of the urethane (meth) acrylate (A1). The same thing is mentioned.

The urethane (meth) acrylate compound (A2) preferably has one or more ethylenically unsaturated groups, and has three or more ethylenically unsaturated groups in terms of the hardness of the cured coating film. It is particularly preferable that it has 6 or more ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (A2) contains is 30 normally, Preferably it is 25 or less.

As a manufacturing method of a urethane (meth) acrylate type compound (A2), it is not specifically limited, for example,
(I): polysiloxane compound (y1), polyvalent isocyanate compound (y2) (polyisocyanate compound (y2) previously reacted with polyol compound (y4) if necessary), hydroxyl group-containing A method in which the (meth) acrylate compound (y3) is charged and reacted in a batch,
(B): A polysiloxane compound (y1) and a polyvalent isocyanate compound (y2) (if necessary, a polyvalent isocyanate compound (x2) previously reacted with a polyol compound (y4)) are reacted. And then reacting the hydroxyl group-containing (meth) acrylate compound (y3),
(C): Polyisocyanate compound (y2) (Polyisocyanate compound (y2) previously reacted with polyol compound (y4) if necessary) and hydroxyl group-containing (meth) acrylate compound (y3) ) And then reacting the polysiloxane compound (y1),
(D): Polyvalent isocyanate compound (y2) (polyisocyanate compound (y2) previously reacted with polyol compound (y4) if necessary) and hydroxyl group-containing (meth) acrylate compound (y3) ), After reacting a part of the polysiloxane compound (y1), and further reacting the remaining hydroxyl group-containing (meth) acrylate compound (y3),
Among these, the method (b) or (2) is preferable, and the method (b) is particularly preferable from the viewpoint of stability of reaction control.

  In addition, what is necessary is just to follow the manufacture example of a well-known general urethane type polyol, when making a polyol type compound (y4) and a polyvalent isocyanate type compound (y2) react previously.

  In the method (b), after reacting the hydroxyl group of the polysiloxane compound (y1) with the isocyanate group of the polyisocyanate compound (y2) under the condition that the isocyanate group remains, the polyisocyanate compound is then reacted. The residual isocyanate group of the compound (y2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (y3).

  The reaction molar ratio of the polysiloxane compound (y1) and the polyvalent isocyanate compound (y2) is, for example, one hydroxyl group of the polysiloxane compound (y1) and the isocyanate group of the polyvalent isocyanate compound (y2). Is two, polysiloxane compound (y1): polyisocyanate compound (y2) 1: about 0.8 to 10, polysiloxane compound (y1) has one hydroxyl group, When the isocyanate group of the polyvalent isocyanate compound (y2) is 3, the polysiloxane compound (y1): polyvalent isocyanate compound (y2) may be about 1: 0.2-5.

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y3), the reaction is terminated when the residual isocyanate group in the reaction system is 0.5% by weight or less, whereby urethane (meta ) An acrylate compound (A2) is obtained.

  The weight of the structural portion derived from the polysiloxane compound (y1) contained in 100 parts by weight of the urethane (meth) acrylate compound (A2) is 0.1 to 80 parts by weight within the above molar ratio range. It is preferable that

  In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin, zinc octoate, Metal salts such as tin octoate, cobalt naphthenate, stannous chloride, stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4 , 0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine, amine catalysts such as N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc. In addition, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, Bismuth sansate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth Examples include bismuth-based catalysts such as bismuth salts of organic acids such as bismuth neodecanoate, bismuth disalicylate, and bismuth digallate. Among them, dibutyltin dilaurate, 1,8-diazabicyclo [5,4,0] Undecene is preferred.

  In such a reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene An organic solvent such as can be used.

  The reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

  The urethane (meth) acrylate compound (A2) thus obtained preferably has a weight average molecular weight of 500 to 50,000, more preferably 500 to 30,000. When the weight average molecular weight is too small, the curing shrinkage tends to be large and the coating film properties tend to decrease. When the weight average molecular weight is too large, the viscosity becomes high and difficult to handle, and the hardness and scratch resistance of the cured coating film tend to decrease.

The viscosity of the urethane (meth) acrylate compound (A2) at 20 ° C. in a 40 wt% methyl isobutyl ketone solution is preferably 5 to 5,000 mPa · s, more preferably 5 to 2,500 mPa · s, and even more preferably 5 It is preferable that it is -10 million mPa * s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured using a B-type viscometer.

  As for the said urethane (meth) acrylate type compound (A2), only 1 type may be used independently and 2 or more types may be used together.

  As the polysiloxane structure-containing urethane (meth) acrylate compound (A), it is preferable to use the urethane (meth) acrylate compound (A1) and / or the urethane (meth) acrylate compound (A2). It is particularly preferable to use urethane (meth) acrylate (A1) in terms of excellent performance.

  Moreover, when using together urethane (meth) acrylate type compound (A1) and (A2), the content rate (weight ratio) of urethane (meth) acrylate type compound (A1) and urethane (meth) acrylate type compound (A2) ) Is preferably (A1) / (A2) = 95/5 to 5/95, particularly preferably (A1) / (A2) = 20/80 to 80/20.

  Next, the reactive fluorine-containing compound (B) will be described.

Reactive fluorine-containing compound (B) in the present invention, the copolymer by copolymerizing a polymerizable component containing a monomer represented by the following following general formula (I) ~ (IV), the following general formula (V) It is characterized by reacting the isocyanate group-containing (meth) acrylate shown , and by having such a structure, it has excellent antifouling performance when used in combination with the urethane (meth) acrylate compound (A). In particular, it is excellent in sustainability in the fingerprint wiping effect.
Hereinafter, the monomers contained in the polymerization component will be described in order.

<Monomer (I)>
It is a monomer represented by the following general formula (I).

In the general formula (I), X ₁ is a perfluoroalkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. The perfluoroalkylene group may be linear or branched, and is preferably linear. Two X ₁ in the formula may be the same or different, preferably the same.

  In general formula (I), perfluoroethyleneoxy groups and difluoromethyleneoxy groups are randomly arranged in square brackets ([]). m + n is an integer of 5-50, preferably an integer of 10-30. m is an integer of 0-50, preferably an integer of 5-20. n is an integer of 0 to 50, preferably an integer of 5 to 15.

In the general formula (I), R ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be linear or branched, and is preferably linear. Two R ^{1 s} in the formula may be the same or different and are preferably the same.

In general formula (I), R ² is a monovalent organic group having two or more (meth) acryloyl groups. When the number of such (meth) acryloyl groups is 1 or less, compatibility with an organic solvent or resin is lowered, fingerprint wiping property is lowered, or surface smoothness is lowered. Two R ² in the formula may be the same or different, and preferably the same.

The number of (meth) acryloyl groups possessed by R ² needs to be 2 or more, preferably 2 to 10, particularly preferably 2 to 6, more preferably 2 to 4, especially Preferably two. Further, R ² is usually one having also one or more urethane bonds, the number of urethane bonds R ² has is the number by one greater than the number of normal (meth) acryloyl groups.

Specific examples of R ² include a monovalent organic group represented by the following general formula (Ia).

