JP5566216B2 - 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), coating film appearance, coating film hardness, and scratch resistance. It is related with the active energy ray hardening-type resin composition which can obtain the coating layer which is excellent in this.

  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. For this reason, various methods for wiping off dirt have been studied, and methods for overcoating a coating agent have been studied in order to improve dirt prevention and dirt removal.

  As a method for improving the antifouling property of the coating layer (antifouling property and stain removability), the coating agent has a fluorine structure or silicone structure for the purpose of improving the water and oil repellency of the coating layer. For example, Patent Document 1 discloses a coating agent in which an ultraviolet curable resin and an oligomer containing a fluorine atom-containing alkylalkoxysilane are used together. In Patent Document 2, active energy is disclosed. A coating agent in which a linear curable compound and a polymerizable fluorine copolymer comprising a polyfluoroalkyl group-containing polymerizable monomer are used in combination is disclosed.

  In addition, urethane acrylate oligomers have the property of curing by irradiation with active energy rays, and after curing, a coating film with high hardness can be obtained, so it is widely used as a coating agent for hard coat applications. Furthermore, a urethane acrylate oligomer having a silicone structure introduced to impart antifouling performance to the coating layer is also known. For example, Patent Document 3 mainly discloses isocyanates and a polysiloxane having one hydroxyl group at both ends. A photocurable resin composition using urethane (meth) acrylate obtained by reacting dimethylsiloxanediol and hydroxyalkyl (meth) acrylates is described.

Japanese Patent Laid-Open No. 10-104403 JP 2002-241446 A JP 2003-192751 A

However, the techniques disclosed in Patent Documents 1 and 2 also provide high antifouling performance because water and oil repellency is imparted to the coating film. However, oligomers and polyfluoros containing fluorine-containing alkylalkoxysilanes are exhibited. Alkyl group-containing polymerizable monomers are not compatible with other resin components (polymers and oligomers) contained in the coating agent, have low solubility in solvents, and fluorine components and silicone components have low compatibility. was there.
Therefore, the design of the coating agent using the above fluorine-based and silicone-based compounds has a considerably low degree of freedom, and it has been very difficult to develop both performances at the same time. For example, it is difficult to use a combination of a urethane acrylate oligomer having a silicone structure introduced in Patent Document 1 and a fluorine-based compound because of their low compatibility.

  In addition, in the technique disclosed in Patent Document 3, although a certain degree of antifouling property is imparted to urethane acrylate, in recent years, with the spread of touch panels, antifouling performance for screens used in various environments. Therefore, depending on the intended use, sufficient performance cannot be exhibited, and further improvement of antifouling performance has been demanded.

  Therefore, in the present invention, under such a background, a coating layer having excellent antifouling performance such as antifouling property and antifouling property and excellent coating film appearance, coating film hardness, and scratch resistance is formed. It is an object of the present invention to provide an active energy ray-curable resin composition useful for the above, a coating agent composition using the same, and a cured coating film.

However, as a result of intensive studies in view of such circumstances, the present inventors have blended a specific amount of a reactive fluorine-containing compound having a specific structure into a polysiloxane structure-containing urethane (meth) acrylate compound having a certain antifouling performance. The active energy ray-curable resin composition thus obtained has excellent compatibility between the two components, has an excellent appearance when blended, and an appearance when a cured coating film is formed, and also has an antifouling property due to the polysiloxane structure. The present inventors have found that the performance and the antifouling performance of the fluorine-containing compound are synergistically exhibited to obtain an excellent antifouling performance, and have completed the present invention.

That is, the gist of the present invention contains a polysiloxane structure-containing urethane (meth) acrylate compound (A), and reactive fluorine-containing compound represented by the following general formula (1) (B), reactive fluorine The compounding quantity of a containing compound (B) is 0.5-200 weight part with respect to 100 weight part of urethane (meth) acrylate type compounds (A), It is related with the active energy ray-curable resin composition characterized by the above-mentioned. Further, the present invention relates to a coating agent composition using such an active energy ray-curable resin composition, and a cured coating film.

