KR20210021955A - Fluorine-based copolymer, slidable surface modifier, curable resin composition, and slidable coating film - Google Patents

Abstract

A fluorine-based copolymer that can obtain a surface excellent in slidability and can be suitably used as a slidable surface modifier, a curable resin composition using the same, and a slidable coating film that is a cured product of the composition. Specifically, _{a polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group represented by C n} F _2n+1- (wherein n is 1 or 2), and an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group. A fluorine-based copolymer characterized in that it is a copolymer containing a polymerizable monomer (a2) as an essential raw material, a slidable surface modifier comprising the same, a curable resin composition containing the same, and a cured coating film thereof as a cured product thereof.

Description

Fluorine-based copolymer, slidable surface modifier, curable resin composition, and slidable coating film

The present invention relates to a fluorine-based copolymer that can form a coating film having good slidability on the surface and can be suitably used as a slidable surface modifier of a specific structure, a curable resin composition using the same, and a slidable coating film that is a cured product thereof. will be.

Fluorine-based surfactants or fluorine-based surface modifiers are widely used in various coating materials, surface modifiers, and the like because they have excellent leveling properties, water and oil repellency, and the like. A cured film obtained by curing a curable resin composition in which this fluorine-based surfactant or a fluorine-based surface modifier (hereinafter, they are collectively referred to as simply “fluorine-based surfactant” in some cases) is cured, exhibits excellent water repellency (oil repellency). In general, a fluorine-based surfactant has a fluorinated hydrocarbon group in the structure of a compound in order to utilize the water-repellent and oil-repellent properties of a fluorine atom, and in one molecule, other structures for expressing compatibility or curability with a curable resin are arranged. It is one compound, and various compounds are provided according to the level of the target performance and the method of use (see, for example, Patent Documents 1 to 2).

In the modern living environment, there are many facilities, devices, and mechanical devices that require or require water repellency, and their types are also such as automobile window glass, automobile painted surfaces, kitchen equipment, kitchen utensils, and exhaust installed on kitchen equipment. Equipment, bathing equipment, toiletries, medical facilities, medical equipment, mirrors, glasses, inkjet printer parts, and so on, are extremely diverse. In addition, in a refrigerator heat exchanger, an air conditioner outdoor unit, and a heat pump heat exchanger for an EV vehicle to be expanded later, water repellency is required from the viewpoint of preventing icing and frosting.

In the above applications, the property (sliding water) that adhered water droplets rapidly flows down due to gravity or the like is further required. In other words, the water-repellent surface only indicates that the water adhering thereto tends to become water, and large water drops fall due to their own weight, but if the slidability is weak, the water drops remain strongly attached to the surface of the object, and fall even if the surface is tilted vertically. There are cases where you don't. Such water droplets adhering to the surface remain as they are, causing various problems. For example, if a large number of water droplets are attached to the windshield of an automobile, there is a problem that the windshield is diffusely reflected by light such as a street lamp, thereby obstructing the driver's vision. In addition, when a material having weak slidability is used in an environment exposed to rainwater such as an exterior material, traces of water flow (rain lines) are generated on the surface, and thus it cannot be said that it is also excellent in stain resistance. The slidability is better as the fall angle of water is small, but the correlation between the contact angle of water and the fall angle has not been confirmed, and a surface modifier that can achieve both water repellency and slidability is required.

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

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

As a result of intensive research, the inventors of the present invention have found that a copolymer comprising a polymerizable monomer having a fluorinated alkyl group having a specific length and a polymerizable unsaturated group, and a polymerizable monomer having a skeleton of an alicyclic hydrocarbon and a polymerizable unsaturated group as essential monomers A, it found out that it became a surface modifier which solves the said subject, and came to complete the present invention.

That is, the present invention is _{a polymerizable monomer (a1) having a fluorinated alkyl group represented by C n} F _2n+1- (wherein n is 1 or 2) and a polymerizable unsaturated group,

Polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group

It is to provide a fluorine-based copolymer characterized by being a copolymer having as an essential raw material, a slidable surface modifier using the same, a curable resin composition containing the same, and a slidable coating film that is a cured product of the composition.

By using the fluorine-based copolymer of the present invention as a surface modifier, a curable resin composition having excellent surface slidability such as a coating film is obtained, and for applications requiring slidability, curing systems such as thermosetting systems and active energy ray curing systems You can select and apply variously.

The fluorine-based copolymer of the present invention is _{polymerized with 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 an alicyclic hydrocarbon skeleton It is characterized in that it is a copolymer containing as an essential raw material a polymerizable monomer (a2) having a sexually unsaturated group.

Conventionally, in order to exhibit water and oil repellency, the higher the number of carbon atoms directly bonded to the fluorine atom is, the more preferable it is. On the other hand, due to the concern about bioaccumulation of the compound having a fluorinated alkyl group, the upper limit of the number of carbon atoms is 6. Therefore, for example, as in Patent Document 2 above, in order to increase the number of fluorine atoms in one molecule (i.e., to increase the fluorine atom content), an ether bond of a fluorinated alkylene chain having 2 to 3 carbon atoms Also provided is a compound having a perfluoroalkylene ether chain, which is connected to each other.

However, as described above, there is no correlation between the water repellency and the water repellency, and the water repellency is poor even on the water repellent surface, the traces of water droplets remain white, or substances in the air contained in rainwater may remain as stems on the surface of the coating film, The present situation was that the water slidability cannot be improved by necessarily using a curable resin composition containing a fluorine-based compound.

_{Among these, it has a fluorinated alkyl group represented by C n} F _2n+1- (where n is 1 or 2) in the compound containing a structure having 1 or 2 carbon atoms to which the fluorine atom is directly bonded. Moreover, it was found that the use of a compound having an alicyclic hydrocarbon skeleton in the compound remarkably improves the slidability of the surface of the coating film.

As a polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group represented by _{C n} F _2n+1- (wherein n is 1 or 2) used in the present invention, the fluorinated alkyl group and polymerizable unsaturated group in the molecule If it is a compound having a group, it can be used without particular limitation. As the fluorinated alkyl group, in particular, n is 1 is preferable from the viewpoint of obtaining a cured product having more excellent slidability. In addition, _{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, such as water repellency , It is preferable to adjust the fluorine atom content rate according to the level of surface smoothness.

Examples of the polymerizable unsaturated group of the polymerizable monomer (a1) include a (meth)acryloyl group, a vinyl group, and a maleimide group. Among these, the (meth)acryloyl group is preferable because the availability of raw materials, the ease of controlling the compatibility with the compounding components in various curable resin compositions, or the polymerization reactivity are good. As the compound having this (meth)acryloyl group, a monomer represented by the following general formula (1) or (2) can be preferably illustrated, for example. In addition, the polymerizable monomer (a1) may be used alone or in combination of two or more.

[In the general formulas (1) and (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 of 1 to 8), Rf is _{a group represented by C n} F _2n+1 (however, n is 1 or 2), and X represents any one of the following formulas (X-1) to (X-10)]

(M in the above formula is an integer of 0 to 8, k is an integer of 0 to 8, and Rf is the same as above)

In addition, in the present invention, "(meth)acrylate" refers to one or both of methacrylate and acrylate, and "(meth)acrylic acid" refers to 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.

