JP6908193B2 - Fluorine-based copolymer, water-sliding surface modifier, curable resin composition, and water-sliding coating - Google Patents

Description

The present invention is a fluorine-based copolymer that can be suitably used as a water-sliding surface modifier having a specific structure capable of forming a coating film having good water-sliding property on the surface, and a curable resin using the same. The present invention relates to a composition and a water-sliding coating film which is a cured product thereof.

Fluorine-based surfactants or fluorine-based surface modifiers are widely used in various coating materials, surface modifiers, and the like because they are excellent in leveling property, water and oil repellency, and the like. A cured film obtained by curing a curable resin composition containing the fluorine-based surfactant or the fluorine-based surface modifier (hereinafter, these may be simply referred to as "fluorine-based surfactant"). Expresses excellent water repellency (oil repellency). Fluorine-based surfactants generally have a fluorinated hydrocarbon group in the structure of a compound in order to utilize the water- and oil-repellent performance of a fluorine atom, and a phase with a curable resin is further contained in one molecule. It is a compound having other structures for exhibiting solubility and curability, and various compounds have been provided depending on a target performance level and a method of use (see, for example, Patent Documents 1 and 2). ).

In modern living environments, there are many facilities, devices and utensils for which water repellency is desired or required, and the types are also automobile window glass, automobile painted surface, kitchen equipment, kitchen utensils, kitchen. There is an extremely wide range of equipment such as exhaust equipment, bathing equipment, washbasin equipment, medical equipment, medical machinery and equipment, mirrors, eyeglasses, and inkjet printer parts. Further, refrigerator heat exchangers, air conditioner outdoor units, and heat pump heat exchangers for EV automobiles, which will grow in the future, are also required to have water repellency from the viewpoint of preventing icing and frosting.

In the above application, the property (water-sliding property) that the attached water droplets quickly flow down due to gravity or the like is required. That is, the water-repellent surface only shows that the water adhering to it tends to become water droplets, and large water droplets fall due to their own weight, but if the water-sliding property is weak, the water droplets remain strongly adhered to the object surface and make the surface vertical. It may not fall even if it is tilted to. Such water droplets adhering to the surface remain as they are, which causes various inconveniences. For example, if a large number of water droplets are left on the windshield of an automobile, the windshield is diffusely reflected by light from a street lamp or the like, which has the disadvantage of obstructing the driver's field of vision. In addition, if a material with weak water-sliding property is used in an environment exposed to rainwater such as an exterior material, traces of water flow (rain streaks) will be left on the surface, and it cannot be said that the material has excellent stain resistance. The smaller the falling angle of water, the better the water-sliding property, but the correlation between the contact angle of water and the falling angle has not been recognized, and a surface modifier capable of achieving both water repellency and water-sliding is required. Has been done.

Japanese Unexamined Patent Publication No. 2013-6928 International release WO2012 / 002361

The problem to be solved by the present invention is a fluorine-based copolymer that can be suitably used as a surface modifier capable of obtaining a surface having excellent water-sliding property, a curable resin composition using the same, and the composition thereof. It is an object of the present invention to provide a water-sliding coating film which is a cured product of a product.

As a result of diligent research, the present inventors have made a polymerizable monomer having a fluorinated alkyl group having a specific length and a polymerizable unsaturated group, and a skeleton of an alicyclic hydrocarbon and a polymerizable unsaturated group. We have found that a copolymer having a polymerizable monomer having and as an essential monomer can be a surface modifier that solves the above problems, and have completed the present invention.

That is, the present invention comprises _{a polymerizable monomer (a1) having a fluorinated alkyl group represented by C n} F _{2n + 1} − (where n is 1 or 2) and a polymerizable unsaturated group.
A polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group,
A fluoropolymer characterized by being a copolymer containing the above as an essential raw material, a water-sliding surface modifier using the same, a curable resin composition containing the same, and a cured product of the composition. It provides a water-sliding coating.

By using the fluorine-based copolymer of the present invention as a surface modifier, a curable resin composition having excellent surface water-sliding properties such as a coating film can be obtained, and thermosetting systems and activities are used in applications where water-sliding properties are required. Various curing systems such as an energy ray curing system can be selected and applied.

The fluoropolymer of the present invention _{is a polymerizable monomer (a1) having a fluorinated alkyl group represented by C n} F _{2n + 1} − (where n is 1 or 2) and a polymerizable unsaturated group. ), And a polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group, as an essential raw material.

Conventionally, in order to exhibit water and oil repellency, it is preferable that the number of carbon atoms to which fluorine atoms are directly bonded is large. It has been said that the upper limit of the number of carbon atoms is 6. Therefore, for example, as in Patent Document 2 described above, in order to increase the number of fluorine atoms in one molecule (that is, to increase the fluorine atom content), a fluorinated alkylene chain having about 2 to 3 carbon atoms is used. Compounds having a perfluoroalkylene ether chain, which are linked by an ether bond, have also been provided.

However, as described above, there is no correlation between water repellency and water repellency, and even on a water repellent surface, water repellency is poor, leaving white after water droplets, or substances in the air contained in rainwater or the like. May remain as streaks on the surface of the coating film, and the current situation is that it is not always possible to improve the water-sliding property by using a curable resin composition containing a fluorine-based compound.

Under such circumstances, the compound contains a structure in which fluorine atoms are directly bonded and has 1 or 2 carbon atoms, that is, represented by C _n F _{2n + 1} − (where n is 1 or 2) in the compound. It has been found that the use of a compound having an alkyl fluorinated group and an alicyclic hydrocarbon skeleton in the compound significantly enhances the water-sliding property on the surface of the coating film.

_{The polymerizable monomer (a1) having a fluorinated alkyl group represented by C n} F _{2n + 1} − (where n is 1 or 2) and a polymerizable unsaturated group used in the present invention is in the molecule. Any compound having the fluorinated alkyl group and a polymerizable unsaturated group can be used without particular limitation. As the fluorinated alkyl group, it is particularly preferable that n is 1 from the viewpoint of obtaining a cured product having more excellent water-sliding property. _{The number of fluorinated alkyl groups represented by C n} F _{2n + 1} − (where n is 1 or 2) in one molecule is not particularly limited, and other performances required for the cured product, For example, it is preferable to adjust the fluorine atom content according to the level of water repellency and surface smoothness.

Examples of the polymerizable unsaturated group contained in the polymerizable monomer (a1) include a (meth) acryloyl group, a vinyl group, a maleimide group, and the like. Among these, the (meth) acryloyl group is preferable because it is easy to obtain a raw material, it is easy to control the compatibility with the compounding components in various curable resin compositions, and it has good polymerization reactivity. As the compound having the (meth) acryloyl group, for example, a monomer represented by the following general formula (1) or (2) can be preferably exemplified. Further, the polymerizable monomer (a1) may be used alone or in combination of two or more.

In [the above general formula ^{(1) (2), R} 1 is a hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or _-C m _H 2m -Rf (m is an integer from 1 to 8 ), Rf is _{a group represented by C n} F _{2n + 1} (where n is 1 or 2), and X is any one group of the following formulas (X-1) to (X-10). show. ]

〔上記式中のｍは０〜８の整数であり、ｋは０〜８の整数であり、Ｒｆは前記と同じである。〕

[In the above formula, m is an integer of 0 to 8, k is an integer of 0 to 8, and Rf is the same as described above. ]

In the present invention, "(meth) acrylate" means one or both of methacrylate and acrylate, and "(meth) acrylic acid" means one or both of methacrylic acid and acrylic acid.

The polymerizable monomer (a2) used in the present invention has an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group.