[Where:
R1, R2, R3 and R4 each independently represents a hydrogen atom or a methyl group.
X ₁ is an alkylene group,
X ₂ is an arylene group,
X ₃ is a substituent X ₄ represented by the following general formula (2) or (3), an alkylene group, or an oxyalkylene group X ₅ is an alkylene group X ₆ is a hydrogen atom or an ester bond residue.
a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60 (however, the order in which the structural units are combined is arbitrary). ]

Since the active energy ray-curable resin composition of the present invention contains a polysiloxane structure-containing urethane (meth) acrylate compound and a reactive fluorine-containing compound having a specific structure, it is cured by irradiation with active energy rays. When used as a coating layer, it is excellent in antifouling performance such as dirt adhesion prevention and dirt removal.
Furthermore, the polysiloxane structure-containing urethane (meth) acrylate compound and the reactive fluorine-containing compound having a specific structure are particularly excellent in compatibility. Therefore, the appearance at the time of blending and the appearance as a cured coating film It is also excellent.

  In addition, the cured coating film obtained from the polysiloxane structure-containing urethane (meth) acrylate compound of the present invention and the reactive fluorine-containing compound having a specific structure is a polysiloxane portion derived from the polysiloxane structure-containing urethane (meth) acrylate compound. In addition, since both fluorine portions derived from the reactive fluorine-containing compound are present near the surface of the cured coating film, the respective performances can be exhibited simultaneously and synergistically, and excellent antifouling performance can be obtained. The reason is not clear, but by using a reactive fluorine-containing compound with a specific structure, optimal compatibility with the polysiloxane structure-containing urethane (meth) acrylate compound can be obtained, resulting in the surface state of the cured coating film. Presumed to be gained.

The present invention is described in detail below.
The active energy ray-curable resin composition of the present invention comprises a polysiloxane structure-containing urethane (meth) acrylate compound (A) and a reactive fluorine-containing compound (B) represented by the general formula (1) as essential components. It contains.
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 a hydroxyl group at one end represented by (4) and a polysiloxane compound having a hydroxyl group at both ends represented by the following general formula (5). It is preferable.
In addition, the said urethane (meth) acrylate type compound (A) may have a structure site | part derived from both general formula (4) and (5).

[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 an oxygen atom. a is an integer of 1 or more, and b is an integer of 1 to 3. ]

[Wherein 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 and c are integers 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 a hydroxyl group at one end represented by the general formula (4). ").) Is explained.

  The urethane (meth) acrylate compound (A1) is a polysiloxane compound (x1) having a hydroxyl group at one end represented by the general formula (4) (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).

For such a polysiloxane compound (x1), R ¹ in the general formula (4) 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 (4) 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 (4) is a hydrocarbon group or an organic group containing an oxygen 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 an oxygen atom include an oxyalkylene group and a polyoxyalkylene group.

  A in general formula (4) 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) 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 (x1) represented by the general formula (4) 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 (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) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and 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 modification -glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Cole 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 pentaerythritol 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. are 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), 50-8000 are preferable, Especially preferably, it is 50-5000, More preferably, it is 600-3000. 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 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 (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 (x2) 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 (x4) 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 (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 (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 polyisocyanate compound (x2) has two isocyanate groups and a hydroxyl group-containing (meth) acrylate compound ( When x3) has one hydroxyl group, the polysiloxane compound (x1): the polyvalent isocyanate compound (x2) is about 0.001 to 1: 1, and the isocyanate group of the polyvalent isocyanate compound (x2) Is 3 and the hydroxyl group-containing (meth) acrylate compound (x3) has one hydroxyl group, the polysiloxane compound (x1): the polyvalent isocyanate compound (x2) is about 0.001 to 2: 1. If it is.

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

  The weight of the structural portion 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. 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 (A1) thus obtained preferably has a weight average molecular weight of 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 of the urethane (meth) acrylate compound (A1) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly 500 to 120,000 mPa · s, more preferably 1,000 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 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 hydroxyl groups at both ends represented by the general formula (5)”. ) ").) Is explained.

[Wherein 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 and c are integers of 1 to 3. ]

  The urethane (meth) acrylate compound (A2) is a polysiloxane compound (y1) having a hydroxyl group at both ends represented by the general formula (5) (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).

In the polysiloxane compound (y1), R ¹ and R ³ in the general formula (5) are a hydrocarbon group or an organic group containing an oxygen 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 an oxygen atom include an oxyalkylene group and a polyoxyalkylene group.