As the alicyclic hydrocarbon skeleton, for example, cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, nor Bornane, decahydronaphthalene, perhydrofluorene, tricyclo[5.2.1.0 ^2.6 ]decane, adamantane, quadricylan, kongreic acid, cuban, spiro[4.4]octane, cyclopentene, cyclohexene, cycloheptene , Cyclooctene, cyclodecene, bicyclo[2.2.2]octa-2-ene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloheptatriene, cyclodecatriene, cyclooctatetraene, norbornylene And alicyclic hydrocarbon skeletons such as octahydronaphthalene, bicyclo[2.2.1]heptadiene, bicyclo[4.3.0]nonadiene, dicyclopentadiene, hexahydroanthracene, and spiro[4.5]decadiene. .

Among these, a skeleton having a crosslinked structure is preferable in that the surface of the resulting coating film has a high hardness, more slidability and antifouling properties, and, for example, adamantane, perhydroindene, decahydronaphthalene, and perhydrofluorene , Perhydroanthracene, perhydrophenanthrene, dicyclopentane, dicyclopentene, perhydroacenaphthene, perhydrophenalene, norbornane, norbornene, etc. are preferable, and in particular, adamantane, dicyclopentane, dicyclo Pentene, norbornane, norbornene are preferred, and adamantane is the most preferred skeleton.

Examples of the polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group, and a maleimide group. Among these, the (meth)acryloyl group is preferable because the availability of raw materials, the ease of controlling the compatibility with the compounding components in various curable resin compositions, or the polymerization reactivity are good.

Hereinafter, a polymerizable monomer having an adamantane skeleton and a polymerizable unsaturated group that 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).

(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, and an acid anhydride group. Among them, a hydroxyl group is preferable from the viewpoint of obtaining a surface modifier having good compatibility with the curable resin composition, or from the viewpoint of being able to easily introduce an active energy ray-curable group into the obtained copolymer.

The bonding position of the organic group and Y having the reactive functional group represented by -XL in the general formula (a2-1) may be bonded to any carbon atom in the adamantane skeleton, and two or more of -XL You may have it. In addition, the hydrogen atom bonded to the carbon atom constituting the adamantane skeleton may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like. In addition, X and Y in the general formula (a2-1) are divalent organic groups or single bonds, but examples of the divalent organic group include a methylene group, a propyl group, and an isopropylidene group having 1 to 8 carbon atoms. An alkylene group is mentioned.

In addition, 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. In addition, the hydrogen atom bonded to the carbon atom constituting the adamantane skeleton in the general formula (a2-1) may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like.

As a more specific example of the polymerizable monomer represented by the said general formula (a2-1), the compound etc. which are represented by the following are mentioned, for example.

Moreover, as a more specific example of the polymerizable monomer represented by general formula (a2-2), the compound etc. which are represented by following are mentioned, for example.

Among the polymerizable monomers having an adamantane skeleton and a (meth)acryloyl group, the above formulas (a2-1-1), (a2-1-3), and (a2) can be made higher in Tg of the coating film. Compounds represented by -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 that 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 compounds represented by the following formula (a2-3).

(In the formula, R represents a hydrogen atom, a methyl group, or CF ₃ )

In addition, 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. In addition, the hydrogen atom bonded to the carbon atom constituting the dicyclopentane skeleton in the general formula (a2-3) may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like.

As a more specific example of the polymerizable monomer represented by the said general formula (a2-3), the compound etc. which are represented by following are mentioned, for example.

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 because the Tg of the coating film can be made higher.

Hereinafter, a polymerizable monomer having a dicyclopentene skeleton and a polymerizable unsaturated group that 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 compounds represented by the following formula (a2-4).

(In the formula, R represents a hydrogen atom, a methyl group, or CF ₃ )

In addition, 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. In addition, the hydrogen atom bonded to the carbon atom constituting the dicyclopentene skeleton in the general formula (a2-3) may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like.

As a more specific example of the polymerizable monomer represented by the said general formula (a2-4), the compound etc. which are represented by following are mentioned, for example.

Among the polymerizable monomers having a dicyclopentene skeleton and a (meth)acryloyl group, the compound represented by the above formulas (a2-4-3) and (a2-4-4) in that the Tg of the coating film can be increased This is desirable.

Hereinafter, a polymerizable monomer having a norbornane skeleton and a polymerizable unsaturated group that 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 compounds represented by the following formula (a2-5).

(In the formula, R represents a hydrogen atom, a methyl group, or CF ₃ )

In addition, 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. In addition, the hydrogen atom bonded to the carbon atom constituting the norbornane skeleton in the general formula (a2-5) may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like.

As a more specific example of the polymerizable monomer represented by the said general formula (a2-5), the compound etc. which are represented by following are mentioned, for example.

Among the polymerizable monomers having a norbornane skeleton and a (meth)acryloyl group, the compound represented by the above formulas (a2-5-3) and (a2-5-4) in that the Tg of the coating film can be increased. This is desirable.

Hereinafter, a polymerizable monomer having a norbornene skeleton and a polymerizable unsaturated group that 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).

(In the formula, R represents a hydrogen atom, a methyl group, or CF ₃ )

In addition, 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. In addition, the hydrogen atom bonded to the carbon atom constituting the norbornene skeleton in the general formula (a2-6) may be partially or entirely substituted with a fluorine atom, an alkyl group, or the like.

As a more specific example of the polymerizable monomer represented by the said general formula (a2-6), the compound etc. which are represented by following are mentioned, for example.

Among the polymerizable monomers having a norbornene skeleton and a (meth)acryloyl group, the compound represented by the above formulas (a2-6-3) and (a2-6-4) in that the Tg of the coating film can be made higher This is desirable.

The fluorine-based copolymer 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, as described above, and an alicyclic It is characterized in that it is a copolymer comprising as an essential raw material a polymerizable monomer (a2) having a formula hydrocarbon skeleton and a polymerizable unsaturated group. Here, the ratio of the polymerizable monomer (a1) and the polymerizable monomer (a2) is a mass ratio of (a1):(a2)=5:95 to 95 since a surface modifier having better compatibility with the curable resin composition is obtained. It is preferable that it is a range of :5, and it is more preferable that it is a range of 10:90-90:10.

As a raw material used to obtain the fluorine-based copolymer of the present invention, a monomer copolymerizable with the above (a1) and (a2) may be used within a range not impairing the effects of the present invention. Examples of the monomers 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, a monomer having a branched alkyl group having 1 to 18 carbon atoms, and the like. I can.

Examples of the polymerizable unsaturated groups of the other copolymerizable monomers include (meth)acryloyl groups, vinyl groups, maleimide groups, and the like, but the polymerizable unsaturated groups of the monomers (a1) and (a2) are ( In the case of a meth)acryloyl group, since copolymerization becomes good, the polymerizable unsaturated group of other monomers is preferably a (meth)acryloyl group.