In the general formula (Ia), R ²⁰ is a (q + 1) -valent organic group, q is 1 or 2, and is specifically represented by the following general formulas (I-a1) to (I-a9). And an (r + 1) -valent organic group.

When q is 1, R ²⁰ includes an organic group having a structure represented by the following formula or a mixed group thereof. Preferable R ²⁰ is a divalent organic group represented by the following general formula (I-a1).

[In formula (I-a2), r1 is an integer of 1 to 12, preferably 6.
In formula (I-a3), R ²⁰⁴ is a substituent such as a halogen atom (eg, Cl, Br, F), an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, etc.), and r4 Is an integer from 0 to 10.
In formula (I-a4), R ²⁰¹ and R ²⁰² are each independently the same substituent as the above-described substituent described as R ²⁰⁴ .
R ²⁰³ represents a single bond, a methylene group (—CH ₂ —), an oxygen atom (—O—), —C (CH ₃ ) ₂ — group, —C (CF ₃ ) ₂ — group, —SO ₂ — group, — A divalent bridging group selected from among C (O) -groups, preferably R ²⁰³ is a methylene group. r2 and r3 are integers independently selected from 0 to 4.
In-formula ^{(I-a5), R 205} is the same substituent as the substituent groups described as ^{R 204.} r5 is an integer selected from 0 to 4.
In formulas (I-a1) to (I-a5), * represents a binding site in common. ]

When q is 2, R ²⁰ includes an organic group having a structure represented by the following formula or a mixed group thereof.

[In formula (I-a6), R ²⁰⁶ represents an alkylene group having 1 to 10, preferably 4 to 8, more preferably 5 to 7 carbon atoms. The alkylene group may be linear or branched, and is preferably linear. In the formula, three R ²⁰⁶ may be the same or different, and preferably the same.
In formula (I-a7), R ²⁰⁷ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. r6 is an integer of 0 to 3, preferably 1.
In-formula ^{(I-a8), R 208} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
In formula (I-a9), r7 and r8 are each independently an integer of 0-5, preferably an integer of 2-3, and r7 + r8 is an integer of 2-10, preferably an integer of 4-6. .
-In formula (I-a6)-(I-a9), * shows a binding site in common. ]

In the formula (Ia), R ²¹ is a (meth) acryloyl group or a monovalent organic group having one or more (meth) acryloyloxy groups. As a specific example of the organic group, for example, one hydroxyl group was removed from hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and tripentaerythritol hepta (meth) acrylate. Groups.

〔式（Ｉ−ａ１０）中、Ａｃは（メタ）アクリロイル基を表し、Ｒ^２１１は炭素原子数１〜５、好ましくは１〜３のアルキル基であり、Ｒ^２１２は単結合、メチレン基またはエチレン基である；ｓについて、Ｒ^２中のｑが１のとき、ｓは１〜３の整数、好ましくは１であり、当該ｑが２のとき、ｓは０〜１の整数、好ましくは０である。〕 R ²¹ is preferably a group represented by the following general formula.

[In the formula (I-a10), Ac represents a (meth) acryloyl group, R ²¹¹ represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and R ²¹² represents a single bond, a methylene group or ethylene. For s, when q in R ² is 1, s is an integer from 1 to 3, preferably 1, and when q is 2, s is an integer from 0 to 1, preferably 0. is there. ]

  The monomer represented by the general formula (I) (hereinafter sometimes referred to as the monomer (I)) can be produced by a known method or can be obtained as a commercial product.

For example, the monomer (I) can be produced by a known method including the following steps when R ² is a group represented by the general formula (Ia) (Japanese Patent Laid-Open No. 2010-159386, And "Polymer International"(2012;61; 65-73)).

(1) reacting a perfluoropolyether diol represented by the following general formula (i) with a diisocyanate compound represented by the following general formula (ii);

〔式（ｉ）中、Ｘ_１、Ｒ^１、ｍ及びｎは上記定義の通りである。〕

[In formula (i), X ₁ , R ¹ , m and n are as defined above. ]

(2) A step of reacting the compound produced in the step (1) with a (meth) acrylate represented by the following general formula (iii).

〔式（ｉｉｉ）中、Ｒ^２１は上記定義の通りである。〕

[In formula (iii), R ²¹ is as defined above. ]

  As the perfluoropolyether diol (i), compounds having hydroxyl groups at both ends of perfluoropolyalkylene oxide, commercially available Fluorolink D10H, Fluorolink D (manufactured by Solvay Solexis) and the like are used.

  Examples of the diisocyanate compound (ii) include hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H12-MDI), cyclohexyl-1,4- Diisocyanate, 4,4′-methylenebis (phenylisocyanate) (MDI) or its isomer, toluene 2,4-diisocyanate (TDI) or its isomer, xylylene diisocyanate, naphthalene-1,5-diisocyanate, metaphenylene diisocyanate, Paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethyl benzene Diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate and the like are used.

  Examples of (meth) acrylate (iii) include (meth) acrylic acid, hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and trimethylolpropane tri (meth) acrylate. , Trimethylolpropane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene gluco Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Hydroxyl group-containing compounds such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate ) Acrylates, and poly (meth) acrylates of adducts of ethylene oxide or propylene oxide to these hydroxyl groups, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) Acrylate , And oligo epoxy (meth) acrylates are used.

The monomer (I) having R ² as a group of the general formula (Ia), wherein R ²⁰ is a group represented by the general formulas (Ia2) to (Ia9) is a diisocyanate in the above production method. It can be produced by using the corresponding di- or triisocyanate compound instead of compound (ii).

  Moreover, Fluorolink AD1700, 5101X, 5113X (made by Solvay Isolex) etc. can be obtained as a commercial item of monomer (I).

For example, the Fluorolink AD1700
In the general formula (I),
Two X ₁ is difluoromethylene group simultaneously,
Two R ¹ are methylene groups at the same time;
m + n is 10-15,
Two R ² are simultaneously represented by the general formula (Ia) [in the formula (Ia),
q is 1,
R ²⁰ is a group represented by the general formula (I-a1),
R ²¹ is a group represented by the general formula (I-a10) <In the formula (I-a10),
R ²¹¹ is an ethyl group or a methyl group,
R ²¹² is a methylene group or a single bond,
s is 1>
Is]
It is estimated that it is (meth) acrylate.

The monomer (I) may contain two or more types of monomers (I) having different X ₁ , R ¹ , R ² , m and / or n.

<Monomer (II)>
Reactivity fluorine-containing compound (B) are those monomers represented by the following general formula (II) (hereinafter, may be referred to as monomer (II).) Obtained by polymerizing a polymerization component containing.

In the general formula (II), X ₂ is a group represented by the following formula (3) or (4).
As the monomer represented by formula (II), the monomer X ₂ is a radical of formula (3), also X ₂ is a monomer mixture of the monomers is a group of formula (4) Good.

〔式（３）および（４）中、＊は結合部位を示す。〕

[In formulas (3) and (4), * indicates a binding site. ]

In general formula (II), R ³ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms. The divalent saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, particularly preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms. And a linear or branched alkylene group, preferably a linear alkylene group.
In such a divalent saturated aliphatic hydrocarbon group, one or more hydrogen atoms may be substituted with a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably a fluorine atom or a chlorine atom is mentioned.