The alicyclic hydrocarbon skeleton may include, for example, cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornan, decahydro, which may be substituted by one or more with any substituent. Naphthalene, perhydrofluorene, tricyclo [5.2.1.0 ^2.6 ] decan, adamantan, quadriciclan, congressan, cuban, spiro [4.4] octane, cyclopentene, cyclohexene, cycloheptane, cyclooctane, cyclodecene, bicyclo [ 2.2.2] Oct-2-ene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloheptatriene, cyclodecatriene, cyclooctatetraene, norbornylene, octahydronaphthalene, bicyclo [2.2.1] Examples thereof include alicyclic hydrocarbon skeletons such as heptadiene, bicyclo [4.3.0] nonadien, dicyclopentadiene, hexahydroanthracene, and spiro [4.5] decadien.

Among these, a skeleton having a crosslinked structure is preferable because the surface of the obtained coating film has high hardness and higher water-sliding property and antifouling property. For example, adamantane, perhydroindene, decahydronaphthalene, etc. Perhydrofluorene, perhydroanthracene, perhydrophenantene, dicyclopentane, dicyclopentene, perhydroacenaften, perhydrophenalene, norbornane, norbornene, etc. are preferred, especially adamantane, dicyclopentane, dicyclopentene, norbornene, norbornene. Preferably, adamantane is the most preferred skeleton.

Examples of the polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group, a maleimide group and the like. Among these, the (meth) acryloyl group is preferable because it is easy to obtain a raw material, it is easy to control the compatibility with the compounding components in various curable resin compositions, and it has good polymerization reactivity.

Hereinafter, a polymerizable monomer having an adamantane skeleton and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having an adamantane skeleton and a (meth) acryloyl group include compounds represented by the following formulas (a2-1) and (a2-2).

（式中、Ｌは反応性官能基を表し、Ｘ及びＹは２価の有機基又は単結合を表し、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, L represents a reactive functional group, X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group or CF _3. )

Examples of the reactive functional group include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, an acid anhydride group and the like. Of these, a hydroxyl group is preferable from the viewpoint of obtaining a surface modifier having good compatibility with the curable resin composition or easily introducing an active energy ray-curable group into the obtained copolymer.

The bonding positions of the organic group having the reactive functional group represented by -XL in the general formula (a2-1) and Y may be bonded to any carbon atom in the adamantane skeleton. , -XL may have two or more. Further, the hydrogen atom bonded to the carbon atom constituting the adamantane skeleton may be partially or wholly substituted with a fluorine atom, an alkyl group or the like. Further, X and Y in the above general formula (a2-1) are divalent organic groups or single bonds, and the divalent organic group includes carbon atoms such as a methylene group, a propyl group and an isopropylidene group. The number 1 to 8 alkylene groups can be mentioned.

Further, in the compound represented by the above formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantane skeleton. Further, the hydrogen atom bonded to the carbon atom constituting the adamantane skeleton in the above general formula (a2-1) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-1) include compounds represented by the following.

Further, as a more specific example of the polymerizable monomer represented by the general formula (a2-2), for example, a compound represented by the following can be mentioned.

Among the polymerizable monomers having an adamantane skeleton and a (meth) acryloyl group, the above formulas (a2-1-1) and (a2-1-3), from the viewpoint that the Tg of the coating film can be made higher. The compounds represented by (a2-1-5), (a2-1-7), (a2-2-1), (a2-2-2), and (a2-2-3) are more preferable.

Hereinafter, a polymerizable monomer having a dicyclopentane skeleton and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a dicyclopentane skeleton and a (meth) acryloyl group include a compound represented by the following formula (a2-3).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentane skeleton. Further, the hydrogen atom bonded to the carbon atom constituting the dicyclopentane skeleton in the above general formula (a2-3) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like. ..

More specific examples of the polymerizable monomer represented by the general formula (a2-3) include compounds represented by the following.

Among the polymerizable monomers having a dicyclopentane skeleton and a (meth) acryloyl group, the compound represented by the above formula (a2-3-2) is preferable from the viewpoint that the Tg of the coating film can be made higher.

Hereinafter, a polymerizable monomer having a dicyclopentene skeleton and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a dicyclopentene skeleton and a (meth) acryloyl group include a compound represented by the following formula (a2-4).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-4), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentene skeleton. Further, the hydrogen atom bonded to the carbon atom constituting the dicyclopentene skeleton in the above general formula (a2-3) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-4) include compounds represented by the following.

Among the polymerizable monomers having a dicyclopentene skeleton and a (meth) acryloyl group, the Tg of the coating film can be made higher, which is represented by the above formulas (a2-4-3) and (a2-4-4). The compound to be used is preferable.

Hereinafter, a polymerizable monomer having a norbornane skeleton and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a norbornane skeleton and a (meth) acryloyl group include a compound represented by the following formula (a2-5).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-5), the (meth) acryloyl group may be bonded to any carbon atom in the norbornane skeleton. Further, the hydrogen atom bonded to the carbon atom constituting the norbornane skeleton in the above general formula (a2-5) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-5) include compounds represented by the following.

Among the polymerizable monomers having a norbornane skeleton and a (meth) acryloyl group, it is represented by the above formulas (a2-5-3) and (a2-5-4) from the viewpoint that the Tg of the coating film can be made higher. Compounds are preferred.

Hereinafter, a polymerizable monomer having a norbornene skeleton and a polymerizable unsaturated group, which can be preferably used as the polymerizable monomer (a2) in the present invention, will be described.

Examples of the polymerizable monomer having a norbornene skeleton and a (meth) acryloyl group include compounds represented by the following formulas (a2-6) and (a2-7).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

Further, in the compound represented by the above formula (a2-6), the (meth) acryloyl group may be bonded to any carbon atom in the norbornene skeleton. Further, the hydrogen atom bonded to the carbon atom constituting the norbornene skeleton in the above general formula (a2-6) may be partially or wholly substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-6) include compounds represented by the following.

Among the polymerizable monomers having a norbornene skeleton and a (meth) acryloyl group, it is represented by the above formulas (a2-6-3) and (a2-6-4) from the viewpoint that the Tg of the coating film can be made higher. Compounds are preferred.

As described above, the fluorocopolymer of the present invention _{is a polymerizable single having a fluorinated alkyl group represented by C n} F _{2n + 1} − (where n is 1 or 2) and a polymerizable unsaturated group. It is characterized by being a copolymer containing a metric (a1) and a polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials. Here, the ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) is a mass ratio (because a surface modifier having better compatibility with the curable resin composition can be obtained). a1): (a2) = preferably in the range of 5:95 to 95: 5, more preferably in the range of 10:90 to 90:10.

As a raw material used for obtaining the fluorine-based copolymer of the present invention, a monomer copolymerizable with the above (a1) and (a2) may be used in combination as long as the effects of the present invention are not impaired. Examples of the monomer that can be used in combination include a monomer having a polyoxyalkylene chain, a monomer having a linear alkyl group having 1 to 18 carbon atoms, and a branched alkyl having 1 to 18 carbon atoms. Monomers having a group and the like can be mentioned.

Examples of the polymerizable unsaturated group contained in the other copolymerizable monomer include a (meth) acryloyl group, a vinyl group, a maleimide group, and the like, and the monomer (a1) and the monomer (a2). ) Is a (meth) acryloyl group, the polymerizable unsaturated group of the other monomer is also a (meth) acryloyl group because the copolymerizability is good. Is preferable.

Examples of the monomer having an oxyalkylene group include a monomer represented by the following general formula (a3-1).