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

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

^{Y 1} and Y ² in the general formula (a3-1) are alkylene groups, but those having a substituent are included in the alkylene group. As a specific example of the -O-(Y ¹ O)n-(Y ² O)m- moiety, the number of repeating units p is 1, m is 0, and the ^{ethylene glycol residue in which Y 1} is ethylene, and the number of repeating units p is 1 And m is 0, Y ¹ is a propylene glycol residue, wherein the number of repeating units p is 1, m is 0, and Y ¹ is a butylene glycol residue, wherein the number of repeating units p is an integer of 2 or more and q a is 0, and Y ¹ is ethylene polyethylene glycol residue, can repeat unit where p is an integer of 2 or more and and q is 0, and Y ¹ is a propylene of polypropylene glycol moiety, the number of repeating units p and q are both an integer of 1 or more And a residue of polyalkylene glycol, such as a residue of a copolymer of ethylene oxide and propylene oxide, in which Y ¹ or Y ^{2 is ethylene and the other is propylene.}

The degree of polymerization of the polyalkylene glycol in the formula (a3-1), that is, the sum of p and q in the general formula (a3-1) is preferably in the range of 1 to 100, more preferably in the range of 2 to 80, and It is more preferable that it is in the range of 3-50. Moreover, ^{the repeating unit including Y 1} and the repeating unit including Y ² may be arranged in a random form or may be arranged in a block form.

^{R 3} in the 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, and polybutylene glycol, and when R ³ has 1 to 6 carbon atoms, The end other than the (meth)acrylic acid ester of the mono(meth)acrylic acid ester of alkylene glycol is sealed by an alkyl group having 1 to 6 carbon atoms.

Among the general formula (a3-1), a monomer having a poly(oxyalkylene) group consisting of a plurality of oxyalkylene groups is preferable, and specific examples include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylic Rate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylic Rate, poly(ethylene 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(meth)acrylate, poly(propylene glycol·butylene glycol) mono(meth)acrylate, polypropylene glycol·polybutylene glycol mono(meth)acrylate, poly(ethylene glycol·butyl Ethylene 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 polytrimethylene glycol mono (meth) acrylate, poly ( Propylene glycol trimethylene glycol) mono(meth)acrylate, polypropylene glycol polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol·tetramethylene glycol) mono(meth)acrylate, polytrimethylene glycol -Polytetramethylene glycol mono(meth)acrylate, poly(butylene glycol trimethylene glycol) mono(meth)acrylate, polybutylene glycol polytrimethylene glycol mono(meth)acrylate, etc. are mentioned. In addition, "poly(ethylene glycol/propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol/polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol. do. The same goes for others. 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 is obtained. )Acrylate, polyethylene glycol/polypropylene glycol mono(meth)acrylate is preferable.

In addition, as a commercial item of a monomer having an oxyalkylene group, for example, Shin-Nakamura Chemical Co., Ltd. ``NK Ester M-20G'', ``NK Ester M-40G'', ``NK Ester M-90G'' , ``NK Ester M-230G'', ``NK Ester AM-90G'', ``NK Ester AMP-10G'', ``NK Ester AMP-20G'', ``NK Ester AMP-60G'', Nichiyu Corporation ``Bren Ma PE-90'', ``Brenma PE-200'', ``Brenma PE-350'', ``Brenma PME-100'', ``Brenma PME-200'', ``Brenma PME-400'', ``Brenma PME -4000", "Brenmar PP-1000", "Brenmar PP-500", "Brenmar PP-800", "Brenmar 70PEP-350B", "Brenmar 55PET-800", "Brenmar 50POEP-800B" ", "Brenmar 10PPB-500B", "Brenmar NCH-5050", "Brenmar AP-400", and "Brenmar AE-350". These monomers having an oxyalkylene group may 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).

(Wherein, 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 cyclic structure having 1 to 18 carbon atoms)

^{In addition, R 5} in the general formula (a3-2) is an alkyl group having a linear, branched or cyclic structure having 1 to 18 carbon atoms, but this alkyl group is an aliphatic or aromatic hydrocarbon group, a hydroxyl group, an epoxy group, etc. You may have a substituent. 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, octyl (meth) acrylate, (Meth)acrylic acid, such as 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. Epoxy group-containing unsaturated monomers such as cidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether, (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxy And unsaturated monomers containing a carboxyl group such as ethylphthalic acid and itaconic acid. These monomers having an alkyl group may be used alone or in combination of two or more.

When other monomers as described above are used in combination with the above monomers (a1) and monomers (a2), the amount used is in the range of 5 to 40 mol% with respect to the total 100 mol of the monomers (a1) and (a2). , In order to obtain a copolymer capable of expressing other effects such as surface hardness and scratch resistance without impairing the slidability, it is preferable, and more preferably in the range of 5 to 30 mol%. desirable. From the viewpoint of slidability, it is most preferable not to use other monomers together.

The fluorine-based copolymer of the present invention includes, for example, a monomer (a1) and a monomer (a2), or other monomers used in combination as necessary, in the presence of living cationic polymerization, living anionic polymerization, living radical polymerization, etc. It is preferably prepared by polymerization. In addition, among these living polymerizations, it is particularly preferable to use living radical polymerization from the viewpoint of easy control of the polymerization reaction.

In the living radical polymerization, a growth reaction proceeds by reversibly generating radicals and reacting with a monomer by a doment species having an active polymerization terminal protected by an atom or an atomic group. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), radical polymerization via nitroxide (NMP), radical polymerization using organic tellurium (TERP). And the like. There is no particular limitation on which of these methods to be used, but the ATRP is preferred because of ease of control and the like. ATRP is polymerized using an organic halide or a sulfonyl halide compound as an initiator, and a metal complex consisting of a transition metal compound and a ligand as a catalyst.

As the polymerization initiator used in ATRP, an organic halogenated compound may be used. Specifically, 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromoxylene, hexakis (α -Bromomethyl)benzene, a carbon atom of 2-halogenated carboxylic acid having 1 to 6 carbon atoms (e.g. 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) The number of 1-6 alkyl ester etc. are mentioned. Further, more specific examples of the alkyl ester of 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate. And ethyl 2-bromoisobutyrate.

The transition metal compound used in ATRP is represented by ^{M n+} X _n. Transition metal M ⁿ⁺ is, 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 Ag ² + can be selected from the group consisting of. In addition, 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 ), tree Plate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR ¹ , CN and R ^{2 It} can be selected from the group consisting of COO. Here, R ¹ represents an aryl, a 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 a halogen 1 to 5 times ( Preferably, it represents a linear or branched C1-C6 alkyl group (preferably a methyl group) which may be substituted with fluorine or chlorine 1 to 3 times). In addition, n represents the formal charge on a metal, and is an integer of 0-7.

The transition metal complex is not particularly limited, but as a preferable one, a transition metal complex of groups 7, 8, 9, 10, and 11 is more preferable, and as a more preferable one, zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent Complexes of valent nickel are mentioned.

As the compound having a ligand capable of coordination with the transition metal described above, a compound having a ligand including at least one nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom capable of coordination with the transition metal through a σ bond, a transition metal and A compound having a ligand containing two or more carbon atoms capable of coordinating via a π bond, and a compound having a ligand capable of coordinating through a transition metal and a µ bond or an η bond are exemplified.

Specific examples of the compound having the ligand include, for example, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyl when the central metal is copper. And complexes with ligands such as polyamines such as diethylenetriamine and hexamethyltris(2-aminoethyl)amine. In addition, as a divalent ruthenium complex, dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichloro p-cymenruthenium, dichloro (norbornadi N) ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonyl chlorohydride tris (triphenylphosphine) ruthenium, etc. are mentioned. . Further, examples of the divalent iron complex include a bistriphenylphosphine complex and a triazacyclononane complex.