The divalent organic group as R ³ is not particularly limited as long as it contains the divalent saturated aliphatic hydrocarbon group, and examples thereof include the divalent saturated aliphatic hydrocarbon group and the divalent saturated fat. And a composite group in which one or more groups selected from a group hydrocarbon group and one or more groups selected from an arylene group are bonded via a linking group.
Such an arylene group is an arylene group having 6 to 15 carbon atoms, and examples thereof include a phenylene group, a naphthylene group, a tolylene group, a xylylene group, an anthranylene group, a phenanthrylene group, and the like. Preferably, the arylene group is a phenylene group, particularly preferably. Is a p-phenylene group.
In the divalent saturated aliphatic hydrocarbon group and arylene group constituting the composite group, a hydrogen atom may be independently substituted with the halogen atom.
Examples of the linking group constituting the composite group include a single bond, an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (—NHCO— or —CONH—), and the like. Can be mentioned.

Specific examples of such R ³ include the following divalent organic groups. In the following specific examples, the left binding site is bonded to X ₂ O.

_{- (CH 2) n1 - (} n1 = 2~10, preferably an integer of 2 to 4)
_{-C 6 H 4 COO (CH 2} ) n2 - (n2 = 2~10, preferably an integer of 2 to 4)
_{-C 6 H 4 (CH 2)} n3 - (n3 = 1~10, preferably an integer of 2 to 4)
—CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n4 − (n4 = 1 to 10, preferably an integer of 2 to 4)
_{-C 6 H 4 CO (OCH 2} CH 2) n5 - (n5 = 1~10, preferably an integer of 2 to 4)

Among the specific examples of R ³ , the following groups are particularly preferable.
_{-C 6 H 4 COO (CH 2} ) n2 - (n2 = 2~10, preferably an integer of 2 to 4)

In general formula (II), R ⁴ is a hydrogen atom or a methyl group, preferably a methyl group.

  Monomer (II) can be produced by a known method.

For example, in monomer (II), R ³ is a group shown below;
_{-C 6 H 4 COO (CH 2} ) n2 - (n2 = 2~10)
Then, based on the following reaction formula, it can be produced by dropping an organic chloride solution of an acid chloride into an organic solvent solution of a hydroxyl group-containing alkyl (meth) acrylate at room temperature.

（式中、Ｘ_２およびＲ^４はそれぞれ一般式（ＩＩ）においてと同様である；_ｎ２は上記と同様である）。

(Wherein, X ₂ and R ⁴ are the same as in general formula (II); _n2 is the same as above).

In addition, for example, in monomer (II), R ³ is the following group;
_{- (CH 2) n1 - (} n1 = 2~10)
Then, based on the following reaction formula, it can be produced by dropping hexafluoropropene trimer into an organic solvent solution of a hydroxyl group-containing alkyl (meth) acrylate at room temperature.

（式中、Ｘ_２およびＲ^４はそれぞれ一般式（ＩＩ）においてと同様である；ｎ１は上記と同様である）。

(Wherein, X ₂ and R ⁴ are the same as in general formula (II); n1 is the same as above).

As the monomer (II), one kind may be used alone, or two or more kinds of monomers having different X ₂ , R ³ and / or R ⁴ may be used in combination.

<Monomer (III)>
Reactive fluorine-containing compound (B) are those monomers represented by the following general formula (III) (hereinafter, may be referred to as monomer (III).) Obtained by polymerizing a polymerization component containing.

In general formula (III), R ⁵ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms.
The divalent saturated aliphatic hydrocarbon group is preferably a group having 1 to 50 carbon atoms, particularly preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. And a linear or branched alkylene group, preferably a linear alkylene group.
In such a divalent saturated aliphatic hydrocarbon group, one or more hydrogen atoms may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom or a chlorine atom.

The divalent organic group as R ⁵ is not particularly limited as long as it contains the divalent saturated aliphatic hydrocarbon group, and examples thereof include the divalent saturated aliphatic hydrocarbon group and the divalent saturated fat. It may be a composite group obtained by bonding two or more groups selected from group hydrocarbon groups through a linking group.
In the divalent saturated aliphatic hydrocarbon group and arylene group constituting the composite group, a hydrogen atom may be independently substituted with the halogen atom.
Examples of the linking group constituting the composite group include an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (—NHCO— or —CONH—), and the like. .

Specific examples of such R ⁵ include the divalent organic groups shown below. In the following specific examples, the left binding site is bonded to a hydroxyl group.

_{- (CH 2) n6 -:} (n6 = 2~10, preferably 2-5 integer)
_{- (CH 2 CH 2 O)} n7 CH 2 CH 2 -: (n7 = 1~20, preferably an integer of 1 to 10)
_{- (CH 2 CH 2 CH 2} O) n8 CH 2 CH 2 CH 2 -: (n8 = 1~10, preferably 2-5 integer)
_{- (CH (CH 3) CH} 2 O) n9 CH (CH 3) CH 2 -: (n9 = 1~10, preferably 2-5 integer)
_{- (CH 2 CH (CH 3} ) O) n10 CH 2 CH (CH 3) -: (n10 = 1~10, preferably 2-5 integer)

Among the above R ⁵ , the following organic groups are particularly preferable.
_{- (CH 2) n6 - (} n6 = 2~10, preferably 2-5 integer)
_{- (CH 2 CH 2 O)} n7 CH 2 CH 2 - (n7 = 1~20, preferably an integer of 1 to 10)

In general formula (III), R ⁶ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

  The monomer (III) represented by the general formula (III) can be obtained as a commercial product or can be produced by a known method.

  Examples of commercially available monomers (III) include 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, polyethylene glycol monomethyl acrylate (trade name “Blenmer AE-400”; manufactured by NOF Corporation), and polyethylene glycol monomethyl acrylate (trade name). “Blemmer AE-200” (manufactured by NOF Corporation) can be obtained.

Monomer (III) may be used alone, or in combination of two or more monomers which R ⁵ and / or R ⁶ are different.

<Monomer (IV)>
Reactive fluorine-containing compound (B) are those monomers represented by the following general formula (IV) (hereinafter, may be referred to as monomer (IV).) Obtained by polymerizing a polymerization component containing.

In the general formula (IV), R ⁷ is a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms. The monovalent organic group is selected from the group consisting of a monovalent saturated aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and groups thereof. Examples include a composite group in which the above groups are bonded through a linking group.
The monovalent saturated aliphatic hydrocarbon group is a linear or branched alkyl group having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms. The group is linear.
The monovalent alicyclic hydrocarbon group usually has 1 to 50 carbon atoms, particularly preferably 1 to 20, and more preferably 1 to 10.
Such monovalent aromatic hydrocarbon group is an aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms.
Examples of the linking group constituting the composite group include a single bond, an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (—NHCO— or —CONH—), and the like. Can be mentioned.
In the monovalent organic group, one or more hydrogen atoms may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom.