（式中、Ｒ^２は水素原子又はメチル基であり、Ｙ^１Ｘ及びＹ^２はそれぞれ独立のアルキレン基であり、ｐ及びｑはそれぞれ０または１以上の整数であり、かつｐとｑとの合計は１以上であり、Ｒ^３は水素原子又は炭素原子数１〜６のアルキル基である。）

(In the formula, R ² is a hydrogen atom or a methyl group, Y ¹ X and Y ² are independent alkylene groups, respectively, p and q are 0 or an integer of 1 or more, respectively, and p and q The total is 1 or more, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

^{Y 1} and Y ² in the above general formula (a3-1) are alkylene groups, and the alkylene groups include those having a substituent. As a specific example of the −O− (Y ¹ O) n− (Y ² O) m− moiety, an ethylene glycol residue in which the number of repetition units p is 1, m is 0, and Y ^{1 is ethylene, repetition.} A propylene glycol residue having a unit number p of 1 and m being 0 and Y ¹ being propylene, a butylene glycol residue having a repeating unit number p of 1 and m being 0 and Y ^{1 being butylene, repeating.} A polyethylene glycol residue in which the number of units p is an integer of 2 or more and q is 0 and Y ¹ is ethylene, and the number of repetitions p is an integer of 2 or more and q is 0 and Y ¹ is propylene. Polyalkylene residues such as ethylene oxide and propylene oxide copolymer residues in which the polypropylene glycol residue, the number of repeating units p and q are both integers of 1 or more, and Y ¹ or Y ^{2 is ethylene and the other is propylene.} Glycol residues can be mentioned.

The degree of polymerization of the polyalkylene glycol in the formula (a3-1), that is, the total of p and q in the general formula (a3-1) is preferably in the range of 1 to 100, and preferably in the range of 2 to 80. More preferably, those in the range of 3 to 50 are more preferable. The ^{repeating unit including Y 1} and the repeating unit including Y ² may be arranged randomly or in a block shape.

^{R 3} in the above general formula (a3-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer is a mono (meth) acrylic acid ester of alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and when R ³ has 1 to 6 carbon atoms, it is an alkylene. The non-(meth) acrylic acid ester of the mono (meth) acrylic acid ester of glycol is sealed with an alkyl group having 1 to 6 carbon atoms.

Among the general formula (a3-1), a monomer having a poly (oxyalkylene) group composed of a plurality of oxyalkylene groups is preferable, and specific examples thereof include polypropylene glycol mono (meth) acrylate and polyethylene glycol mono (). Meta) acrylate, polytrimethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (Ethethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate, polypropylene glycol / polytetramethylene glycol mono (Meta) acrylate, poly (propylene glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene Glycol mono (meth) acrylate, poly (tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / Trimethylene glycol) mono (meth) acrylate, polyethylene glycol / polyethylene glycol mono (meth) acrylate, poly (propylene glycol / trimethylene glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono (meth) acrylate , Poly (trimethylethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, polybutylene glycol -Polyethylene glycol mono (meth) acrylate and the like can be mentioned. In addition, "poly (ethylene glycol / propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol / polypropylene glycol" is a block copolymer of ethylene glycol and propylene glycol. means. The same is true for other things. In the present invention, when a monomer having an oxyalkylene group is used, a copolymer having good compatibility with other components in the curable resin composition can be obtained. Therefore, polypropylene glycol mono (meth) Acrylate, polyethylene glycol mono (meth) acrylate, and polyethylene glycol / polypropylene glycol mono (meth) acrylate are preferable.

Examples of commercially available products of monomers having an oxyalkylene group include "NK ester M-20G", "NK ester M-40G", and "NK ester M-90G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "NK Ester M-230G", "NK Ester AM-90G", "NK Ester AMP-10G", "NK Ester AMP-20G", "NK Ester AMP-60G", "Blemmer PE-" manufactured by Nichiyu Co., Ltd. 90 ”,“ Blemmer PE-200 ”,“ Brenmer PE-350 ”,“ Brenmer PME-100 ”,“ Brenmer PME-200 ”,“ Brenmer PME-400 ”,“ Brenmer PME-4000 ”,“ Brenmer PP-1000 ” , "Blemmer PP-500", "Blemmer PP-800", "Blemmer 70PEP-350B", "Blemmer 55PET-800", "Blemmer 50 POEP-800B", "Blemmer 10PPB-500B", "Blemmer NKH-5050" , "Blemmer AP-400", "Blemmer AE-350" and the like. These monomers having an oxyalkylene group can be used alone or in combination of two or more.

Examples of the monomer having an alkyl group include a monomer represented by the following general formula (a3-2).

（式中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は水素原子又は炭素原子数１〜１８の直鎖状、分岐状又は環構造を有するアルキル基である。）

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a hydrogen atom or an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)

^{In addition, R 5} in the above general formula (a3-2) is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms, and this alkyl group is an aliphatic or aromatic group. It may have a substituent such as a hydrocarbon group, a hydroxyl group, or an epoxy group. Specific examples of the monomer represented by the above formula (a3-2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and octyl (meth) acrylate. Alkyl esters with 1 to 18 carbon atoms, glycidyl methacrylate, 4-hydroxy, etc. of (meth) acrylic acids such as 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate. Epoxy group-containing unsaturated monomers such as butyl acrylate glycidyl ether, carboxyls such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and itaconic acid. Group-containing unsaturated monomers and the like can be mentioned. These alkyl group-containing monomers can be used alone or in combination of two or more.

When the above-mentioned monomer (a1) and the monomer (a2) are used in combination with the other monomer as described above, the amount used is 100 mol in total of the monomer (a1) and the monomer (a2). It is preferable that the content is in the range of 5 to 40 mol%, because a copolymer capable of exhibiting other effects such as surface hardness and scratch resistance without impairing the water-sliding property can be obtained. More preferably, it is in the range of ~ 30 mol%. From the viewpoint of water slipperiness, it is most preferable not to use other monomers in combination.

In the fluorine-based copolymer of the present invention, for example, a monomer (a1) and a monomer (a2), or other monomers used in combination as necessary, can be subjected to living cationic polymerization in the coexistence of them. It is preferably produced by living polymerization such as living anionic polymerization and living radical polymerization. Further, among these living polymerizations, it is particularly preferable to use living radical polymerization because the polymerization reaction can be easily controlled.

In the living radical polymerization, the growth reaction proceeds when the Dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly generates radicals and reacts with the monomer. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and radical polymerization using organic tellurium (TERP). Can be mentioned. Which of these methods is used is not particularly limited, but the ATRP is preferable from the viewpoint of ease of control and the like. ATRP is polymerized using an organic halide, a sulfonyl halide compound or the like as an initiator, and a metal complex composed of a transition metal compound and a ligand as a catalyst.

An organic halogenated compound can be used as the polymerization initiator used in the ATRP. Specifically, 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α, α'-dichloroxylene, α, α'-dibromoxylene, hexakis (α-). Bromomethyl) benzene, a 2-halogenated carboxylic acid having 1 to 6 carbon atoms (for example, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) having 1 to 6 carbon atoms. Examples thereof include alkyl esters. Further, more specific examples of the alkyl ester having 1 to 6 carbon atoms of the 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, and the like. Examples thereof include methyl 2-bromopropionate and ethyl 2-bromoisobutyrate.

The transition metal compound used in the ATRP is represented by ^{M n +} X _n. The transition metals M ^{n +} are Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ And can be selected from the group consisting of ^{Ag 2+.} Further, X is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (S0 ₄ ) _1/2 , (P0 ₄ ) _1/3 , (HP0 ₄ ) _1/2 , (H ₂ P0 ₄ ), and a triflate. , Hexafluorophosphate, methane sulfonate, aryl sulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an aryl, linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ² is a hydrogen atom or halogen and 1 to 5 carbon atoms. It represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted with fluorine or chlorine 1 to 6 times (preferably 1 to 3 times). Further, n represents a formal charge on the metal and is an integer of 0-7.

The transition metal complex is not particularly limited, but preferably, the transition metal complex of groups 7, 8, 9, 10, and 11 is preferable, and more preferably, 0-valent copper, monovalent copper, and divalent ruthenium. Examples include divalent iron or divalent nickel complexes.