In addition, in the living radical polymerization, it is preferable to use a solvent. Examples of the solvent to be 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-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohol solvents such as methanol, ethanol, and isopropanol; And aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. In addition, within the range not impairing the effects of the present invention, for example, chlorinated fluorohydrocarbons (especially 2 to 5 carbon atoms), especially HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2) ,2,3,3-tetrachlorohexafluorobutane), hexafluoroxylene, fluorine-based ether, and the like can be used. In addition, these solvents may be used alone or in combination of two or more.

In the above 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.

In addition, when the copolymer of the present invention is produced by the above production method, the metal resulting from the transition metal compound may remain in the copolymer. Therefore, in the case of using the surface modifier of the present invention for a use in which a problem occurs when the metal remains, it is preferable to remove the residual metal using activated alumina or the like after the polymerization reaction.

Since the weight average molecular weight (Mw) of the copolymer of the present invention is a surface modifier to obtain a more robust coating film surface, the range of 3000 to 500,000 is preferable, the range of 10000 to 30000 is more preferable, and the range of 15000 to 20000 is more preferable. Do. In addition, the dispersion degree (Mw/Mn) is preferably 1.50 or less, more preferably 1.00 to 1.50, and still more preferably 1.00 to 1.40, from the viewpoint of obtaining a surface having more uniform slidability. .

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"). In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: ``HLC-8220 GPC'' manufactured by Tosoh Corporation,

Column: Tosoh Corporation guard column "HHR-H" (6.0mmID×4cm) + Tosoh Corporation's "TSK-GEL GMHHR-N" (7.8mmID×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmID×30cm) manufactured by Shiki Corporation + "TSK-GEL GMHHR-N" (7.8mmID×30cm) manufactured by Tosoh Corporation + " TSK-GEL GMHHR-N"(7.8mmID×30cm)

Detector: ELSD ("ELSD2000" manufactured by Alltech Japan)

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 rate 1.0 ml/min

Sample: 1.0 mass% tetrahydrofuran solution in terms of resin solid content was filtered through a micro filter (5 μl).

Standard sample: In accordance with the measurement manual of the "GPC-8020 model II data analysis version 4.30", the following monodisperse polystyrene having a known molecular weight was used.

(Monodisperse 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

In addition, in the case of containing reactive functional groups such as hydroxyl group, isocyanate group, epoxy group, carboxy group, carboxylic acid halide group, and acid anhydride group in the copolymer of the present invention, that is, when copolymerization is performed using a monomer containing these reactive functional groups, , Since the fluorine-based copolymer of the present invention can be fixed to the surface of the coating film by chemical bonding with the curable resin in the case of a curable resin composition described later using these reactive functional groups, from the viewpoint of maintaining the long-term performance of slidability It is desirable. Further, by using these reactive functional groups, an active energy ray-curable group can also be introduced into the surface modifier.

The method of including the above-described reactive functional group in the copolymer of the present invention is not particularly limited, and as the monomer (a1) and the monomer (a2), a method of using a monomer having these reactive functional groups, or a monomer (a1) As other monomers to be used in combination with (a2), a method of using a monomer having these reactive functional groups in combination is exemplified.

As a monomer having the above-described reactive functional group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy Butyl (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)acryloyloxy Hydroxyl-containing unsaturated monomers such as ethyl-2-hydroxyethylphthalate and terminal hydroxyl-containing lactone-modified (meth)acrylate; Isocyanate group-containing unsaturated monomers such as 2-(meth)acryloyloxyethyl isocyanate and 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and itaconic acid; And carboxylic 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 introduced into the reaction system at the same time as the monomers (a1) and (a2), and copolymerized by the polymerization method described above, whereby the reactive functional groups can be introduced into the obtained copolymer.

In addition, by reacting a copolymer having a reactive functional group obtained by the copolymerization reaction with a group capable of reacting with the reactive functional group and a compound having 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-described monomer having an isocyanate group, a glycidyl group, a carboxyl group, an acid anhydride group, etc. that can react with this can be reacted, and in the case of a copolymer having a carboxyl group, A monomer having a glycidyl 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 in the range of 30 to 120°C, and in the presence of a catalyst or a polymerization inhibitor. , If necessary, it can be carried out in an organic solvent.

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 di- A method in which butyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, or the like is used and reacted at a reaction temperature of 40 to 120°C, particularly 60 to 90°C is preferable.

In addition, in the case of reacting a glycidyl group and a carboxyl group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, etc. are used as polymerization inhibitors. Using tertiary amines such as ethylamine, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, and quaternary phosphoniums such as tetrabutylphosphonium chloride. , It is preferable to react at a reaction temperature of 80 to 150°C, particularly 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, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene And the like. These may be appropriately selected in consideration of the boiling point and compatibility.

The content of fluorine atoms 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%, and in the range of 5 to 25 wt%, from the viewpoint of a more excellent balance between good leveling properties and slidability The range of is more preferable. In addition, the fluorine atom content rate 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 fluorine-based copolymer in the curable resin composition differs depending on the type of curable resin to be combined, the coating method, the target film thickness, etc., but from the viewpoint of high slidability and good leveling property on the surface of the coating film, 100 mass of solid content in the composition It is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 2 parts by mass with respect to parts.

As the curable resin composition, for example, as a paint, natural resins such as petroleum resin paint, shellac paint, rosin paint, cellulose paint, rubber paint, coating paint, cashew resin paint, oil vehicle paint, etc. Paint used; Paints using synthetic resins such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, fluorine resin paints, etc. Can be mentioned.

In addition, in addition to the coating composition exemplified above, the fluorine-based copolymer of the present invention can also be used for active energy ray-curable compositions. At this time, as described above, the use of an active energy ray-curable group introduced into the side chain of the copolymer used as the surface modifier can firmly fix the modifier on the surface of the coating film, so that the long-term performance stability of the slidability is excellent. It is preferable from the point of view. This active energy ray-curable composition contains an active energy ray-curable resin or an active energy ray-curable monomer as its main component. In addition, the above-described active energy ray-curable resin and active energy ray-curable monomer may be used individually, respectively, or may be used in combination.

The active energy ray-curable resin is, for example, a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic (meth) acrylate resin, Maleimide group-containing resins and the like are mentioned, but urethane (meth)acrylate resins are particularly preferred from the viewpoints of transparency and low shrinkage.

The urethane (meth)acrylate resin used herein includes 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. I can.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and 2-methyl-1,5-pentane. Diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and cyclohexyl diisocyanate. In addition, as the aromatic polyisocyanate compound, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc. Can be lifted.

Examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (Meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, hydroxypivalate neopentyl glycol mono Mono(meth)acrylates of dihydric alcohols such as (meth)acrylates; Trimethylolpropanedi(meth)acrylate, ethoxylated trimethylolpropane (meth)acrylate, propoxylated trimethylolpropanedi(meth)acrylate, glycerindi(meth)acrylate, bis(2-(meth)acrylate Mono or di(meth)acrylates of trihydric alcohols such as royloxyethyl)hydroxyethyl isocyanurate, or hydroxyl group-containing mono and di(meth) in which some of these alcoholic hydroxyl groups are modified with ε-caprolactone Acrylate; A compound having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryloyl group such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or , A hydroxyl group-containing polyfunctional (meth)acrylate obtained by further modifying the compound with ε-caprolactone; (Meth)acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate compound; (Meth)acrylate compounds having block-structured oxyalkylene chains such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; (Meth)acrylate compounds having an oxyalkylene chain having a random structure such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. I can.

