CN112334501B - Fluorine-based copolymer, water-repellent surface modifier, curable resin composition, and water-repellent coating film - Google Patents

Abstract

Provided are a fluorine-based copolymer which can provide a surface having excellent water-slipping properties and can be suitably used as a water-slipping surface modifier, a curable resin composition using the same, and a water-slipping coating film which is a cured product of the composition. Specifically, a fluorine-containing copolymer, a water-repellent surface modifier comprising the fluorine-containing copolymer, a curable resin composition comprising the fluorine-containing copolymer, and a cured coating film as a cured product of the curable resin composition are used, and the fluorine-containing copolymer is characterized by having C _n F _2n+1 A polymerizable monomer (a1) containing a fluoroalkyl group represented by the general formula (1) or (2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) containing an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials.

Description

Fluorine-based copolymer, hydroplaning surface modifier, curable resin composition, and hydroplaning Sexual coating

technical field

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

Background technique

Fluorine-based surfactants or fluorine-based surface modifiers are widely used for various coating materials, surface modifiers, and the like due to their excellent leveling properties, water and oil repellency, and the like. The cured film obtained by curing the curable resin composition containing the fluorine-based surfactant or fluorine-based surface modifier (hereinafter, these may be abbreviated as "fluorine-based surfactant" in some cases) exhibits excellent performance Water repellency (oil repellency). Fluorine-based surfactants are generally compounds having a fluorohydrocarbon group in the structure of the compound in order to utilize the water- and oil-repellent properties of fluorine atoms, and are arranged in one molecule to express compatibility with curable resins. and curable compounds of other structures, various compounds can be provided according to the target performance level and usage method (for example, refer to Patent Documents 1 to 2).

In the modern living environment, there are many equipment, devices, and mechanical appliances that want or need water repellency, and their types also include automotive window glass, automotive painted surfaces, kitchen equipment, kitchen supplies, and exhaust devices attached to kitchen equipment. , bathing equipment, washbasin equipment, medical facilities, medical machinery and equipment, mirrors, glasses, inkjet printer parts, etc., are extremely extensive. In addition, water repellency is also required for refrigerator heat exchangers, air conditioner outdoor units, and heat pump heat exchangers for EV vehicles, which will be greatly developed in the future, from the viewpoint of preventing freezing and frosting.

In the above-mentioned applications, the property that the attached water droplets flow down rapidly under the action of gravity or the like (hydroplaning) is also required. That is, the water repellent surface only means that the water attached to it is easy to form water droplets, and the large water droplets fall down due to their own weight, and if the water slidability is poor, the water droplets are firmly attached to the surface of the object. The degree does not drop. The retention of the water droplets adhering to the surface in this state causes various problems. For example, in a state where many water droplets are attached to the windshield of an automobile, there is a problem in that the windshield is diffusely reflected by light from street lamps and the like, and the driver's field of vision is obstructed. In addition, when a material with poor water slidability is used in an environment exposed to rainwater, such as an exterior material, traces of water flow (rain marks) adhere to the surface, and it cannot be said that it is excellent in stain resistance. The smaller the slip angle of water, the better the water slidability. However, the correlation between the contact angle of water and the slip angle has not been confirmed, and a surface modifier capable of both water repellency and water slidability is required.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2013-6928

Patent Document 2: International Publication No. WO2012/002361

SUMMARY OF THE INVENTION

Invention to solve problem

The problem to be solved by the present invention is to provide a fluorine-based copolymer which can be suitably used as a surface modifier, a curable resin composition using the same, and a cured product of the composition, which can obtain a surface excellent in water slidability. slippery water coating.

solution to the problem

The inventors of the present invention have conducted intensive studies and, as a result, found that a polymerizable monomer having a fluoroalkyl group and a polymerizable unsaturated group having a specific length, and a polymerizable monomer having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group The present invention has been accomplished by making a copolymer of a monomer as an essential monomer as a surface modifier for solving the above-mentioned problems.

That is, the present invention provides a fluorine-based copolymer, a water-slidable surface modifier using the same, a curable resin composition containing the same, and a water-slidable coating film as a cured product of the composition, wherein the fluorine-based copolymer is It is characterized in that a polymerizable monomer (a1) having a fluoroalkyl group represented by C _n F _2n+1 - (wherein n is 1 or 2) and a polymerizable unsaturated group, and an alicyclic A copolymer of the formula hydrocarbon skeleton and a polymerizable monomer (a2) having a polymerizable unsaturated group as essential raw materials.

effect of invention

By using the fluorine-based copolymer of the present invention as a surface modifier, a curable resin composition excellent in water slidability on the surface of a coating film or the like can be obtained, and various thermosetting systems, active energy rays can be selected for applications requiring water slidability Curing systems and other curing systems are used.