Examples of the compound having a ligand capable of coordinating with the transition metal include a ligand containing one or more nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with the transition metal via a σ bond. A compound having a ligand having two or more carbon atoms that can be coordinated with a transition metal via a π bond, and a compound having a ligand having a ligand capable of coordinating with a transition metal via a μ bond or an η bond. Can be mentioned.

Specific examples of the compound having the above-mentioned ligand include 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexa, when the central metal is copper. Examples thereof include a complex with a ligand such as a polyamine such as methyltris (2-aminoethyl) amine. Examples of the divalent ruthenium complex include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichlorop-simenruthenium, and dichloro (norbornadiene) ruthenium. Examples thereof include cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, and carbonylchlorohydridotris (triphenylphosphine) ruthenium. Further, examples of the divalent iron complex include a bistriphenylphosphine complex and a triazacyclononane complex.

Further, in the above-mentioned living radical polymerization, it is preferable to use a solvent. Examples of the solvent used include ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; toluene and Aromatic solvents such as xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol and isopropanol; aprotonic polar solvents such as dimethylformamide and dimethyl sulfoxide. Further, as long as the effects of the present invention are not impaired, for example, chlorinated fluorinated hydrocarbons (particularly 2 to 5 carbon atoms), particularly HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2, 2,3,3-tetrachlorohexafluorobutane,), hexafluoroxylene, fluorine-based ether and the like can be used. In addition, these solvents can be used alone or in combination of two or more.

In the production method, it is preferable to carry out living radical polymerization of a mixture of monomers in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinating with the transition metal, and a solvent. ..

The polymerization temperature during living radical polymerization is preferably in the range of room temperature to 120 ° C.

Further, when the copolymer of the present invention is produced by the above-mentioned production method, a metal due to the transition metal compound may remain in the copolymer. Therefore, when the surface modifier of the present invention is used in an application that causes a problem when the metal remains, it is preferable to remove the residual metal by using activated alumina or the like after the polymerization reaction.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 3000 to 50000, more preferably 1000 to 30000, and more preferably 1500 to 1500, because it is a surface modifier that can obtain a firmer coating film surface. The range of 20000 is more preferred. The dispersity (Mw / Mn) is preferably 1.50 or less, more preferably 1.00 to 1.50, and 1.00 to 1.00, from the viewpoint of obtaining a surface having more uniform water-sliding property. The range of 1.40 is more preferred.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions of GPC are as follows.

[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-" GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec Japan Co., Ltd.)
Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran (THF)
Flow velocity 1.0 ml / min Sample: A solution of 1.0 mass% tetrahydrofuran in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30".

(Unidispersed polystyrene)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation
"F-550" manufactured by Tosoh Corporation

Further, when the copolymer of the present invention contains reactive functional groups such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group and an acid anhydride group, that is, these reactive functional groups are used. In the case of copolymerization using the containing monomer, these reactive functional groups are utilized to form a present on the surface of the coating film by a chemical bond with the curable resin when the curable resin composition described later is prepared. Since the fluorine-based copolymer of the present invention can be immobilized, it is preferable from the viewpoint of maintaining the long-term performance of water-sliding property. Furthermore, these reactive functional groups can be used to introduce active energy ray-curable groups into the surface modifier.

The method for incorporating the above-mentioned reactive functional group in the copolymer of the present invention is not particularly limited, and the above-mentioned reactive functional groups are used as the monomer (a1) and the monomer (a2). Examples thereof include a method using a monomer having a group and a method using a monomer having these reactive functional groups as another monomer used in combination with the monomers (a1) and (a2).

Examples of the monomer having a reactive functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate, etc. Hydroxyl group-containing unsaturated monomer; isocyanate group-containing unsaturated monomer such as 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate; glycidyl methacrylate, 4-hydroxybutyl Epoxy group-containing unsaturated monomer such as acrylate glycidyl ether; carboxyl groups such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and itaconic acid. Contains unsaturated monomers; examples thereof include carboxylic acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. These monomers may be used alone or in combination of two or more.

The monomers having these reactive functional groups are charged into the reaction system at the same time as the monomer (a1) and the monomer (a2), and are copolymerized by the above-mentioned polymerization method to obtain the same weight. Reactive functional groups can be introduced into the coalescence.

Further, by reacting the copolymer having a reactive functional group obtained by the copolymerization reaction with a compound having a group capable of reacting with the reactive functional group and an active energy ray-curable group. , An active energy ray-curable group can be introduced into the side chain of the copolymer, and an active energy ray-curable surface modifier can be obtained.

For example, in the case of a copolymer having a hydroxyl group, the above-mentioned monomer having an isocyanate group, a glycidyl group, a carboxy group, an acid anhydride group, etc. capable of reacting with the copolymer can be reacted and has a carboxy group. In the case of a copolymer, a monomer having a glucidyl group and a hydroxyl group can be reacted, and in the case of a copolymer having an isocyanate group, a monomer having a hydroxyl group can be reacted.

When the monomer is reacted with the copolymer, it is preferable that the active energy ray-curable functional group does not react. For example, the temperature condition is adjusted to the range of 30 to 120 ° C. It can be carried out in an organic solvent in the presence of a polymerization inhibitor, if necessary.

Specifically, when reacting a hydroxyl group with an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, or the like is used as a polymerization inhibitor, and a urethanization reaction catalyst is used. As the above, a method of using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate and the like and reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferable.

When the glucidyl group and the carboxy group are reacted, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and triethylamine is used as an esterification reaction catalyst. , Etc., quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. are used, and the reaction temperature is 80. It is preferable to react at ~ 150 ° C., particularly at 100 to 120 ° C.

The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, etc. Examples thereof include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of boiling point and compatibility.

The fluorine atom content in the fluorine-based copolymer of the present invention is preferably in the range of 5 to 40 wt%, more preferably in the range of 5 to 30 wt%, from the viewpoint of excellent balance between good leveling property and water-sliding property. The range of 5 to 25 wt% is more preferable. The fluorine atom content can be measured by combustion ion chromatography.

The curable resin composition of the present invention contains the fluorine-based copolymer of the present invention. The content of the fluoropolymer in the curable resin composition varies depending on the type of curable resin to be combined, the coating method, the target film thickness, etc., but it has high water-sliding property and leveling property on the coating surface. From the viewpoint of goodness, 0.001 to 10 parts by mass is preferable, 0.01 to 5 parts by mass is more preferable, and 0.01 to 2 parts by mass is further preferable with respect to 100 parts by mass of the solid content in the composition. ..

As the curable resin composition, for example, natural resins such as petroleum resin paints, cellac paints, rosin paints, cellulose paints, rubber paints, lacquer paints, cashew resin paints, and oil-based vehicle paints are used for paints. Paints that were used: For synthetic resins such as phenol resin paint, alkyd resin paint, unsaturated polyester resin paint, amino resin paint, epoxy resin paint, vinyl resin paint, acrylic resin paint, polyurethane resin paint, silicone resin paint, fluororesin paint, etc. Examples include the paint that was used.

Further, in addition to the coating composition exemplified above, the fluorine-based copolymer of the present invention can be used for the active energy ray-curable composition. At this time, as described above, by using a copolymer having an active energy ray-curable group introduced into the side chain of the copolymer used as the surface modifier, the modifier can be firmly fixed on the coating film surface. Therefore, it is preferable because it is excellent in long-term performance stability of water sliding property. This active energy ray-curable composition contains an active energy ray-curable resin or an active energy ray-curable monomer as a main component thereof. The active energy ray-curable resin and the active energy ray-curable monomer may be used alone or in combination.

Examples of the active energy ray-curable resin include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, maleimide group-containing resin, and the like. However, urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency, low shrinkage, and the like.

The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. And so on.