The reaction of the above-described aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing acrylate compound can be carried out, for example, in the presence of a urethanization catalyst, by a conventional method. Examples of the urethanization catalyst usable here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; Phosphines such as triphenylphosphine and triethylphosphine; Organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and octylate tin; Organometallic compounds, such as zinc octylate, are mentioned.

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

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, and α,β-unsaturated dibasic acid Examples of the base acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. 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. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetra Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di-(4-hydroxypropoxydiphenyl)propane, and the like. In addition, oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

Next, as the epoxy vinyl ester resin, what is obtained by reacting (meth)acrylic acid with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin. Can be lifted.

In addition, as maleimide group-containing resin, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, and a bifunctional maleimide obtained by esterifying maleimide acetic acid and polytetramethylene glycol An ester compound, a tetrafunctional maleimide ester compound obtained by esterifying a tetraethylene oxide adduct of maleimidecaproic acid and pentaerythritol, and a polyfunctional maleimide ester compound obtained by esterifying a maleimide acetic acid and a polyhydric alcohol compound. . These active energy ray-curable resins may be used alone or in combination of two or more.

As the active energy ray-curable monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, a number average molecular weight in the range of 150 to 1000 Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, number average molecular weight in the range of 150 to 1000 Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexane Dioldi(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , Dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropanedi(meth)acrylate, dipentaerythritol penta(meth)acrylate, dicyclopentenyl(meth)acrylate, Methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) ) Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) Acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-butoxyethyl (Meth)acrylate, 2-(diethylamino)ethyl(meth)acrylate, 2-(dimethylamino)ethyl(meth)acrylate, γ-(meth)acryloxypropyltrimethoxysilane, 2-methoxy Ethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, nonylphenoxypoly Propylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, polybutadiene (meth)acrylate, polyethylene glycol-poly Propylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polystyrylethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth) )Acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, methoxylated cyclodecatrien (meth)acrylate, phenyl (meth)acrylate; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearyl Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethylcarbonate, 2-maleimideethyl-propylcarbonate, N-ethyl-(2-maleimideethyl)carbamate, N, Maleimides such as N-hexamethylenebismaleimide, polypropylene glycol-bis(3-maleimidepropyl)ether, bis(2-maleimideethyl)carbonate, and 1,4-dimaleimidecyclohexane. have.

Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. A polyfunctional (meth)acrylate having a bifunctional or higher function is preferable. These active energy ray-curable monomers may be used alone or in combination of two or more.

The active energy ray-curable composition can be applied to a substrate and then applied to a substrate to form a cured coating film by irradiating with an active energy ray. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When making a cured coating film by irradiating ultraviolet rays as an active energy ray, it is preferable to add a photoinitiator to the active energy ray-curable composition to improve curability. Further, if necessary, a photosensitizer may be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it is rapidly cured without using a photoinitiator or a photosensitizer, so it is not particularly necessary to add a photoinitiator or a photosensitizer.

Examples of the photopolymerization initiator include an intramolecular cleavage type photopolymerization initiator and a hydrogen extraction type photopolymerization initiator. Examples of the intramolecular cleavage photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2 -Hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl Acetophenone-based compounds such as 2-morpholino(4-thiomethylphenyl)propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone;

Benzoins, such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Benzyl, methylphenylglyoxy ester, and the like.

Examples of the hydrogen drawing photopolymerization initiator include benzophenone, o-benzoyl benzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl- Benzophenone compounds such as diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone ; Thioxanthone compounds, such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichloro thioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc. are mentioned.

Among the photopolymerization initiators described above, 1-hydroxycyclohexylphenyl ketone and benzophenone are preferred from the viewpoint of excellent compatibility with the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition, In particular, 1-hydroxycyclohexylphenyl ketone is preferred. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, as the photosensitizer, for example, amines such as aliphatic amines and aromatic amines, urea such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfo Sulfur compounds, such as an acid, etc. are mentioned.

The amount of these photoinitiators and photosensitizers to be used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 0.3 to 7 parts by mass, respectively, based on 100 parts by mass of the nonvolatile component in the active energy ray-curable composition. More preferable.

In addition, in the coating composition, if necessary, an organic solvent; Coloring agents such as pigments, dyes, and carbon; Inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; High-grade fatty acid, acrylic resin, phenolic resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluorine resin (PTFE (polytetrafluoro) Roethylene), etc.), various resin fine powders such as polyethylene and polypropylene; Antistatic agent, viscosity modifier, light stabilizer, weather stabilizer, heat stabilizer, antioxidant, rust inhibitor, slip agent, wax, gloss modifier, release agent, compatibilizer, conductivity modifier, dispersant, dispersion stabilizer, thickener, anti-settling agent, silicone or hydrocarbon based It is possible to add various additives such as surfactants as appropriate.

The organic solvent is useful for appropriately adjusting the solution viscosity of the coating composition, and in particular, in order to perform thin film coating, it becomes easy to adjust the film thickness. Examples of the organic solvent usable 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; Ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. are mentioned. These solvents may be used alone or in combination of two or more.

In addition, the coating method of the above composition differs depending on the application, but, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheeler coater, a spin coater, Coating methods using dipping, screen printing, spraying, applicators, bar coaters, electrostatic painting, or the like, or molding methods using various molds may be mentioned.

Further, the fluorine-based copolymer of the present invention can also be used for resist applications. Resist applications consist of the fluorine-based copolymer of the present invention and a photoresist, and this photoresist comprises (1) an alkali-soluble resin, (2) a radiation-sensitive material (photosensitive material), (3) a solvent, and, if necessary, (4) It may contain other additives.

Examples of the (1) alkali-soluble resin include a resin soluble in an alkaline solution, which is a developer used for patterning a resist. Examples of the alkali-soluble resin include, for example, selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, fluoroglycinol, and hydroquinone, and alkyl substituted or halogen substituted aromatic compounds thereof. Novolac resin obtained by condensing at least one type with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde, vinylphenol compounds such as o-vinylphenol, m-vinylphenol, p-vinylphenol and α-methylvinylphenol, and these Polymers or copolymers of halogen-substituted compounds of, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid polymers or copolymers such as hydroxyethyl (meth)acrylate, polyvinyl alcohol, and some of the hydroxyl groups of the above various resins Further, a modified resin in which a radiation sensitive group such as a quinone diazide group, a naphthoquinone azide group, an aromatic azide group, and an aromatic cinnamoyl group is introduced can be further mentioned. These alkali-soluble resins may be used alone or in combination of two or more.

In addition, as the alkali-soluble resin, it is possible to use a urethane resin containing an acidic group such as carboxylic acid or sulfonic acid in its molecule, and it is also possible to use this urethane resin in combination with the alkali-soluble resin described above.

(2) As a radiosensitive material (photosensitive material), an alkali-soluble resin is mixed with the alkali-soluble resin and irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron rays, ion rays, molecular rays, γ rays, etc. Any material that changes the solubility in the developer can be used.