Detailed ways

The fluorine-based copolymer of the present invention is characterized in that it is a polymerizable monomer having a fluoroalkyl group represented by C _n F _2n+1 - (wherein n is 1 or 2) and a polymerizable unsaturated group. (a1) and a copolymer having an alicyclic hydrocarbon skeleton and a polymerizable monomer (a2) having a polymerizable unsaturated group as essential raw materials.

Conventionally, it has been considered that the larger the number of carbon atoms to which fluorine atoms are directly bonded, the better the water and oil repellency. The upper limit of the number of carbon atoms is set to 6. Therefore, for example, in order to increase the number of fluorine atoms in one molecule (that is, to increase the fluorine atom content rate), for example, as in the above-mentioned Patent Document 2, an ether bond having a fluoroalkylene chain having about 2 to 3 carbon atoms is provided. A compound formed of a linked perfluoroalkylene ether chain.

However, as described above, no correlation has been confirmed between water repellency and water slidability, and even a water repellent surface may have poor water slidability, white marks may remain after dripping, or residues contained in rainwater or the like may remain on the surface of the coating film. In the case of streaks formed by substances in the air, the current situation is that the use of a curable resin composition containing a fluorine-based compound does not necessarily provide good water slidability.

In such a case, it was found that the use of a compound containing a structure in which the number of carbon atoms to which a fluorine atom is directly bonded is 1 or 2, that is, a compound having a C A fluoroalkyl group represented by _n F _2n+1 - (wherein, n is 1 or 2) and has an alicyclic hydrocarbon skeleton in the compound.

As the polymerizable monomer (a1) having a fluoroalkyl group represented by C _n F _2n+1 - (wherein n is 1 or 2) and a polymerizable unsaturated group used in the present invention, as long as it is in the molecule The compound having the above-mentioned fluoroalkyl group and a polymerizable unsaturated group can be used without particular limitation. As said fluoroalkyl group, it is especially preferable that n is 1 from a viewpoint of obtaining the hardened|cured material which is more excellent in water slidability. It should be noted that the number of fluoroalkyl groups represented by C _n F _2n+1 - (wherein n is 1 or 2) in one molecule is not particularly limited, and is preferably based on other properties required for the cured product, such as The fluorine atom content is adjusted according to the level of water repellency and surface smoothness.

As a polymerizable unsaturated group which the said polymerizable monomer (a1) has, a (meth)acryloyl group, a vinyl group, a maleimide group etc. are mentioned, for example. Among these, a (meth)acryloyl group is preferable from the viewpoints of easy availability of raw materials, ease of controlling compatibility with various compounding components in the curable resin composition, or good polymerization reactivity. As the compound having the (meth)acryloyl group, for example, a monomer represented by the following general formula (1) or (2) can be preferably exemplified. Moreover, as for the said polymerizable monomer (a1), only 1 type may be used and 2 or more types may be used together.

[In the above 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 (wherein, n is 1 or 2), and X represents any group in the following formulae (X-1) to (X-10). ]

-OC _m H _2m - (X-1)

-OCH ₂ CH ₂ OCH ₂ - (X-2)

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

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

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

Examples of the above-mentioned alicyclic hydrocarbon skeleton include cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl (dicyclohexyl) which may be mono- or polysubstituted by any substituent. ), tricyclohexyl (tercyclohexyl), norbornane, decalin, perhydrofluorene, tricyclo[5.2.1.0 ^2.6 ] decane, adamantane, tetracycloheptane, bisadamantane, cubic alkane, spiro[4.4 ]octane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, bicyclo[2.2.2]oct-2-ene, cyclohexadiene, cycloheptadiene, cyclooctadiene , cycloheptatriene, cyclodecatriene, cyclooctatetraene, norbornene, octahydronaphthalene, bicyclo[2.2.1]heptadiene, bicyclo[4.3.0]nonadiene, dicyclopentadiene, Alicyclic hydrocarbon skeletons such as hexahydroanthracene and spiro[4.5]decadiene.