Examples of the aliphatic polyisethylene compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanis, octamethylene diisocyanate, decamethylene diisocyanis, 2-methyl-1,5-pentanediisocyanis, and 3-methyl-. 1,5-Pentane diisocyanis, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanis, isophoron diisocyanis, norbornan diisocyanate, hydrogenated diphenylmethane diisocyanis , Hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxamethylene diisocyanate, cyclohexamethylene diisocyanate and the like, and examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like. Examples thereof include xylylene diisocyanate, 1,5-naphthalenedi isocyanate, trizine diisocyanate, and p-phenylenedi isocyanate.

Examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,5. -Pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate of hydroxypivalate, and other dihydric alcohol mono (meth) ) Acrylate: Trimethylol propanedi (meth) acrylate, ethoxylated trimethylol propane (meth) acrylate, propoxylated trimethylol propandi (meth) acrylate, glycerindi (meth) acrylate, bis (2- (meth) acryloyloxyethyl) ) Mono or di (meth) acrylates of trivalent alcohols such as hydroxyethyl isocyanurate, or hydroxyl group-containing mono and di (meth) acrylates in which some of these alcoholic hydroxyl groups are modified with ε-caprolactone; pentaerythritol tri. A compound having a monofunctional hydroxyl group and a trifunctional or higher (meth) acryloyl group such as (meth) acrylate, ditrimethylolpropantri (meth) acrylate, dipentaerythritol penta (meth) acrylate, or a compound obtained by further ε-. Caprolactone-modified hydroxyl group-containing polyfunctional (meth) acrylate; oxyalkylene chains such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate. (Meta) acrylate compound having (meth) acrylate compound having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate; poly (ethylene glycol) Examples thereof include (meth) acrylate compounds having an oxyalkylene chain having a random structure such as −tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxy group-containing acrylate compound can be carried out by a conventional method, for example, in the presence of a urethanization catalyst. Specific examples of the urethanization catalysts that can be used here are amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; hoffins such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate and octyl. Organic tin compounds such as tin diacetate, dibutyltin diacetate and tin octylate; organometal compounds such as zinc octylate can be mentioned.

Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound have excellent transparency of the cured coating film and good sensitivity to active energy rays. It is preferable because it has excellent curability.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols. Examples of α, β-unsaturated dibasic acid or acid anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof. The aromatic saturated dibasic acid or its acid anhydride includes phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, phthalic anhydride and these. Esters and the like can be mentioned. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and esters thereof. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, and triethylene glycol. Tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like, and others. Similarly, oxides such as ethylene oxide and propylene oxide can be used.

Next, as the epoxy vinyl ester resin, (meth) acrylic acid is reacted with the epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. What can be obtained is mentioned.

Examples of the maleimide group-containing resin include a bifunctional maleimide urethane compound obtained by urethaneizing N-hydroxyethyl maleimide and isophorone diisocyanate, and a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol. Examples thereof include a tetrafunctional maleimide ester compound obtained by esterifying maleimide caproic acid and a tetraethylene oxide adduct of pentaerythritol, and a polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyhydric alcohol compound. These active energy ray-curable resins can be used alone or in combination of two or more.

Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene having a number average molecular weight in the range of 150 to 1000. Glycoldi (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) having a number average molecular weight in the range of 150 to 1000. Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalic acid Ester Neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethyl propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaeryth Lutortetra (meth) acrylate, trimethylolpropandi (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl ( Meta) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Aliphatic alkyl (meth) acrylates such as isostearyl (meth) acrylates, glycerol (meth) acrylates, 2-hydroxyethyl (meth) acrylates, 3-chloro-2-hydroxypropyl (meth) acrylates, glycidyl (meth) acrylates, Allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (meth) acryloxipropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropi Lenglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxyylated cyclodecatorien (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N- Ppropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethyl carbonate, 2-maleimideethyl -Propyl carbonate, N-ethyl- (2-maleimideethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidepropyl) ether, bis (2-maleimideethyl) carbonate, 1,4- Examples thereof include maleimides such as dimaleimide cyclohexane.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate, which are particularly excellent in the hardness of the cured coating film. Bifunctional or higher functional (meth) acrylates such as meta) acrylates are preferred. These active energy ray-curable monomers can be used alone or in combination of two or more.

The active energy ray-curable composition can be made into a cured coating film by applying the active energy ray-curable composition to a substrate and then irradiating the substrate with active energy rays. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve the curability. Further, if necessary, a photosensitizer can be further added to improve the curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or a photosensitizer. There is no need to add a photosensitizer.

Examples of the photopolymerization initiator include an intracellular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, and 1- (4-isopropylphenyl) -2-hydroxy. -2-Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetphenone compounds such as methylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;

Benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl , Methylphenylglioxyester and the like.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoyl benzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and the like. Benzophenone compounds such as acrylicized benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Mihira-ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacrydone, Examples thereof include 2-ethylanthraquinone, 9,10-phenanthrene quinone and benzophenone.

Among the above photopolymerization initiators, 1-hydroxycyclohexylphenylketone is excellent in compatibility with the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition. , And benzophenone are preferable, and 1-hydroxycyclohexylphenyl ketone is particularly preferable. These photopolymerization initiators can be used alone or in combination of two or more.

Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate and the like. Examples of sulfur compounds.

The amount of these photopolymerization initiator and photosensitizer used is preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass, respectively, with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition. % Is more preferable, and 0.3 to 7 parts by mass is further preferable.

Further, in the above-mentioned coating composition, if necessary, an organic solvent; a pigment, a dye, a colorant such as carbon; an inorganic substance such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate, etc. Powder; higher fatty acid, acrylic resin, phenol resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin (PTFE (polytetrafluoroethylene) ) Etc.), various resin fine powders such as polyethylene and polypropylene; antistatic agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, antioxidants, rust preventives, slip agents, waxes, gloss adjusters , Mold release agents, compatibilizers, conductivity modifiers, dispersants, dispersion stabilizers, thickeners, anti-settling agents, silicone-based or hydrocarbon-based surfactants, and other various additives can be added as appropriate. be.

The organic solvent is useful for appropriately adjusting the solution viscosity of the coating composition, and particularly for thin film coating, it becomes easy to adjust the film thickness. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; methyl ethyl ketone, Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents may be used alone or in combination of two or more.

The coating method of the above composition varies depending on the application, but for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, screen. Examples thereof include a coating method using printing, spraying, an applicator, a bar coater, electrostatic coating, and a molding method using various molds.

Further, the fluorine-based copolymer of the present invention can also be used for resist applications. The resist application comprises the fluoropolymer of the present invention and a photoresist agent, and the photoresist agent is (1) an alkali-soluble resin, (2) a radiation-sensitive substance (photosensitive substance), and (3) a solvent. , And, if desired, (4) other additives can be included.

Examples of the (1) alkali-soluble resin include resins that are soluble in an alkaline solution, which is a developing solution used when patterning a resist. Examples of the alkali-soluble resin include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, fluoroglycinol, and hydroquinone, and at least one selected from these alkyl-substituted or halogen-substituted aromatic compounds and formaldehyde. Novolak resin obtained by condensing aldehyde compounds such as acetaldehyde and benzaldehyde, vinylphenol compounds such as o-vinylphenol, m-vinylphenol, p-vinylphenol, α-methylvinylphenol, and the weight of these halogen-substituted compounds. Acrylic acid-based or methacrylic acid-based polymers or copolymers such as coalesced or copolymers, acrylic acid, methacrylic acid, and hydroxyethyl (meth) acrylate, polyvinyl alcohol, and some of the hydroxyl groups of the above various resins. Examples thereof include a modified resin into which a radioactive ray-sensitive group such as a quinone diazide group, a naphthoquinone azide group, an aromatic azide group, and an aromatic cinnamoyl group has been introduced. These alkali-soluble resins can be used alone or in combination of two or more.