Examples of the radiation-sensitive material include quinone diazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, and organic acid amides. Compounds, organic acid imide compounds, and poly(olefin sulfone) compounds described in Japanese Unexamined Patent Application Publication No. 59-152, and the like.

Examples of the quinone diazide compound include 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, and 1,2-naphthoquinone Diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, others 1,2-benzoquinone Zide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide- And sulfonic acid chlorides of quinone diazide derivatives such as 4-sulfonic acid chloride and 2,1-naphthoquinone diazide-5-sulfonic acid chloride.

As the diazo compound, for example, a salt of a condensation product of p-diazodiphenylamine and formaldehyde or acetaldehyde, for example, hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the condensation A diazo resin inorganic salt as a reaction product with water, and a diazo resin organic salt as a reaction product of the condensate and sulfonic acids as described in the specification of USP3,300,309.

As the azide compound and the diazide compound, for example, azidechalconic acid, diazidebenzalmethylcyclohexanone and azidecinnamyldenacetophenones as described in Japanese Unexamined Patent Application Publication No. 58-203438, And aromatic azide compounds or aromatic diazide compounds described in Japanese Chemical Society Journal No. 12, p1708-1714 (1983).

As the halogenated organic compound, for example, if it is a halide of an organic compound, it can be used, but as specific examples, a halogen-containing oxadiazole-based compound, a halogen-containing triazine-based compound, a halogen-containing acetophenone-based compound, 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 compound, halogen-containing aromatic hydrocarbon Various compounds such as compounds, other halogen-containing heterocyclic compounds, and sulphenyl halide compounds, such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3- Chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, Bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxyl) Compounds used as halogen-based flame retardants such as -3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, dichlorophenyltrichloroethane Compounds used as organic chloro-based pesticides, such as, etc. are also mentioned.

As said organic acid ester, a carboxylic acid ester, a sulfonic acid ester, etc. are mentioned, for example. Further, examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. In addition, examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances may 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, methyl isobutyl ketone, and butyrolactone; Alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane;

Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and 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 Esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Monocarboxylic acid esters such as 2-methoxy butyl propionate;

Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; Propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; Halogenated hydrocarbons such as trichloroethylene, Fron solvent, HCFC and HFC; Completely fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; Polar solvents such as dimethylacetiamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone, etc. Solvents are mentioned. These solvents may be used alone or in combination of two or more.

Examples of the method of applying the composition adjusted for resist use include spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, and gravure coating, and the composition is filtered through a filter before application. Thus, solid impurities can also be removed.

Examples of active energy rays for curing the composition prepared for use in the above resist include active energy rays such as light, electron beam, and radiation. As a specific energy source or curing device, for example, a sterilizing lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high pressure mercury lamp for radiation, a medium or high pressure mercury lamp, an ultra high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Ultraviolet rays, or electron beams generated by a scanning type or curtain type electron beam accelerator. Moreover, in the case of curing with an electron beam, mixing of a polymerization initiator is unnecessary.

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

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, unless limited, parts and% are based on the amount of substances.

Synthesis Example 1

To 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 added as solvents, and at 25°C, It stirred for 1 hour under a nitrogen stream. 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). When the molecular weight of the copolymer (1) was measured by GPC, it was a weight average molecular weight (Mw) 15,200 and a number average molecular weight (Mn) 12,100.

Synthesis Example 2

To a nitrogen-substituted flask, 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 added as solvents, and at 25° C. under a nitrogen stream It 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 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, it was a weight average molecular weight (Mw) 12,300 and a number average molecular weight (Mn) 9,500.

Synthesis Example 3

To a nitrogen-substituted flask, 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 added as solvents, and at 25° C., a nitrogen stream It stirred for 1 hour under. 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 (3). When the molecular weight of the copolymer (3) was measured by GPC, it was a weight average molecular weight (Mw) 9,800 and a number average molecular weight (Mn) 7,800.

Synthesis Example 4

To a nitrogen-substituted flask, 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 added as solvents, and at 25° C., a nitrogen stream It stirred for 1 hour under. 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 (4). When the molecular weight of the copolymer (4) was measured by GPC, it was a weight average molecular weight (Mw) 13,500 and a number average molecular weight (Mn) 10,500.

Synthesis Example 5

To a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone, 45 parts by mass of 1-adamantyl methacrylate, and 30 parts by mass of 2,2,3,3,3-pentafluoropropyl methacrylate were added as solvents. The mixture was stirred at 25° C. for 1 hour under a nitrogen stream. 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). When the molecular weight of the copolymer (5) was measured by GPC, it was a weight average molecular weight (Mw) 14,800 and a number average molecular weight (Mn) 11,700.

Synthesis Example 6

In a nitrogen-substituted flask, as a solvent, 84 parts by mass of methyl ethyl ketone, 34 parts by mass of 1-adamantyl methacrylate, 24 parts by mass of 1,1,1,3,3,3-hexafluoroisopropyl methacrylic acid Part was added, and the mixture was stirred at 25° C. for 1 hour under a nitrogen stream. 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 (6). When the molecular weight of the copolymer (6) was measured by GPC, the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,500.

Synthesis Example 7

To a nitrogen-substituted flask, 110 parts by mass of methyl ethyl ketone and 50 parts by mass of 1-adamantyl methacrylate were added as solvents, followed by stirring at 25° C. under a nitrogen stream for 1 hour. Next, 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, and 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, followed by reaction for 12 hours. Then, 25 mass parts of 2,2,2-trifluoroethyl methacrylate was added, and it was made to react for 12 hours more. 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 (7). When the molecular weight of the copolymer (7) was measured by GPC, it was a weight average molecular weight (Mw) 15,300 and a number average molecular weight (Mn) 11,500.

Synthesis Example 8

To a nitrogen-substituted flask, 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 added as solvents, and at 25° C., It stirred for 1 hour under a nitrogen stream. 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). When the molecular weight of the copolymer (8) was measured by GPC, it was a weight average molecular weight (Mw) 5,200 and a number average molecular weight (Mn) 4,200.

Synthesis Example 9

To 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 added as solvents, and at 25°C, It stirred for 1 hour under a nitrogen stream. 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. Thereafter, 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 the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (9). When the molecular weight of the copolymer (9) was measured by GPC, it was a weight average molecular weight (Mw) 22,100 and a number average molecular weight (Mn) 18,200.

Comparative Synthesis Example 1

To 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 added as a solvent, and at 25° C. under a nitrogen stream It stirred for 1 hour. Next, 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, it was a weight average molecular weight (Mw) 14,600 and a number average molecular weight (Mn) 12,300.

Comparative Synthesis Example 2

To a nitrogen-substituted flask, 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 added as solvents, and at 25° C., a nitrogen stream It stirred for 1 hour under. 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). When the molecular weight of the copolymer (11) was measured by GPC, it was a weight average molecular weight (Mw) of 13,100 and a number average molecular weight (Mn) of 10,800.

Comparative Synthesis Example 3

To 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 added as solvents, and at 25° C., nitrogen It stirred for 1 hour under an airflow. 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). When the molecular weight of the copolymer (12) was measured by GPC, it was a weight average molecular weight (Mw) 14,600 and a number average molecular weight (Mn) 11,700.