Among these, from the viewpoints of high hardness, water slidability, and antifouling properties of the resulting coating film surface, a skeleton having a bridged structure is preferable, and for example, adamantane, perhydroindene, decalin, and perhydrofluorene are preferable , perhydroanthracene, perhydrophenanthrene, dicyclopentane, dicyclopentene, perhydroacenaphthene, perhydrophenarene, norbornane, norbornene, etc., particularly preferred adamantane, dicyclopentane, bicyclic Pentene, norbornane, norbornene, adamantane are the most preferred skeletons.

As said polymerizable unsaturated group, a (meth)acryloyl group, a vinyl group, a maleimide group etc. are mentioned, for example. Among these, a (meth)acryloyl group is preferable from the viewpoints of easy availability of raw materials, ease of controlling compatibility with various compounding components in the curable resin composition, or good polymerization reactivity.

Hereinafter, the 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.

As a polymerizable monomer which has the said adamantane skeleton and a (meth)acryloyl group, the compound etc. which are represented by following formula (a2-1) and (a2-2) are mentioned, for example.

(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 .)

As said reactive functional group, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, an acid anhydride group, etc. are mentioned, for example. Among them, a hydroxyl group is preferred from the viewpoint of obtaining a surface modifier having good compatibility with the curable resin composition, or allowing easy introduction of an active energy ray-curable group into the obtained copolymer.

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

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 atoms bonded to the carbon atoms constituting the adamantane skeleton in the general formula (a2-1) may be partially or entirely substituted with fluorine atoms, alkyl groups, 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 shown below 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 shown below are mentioned, for example.

Among the polymerizable monomers having an adamantane skeleton and a (meth)acryloyl group, the above-mentioned formulas (a2-1-1) and (a2-1-3) are more preferable because the Tg of the coating film can be further increased. ), (a2-1-5), (a2-1-7), (a2-2-1), (a2-2-2), (a2-2-3) compounds.

Hereinafter, the 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.

As a polymerizable monomer which has the said dicyclopentane skeleton and a (meth)acryloyl group, the compound etc. which are represented by following formula (a2-3) are mentioned, for example.

(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 atoms bonded to the carbon atoms constituting the dicyclopentane skeleton in the above-mentioned 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 shown below 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 it can further increase the Tg of the coating film.

Hereinafter, the 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.

As a polymerizable monomer which has the said dicyclopentene skeleton and a (meth)acryloyl group, the compound etc. which are represented by following formula (a2-4) are mentioned, for example.

(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 atoms bonded to the carbon atoms constituting the dicyclopentene skeleton in the above-mentioned 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 shown below are mentioned, for example.

Among the polymerizable monomers having a dicyclopentene skeleton and a (meth)acryloyl group, the above-mentioned formula (a2-4-3) (a2-4-4) is preferable from the viewpoint that the Tg of the coating film can be further increased compounds shown.

Hereinafter, the 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.

As a polymerizable monomer which has the said norbornane skeleton and a (meth)acryloyl group, the compound etc. which are represented by following formula (a2-5) are mentioned, for example.

(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 atoms bonded to the carbon atoms constituting the norbornane skeleton in the above-mentioned 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 shown below are mentioned, for example.

Among the polymerizable monomers having a norbornane skeleton and a (meth)acryloyl group, those represented by the above formulae (a2-5-3) (a2-5-4) are preferred from the viewpoint that the Tg of the coating film can be further increased. compounds shown.

Hereinafter, the 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.

As a polymerizable monomer which has the said norbornene skeleton and a (meth)acryloyl group, the compound etc. which are represented by following formula (a2-6), (a2-7), etc. are mentioned, for example.

(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 atoms bonded to the carbon atoms constituting the norbornene skeleton in the above-mentioned 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 shown below are mentioned, for example.

Among the polymerizable monomers having a norbornene skeleton and a (meth)acryloyl group, the above-mentioned formulae (a2-6-3) and (a2-6-4) are preferable from the viewpoint that the Tg of the coating film can be further increased compounds shown.

As described above, the fluorine-based copolymer of the present invention is characterized in that it has a fluoroalkyl group represented by C _n F _2n+1 - (wherein, n is 1 or 2) and a polymerizable unsaturated group. A copolymer of a polymerizable monomer (a1) and a polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials. Here, from the viewpoint of obtaining a surface modifier having better compatibility with the curable resin composition, the ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) is preferably ( a1): (a2)=5: The range of 95-95:5, More preferably, it is the range of 10:90-90:10.

As a raw material used to obtain the fluorine-based copolymer of the present invention, monomers copolymerizable with the above-mentioned (a1) and (a2) can be used in combination within a range not impairing the effects of the present invention. Examples of monomers that can be used in combination include monomers having a polyoxyalkylene chain, monomers having a linear alkyl group having 1 to 18 carbon atoms, and branched monomers having 1 to 18 carbon atoms. Alkyl monomers, etc.