Further, as the alkali-soluble resin, a urethane resin containing an acidic group such as a carboxylic acid or a sulfonic acid in the molecule can be used, and this urethane resin can be used in combination with the above-mentioned alkali-soluble resin. It is possible.

(2) As the radiosensitive substance (photosensitive substance), it is mixed with the above alkali-soluble resin and irradiated with ultraviolet rays, far ultraviolet rays, excima laser light, X-rays, electron beams, ion beams, molecular beams, γ rays, etc. By doing so, any substance that changes the solubility of the alkali-soluble resin in the developing solution can be used.

Examples of the radiation-sensitive substance include quinone diazide compounds, diazo compounds, diazido compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organic metal compounds, organic acid ester compounds, and organic acids. Examples thereof include amide compounds, organic acidimide compounds, and poly (olefin sulfone) compounds described in JP-A-59-152.

Examples of the quinone diazide compound include 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2, 1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, other 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride , 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride and other sulfonic acid chlorides of quinonediazide derivatives. Be done.

Examples of the diazo compound include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or perioate and the condensate. Examples thereof include diazo resin inorganic salts which are reactive organisms with diazo resin, and diazo resin organic salts which are reaction products of the condensate and sulfonic acids as described in USP 3,300,309.

Examples of the azide compound and the azide compound include azidochalcone acid, diazidobenzalmethylcyclohexanones and azidocinnamylideneacetophenones as described in JP-A-58-203438, Journal of the Japanese Society of Chemistry No. 12, p1708-1714 (1983), aromatic azide compounds, aromatic diazide compounds and the like can be mentioned.

As the halogenated organic compound, for example, a halide of an organic compound can be used, and specific examples thereof include a halogen-containing oxadiazole-based compound, a halogen-containing triazine-based compound, a halogen-containing acetophenone-based compound, and a halogen. Containing benzophenone-based compound, halogen-containing sulfoxide-based compound, halogen-containing sulfone-based compound, halogen-containing thiazole-based compound, halogen-containing oxazole-based compound, halogen-containing trisol-based compound, halogen-containing 2-pyrone-based compound, halogen-containing aliphatic hydrocarbon-based Various compounds such as compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds and sulfenyl halide compounds, such as tris (2,3-dibromopropyl) phosphate and tris (2,3-dibromo-). 3-Chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (bromoethyl ether) Tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2 Examples thereof include compounds used as halogen-based flame retardants such as −bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, and compounds used as organic chloro pesticides such as dichlorophenyltrichloroethane.

Examples of the organic acid ester include carboxylic acid ester and sulfonic acid ester. Examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Further, examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances can be used alone or in combination of two or more.

(3) Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methylisobutylketone and butyrolactone; methanol, ethanol, n-propyl alcohol and iso-propyl alcohol. , N-Butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol and other alcohols; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane and other ethers;

Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate , Ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate and other esters, 2- Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Monocarboxylic acid esters such as butyl propionate;

Cellosolvents such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc. Diethyl glycols such as dietyl glycol monomethyl ether, dietyl glycol monoethyl ether, dietyl glycol dimethyl ether, dietyl glycol diethyl ether, dietyl glycol methyl ethyl ether; trichloroethylene, flone solvent, etc. Halogenized hydrocarbons such as HCFC and HFC; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; dimethylacetylamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone and the like. Examples of the solvent such as polar solvent are described in the book "Solvent Pocket Handbook" (edited by Organic Synthetic Chemistry Association, Ohm Co., Ltd.). These solvents can be used alone or in combination of two or more.

Examples of the coating method of the composition adjusted for the resist application include spin coating, roll coating, dip coating, spray coating, plaid coating, slit coating, curtain coating, gravure coating and the like, and the composition is filtered before coating. It can also be filtered by to remove solid impurities.

Examples of the active energy beam for curing the composition prepared for the resist use include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Examples thereof include ultraviolet rays using the above as a light source, or electron beams produced by a scanning type or curtain type electron beam accelerator. When curing with an electron beam, it is not necessary to add a polymerization initiator.

Among these active energy rays, ultraviolet rays are particularly preferable. Further, irradiation in an atmosphere of an inert gas such as nitrogen gas is preferable because the surface curability of the coating film is improved. Further, if necessary, heat may be used in combination as an energy source, and heat treatment may be performed after curing with active energy rays.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the example, unless otherwise specified, parts and% are based on the amount of substance.

Synthesis example 1
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone, 50 parts by mass of 1-adamantyl methacrylate and 25 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. .. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (1). As a result of measuring the molecular weight of the copolymer (1) by GPC, the weight average molecular weight (Mw) was 15,200 and the number average molecular weight (Mn) was 12,100.

Synthesis example 2
86 parts by mass of methyl ethyl ketone, 36 parts by mass of cyclohexyl methacrylate and 24 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged in a nitrogen-substituted flask as a solvent, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. .. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (2). As a result of measuring the molecular weight of the copolymer (2) by GPC, the weight average molecular weight (Mw) was 12,300 and the number average molecular weight (Mn) was 9,500.

Synthesis example 3
68 parts by mass of methyl ethyl ketone, 32 parts by mass of isobornyl methacrylate and 16 parts by mass of 2,2,2-trifluoroethyl methacrylate were placed in a nitrogen-substituted flask as a solvent, and the temperature was 25 ° C. for 1 hour under a nitrogen stream. Stirred. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (3). As a result of measuring the molecular weight of the copolymer (3) by GPC, the weight average molecular weight (Mw) was 9,800 and the number average molecular weight (Mn) was 7,800.

Synthesis example 4
95 parts by mass of methyl ethyl ketone, 44 parts by mass of dicyclopentanyl methacrylate and 22 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged into a nitrogen-substituted flask and stirred at 25 ° C. under a nitrogen stream for 1 hour. did. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (4). As a result of measuring the molecular weight of the copolymer (4) by GPC, the weight average molecular weight (Mw) was 13,500 and the number average molecular weight (Mn) was 10,500.

Synthesis example 5
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone and 45 parts by mass of 1-adamantyl methacrylate and 30 parts by mass of 2,2,3,3,3-pentafluoropropyl methacrylate were charged as solvents and placed at 25 ° C. under a nitrogen stream. The mixture was stirred for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 g of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (5). As a result of measuring the molecular weight of the copolymer (5) by GPC, the weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,700.

Synthesis example 6
In a nitrogen-substituted flask, 84 parts by mass of methyl ethyl ketone, 34 parts by mass of 1-adamantyl methacrylate and 24 parts by mass of methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl were charged as solvents, and the temperature was 25 ° C. It was stirred underneath for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (6). As a result of measuring the molecular weight of the copolymer (6) by GPC, the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,500.

Synthesis example 7
110 parts by mass of methyl ethyl ketone and 50 parts by mass of 1-adamantyl methacrylate were charged into a nitrogen-substituted flask as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, the temperature was raised to 60 ° C., 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted for 12 hours. .. Then, 25 parts by mass of 2,2,2-trifluoroethyl methacrylate was added, and the mixture was further reacted for 12 hours. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (7). As a result of measuring the molecular weight of the copolymer (7) by GPC, the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 11,500.

Synthesis example 8
108 parts by mass of methyl ethyl ketone, 53 parts by mass of 1-adamantyl methacrylate and 27 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged into a nitrogen-substituted flask and stirred at 25 ° C. under a nitrogen stream for 1 hour. .. Then, 6.2 parts by mass of 2,2'-bipyridyl and 1.8 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 3.9 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (8). As a result of measuring the molecular weight of the copolymer (8) by GPC, the weight average molecular weight (Mw) was 5,200 and the number average molecular weight (Mn) was 4,200.