R ² in the general formula (5) 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 (5) 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 (y1) is usually preferably from 100 to 50,000, particularly preferably from 500 to 10,000, more preferably from 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 (y1) include “X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., “ Examples of such products include Sailor Plane FM-4411, Silaplane FM-4421, Silaplane FM-4425, and “Macromonomer HK-20” manufactured by Toagosei Co., Ltd.

  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 2 or more ethylenically unsaturated groups, and has 4 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 polyisocyanate compound (y2) (if necessary, a polyisocyanate compound (y2) 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 (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 (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 between the polysiloxane compound (y1) and the polyvalent isocyanate compound (y2) is, for example, that the polyisocyanate compound (y2) has two isocyanate groups and a hydroxyl group-containing (meth) acrylate compound ( When y3) has one hydroxyl group, the polysiloxane compound (y1): the polyvalent isocyanate compound (y2) is about 0.001 to 1: 1, and the isocyanate group of the polyvalent isocyanate compound (y2). Is three and when the hydroxyl group-containing (meth) acrylate compound (y3) has one hydroxyl group, the polysiloxane compound (y1): the polyvalent isocyanate compound (y2) is about 0.001 to 2: 1. If it is.

  In the addition reaction between the reactive organism 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.

  Moreover, the weight of the structural part 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. 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 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 (A2) 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.

The viscosity of the urethane (meth) acrylate compound (A2) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly 500 to 120,000 mPa · s, more preferably 1,000 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 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 mixture ratio (weight ratio) of urethane (meth) acrylate type compound (A1) and urethane (meth) acrylate type compound (A2) ) Is preferably (A1) / (A2) = 5/95 to 95/5, particularly preferably (A1) / (A2) = 20/80 to 80/20.

  Next, the reactive fluorine-containing compound (B) represented by the following general formula (1) will be described.

[Where:
R1, R2, R3 and R4 each independently represents a hydrogen atom or a methyl group.
X ₁ is an alkylene group,
X ₂ is an arylene group,
X ₃ is a substituent X ₄ represented by the following general formula (2) or (3), an alkylene group, or an oxyalkylene group X ₅ is an alkylene group X ₆ is a hydrogen atom or an ester bond residue.
a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60 (however, the order in which the structural units are combined is arbitrary). ]

The reactive fluorine-containing compound (B) represented by the general formula (1) is characterized in that the structure contains a fluorine atom-containing structural moiety represented by X ₃ and a (meth) acryloyl group. By having such a structure, it is possible to exhibit excellent antifouling performance when used in combination with the urethane (meth) acrylate compound (A). Particularly when X ₄ is an oxyalkylene group, the compatibility with the urethane (meth) acrylate compound (A) is particularly improved, which is preferable.

  R1 to R4 in the general formula (1) are each independently a hydrogen atom or a methyl group.

X < ₁ > in General formula (1) is an alkylene group, As carbon number of an alkylene group, it is 1-12 normally, Preferably it is 1-8, Most preferably, it is 1-4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

X ₂ in the general formula (1) is an arylene group, and the number of carbon atoms of the arylene group is usually 6 to 12, preferably 6. Specific examples include a phenylene group and a naphthylene group.

X ₃ in the general formula (1) is a fluorine atom-containing substituent represented by the following general formula (2) or (3).

  In the reactive fluorine-containing compound (B), when a is 2 or more, it may contain both the substituents represented by the general formulas (2) and (3), or only one of them. It may be a thing.

X ₄ in the general formula (1) is an alkylene group or an oxyalkylene group.
As carbon number of an alkylene group, it is 1-12 normally, Preferably it is 1-8, Most preferably, it is 1-4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

  In the case of an oxyalkylene group, it may be a structure represented by the following general formula (7). When n is a polyoxyalkylene group of 2 or more, it may be a homopolymer of the same oxyalkylene chain or different. The oxyalkylene chain may be random or block copolymerized.

(In the formula, Y is an alkylene group, and n is an integer of 1 or more.)

  Y in the general formula (5) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

  N in General formula (5) is an integer greater than or equal to 1, Preferably it is 1-30, Most preferably, it is 2-20, More preferably, it is 5-15.