Specific examples of R ⁷ include the following monovalent organic groups.
Hydrogen atom general formula _{;-( CH 2) n11 CH 3 (} n11 = 0~20, alkyl group represented by preferably 0-2),
2-ethylhexyl group isooctyl group cyclohexyl group isobornyl group dicyclopentanyl group benzyl group,
General formula; — (CH ₂ CH ₂ O) _n12 CH ₃ ( _n12 = 1 to 10) and an ethylene oxide-containing group.

Among the above R ⁷ , the following groups are particularly preferable.
An alkyl group represented by a hydrogen atom and a general formula: — (CH ₂ ) _n11 CH ₃ (n11 = 0 to 20, preferably 0 to 2).

In general formula (IV), R ⁸ is a hydrogen atom or a methyl group, preferably a methyl group.

  Monomer (IV) can also be obtained as a commercial item, and can also be manufactured by a well-known method.

  Examples of commercially available monomers (IV) include methacrylic acid, methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearyl methacrylate and the like.

Monomer (IV) may be used alone, or in combination of two or more monomers which R ⁷ and / or R8 are different.

<Monomer (V)>
The reactive fluorine-containing compound (B) of the present invention, the general formula (I) ~ monomer by polymerizing a polymerizable component that Yusuke containing as an essential component a polymer represented by (IV) (X), the following general Ru reactive fluorine-containing compound der obtained by reacting an isocyanate group-containing (meth) acrylate represented by the formula (V).
The polymer (X) is Der those having a functional group reactive with the isocyanate group of the compound represented by the general formula (V) is, as a functional group, a hydroxyl group, but a carboxyl group, an isocyanate group It is preferable that it is a hydroxyl group at the point which is excellent in the reactivity with.

Hereinafter, the reaction of the polymer (X) is a monomer (I) ~ a polymerization component and the polymerization comprising polymer containing all the (IV), an isocyanate group-containing represented by the general formula (V) (meth) acrylate An example will be described.

[In General Formula (V), R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, and the saturated aliphatic hydrocarbon group may have an ether bond. good. R ⁹ is preferably a divalent saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms.
In general formula (V), p is an integer of 1 or 2, and is preferably 1. p is determined depending on the valence of R ^9, for example p when R ⁹ is a divalent is 1, for example p when R ⁹ is a trivalent is 2.
In the general formula (V), R ¹⁰ is a hydrogen atom or a methyl group, preferably a hydrogen atom. ]

  The isocyanate group-containing (meth) acrylate represented by the general formula (V) (hereinafter simply referred to as (meth) acrylate (V)) can be obtained as a commercial product or can be produced by a known method. .

  As a commercially available product of (meth) acrylate (V), compound name; 2-methacryloyloxyethyl isocyanate (trade name “Karenz MOI”; manufactured by Showa Denko KK), compound name; 2-acryloyloxyethyl isocyanate (trade name “Karenz AOI”) "; Showa Denko Co., Ltd.), compound name; 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name" Karenz BEI "; Showa Denko Co., Ltd.) and the like are available.

Such (meth) acrylate (V) may be used alone or in combination of two or more monomers having different R ⁹ and / or R ¹⁰ .

  The polymer (X) can be produced by a known general polymerization method, for example, the monomers (I) to (IV) are mixed at a desired ratio, a polymerization initiator is added, and an organic solvent is added. In the presence of, the reaction may be carried out at room temperature to about 100 ° C. for about 1 to 24 hours. Thereby, the reaction proceeds quantitatively, and the mixing order of the monomers (I) to (IV) is not particularly limited.

  As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide and the like can be used. The organic solvent is not particularly limited as long as the above reaction proceeds, and examples thereof include an aprotic solvent. Preferred examples of the aprotic solvent include dimethoxyethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, toluene, and propylene glycol monomethyl ether acetate. The organic solvent may be used alone or in combination of two or more.

The reaction between the polymer (X) and the (meth) acrylate (V) is performed, for example, by mixing (meth) acrylate (V) at a predetermined ratio with respect to the obtained copolymer solution, and -20 to 100 What is necessary is just to stir at 1 to 48 hours at ° C, preferably 20 to 90 ° C.
Thereby, the hydroxyl group derived from monomer (III) in polymer (X) reacts with the isocyanate group of (meth) acrylate (V) to form a urethane bond, and the reactive fluorine-containing compound of the present invention is obtained. Will be. At this time, the mixed (meth) acrylate (V) reacts quantitatively.

  In the reaction, an alkaline catalyst may be used. The alkaline catalyst is not particularly limited as long as the above reaction proceeds. For example, an organic alkaline catalyst such as triethylamine, tributylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane is preferable, and particularly preferable. 1,4-diazabicyclo [2.2.2] octane. The alkaline catalyst may be used alone or in combination of two or more.

  In the polymer (X), the content ratios of the monomers (I) to (IV) with respect to the entire constituent polymerization components of the polymer (X) are a to d (% by weight), respectively, and the monomer (V) to the monomer (III) Where a is a polymerization ratio of e (mol%), a is 10 to 70% by weight, b is 10 to 70% by weight, c is 10 to 30% by weight, d is 5 to 40% by weight, and e is 20 to 100%. It is preferable that a is 15% by weight, particularly preferably, a is 15 to 50% by weight, b is 15 to 65% by weight, c is 10 to 20% by weight, d is 5 to 35% by weight, and e is 30 to 80% by weight. %

  In the above, if a is too small, water repellency and oil repellency are reduced from the beginning, and fingerprint wiping persistence tends to be reduced. If b is too small, oil repellency persistence and fingerprint wiping persistence tends to be decreased. If c is too small, the durability tends to decrease in all of the water repellency, oil repellency and fingerprint wiping property. If d is too small, the fingerprint wiping property tends to decrease, and e is too small. And, there is a tendency that the sustainability with respect to water repellency, oil repellency and fingerprint wiping property is lowered.

In addition, it is particularly preferable that a, b, c, d, and e satisfy the above range and further satisfy the following relationship.
-It is preferable that a + b is 40 to 80 weight%, Most preferably, it is 45 to 78 weight%.
-It is preferable that b / a is 0.1-5, Most preferably, it is 0.1-4.
-(A + b) / c is preferably 1.3 to 8, particularly preferably 2.2 to 5.
-It is preferable that d / c is 0.2-2, Most preferably, it is 0.4-1.5.

  The weight average molecular weight of the reactive fluorine-containing compound (B) is preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000. If the weight average molecular weight is too small, the production tends to be difficult, and if too large, the compatibility tends to decrease.

The weight average molecular weight of the reactive fluorine-containing compound (B) is a value measured under the following conditions using the following apparatus.
Equipment: ACQUITY UPLC H-Class (Waters)
Detector: ACQUITY UPLC ELS detector (Waters)
Column: TSKgel α-5000 (φ7.8 mm × 30 cm) (Tosoh)
Guard column: TSK guard α (φ6.0mm × 4cm) (Tosoh)
Solvent: Tetrahydrofuran (Kanto Chemical)
Flow rate: 0.6 mL / min
Column temperature: 40 ° C
Sample concentration 0.2-0.3wt%
Injection volume: 0.01 mL
Molecular weight calibration: monodisperse polyethylene glycol (Tosoh)

  The content (solid content) of the reactive fluorine-containing compound (B) is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A) (solid content). Especially preferably, it is 0.1-50 weight part, More preferably, it is 0.5-10 weight part. If the blending amount is too large, the compatibility tends to decrease and phase separation may occur, or the coating film tends to become cloudy when coated, and if it is too small, the antifouling performance tends to be insufficient. .