Synthesis example 9
In a nitrogen-substituted flask, 92 parts by mass of methyl ethyl ketone, 42 parts by mass of 1-adamantyl methacrylate and 21 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. .. Next, 1.1 parts by mass of 2,2′-bipyridyl and 0.3 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 0.68 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 5.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (9). As a result of measuring the molecular weight of the copolymer (9) by GPC, the weight average molecular weight (Mw) was 22,100 and the number average molecular weight (Mn) was 18,200.

Comparative synthesis example 1
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone, 50 parts by mass of isodecyl methacrylate, and 25 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (10). As a result of measuring the molecular weight of the copolymer (10) by GPC, the weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 12,300.

Comparative synthesis example 2
95 parts by mass of methyl ethyl ketone, 37 parts by mass of tertiary butyl methacrylate and 29 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged into a nitrogen-substituted flask and stirred at 25 ° C. under a nitrogen stream for 1 hour. .. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (11). As a result of measuring the molecular weight of the copolymer (11) by GPC, the weight average molecular weight (Mw) was 13,100 and the number average molecular weight (Mn) was 10,800.

Comparative synthesis example 3
In a nitrogen-substituted flask, 104 parts by mass of methyl ethyl ketone, 36 parts by mass of 1-adamantyl methacrylate and 36 parts by mass of 2- (perfluorobutyl) ethyl methacrylate were charged as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (12). As a result of measuring the molecular weight of the copolymer (12) by GPC, the weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 11,700.

Comparative synthesis example 4
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone and 33 parts by mass of 1-adamantyl methacrylate as solvents, 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca 43 parts by mass of fluorooctyl methacrylate was charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (13). As a result of measuring the molecular weight of the copolymer (13) by GPC, the weight average molecular weight (Mw) was 15,400 and the number average molecular weight (Mn) was 12,300.

Synthesis example 10
55 parts by mass of methyl ethyl ketone, 55 parts by mass of 2-propanol, 51 parts by mass of 3-hydroxy-1-adamantyl methacrylate, and 24 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged into a nitrogen-substituted flask as solvents. The mixture was stirred at ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (14). As a result of measuring the molecular weight of this copolymer (14) by GPC, it was found that the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,100.

Synthesis example 11
45 parts by mass of methyl ethyl ketone and 45 parts by mass of 2-propanol, 20 parts by mass of 1-adamantyl methacrylate, 22 parts by mass of 3-hydroxy-1-adamantyl methacrylate, 2,2,2-trifluoroethyl methacrylate as solvents in a nitrogen-substituted flask. 21 parts by mass of the solvent was charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Then, 9.03 g of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (15). As a result of measuring the molecular weight of this copolymer (15) by GPC, it was found that the weight average molecular weight (Mw) was 12,600 and the number average molecular weight (Mn) was 10,100.

Synthesis example 12
In a nitrogen-substituted flask, 47 parts by mass of methyl ethyl ketone and 47 parts by mass of 2-propanol, 25 parts by mass of 1-adamantyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, and 26 parts by mass of 2,2,2-trifluoroethyl methacrylate as solvents. The parts were charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (16). As a result of measuring the molecular weight of this copolymer (16) by GPC, it was found that the weight average molecular weight (Mw) was 13,800 and the number average molecular weight (Mn) was 10,700.

Comparative synthesis example 5
55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol, 34 parts by mass of 3-hydroxy-1-adamantyl methacrylate, 3,3,4,4,5,6,6,7, in a nitrogen-substituted flask. 41 parts by mass of 7,8,8,8-tridecafluorooctyl methacrylate was charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (17). As a result of measuring the molecular weight of this copolymer (17) by GPC, it was found that the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 12,100.

Comparative synthesis example 6
In a nitrogen-substituted flask, 43 parts by mass of methyl ethyl ketone and 43 parts by mass of 2-propanol, 19 parts by mass of 2-hydroxyethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8 as solvents. , 8,8-Tridecafluorooctyl methacrylate (41 parts by mass) was charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (18). As a result of measuring the molecular weight of this copolymer (18) by GPC, it was found that the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,700.

Comparative synthesis example 7
In a nitrogen-substituted flask, 56 parts by mass of methyl ethyl ketone and 56 parts by mass of 2-propanol, 60 parts by mass of a methacrylate containing a polypropylene oxide chain, and 18 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and nitrogen was charged at 25 ° C. The mixture was stirred under an air stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (19). As a result of measuring the molecular weight of this copolymer (19) by GPC, it was found that the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,900.

Comparative synthesis example 8
In a nitrogen-substituted flask, 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as solvents, 42 parts by mass of methacrylate containing a polypropylene oxide chain, 3,3,4,4,5,5,6,6,7,7,8 , 8,8-Tridecafluorooctyl methacrylate (33 parts by mass) was charged and stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (20). As a result of measuring the molecular weight of this copolymer (20) by GPC, it was found that the weight average molecular weight (Mw) was 15,100 and the number average molecular weight (Mn) was 11,800.

Synthesis example 13
75 parts by mass of the copolymer (14) obtained in Synthesis Example 10 was dissolved in 75 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") in a flask substituted with dry air, and octyl was used as a urethanization catalyst. 0.03 parts by mass of tin acetate and 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor were added, and the temperature was raised to 75 ° C. Under an atmosphere of dry air, 30 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as "AOI") was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 75 ° C. for 1 hour, then heated to 80 ° C. and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product by eliminating the absorption of the isocyanate group. Then, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of the copolymer (21). As a result of measuring the molecular weight of this copolymer (21) by GPC, the weight average molecular weight was 19,900 and the number average molecular weight was 17,600.

Synthesis example 14
66 parts by mass of the copolymer (16) obtained in Synthesis Example 15 was dissolved in 66 parts by mass of PGMEA in a flask substituted with dry air, 0.02 parts by mass of tin octylate as a urethanization catalyst, and p-methoxyphenol as a polymerization inhibitor. 0.03 parts by mass was added and the temperature was raised to 75 ° C. Under an atmosphere of dry air, 16 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 75 ° C. for 1 hour, then heated to 80 ° C. and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product by eliminating the absorption of the isocyanate group. Then, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of the copolymer (22). As a result of measuring the molecular weight of this copolymer (22) by GPC, the weight average molecular weight was 15,900 and the number average molecular weight was 13,700.

Comparative synthesis example 9
In a flask substituted with dry air, 75 parts by mass of the copolymer (17) obtained in Comparative Synthesis Example 5 was dissolved in 75 parts by mass of propiPGMEA, 0.03 part by mass of tin octylate as a urethanization catalyst, and p- as a polymerization inhibitor. 0.04 parts by mass of methoxyphenol was added and the temperature was raised to 75 ° C. Under an atmosphere of dry air, 20 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 75 ° C. for 1 hour, then heated to 80 ° C. and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product by eliminating the absorption of the isocyanate group. Then, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of the copolymer (23). As a result of measuring the molecular weight of this copolymer (23) by GPC, the weight average molecular weight was 17,100 and the number average molecular weight was 13,400.

Comparative synthesis example 10
60 parts by mass of the copolymer (18) obtained in Comparative Synthesis Example 6 was dissolved in 60 parts by mass of propi PGMEA in a flask substituted with dry air, 0.02 parts by mass of tin octylate as a urethanization catalyst, and p- as a polymerization inhibitor. 0.03 part by mass of methoxyphenol was added and the temperature was raised to 75 ° C. Under an atmosphere of dry air, 21 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 75 ° C. for 1 hour, then heated to 80 ° C. and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product by eliminating the absorption of the isocyanate group. Then, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of the copolymer (24). As a result of measuring the molecular weight of this copolymer (24) by GPC, the weight average molecular weight was 17,000 and the number average molecular weight was 13,300.