X ₅ in the general formula (1) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, particularly preferably 1 to 4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

X ₆ in the general formula (1) is a hydrogen atom or an ester bond residue.
Examples of the ester bond residue include a monovalent saturated hydrocarbon group or an aryl group.
The monovalent saturated hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specifically, a straight chain alkyl group such as a methyl group or an ethyl group, a branched alkyl group such as an isooctyl group or a 2-ethylhexyl group, an alicyclic alkyl group such as a cyclohexyl group, an isobornyl group, or a dicyclopentanyl group Can be mentioned.
As an aryl group, a C6-C20 thing, Preferably a C6-C15 thing is mentioned. Specific examples include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group.

X ₁ , X ₂ , X ₄ , X ₅ , X ₆ may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, Examples thereof include 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 _{X 1, X 2, X 4} , X 5, X 6 .

In general formula (1), a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60. Furthermore,
The ratio of a to (b + c + d) is preferably 0.1 ≦ a / (b + c + d) ≦ 10, particularly preferably 0.1 ≦ a / (b + c + d) ≦ 8,
The ratio of c to (b + c) is preferably 0 ≦ c / (b + c) <0.95, particularly preferably 0 ≦ c / (b + c) <0.9,
The ratio of d to (a + b + c) is preferably 0 ≦ d / (a + b + c) ≦ 5, particularly preferably 0 ≦ d / (a + b + c) ≦ 3.

  In addition, when a to d in the general formula (1) are integers of 2 or more, each structural site enclosed by [] in the general formula (1) may be the same structure or different structures. May be repeated.

  The weight average molecular weight of the reactive fluorine-containing compound (B) is usually 1,000 to 100,000, preferably 2,500 to 40,000, particularly preferably 3,000 to 30,000.

  The production method of the reactive fluorine-containing compound (B) is not particularly limited, and may be according to a known general fluorine-containing compound production method, for example, according to the method described in JP 2010-47680 A. That's fine.

The amount of the reactive fluorine-containing compound (B) is a urethane (meth) acrylate compound (A) 200 parts by weight der 0.5 to 100 parts by weight of is, particularly preferably 2 to 200 parts by weight, more Preferably it is 5-100 weight part. If the blending amount is too large, the compatibility is lowered and phase separation tends to occur or the coating film becomes cloudy. If the blending amount 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. In addition, when there is too little ethylenically unsaturated compound (C), there exists a tendency for coating-film hardness and abrasion resistance to fall.

  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 (6) even when used in various applications. It is preferable in that it is easy to impart physical properties.

[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 (6) (hereinafter sometimes abbreviated as “urethane (meth) acrylate compound (C1-1)”) is a polyvalent isocyanate compound. And a hydroxyl group-containing (meth) acrylate compound.

  A in the general formula (6) may be an integer of 2 to 50, preferably 2 to 20, and 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 (x2) and the hydroxyl group-containing (meth) acrylate compound (x3) may be charged into the reactor or reacted separately.

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. When using a 2-3 functional polyfunctional oligomer, 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 blending amount 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 (1), preferably an 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, screen printing, and the like.

  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 and the like (film, sheet, cup) Etc.), metal, 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, a high pressure mercury lamp emitting ultra-high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless lamp, etc. Irradiation of about / cm ² is sufficient.
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.

Hereinafter, the present invention will be described more specifically with reference to examples.
In the examples, “%” and “parts” are based on weight unless otherwise specified.

  As the polysiloxane structure-containing urethane (meth) acrylate compound (A), polysiloxane group-containing urethane (meth) acrylate compounds [A-1] and [A-2] were 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%) 39.9 g, general formula (4 polysiloxane compound represented by) (x1) (R ¹ = butyl, R ² = _{^{methyl, R 3 = -C 3 H 6}} OC 2 H 4 -, a = 80, b = 1, a hydroxyl value 12 mgKOH / g) 310.9 g, dibutyltin dilaurate 0.10 g, and methyl ethyl ketone 500 g were charged and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 0.99%, dipentaerythritol pentaacrylate (x3 ) [A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / )] 149.2 g, 2,6-di-tert-butylcresol 0.4 g was added dropwise over about 1 hour, the reaction was continued as it was, and when the isocyanate group disappeared, the reaction was terminated and the polysiloxane group contained A urethane (meth) acrylate compound [A-1] solution was obtained (solid content concentration 50%).
In addition, the said polysiloxane group containing urethane (meth) acrylate type compound [A-1] corresponds to the urethane (meth) acrylate type compound (A1) in the text.