Comparative Synthesis Example 4

In a nitrogen-substituted flask, as a solvent, 109 parts by mass of methyl ethyl ketone and 33 parts by mass of 1-adamantyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8, 43 parts by mass of 8,8-tridecafluorooctyl methacrylate was added, followed by stirring 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 (13). As a result of measuring the molecular weight of the copolymer (13) by GPC, it was a weight average molecular weight (Mw) 15,400 and a number average molecular weight (Mn) 12,300.

Synthesis Example 10

In a nitrogen-substituted flask, as solvents, 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, 2,2,2-trifluoroethyl methacrylate 24 parts by mass of acrylate was added, and the mixture was stirred at 25°C for 1 hour under a nitrogen stream. 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. Subsequently, 9.0 g of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (14). When the molecular weight of this copolymer (14) was measured by GPC, it was a weight average molecular weight (Mw) 15,800 and a number average molecular weight (Mn) 12,100.

Synthesis Example 11

In a nitrogen-substituted flask, as solvents, 45 parts by mass of methyl ethyl ketone, 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 21 parts by mass was added, followed by stirring at 25°C for 1 hour under a nitrogen stream. 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. Subsequently, 9.03 g of activated alumina was added and stirred to the obtained reaction product. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (15). When the molecular weight of this copolymer (15) was measured by GPC, it was a weight average molecular weight (Mw) 12,600 and a number average molecular weight (Mn) 10,100.

Synthesis Example 12

In a nitrogen-substituted flask, as solvents, 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, 2,2, 26 parts by mass of 2-trifluoroethyl methacrylate was added, followed by stirring 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. Subsequently, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (16). When the molecular weight of this copolymer (16) was measured by GPC, it was a weight average molecular weight (Mw) 13,800 and a number average molecular weight (Mn) 10,700.

Comparative Synthesis Example 5

In a nitrogen-substituted flask, as solvents, 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, 3,3,4,4,5,5 41 parts by mass of ,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate was added, followed by stirring 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. Subsequently, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (17). When the molecular weight of this copolymer (17) was measured by GPC, it was a weight average molecular weight (Mw) 15,300 and a number average molecular weight (Mn) 12,100.

Comparative Synthesis Example 6

In a nitrogen-substituted flask, as solvents, 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, 41 parts by mass of 7,7,8,8,8-tridecafluorooctyl methacrylate was added, followed by stirring 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. Subsequently, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (18). When the molecular weight of this copolymer (18) was measured by GPC, it was a weight average molecular weight (Mw) 11,500 and a number average molecular weight (Mn) 9,700.

Comparative Synthesis Example 7

In a nitrogen-substituted flask, as a solvent, 56 parts by mass of methyl ethyl ketone and 56 parts by mass of 2-propanol, 60 parts by mass of polypropylene oxide chain-containing methacrylate, and 18 parts by mass of 2,2,2-trifluoroethyl methacrylate Then, the mixture was stirred at 25° C. for 1 hour under a nitrogen stream. 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. Subsequently, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (19). When the molecular weight of this copolymer (19) was measured by GPC, it was a weight average molecular weight (Mw) 15,800 and a number average molecular weight (Mn) 12,900.

Comparative Synthesis Example 8

In a nitrogen-substituted flask, as a solvent, 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol, 42 parts by mass of polypropylene oxide chain-containing methacrylate, 3,3,4,4,5,5,6,6, 33 parts by mass of 7,7,8,8,8-tridecafluorooctyl methacrylate was added, followed by stirring 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. Subsequently, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (20). When the molecular weight of this copolymer (20) was measured by GPC, it was a weight average molecular weight (Mw) 15,100 and a number average molecular weight (Mn) 11,800.

Synthesis Example 13

In a dry air-substituted flask, 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''), and 0.03 tin octylate as a urethanization catalyst. As a mass part and a polymerization inhibitor, 0.04 mass part of p-methoxyphenol was added, and the temperature was raised to 75 degreeC. In a dry air atmosphere, 30 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as "AOI") was dripped over 1 hour. After completion of the dropwise addition, after stirring at 75°C for 1 hour, the temperature was raised to 80°C and stirred for 3 hours. In addition, the completion of the reaction confirmed that absorption of the isocyanate group disappeared by measuring the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20 mass% of the copolymer (21). When the molecular weight of this copolymer (21) was measured by GPC, it was a weight average molecular weight of 19,900 and a number average molecular weight of 17,600.

Synthesis Example 14

In a flask purged with dry air, 66 parts by mass of the copolymer (16) obtained in Synthesis Example 15 was dissolved in 66 parts by mass of PGMEA, 0.02 parts by mass of tin octylate as a urethane catalyst, and 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor. Then, it heated up to 75 degreeC. In a dry air atmosphere, 16 parts by mass of AOI was dripped over 1 hour. After completion of the dropwise addition, after stirring at 75°C for 1 hour, the temperature was raised to 80°C and stirred for 3 hours. In addition, the completion of the reaction confirmed that absorption of the isocyanate group disappeared by measuring the IR spectrum of the reactant. Next, PGMEA was diluted, and the PGMEA solution containing 20 mass% of the copolymer (22) was obtained. When the molecular weight of this copolymer (22) was measured by GPC, it was a weight average molecular weight of 15,900 and a number average molecular weight of 13,700.

Comparative Synthesis Example 9

In a dry air-substituted flask, 75 parts by mass of the copolymer (17) obtained in Comparative Synthesis Example 5 was dissolved in 75 parts by mass of PGMEA, and 0.03 parts by mass of tin octylate as a urethanization catalyst, and 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor. After adding parts, it heated up to 75 degreeC. In a dry air atmosphere, 20 parts by mass of AOI was dripped over 1 hour. After completion of the dropwise addition, after stirring at 75°C for 1 hour, the temperature was raised to 80°C and stirred for 3 hours. In addition, the completion of the reaction confirmed that absorption of the isocyanate group disappeared by measuring the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20 mass% of the copolymer (23). When the molecular weight of this copolymer (23) was measured by GPC, it was a weight average molecular weight of 17,100 and a number average molecular weight of 13,400.

Comparative Synthesis Example 10

In a flask purged with dry air, 60 parts by mass of the copolymer (18) obtained in Comparative Synthesis Example 6 was dissolved in 60 parts by mass of PGMEA, 0.02 parts by mass of tin octylate as a urethane catalyst, and 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor. After adding parts, it heated up to 75 degreeC. In a dry air atmosphere, 21 parts by mass of AOI was dripped over 1 hour. After completion of the dropwise addition, after stirring at 75°C for 1 hour, the temperature was raised to 80°C and stirred for 3 hours. In addition, the completion of the reaction confirmed that absorption of the isocyanate group disappeared by measuring the IR spectrum of the reactant. Next, PGMEA was diluted, and the PGMEA solution containing 20 mass% of the copolymer (24) was obtained. As a result of measuring the molecular weight of this copolymer (24) by GPC, it was a weight average molecular weight of 17,000 and a number average molecular weight of 13,300.