  In the present invention, in addition to the urethane (meth) acrylate compound (A) and the reactive fluorine-containing compound (B), an ethylenically unsaturated compound [however, excluding (A) and (B)] (C) (Hereinafter, it may be described as “ethylenically unsaturated compound (C)”) is preferable from the viewpoint of excellent coating film hardness and scratch resistance.

  The content of the ethylenically unsaturated compound (C) is preferably from 0 to 99% by weight, particularly preferably from 25 to 98% by weight, particularly preferably based on the whole components (A) to (C). Is 50 to 97% by weight, more preferably 75 to 96% by weight. When the content of the ethylenically unsaturated compound [excluding (A) and (B)] (C) is too large, sufficient antifouling performance tends to be not obtained.

  The ethylenically unsaturated compound [excluding (A) and (B)] (C) is, for example, a urethane (meth) acrylate compound (C1) and / or an ethylenically unsaturated monomer (C2). preferable.

  The urethane (meth) acrylate compound (C1) is also required to be a urethane (meth) acrylate compound (C1-1) represented by the following general formula (5) even when used for various purposes. It is preferable in that it is easy to impart physical properties.

〔式中、Ｒ¹は多価イソシアネート系化合物のウレタン結合残基、Ｒ²は水酸基含有（メタ）アクリレート系化合物のウレタン結合残基、ａは２〜５０の整数である。〕

[Wherein, R ¹ is a urethane bond residue of a polyvalent isocyanate compound, R ² is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound, and a is an integer of 2 to 50. ]

  The urethane (meth) acrylate (C1-1) represented by the general formula (5) (hereinafter sometimes abbreviated as “urethane (meth) acrylate-based compound (C1-1)”) is a polyvalent isocyanate-based compound. And a hydroxyl group-containing (meth) acrylate compound.

  In the general formula (5), a may be an integer of 2 to 50, preferably 2 to 20, particularly preferably 2 to 10.

  Examples of the polyvalent isocyanate compound are the same as those exemplified as the polyvalent isocyanate compound (x2) in the description of the urethane (meth) acrylate (A1), or the polyvalent isocyanate compound. What reacted (x2) and the polyol type compound (x4) is mentioned.

  Examples of such a hydroxyl group-containing (meth) acrylate compound include those exemplified as the hydroxyl group-containing (meth) acrylate compound (x3) in the description of the urethane (meth) acrylate (A1). It is done.

  What is necessary is just to manufacture the manufacturing method of a urethane (meth) acrylate type compound (C1-1) according to the manufacturing method of a well-known general urethane (meth) acrylate type compound. For example, the polyvalent isocyanate compound and the hydroxyl group-containing (meth) acrylate compound may be charged into the reactor or separately and reacted.

The reaction molar ratio between the polyvalent isocyanate compound and the hydroxyl group-containing (meth) acrylate compound is, for example, that the polyisocyanate compound has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound has one hydroxyl group. In the case of individual, the polyvalent isocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 2 to 3, the polyisocyanate compound has three isocyanate groups, and the hydroxyl group-containing (meth) acrylate compound. When the compound has one hydroxyl group, the ratio of polyisocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 3-4.
In the addition reaction between the polyvalent isocyanate compound and the hydroxyl group-containing (meth) acrylate compound, the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (C1-1) is obtained.

The number of ethylenically unsaturated groups contained in the urethane (meth) acrylate compound (C1-1) obtained above is preferably 2-30, particularly preferably 3-20, and more preferably 6. ~ 15.
If the number of ethylenically unsaturated groups is too small, there is a tendency that the hardness and scratch resistance of the coating film cannot be obtained. If the number is too large, the curing shrinkage of the coating film increases and the adhesion to the substrate decreases, or the coating film becomes brittle. There is a tendency to become.

  The weight average molecular weight of the urethane (meth) acrylate compound (C1) is preferably 700 to 50,000, more preferably 800 to 30,000, and particularly preferably 1000 to 10,000. If the weight average molecular weight is too small, it tends to be difficult to maintain a balance between the coating film hardness and the shrinkage resistance, or the wettability to the substrate tends to decrease, and the weight average molecular weight is too large. , It tends to be difficult to maintain scratch resistance and hardness.

The viscosity of the urethane (meth) acrylate compound (C1) at 60 ° C. is preferably 200 to 150,000 mPa · s, particularly 500 to 120,000 mPa · s, more preferably 500 to 100,000 mPa · s. Preferably there is. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

  As said ethylenically unsaturated monomer (C2), if it is an ethylenically unsaturated monomer (however, urethane (meth) acrylate type compound (except C1)) which has one or more ethylenically unsaturated groups in 1 molecule. For example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer can be used.

  The monofunctional monomer may be any monomer containing one ethylenically unsaturated group, such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Fester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  In addition to the monofunctional monomer, there may be mentioned a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, and acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like. Examples of 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) Examples include acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene Oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene Side modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) ) Acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

  These ethylenically unsaturated monomers (C2) may be used alone or in combination of two or more.

The ethylenically unsaturated monomer (C2) is preferably a monomer containing one or more ethylenically unsaturated groups, and particularly preferably a monomer containing two or more ethylenically unsaturated groups having a high hardness. In view of obtaining a coating film, the monomer is more preferably a monomer containing three or more ethylenically unsaturated groups.
Specifically, a pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate is required to obtain a coating film having high hardness. Is preferred.

  As the ethylenically unsaturated compound (C), the content ratio (weight ratio) of (C1) and (C2) when the urethane (meth) acrylate compound (C1) and the ethylenically unsaturated monomer (C2) are used in combination. (C1) :( C2) = 5: 95 to 95: 5 is preferable, and (C1) :( C2) = 20: 80 to 80:20 is particularly preferable.

In this invention, a photoinitiator (D) can be contained further.
Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ben such as ether Ins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy -3 Thioxanthones such as 4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- And acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, these photoinitiators (D) may be used individually by 1 type, and may use 2 or more types together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  The content of the photopolymerization initiator (D) is the sum of the urethane (meth) acrylate compound (A), the reactive fluorine-containing compound (B), and the ethylenically unsaturated compound (C) used as necessary. It is preferable that it is 0.1-10 weight part with respect to 100 weight part, More preferably, it is 1-8 weight part, Especially preferably, it is 1-5 weight part. If the amount is too small, the curing rate in the case of ultraviolet curing tends to be extremely slow, and if too large, the curability is not improved and is inefficient.

  In the present invention, in addition to the components (A) to (D), fillers, electrolyte salts, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents. , Stabilizers, antifoaming agents, leveling agents, thixotropy imparting agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, crosslinking agents, and the like can also be blended.

  In addition to these, unsaturated polyester resins, vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, urea resins, melamine resins for the purpose of suppressing the curing shrinkage of the coating film Polymers such as polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers, and cellulose derivatives such as nitrocellulose and cellulose acetate butyrate may be blended.