・ <Production of polysiloxane group-containing urethane (meth) acrylate-based compound [A-2]>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, hexamethylene diisocyanate trimer (y2) (isocyanate group content 21.0%) 90.6 g, general formula (5 ) Polysiloxane compound (y1) (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 (y3) [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 (y3) [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-2] A solution was obtained (solid content concentration 50%).
In addition, the said polysiloxane group containing urethane (meth) acrylate type compound [A-2] corresponds to the urethane (meth) acrylate type compound (A2) in the text.

  As the reactive fluorine-containing compound (B), [B-1] to [B-5] and [B′-1] to [B′-2] shown in Table 1 below were prepared.

In the table,
* 1 contains two types of the following structural sites in the general formula (1). (D, R4, X ₆ ) = (10, CH _3- , H), (5, CH _3- , Isobornyl).
* 2 contains two types of the following structural sites in the general formula (1). (D, R4, X ₆ ) = (10, CH _3- , CH _3- ), (5, CH _3- , H).
※ 3 is the general formula (1) the following structural site in those two types containing, _{respectively, (d, R4, X 6} ) = (10, H, 4- (glycidyloxy) butyl), (5, CH _3- , CH _3- ).

As the ethylenically unsaturated compound (C), an ethylenically unsaturated compound [C-1] was produced according to the following method.
・ <Ethylenically unsaturated compound [C-1]>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 188.2 g of isophorone diisocyanate (isocyanate group content 37.8%), pentaerythritol triacrylate [pentaerythritol triacrylate and pentaerythritol Tetraacrylate mixture (hydroxyl value 120 mg KOH / g)] 811.8 g, 2,6-di-tert-butylcresol 0.4 g, dibutyltin dilaurate 0.10 g, and reacted at 60 ° C. At the time of disappearance, the reaction was terminated to obtain an ethylenically unsaturated compound [C-1].
The ethylenically unsaturated compound [C-1] corresponds to the urethane (meth) acrylate compound (C1-1) in the text.

  As a photopolymerization initiator (D), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”) [D-1] was prepared.

<Examples 1-9 and Comparative Examples 1-5>
[Production of active energy ray-curable resin composition]
The polysiloxane structure-containing urethane (meth) acrylate [A], the reactive fluorine-containing compound [B], and the ethylenically unsaturated compound [C] are blended so as to have the ratio shown in Table 2 in terms of solid content. 4 parts by weight of a photopolymerization initiator [D] (manufactured by BASF Japan, “Irgacure 184”) is added to 100 parts by weight of [A], [B], and [C], and the photopolymerization initiator is removed. The solid content was diluted with methyl ethyl ketone so as to have a concentration of 50% to obtain an active energy ray-curable resin composition solution. The following evaluation was performed about the obtained active energy ray hardening-type resin composition solution.

[Appearance of liquid mixture]
The appearance of the active energy ray-curable resin composition solution was observed.
(Evaluation)
○ ・ ・ ・ Uniform and transparent △ ・ ・ ・ White turbidity × ・ ・ ・ Phase separation occurred and aggregates settled

Next, the active energy ray-curable resin composition solution was applied on a PET film using a 50 μm applicator so that the film thickness after drying was 15 μm, and dried at 60 ° C. for 5 minutes. Using a high pressure mercury lamp 80W and one lamp, two passes of UV irradiation (cumulative irradiation dose 450 mJ / cm ² ) at a conveyor speed of 5.1 m / min from a height of 18 cm, a cured coating film (film thickness 15 μm) The following evaluation was performed.

[Appearance of coating film]
○ ・ ・ ・ Transparent and free of foreign matter × ・ ・ ・ White turbidity and aggregates on the coating surface

[Anti-fouling]
・ [Fingerprint wipeability]
A fingerprint was pressed against the cured coating film with a finger, and the coating film after wiping with Kimwipe was observed and evaluated as follows.
◎ ・ ・ ・ Can be wiped clean once or twice with light force ○ ・ ・ ・ Can be wiped by rubbing more than 3 times with light force △ ・ ・ ・ Can be wiped by rubbing many times × ・ ・ ・ Wipe many times It's hard to wipe fingerprints. [Magic ink wiping properties]
One round-trip line was drawn on the cured coating film with blue magic ink and allowed to stand for 24 hours, and then the coating film after wiping with a waste cloth was observed and evaluated as follows.
○ ・ ・ ・ Can be wiped clean △ ・ ・ ・ While it can be wiped off