Comparative Synthesis Example 11

In a dry air-substituted flask, 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, and 0.006 parts by mass of p-methoxyphenol as a polymerization inhibitor And 3.3 parts by mass of triethylamine 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 maintaining the inside of the flask at 10°C. After completion of the dropwise addition, the mixture was stirred at 10°C for 1 hour, heated and stirred at 30°C for 1 hour, heated to 50°C and stirred for 10 hours to react, and gas chromatography measurement confirmed disappearance of methacrylic acid chloride. Became. Subsequently, 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 left standing to separate and remove the aqueous layer. 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 left to stand for 1 day to completely dehydrate, and then the dehydrating agent was separated by filtration.

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and per molecule, there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms is an average of 46 In addition, the number average molecular weight by GPC is 1,500)

Subsequently, by distilling off the solvent under reduced pressure, a compound having a poly(perfluoroalkylene ether) chain represented by the following formula was obtained.

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and per molecule, there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms is an average of 46 to be)

Comparative Synthesis Example 12

To a nitrogen-substituted flask, 100 parts by mass of methyl isobutyl ketone was added as a solvent, and the temperature was raised to 95°C while stirring under a nitrogen stream. Next, 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 and 120 parts by mass of methylisobutyl ketone Three kinds of dripping liquids are set in separate dripping devices, respectively, of the dissolved monomer solution and the 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 methyl isobutyl ketone. Then, while maintaining the inside of the flask at 95°C, it was dripped over 3 hours at the same time. After completion of the dropwise addition, the mixture was stirred at 95°C for 5 hours, and then stirred at 105°C for 2 hours, and then 262.1 parts by mass of the solvent were distilled off under reduced pressure to obtain a solution of the copolymer (26).

Subsequently, to the polymer (25) solution obtained above, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream, and 75°C was maintained. While doing, 29.9 parts by mass of AOI was dripped over 1 hour. After completion of the dropwise addition, the mixture was stirred at 75°C for 1 hour, then heated to 80°C and stirred for 4 hours to confirm disappearance of the isocyanate group by IR spectrum measurement, and 362 parts by mass of methyl isobutyl ketone was added to the fluorinated polymerizable resin ( 26) was obtained in a methyl isobutyl ketone solution containing 20% by mass.

Measurement of the falling angle in the cured coating film

The evaluation of the rolling angle of the surface of the coating film was performed by measuring the rolling angle of water. In addition, for the evaluation of slipperiness, Kyowa Gaimen Chemicals DM-500 was used. A water droplet of 50 µL was dripped on the substrate, the stage was tilted at a speed of 2°/sec, and the angle at which the water droplet started to move was taken as the value of the fall angle. The measurement was performed 5 times, and the average value was taken as the value.

<Evaluation in UV-cured coating film>

125 parts by mass of UV-curable urethane acrylate resin ("Unidic 17-806" manufactured by DIC Corporation; 80% by mass of resin content butyl acetate solution), 1-hydroxycyclohexylphenylketone (manufactured by BASF Japan) as a photopolymerization initiator ``Irgacure 184'' manufactured by Geisha) 5 parts by mass, 54 parts by mass of toluene, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, 28 parts by mass of propylene glycol monomethyl ether are mixed and dissolved, and the active energy ray curable type The base resin composition of the composition was obtained. To 268 parts by mass of the obtained base resin composition, 1 part by mass of the compound obtained in Synthesis Example was added and uniformly mixed to obtain an active energy ray-curable composition. Subsequently, this active energy ray-curable composition was applied on a 1 mm-thick 7 cm x 7 cm glass plate with a spin coater, and then put 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 (in a nitrogen atmosphere, a high-pressure mercury lamp, and an ultraviolet irradiation amount of 2 kJ/m 2) to obtain a cured coating film. And the rolling angle of the obtained coating film was measured.

[Table 1]

<Evaluation in thermosetting coating film>

100 parts by mass of Ceranate SSA-500 manufactured by DIC Corporation, 186 parts by mass of Banoc DN-980, 0.1% by mass of the compound obtained above were added in a solid content ratio, diluted with butyl acetate, and a solution was prepared so as to be 40%. did. 1 mL of the crude solution was coated on a glass substrate having a thickness of 1 mm and a length of 15 cm x a width of 7 cm with a 6 mil applicator. Then, it dried at 23 degreeC for 7 days, the coating film was produced, and the slip angle was measured.

[Table 2]

Comparative Synthesis Example 13

To a nitrogen-substituted flask, 109 parts by mass of methyl ethyl ketone and 75 parts by mass of 2,2,2-trifluoroethyl methacrylate were added as solvents, followed by stirring at 25° C. for 1 hour under a nitrogen stream. Next, 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 (27). When the molecular weight of the copolymer (27) was measured by GPC, it was a weight average molecular weight (Mw) 15,100 and a number average molecular weight (Mn) 11,600.

Synthesis Example 15

To 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 added as solvents, and at 25°C, It stirred for 1 hour under a nitrogen stream. Next, 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). When the molecular weight of the copolymer (28) was measured by GPC, it was a weight average molecular weight (Mw) 14,800 and a number average molecular weight (Mn) 11,800.

Synthesis Example 16

To 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 added as solvents, and at 25°C, It stirred for 1 hour under a nitrogen stream. Next, 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 (29). When the molecular weight of the copolymer (29) was measured by GPC, it was a weight average molecular weight (Mw) 15,500 and a number average molecular weight (Mn) 12,400.

Comparative Synthesis Example 14

To a nitrogen-substituted flask, 110 parts by mass of methyl ethyl ketone and 75 parts by mass of 1-adamantyl methacrylate were added as solvents, followed by stirring at 25° C. under a nitrogen stream for 1 hour. Next, 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). When the molecular weight of the copolymer (30) was measured by GPC, it was a weight average molecular weight (Mw) 15,200 and a number average molecular weight (Mn) 11,600.

[Table 3]

Claims (11)

A polymerizable monomer (a1) having a fluorinated alkyl group represented by C _n F _2n+1- (wherein n is 1 or 2) and a polymerizable unsaturated group, and
Polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group
A fluorine-based copolymer characterized in that it is a copolymer having as an essential raw material. The method of claim 1,
A fluorine-based copolymer in which the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is a crosslinkable hydrocarbon skeleton. The method according to claim 1 or 2,
A fluorine-based copolymer in which the ratio (Mw/Mn) of the copolymer to the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.00 to 1.40. The method according to any one of claims 1 to 3,
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. The method according to any one of claims 1 to 4,
The fluorine-based copolymer in which the polymerizable monomer (a1) is a monomer represented by the following general formula (1) or (2).

[In the general formulas (1) and (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 of 1 to 8), Rf is _{a group represented by C n} F _2n+1 (however, n is 1 or 2), and X represents any one of the following formulas (X-1) to (X-10)]

(M in the above formula is an integer of 1 to 8, k is an integer of 0 to 8, and Rf is the same as above) The method according to any one of claims 1 to 5,
The fluorine-based copolymer in which the polymerizable monomer (a2) further has a hydroxyl group. The method according to any one of claims 1 to 5,
A fluorine-based copolymer wherein the copolymer further has an active energy ray-curable group. The method according to any one of claims 1 to 7,
A fluorine-based copolymer wherein the copolymer is a random copolymer. A water lubricating surface modifier comprising the copolymer according to any one of claims 1 to 8. A curable resin composition comprising the fluorine-based copolymer according to any one of claims 1 to 8 and a curable resin. A slidable coating film which is a cured film of the curable resin composition according to claim 10.