  Thus, the polysiloxane structure-containing urethane (meth) acrylate compound (A) of the present invention and the reactive fluorine-containing compound (B) represented by the general formula (I), preferably the ethylenically unsaturated compound (C) are contained. An active energy ray-curable resin composition is obtained.

Such a resin composition can be used by blending an organic solvent and adjusting the viscosity as necessary, and is usually diluted to 10 to 70% by weight, preferably 20 to 60% by weight. Can be applied.
Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene Aromatic glycols such as propylene glycol monomethyl ether, acetates such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

In producing the active energy ray-curable resin composition of the present invention, the polysiloxane structure-containing urethane (meth) acrylate compound (A), the reactive fluorine-containing compound (B), and the ethylenically unsaturated compound (C) The method of blending the photoinitiator (D) is not particularly limited, and the separately produced components (A) to (D) may be blended in various orders. First, (A) and After producing (C) in the same reaction system, (B) and (D) may then be blended. When an organic solvent such as ethyl acetate or methyl isobutyl ketone is used, the organic solvent may be added to the above mixture, or the respective compositions may be dissolved in the organic solvent and then mixed.
Among these, the method of adding (D) at the end after blending (A), (B), (C) is preferably used.

  The active energy ray-curable resin composition of the present invention is useful as a coating agent composition, and is effectively used as a curable resin composition for coating film formation, such as a top coat agent and an anchor coat agent for various substrates. After the active energy ray-curable resin composition is applied to the base material (if the composition diluted with an organic solvent is applied, it is further dried) and then irradiated with active energy rays. Can be cured.

  The coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, dispenser, screen printing, and ink jet printing.

  The coating film thickness (film thickness after curing) is usually preferably 1 to 50 μm, particularly preferably 3 to 30 μm.

  Examples of the base material to be coated include polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, acrylic resin, and their molded products (films). , Sheets, cups, etc.), plastic substrates of photo-curing resins (acrylic, epoxy, etc.), metals, glass and the like.

  As such active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (F).

As a method of curing by ultraviolet irradiation, using a high-pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, an LED lamp, etc. What is necessary is just to irradiate about 100-3000 mJ / cm < ² >.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
Thus, a cured coating film obtained by irradiating the coating agent composition of the present invention with active energy rays is obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight basis.

  As the polysiloxane structure-containing urethane (meth) acrylate compound (A), a polysiloxane group-containing urethane (meth) acrylate compound was produced according to the following method.

<Production of polysiloxane group-containing urethane (meth) acrylate-based compound (A-1)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, hexamethylene diisocyanate trimer (x2) (isocyanate group content 21.0%) 90.6 g, general formula (1 ) Polysiloxane compound (x1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, a = 9, b = 1, c = 1, hydroxyl value 120 mg KOH / g) 70.6 g, dipentaerythritol pentaacrylate (x3) [mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate acrylate (hydroxyl value 50 mg KOH / g)] 169 .4 g, dibutyltin dilaurate 0.10 g, and methyl ethyl ketone 500 g were allowed to react at 60 ° C. for 3 hours. When the isocyanate group reached 0.76%, dipentaerythritol pentaacrylate (x3) [mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)] 169.4 g, 2 , 6-di-tert-butylcresol (0.4 g) was added dropwise over about 1 hour, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared, and the polysiloxane group-containing urethane (meth) acrylate compound (A-1) A solution (solid concentration 50%) was obtained.
The polysiloxane group-containing urethane (meth) acrylate compound (A-1) corresponds to the urethane (meth) acrylate compound (A1) in the text.

  As a urethane (meth) acrylate compound not containing a polysiloxane structure, a urethane (meth) acrylate compound (A′-1) was produced according to the following method.

<Production of urethane (meth) acrylate compound (A'-1) not containing polysiloxane group>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, hexamethylene diisocyanate trimer (x2) (isocyanate group content 21.0%) 73.6 g, dipentaerythritol penta Acrylate (x3) [mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)], 426.4 g, 0.4 g of 2,6-di-tert-butylcresol was added dropwise over about 1 hour. Then, the reaction was continued as it was, and when the isocyanate group disappeared, the reaction was terminated to obtain a urethane (meth) acrylate compound (A′-1) containing no polysiloxane group.

  A reactive fluorine-containing compound (B) was produced according to the following method.

[Production Example 1] In a three-necked flask (3 L) equipped with a dropping funnel, 30.1 g (1.0 mol) of 2-hydroxyethyl methacrylate, 111.1 g (1.1 mol) of triethylamine, and 600 g of ethyl acetate were put. . The dropping funnel was charged with 586.5 g (1.0 mol) of a fluorinated acid chloride represented by the following formula (6) and 100 g of ethyl acetate and gradually added dropwise to the solution in the flask with stirring over about 60 minutes. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.

In Formula (6), Rf ¹ is a group represented by Formula (3) or (4), and the fluorine-containing acid chloride represented by Formula (6) above has Rf ¹ represented by Formula (3). It is a mixture of a compound having a structure and a compound having a structure in which Rf ¹ is represented by the formula (4).

［式（ＩＩ−１）中、Ｒｆ^１は前記式（３）または（４）で示される基であり、上記式（ＩＩ−１）で表される反応性フッ素含有メタクリレートは、Ｒｆ^１が式（３）で示される構造の化合物とＲｆ^１が式（４）で示される構造の化合物の混合物である。］ The reaction mixture was added with 1050 g of 1N hydrochloric acid to stop the reaction, and then the reaction mixture was transferred into a 3 L beaker, and then washed with 1 L of water three times. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 634.8 g (yield 93%) of a reactive fluorine-containing methacrylate represented by the following formula (II-1). Table 1 shows 1H-NMR data of the obtained reactive fluorine-containing methacrylate (II-1).

Wherein (II-1), Rf ¹ is a group represented by the formula (3) or (4), reactive fluorine-containing methacrylate represented by the formula (II-1), Rf ¹ has the formula The compound having the structure represented by (3) and Rf ¹ is a mixture of the compound having the structure represented by formula (4). ]

[Table 1]
[The ¹ H-NMR data of a fluorine-containing methacrylate]

[Production Example 2]
In a three-necked flask (100 mL) equipped with a condenser tube, 7.32 g (10.8 mmol) of the fluorine-containing methacrylate (II-1) synthesized in Production Example 1, Fluorolink AD1700 “manufactured by Solvay Isolex” (I -1) 3.48 g, Blemmer AE-400 (polyethylene glycol monomethyl acrylate) “manufactured by NOF Corporation” (III-1) 2.42 g (4.7 mmol), methacrylic acid (IV-1) 1.16 g (13. 4 mmol), methyl methacrylate (IV-2) 1.68 g (16.8 mmol), methyl isobutyl ketone 22.25 g, 2,2′-azobisisobutyronitrile 0.13 g (0.8 mmol), lauryl mercaptan 1 .60 g (7.9 mmol) was added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each (meth) acrylate in 1H-NMR. Specifically, (II-1) methacryl groups 5.60 ppm, 6.15 ppm, (I-1) acrylic groups 5.83-5.87 ppm, 6.11-6.18 ppm, 6.42-6 .46 ppm, (III-1) acrylic group 5.83-5.85 ppm, 6.11-6.18 ppm, 6.40-6.44 ppm, (IV-1) methacryl group 5.62-5.74 ppm , 6.14-6.31 ppm, disappearance of peaks of (IV-2) methacrylic groups 5.53-5.58 ppm, 6.07-6.13 ppm. The desired copolymer was obtained quantitatively (40% methyl isobutyl ketone solution).