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

[Abrasion resistance]
The cured film was visually observed for the degree of scratching on the surface of steel wool # 0000 subjected to a load of 300 g after 10 reciprocations on the surface of the cured film, and evaluated as follows.
◎ ・ ・ ・ No damage at all ○ ・ ・ ・ Slightly scratched △ ・ ・ ・ Slightly scratched × ・ ・ ・ Thin film is whitened due to damage

  The evaluation results of the above examples and comparative examples are shown together in Table 2.

The cured coating film obtained from the active energy ray-curable resin composition of the example shows good results for both fingerprint and magic ink, and has excellent coating film hardness and scratch resistance. A cured coating was obtained.
In Comparative Examples 1 and 2, when the active energy ray-curable resin composition does not contain a reactive fluorine-containing compound, the fingerprint wiping property is inferior. In Comparative Example 3, the active energy ray-curable resin composition is When the polysiloxane structure-containing urethane (meth) acrylate was not contained, the wiping property of the magic ink was inferior.
Further, in Comparative Examples 4 and 5, a reactive fluorine-containing compound other than the structure specified in the claims of the present application was used, but a uniform coating film could not be obtained or sufficient fingerprint wiping property could not be obtained. It became.

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 usefully used for coating applications such as an anchor coating agent and a magnetic powder coating binder.
It can also be used as a paint, ink, pressure-sensitive adhesive, adhesive, adhesive or the like.

Claims (9)

Polysiloxane structure-containing urethane (meth) acrylate compound (A), and reactive fluorine-containing compound (B) represented by the following general formula (1)
The compounding quantity of the reactive fluorine-containing compound (B) is 0.5 to 200 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). An active energy ray-curable resin composition.
[Where:
R1, R2, R3 and R4 each independently represents a hydrogen atom or a methyl group.
X ₁ is an alkylene group,
X ₂ is an arylene group,
X ₃ is a substituent X ₄ represented by the following general formula (2) or (3), an alkylene group, or an oxyalkylene group X ₅ is an alkylene group X ₆ is a hydrogen atom or an ester bond residue.
a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60 (however, the order in which the structural units are combined is arbitrary). ]
The polysiloxane structure-containing urethane (meth) acrylate compound (A) is a polysiloxane compound having a hydroxyl group at one end represented by the following general formula (4), a polyvalent isocyanate compound, and a hydroxyl group-containing (meth) acrylate compound. 2. The active energy ray-curable resin composition according to claim 1, which is a polysiloxane structure-containing urethane (meth) acrylate-based compound (A1) obtained by reacting.
[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 an oxygen atom. a is an integer of 1 or more, and b is an integer of 1 to 3. ] Polysiloxane structure-containing urethane (meth) acrylate compound (A) is represented by the following general formula (5): a polysiloxane compound having a hydroxyl group at both ends, a polyvalent isocyanate compound, and a hydroxyl group-containing (meth) acrylate compound 2. The active energy ray-curable resin composition according to claim 1, which comprises a polysiloxane structure-containing urethane (meth) acrylate-based compound (A2) obtained by reacting a polysiloxane structure.
[Wherein 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 and c are integers of 1 to 3. ]   The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the reactive fluorine-containing compound (B) has a weight average molecular weight of 1,000 to 100,000. Ethylenically unsaturated compounds [However, (A) and (B) except] (C) according to claim 1-4 active energy ray-curable resin composition according to any one of which is characterized by containing a. An ethylenically unsaturated compound [except (A) and (B)] (C) is a urethane (meth) acrylate compound (C1) and / or an ethylenically unsaturated monomer (C2). The active energy ray-curable resin composition according to claim 5 . Urethane (meth) acrylate compound (C1) is active energy ray according to claim 6, characterized by containing a urethane (meth) acrylate compound (C1-1) represented by the following general formula (6) Mold resin composition.
[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. ] Coating composition which is characterized in that it consists claim 1-7 active energy ray-curable resin composition according to any one of. A cured coating film obtained by irradiating the coating agent composition according to claim 8 with active energy rays.