Comparative synthesis example 11
In a flask substituted with dry air, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula, 10 parts by mass of diisopropyl ether as a solvent, 0.006 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 3.3 parts by mass of triethylamine was charged as a neutralizing agent, stirring was started under an air stream, and 3.1 parts by mass of methacrylic acid chloride was added dropwise over 2 hours while keeping the inside of the flask at 10 ° C. After completion of the dropping, the reaction was carried out by stirring at 10 ° C. for 1 hour, raising the temperature to 30 ° C. for 1 hour, then raising the temperature to 50 ° C. and stirring for 10 hours, and measuring methacrylic acid by gas chromatography measurement. The disappearance of the chromate was confirmed. Then, after adding 70 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then allowed to stand to separate and remove the aqueous layer, and the washing was repeated three times. Next, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day to completely dehydrate, and then the dehydrating agent was filtered off. ..

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣによる数平均分子量は１，５００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and each molecule has an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms is large. The average is 46. The number average molecular weight by GPC is 1,500.)

Then, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula.

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and each molecule has an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms is large. The average is 46.)

Comparative synthesis example 12
100 parts by mass of methyl isobutyl ketone was charged into a nitrogen-substituted flask as a solvent, and the temperature was raised to 95 ° C. with stirring under a nitrogen stream. Next, a monomer obtained by dissolving 20 parts by mass of the compound having a poly (perfluoroalkylene ether) chain obtained in Comparative Synthesis Example 11 and 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate in 120 parts by mass of methyl isobutyl ketone. Separate dropping devices for three types of dropping solutions, that is, a solution and a polymerization initiator solution in which 10.5 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator is dissolved in 80 parts by mass of methylisobutylketone. And the inside of the flask was kept at 95 ° C. and simultaneously added dropwise over 3 hours. After completion of the dropping, the mixture was stirred at 95 ° C. for 5 hours, then at 105 ° C. for 2 hours, and then 262.1 parts by mass of the solvent was distilled off under reduced pressure to obtain a solution of the copolymer (26).

Next, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanization catalyst were added to the polymer (25) solution obtained above, and the mixture was stirred under an air stream. Starting, 29.9 parts by mass of AOI was added dropwise over 1 hour while maintaining 75 ° C. After completion of the dropping, the mixture was stirred at 75 ° C. for 1 hour, then heated to 80 ° C. and stirred for 4 hours to confirm the disappearance of the isocyanate group by IR spectrum measurement, and 362 parts by mass of methyl isobutyl ketone was added to contain fluorine. A methyl isobutyl ketone solution containing 20% by mass of the polymerizable resin (26) was obtained.

Measurement of the fall angle of the cured coating film The fall angle of the coating film surface was evaluated by measuring the fall angle of water. A DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used for the evaluation of slipperiness. 50 μL of water droplets were dropped onto the base material, the stage was tilted at a speed of 2 ° / sec, and the angle at which the water droplets started to move was taken as the value of the fall angle. The measurement was performed 5 times, and the average value was used as a value.

<Evaluation with UV curable coating film>
UV curable urethane acrylate resin (“Unidic 17-806” manufactured by DIC Co., Ltd .; butyl acetate solution with a resin content of 80% by mass) 125 parts by mass, 1-hydroxycyclohexylphenylketone as a photopolymerization initiator (manufactured by BASF Japan Co., Ltd.) "Irgacure 184") 5 parts by mass of toluene, 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether are mixed and dissolved to form an active energy ray-curable composition. The base resin composition of the above was obtained. To 268 parts by mass of the obtained base resin composition, 1 part by mass of the compound obtained in the synthesis example was added and uniformly mixed to obtain an active energy ray-curable composition. Next, this active energy ray-curable composition was applied to a glass plate having a thickness of 1 mm and a length of 7 cm and a width of 7 cm with a spin coater, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was irradiated with ultraviolet rays with an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m 2) to obtain a cured coating film. Then, the fall angle of the obtained coating film was measured.

<Evaluation with thermosetting coating film>
100 parts by mass of Ceranate SSA-500 manufactured by DIC Corporation, 186 parts by mass of Burnock DN-980, 0.1% by mass of the compound obtained above was added in terms of solid content ratio, and diluted with butyl acetate to 40%. The solution was prepared so as to be. 1 mL of the prepared solution was applied to a glass substrate having a thickness of 1 mm and a length of 15 cm and a width of 7 cm with a 6 mil applicator. Then, it was dried at 23 ° C. for 7 days to prepare a coating film, and the fall angle was measured.

Comparative synthesis example 13
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone and 75 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (27). As a result of measuring the molecular weight of the copolymer (27) by GPC, the weight average molecular weight (Mw) was 15,100 and the number average molecular weight (Mn) was 11,600.

Synthesis example 15
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone, 9.5 parts by mass of 1-adamantyl methacrylate and 65 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and 1 by mass at 25 ° C. under a nitrogen stream. Stirred for hours. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (28). As a result of measuring the molecular weight of the copolymer (28) by GPC, the weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,800.

Synthesis example 16
In a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone, 69 parts by mass of 1-adamantyl methacrylate and 5.9 parts by mass of 2,2,2-trifluoroethyl methacrylate were charged as solvents, and the temperature was 25 ° C. for 1 hour under a nitrogen stream. Stirred. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (29). As a result of measuring the molecular weight of the copolymer (29) by GPC, the weight average molecular weight (Mw) was 15,500 and the number average molecular weight (Mn) was 12,400.

Comparative synthesis example 14
110 parts by mass of methyl ethyl ketone and 75 parts by mass of 1-adamantyl methacrylate were charged into a nitrogen-substituted flask as solvents, and the mixture was stirred at 25 ° C. under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2,2'-bipyridyl and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60 ° C. Then, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ° C. for 12 hours under a nitrogen stream. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (30). As a result of measuring the molecular weight of the copolymer (30) by GPC, the weight average molecular weight (Mw) was 15,200 and the number average molecular weight (Mn) was 11,600.

Claims (7)

A cured film of a curable resin composition containing a fluorine-based copolymer and a curable resin, and a water-sliding coating film containing the fluorine-based copolymer.
The content of the fluorine-based copolymer in the curable composition is 0.001 to 10 parts by mass with respect to 100 parts by mass of solid content.
The curable resin is selected from the group consisting of urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and maleimide group-containing resin. One or more types of active energy ray-curable resin,
The fluorine-based copolymer is polymerizable with a polymerizable monomer (a1) having a fluorinated alkyl group represented by the following general formula (1) and a polymerizable unsaturated group, and an alicyclic hydrocarbon skeleton. A copolymer containing a polymerizable monomer (a2) having an unsaturated group as an essential raw material, and the ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2). Is a fluorine-based copolymer having a mass ratio of (a1) :( a2) = 5: 95 to 40:60.

[In the general formula (1), ^{R 1} is hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or _-C m _H 2m -Rf (where m is an integer from 1 to 8), Rf Is _{a group represented by C n} F _{2n + 1} (where n is 1 or 2), and X represents any one group of the following formulas (X-1) to (X-10). ]

[In the above formula, m is an integer of 1 to 8, k is an integer of 0 to 8, and Rf is the same as described above. However, when m in the above formula (X-1) is 2 or 3, the alkylene group represented by Cm H _{2 m is a straight chain.} ] The water-sliding coating film according to claim 1, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is a bridged ring hydrocarbon skeleton. The water-sliding property according to claim 1 or 2, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the fluorine-based copolymer is in the range of 1.00 to 1.40. Coating film. The one according to any one of claims 1 to 3, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a norbornane ring, or a norbornene ring. Water-sliding coating. The water-sliding coating film according to any one of claims 1 to 4 , wherein the polymerizable monomer (a2) further has a hydroxyl group. The water-sliding coating film according to any one of claims 1 to 5 , wherein the fluorine-based copolymer further has an active energy ray-curable group. The water-sliding coating film according to any one of claims 1 to 6 , wherein the fluorine-based copolymer is a random copolymer.