  The obtained copolymer was adjusted by adding methyl isobutyl ketone so that the solid content concentration would be 20%, and 0.5 equivalent of monomer (V-1: 2) with respect to monomer (III-1). -(Isociateethyl) acrylate) and 0.01 equivalent of 1,4-diazabicyclo [2.2.2] octane were added, and stirring of the reaction solution was continued at 50 ° C. for 20 hours. The completion of the reaction was confirmed by disappearance of -N = C = O absorption (2275-2250 cm-1) using FT-IR. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC. The measurement results are shown in Table 2. Moreover, when 1H-NMR of the obtained fluorine-containing oligomer was measured, peaks derived from acrylate groups (5.82-5.85 ppm, 6.07-6.14 ppm, 6.38-6.43 ppm) were observed. From this, it was confirmed to have a reactive group.

  Furthermore, in Production Example 2, the types and blending amounts of the monomer components (I) to (V) are changed as shown in Table 2 below, and the fluorine-containing compounds (B′-1) to (B′-3) are changed. Manufactured. In the production of the fluorine-containing compound (B′-1), propylene glycol monomethyl ether acetate is used instead of methyl isobutyl ketone, and in the production of the fluorine-containing compound (B′-3), ethyl acetate is used instead of methyl isobutyl ketone. Was used.

In the above [Table 2],
(I-1) is a tetrafunctional urethane (meth) acrylate (manufactured by Solvay Isolex; trade name “Fluorolink AD1700”),
(I-2) is a linear fluorine acrylate (CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OC (═O) CH═CH ₂ ),
(I-3) is a bifunctional urethane (meth) acrylate (manufactured by Solvay Isolex; trade name “Fluorolink MD700”),
(II-1) is Rf ¹ OC ₆ H ₄ CO ₂ (CH ₂ ) ₂ OC (═O) C (CH ₃ ) ═CH ₂ (Rf ¹ is represented by the general formulas (2) and (3). A mixed group of
(III-1) is HO (CH ₂ CH ₂ O) _n C (═O) CH═CH ₂ ) n≈10 (manufactured by NOF Corporation; trade name “Blemmer AE-400”),
(IV-1) is methacrylic acid,
(IV-2) is methyl methacrylate.
The weight average molecular weight is a value measured using a PEG standard as described above.

  In addition, a perfluoropolyether surface modifier (manufactured by DIC; trade name “Megafac RS-75”) was prepared as the reactive fluorine-containing compound (B-2).

The following were prepared as the photopolymerization initiator (C).
(C-1): 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan; trade name “Irgacure 184”) was prepared.

<Examples 1-4>
[Production of activated energy ray-curable resin composition]
The above reactive fluorine-containing compound [B] is blended in the amount shown in Table 3 with 100 parts (solid content) of the above polysiloxane structure-containing urethane (meth) acrylate [A], and [A] and [B]. 4 parts of photopolymerization initiator [C] (manufactured by BASF Japan; trade name “IRGAGUA 184”) is blended with respect to a total of 100 parts by weight, and diluted with methyl isobutyl ketone so that the solid content is 50%. Then, an active energy ray-curable resin composition was obtained.

<Comparative Example 1>
In Example 1, an active energy ray-curable resin composition was obtained in the same manner except that the reactive fluorine-containing compound (B′-1) was used instead of the reactive fluorine compound (B-1).

<Comparative example 2>
In Example 1, an active energy ray-curable resin composition was obtained in the same manner except that the reactive fluorine-containing compound (B′-2) was used instead of the reactive fluorine compound (B-1).

<Comparative Example 3>
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the reactive fluorine-containing compound (B′-3) was used instead of the reactive fluorine compound (B-1).

<Comparative Example 4>
In Example 1, an active energy ray-curable resin composition was obtained in the same manner except that the reactive fluorine-containing compound (B-1) was not used.

<Comparative Example 5>
In Example 1, in place of the polysiloxane structure-containing urethane (meth) acrylate (A-1), except that a urethane (meth) acrylate (A′-1) not containing a polysiloxane structure was used, An active energy ray-curable resin composition was obtained.

About the obtained active energy ray curable resin composition, the external appearance of the liquid mixture was evaluated.
[Formulated liquid appearance]
The appearance of the active energy ray-curable resin composition was observed and evaluated as follows.
○ ・ ・ ・ Uniform and transparent △ ・ ・ ・ White turbidity × ・ ・ ・ Phase separation occurred and aggregates settled

  Next, the active energy ray-curable resin composition is dried on a PET film (Toyobo Co., Ltd .; trade name “Cosmo Sunshine A4300”, film thickness 125 μm) using a 50 μm applicator. After coating at 15 μm and drying at 60 ° C. for 5 minutes, using a high pressure mercury lamp lamp 80W and one lamp, two passes of UV irradiation (accumulation from a height of 18 cm to a conveyor speed of 5.1 m / min) An irradiation dose of 450 mJ / cm <2> was performed to form a cured coating film (film thickness of 15 [mu] m), and the following evaluation was performed.

[Appearance of coating film]
The cured coating film after ultraviolet irradiation was visually observed and evaluated as follows.
○ ・ ・ ・ Transparent and free of foreign matter × ・ ・ ・ White turbidity and aggregates on the coating surface

[Flatness]
The cured coating film surface after ultraviolet irradiation was visually observed and evaluated as follows.
(Evaluation)
○ ・ ・ ・ No streaks, repels, etc. × ・ ・ ・ There are streaks, repels, etc.

[Coating hardness]
About the cured coating film surface, the pencil hardness was measured according to JISK5600-5-4.

[Abrasion resistance]
The cured coating film was visually observed for the degree of scratching on the surface after steel wool # 0000 subjected to a load of 300 g was reciprocated 10 times on the surface of the cured coating film and evaluated as follows.
◎ ・ ・ ・ No scratches ○ ・ ・ ・ Slightly scratched △ ・ ・ ・ Slightly scratched

[Anti-fouling]
(1) Initial water repellency The contact angle of water with respect to the surface of the cured coating film immediately after preparation was measured with a contact angle measuring device (manufactured by Kyowa Interface Chemical; DropMaster 600) and evaluated as follows.
○ ・ ・ ・ Water contact angle is over 90 degrees × ・ ・ ・ Water contact angle is 90 degrees or less

(2) Sustained water repellency The contact angle of water on the cured coating film after drying and drying 100 times with a professional wipe (made by Daio Paper Co., Ltd., trade name: Ériere Prowipe Soft Micro Wiper S220) with the cured coating film surface wetted with ethanol. Was measured by the same method as the initial water repellency and evaluated as follows.
○ ・ ・ ・ Water contact angle after wiping is over 90 degrees × ・ ・ ・ Water contact angle after wiping is 90 degrees or less, or initial contact angle is 90 degrees or less

(3) Initial oil repellency The contact angle of oleic acid to the cured coating film surface immediately after production was measured with a contact angle measuring device (manufactured by Kyowa Interface Chemical; DropMaster 600) and evaluated as follows.
○ ・ ・ ・ Contact angle of oleic acid is over 35 degrees × ・ ・ ・ Contact angle of oleic acid is 35 degrees or less

(4) Oil repellency persistence The oleic acid contact with the cured coating film after drying 100 times with a ProWipe (made by Daio Paper Co., Ltd., trade name: Ériere Prowipe Soft Micro Wiper S220) with the cured coating surface wet with ethanol. The corners were measured by the same method as the above initial oil repellency and evaluated as follows.
○ ... Contact angle of oleic acid after wiping is over 35 degrees × ... Contact angle of oleic acid after wiping is 35 degrees or less,
Or the initial contact angle is 35 degrees or less

(5) Initial fingerprint wiping property A fingerprint is adhered to the surface of the cured coating film, and the fingerprint is wiped with a professional wipe (made by Daio Paper Co., Ltd., trade name: Erière Prowipe Soft Micro Wiper S220) until the fingerprint disappears. Measured) and evaluated as follows. In addition, the number of wiping offs when applied without adding the reactive fluorine-containing compound (B) was 10 times.
○: Less than 7 times of wiping ×… More than 7 times of wiping or whitening

(6) Persistence of fingerprint wiping 100% of the cured coating surface is wiped back and forth with Pro Wipe (trade name: Erière Pro Wipe Soft Micro Wiper S220, made by Daio Paper Co., Ltd.) wetted with ethanol. The property was measured by the same method as the fingerprint wiping property. In addition, the number of wiping offs when applied without adding the reactive fluorine-containing compound (B) was 10 times.
○: Less than 7 times of wiping ×… More than 7 times of wiping or whitening

(7) Initial magic ink wiping property A line is drawn with a blue ink magic in one reciprocation on the cured coating film surface, left for 24 hours, and the coating film after wiping with a waste cloth is observed and evaluated as follows. did.
○ ・ ・ ・ Can be wiped clean △ ・ ・ ・ While it can be wiped off

  The evaluation results of the above examples and comparative examples are shown together in Table 3.

  The activated energy ray curable resin composition solutions of Examples 1 to 4 have good compatibility and good appearance of the liquid mixture, and the cured coating films obtained from the activated energy ray curable resin composition solutions have surface characteristics. Excellent results (surface smoothness, coating film hardness, scratch resistance) and antifouling properties (water repellency, oil repellency, fingerprint wiping property, etc.) were also obtained. In particular, it was found that a cured coating film excellent in fingerprint wiping persistence in antifouling properties can be obtained.

  In particular, in Example 4 in which two types of (B-1) and (B-2) were used in combination as the reactive fluorine-containing compound (B), it was found that a cured coating film having very excellent fingerprint wiping properties was obtained. .

  In Comparative Example 1, when the reactive fluorine-containing compound (B) does not contain the monomer component (I) (perfluoropolyether group-containing tetrafunctional acrylate component), the surface properties of the resulting cured coating film are Similarly, the antifouling property was excellent and the initial antifouling property was excellent, but the fingerprint wiping persistence was inferior to that of the example and was not sufficient.

  In Comparative Examples 2 and 3, the reactive fluorine-containing compound (B) is replaced with a perfluoropolyether group-containing bifunctional acrylate or perfluoropolyester instead of the monomer component (I) (perfluoropolyether group-containing tetrafunctional acrylate component). When the ether group-containing monofunctional acrylate was contained, the compatibility of the active energy ray-curable resin composition solution was poor and a cured coating film could not be obtained.

  In Comparative Example 4, it can be seen that when the reactive fluorine compound (B) is not contained, the coating film has very poor fingerprint wiping properties.

  In Comparative Example 5, even if the reactive fluorine-containing compound (B) contains the monomer component (I), the active energy ray-curable resin composition does not contain the polysiloxane structure-containing urethane (meth) acrylate (A). In this case, the coating film was inferior in the wiping property of the magic ink, and the stain removal property was not sufficient.

The active energy ray-curable resin composition of the present invention is excellent in antifouling performance such as dirt adhesion prevention and dirt removal, and excellent in coating film hardness and scratch resistance. It can be effectively used for coating applications such as anchor coating agents and magnetic powder coating binders.
It can also be used as a paint, ink, pressure-sensitive adhesive, adhesive, adhesive or the like.

Claims (6)

Polysiloxane structure-containing urethane (meth) acrylate compound (A), and reactivity fluorine-containing compound (B) containing,
An isocyanate represented by the following general formula (V) is obtained by copolymerizing the reactive fluorine-containing compound (B) with a polymerization component containing monomers represented by the general formulas (I) to (IV). An active energy ray-curable resin composition, which is a reactive fluorine-containing compound obtained by reacting a group-containing (meth) acrylate .

[In general formula (I),
R ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, R ² is a monovalent organic group X ₂ having two or more (meth) acryloyl groups, is a perfluoroalkylene having 1 to 5 carbon atoms The group m + n is an integer from 5 to 50. ]

[In general formula (II),
R ³ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms, and may be substituted with a halogen atom.
R ⁴ is a hydrogen atom or a methyl group.
X ₂ is a group represented by the following general formula (3) or (4). ]

[In General Formulas (3) and (4), * indicates a binding site. ]

[In general formula (III),
R ⁵ is a divalent organic group containing a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, which may be substituted with a halogen atom, and the saturated aliphatic hydrocarbon group includes May have an ether bond, an ester bond, an amide bond or an aryl group.
R ⁶ is a hydrogen atom or a methyl group. ]

[In general formula (IV),
R ⁷ is a monovalent organic group having 1 to 50 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
R ⁸ is a hydrogen atom or a methyl group. ]

[In general formula (V),
R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, and the saturated aliphatic hydrocarbon group may have an ether bond.
R ¹⁰ is a hydrogen atom or a methyl group.
p is an integer of 1 or 2. ] The polysiloxane structure-containing urethane (meth) acrylate compound (A) is represented by the following general formula (1): a polysiloxane compound having a hydroxyl group at both ends, a polyvalent isocyanate compound, and a hydroxyl group-containing (meth) acrylate compound polysiloxane structure-containing urethane (meth) acrylate compound (A1) according to claim 1 active energy ray curable resin composition, wherein it is obtained by reacting.

[In the general formula, R ¹ and R ³ represent a hydrocarbon group or an organic group containing an oxygen atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more. , B
, C is an integer of 1 to 3. ] The active energy ray-curable resin composition according to claim 1 or 2 , wherein the reactive fluorine-containing compound (B) has a weight average molecular weight of 2,000 to 20,000. The content of the reactive fluorine-containing compound (B) (solid content) is 0.01 to 1 with respect to 100 parts by weight of the polysiloxane structure-containing urethane (meth) acrylate compound (A) (solid content).
00 claims 1-3 active energy ray curable resin composition according to any one of which is a part by weight. Claim 1-4 coating composition characterized by comprising a radiation-curable resin composition according to any. A cured coating film obtained by irradiating the coating agent composition according to claim 5 with active energy rays.