Examples of the polymerizable unsaturated group contained in the above-mentioned other copolymerizable monomers include (meth)acryloyl groups, vinyl groups, maleimide groups, and the like. Among the above-mentioned monomers (a1) and (a2) When the polymerizable unsaturated group possessed by ) is a (meth)acryloyl group, the polymerizable unsaturated group possessed by other monomers is also preferably a (meth)acryloyl group from the viewpoint of good copolymerizability .

As a monomer which has the said oxyalkylene group, the monomer represented by following general formula (a3-1) is mentioned.

(in the formula, R ² is a hydrogen atom or a methyl group, Y ¹ X and Y ² are independently alkylene groups, p and q are respectively 0 or an integer of 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 above-mentioned general formula (a3-1) are alkylene groups, and the alkylene groups also include those having a substituent. Specific examples of the -O-(Y ¹ O)n-(Y ² O)m- moiety include ethylene glycol residues in which the number of repeating units p is 1, m is 0, and Y ¹ is ethylene ; The number of repeating units p is 1, m is 0, and Y ¹ is a propylene glycol residue; The number of repeating units p is 1, m is 0, and Y ¹ is butylene glycol residues of butylene; Repeating units A polyethylene glycol residue in which the number p is an integer of 2 or more, q is 0, and Y ¹ is ethylene; the number of repeating units p is an integer of 2 or more, q is 0, and Y ¹ is propylene Propylene glycol residues; residues of copolymers of ethylene oxide and propylene oxide in which the number of repeating units p and q are both integers of 1 or more, and Y ¹ or Y ² is ethylene and the other is propylene Residues of polyalkylene glycols.

The degree of polymerization of the polyalkylene glycol in the above 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, and more preferably in the range of 2 to 80 , more preferably in the range of 3-50. It should be noted that the repeating unit including Y ¹ and the repeating unit including Y ² may be arranged in a random shape or in a block shape.

R ³ in the above general formula (a3-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer is a mono(meth)acrylate of an alkylene glycol such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and when R ³ is an alkyl group having 1 to 6 carbon atoms, A monomer in which the terminal of the non-(meth)acrylate in the mono(meth)acrylate which is an alkylene glycol is blocked with an alkyl group having 1 to 6 carbon atoms.

In the above general formula (a3-1), a monomer having a poly(oxyalkylene) containing a plurality of oxyalkylene groups is preferable, and specific examples thereof include polypropylene glycol mono(meth)acrylate, polyethylene glycol Glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol propylene glycol) mono(meth)acrylate base) acrylate, polyethylene glycol · polypropylene glycol mono(meth)acrylate, poly(ethylene glycol · tetramethylene glycol) mono(meth)acrylate, polyethylene glycol · polytetramethylene base 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/butylene glycol) mono(meth)acrylate, polyethylene glycol Alcohol/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)acrylic acid Esters, poly(propylene glycol · trimethylene glycol) mono(meth)acrylate, polypropylene glycol · polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol · tetramethylene diol) Alcohol) mono(meth)acrylate, polytrimethylene glycol, polytetramethylene glycol mono(meth)acrylate, poly(butylene glycol, trimethylene glycol) mono(meth)acrylic acid ester, polybutylene glycol and polytrimethylene glycol mono(meth)acrylate, etc. 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. The same goes for other substances. In the present invention, when a monomer having an oxyalkylene group is used, polypropylene glycol mono(meth)acrylic acid is preferable from the viewpoint of obtaining a copolymer having good compatibility with other components in the curable resin composition ester, polyethylene glycol mono(meth)acrylate, polyethylene glycol and polypropylene glycol mono(meth)acrylate.

Moreover, as a commercial item of the monomer which has an oxyalkylene group, "NK ESTER M-20G", "NK ESTER M-40G", "NK ESTER M-90G" made by Shin-Nakamura Chemical Industry Co., Ltd. are mentioned, for example. ", "NK ESTER M-230G", "NKESTER AM-90G", "NK ESTER AMP-10G", "NK ESTER AMP-20G", "NK ESTER AMP-60G"; "BLEMMER PE" manufactured by NOF Corporation -90", "BLEMMER PE-200", "BLEMMER PE-350", "BLEMMER PME-100", "BLEMMER PME-200", "BLEMMER PME-400", "BLEMMER PME-4000", "BLEMMER PP- 1000", "BLEMMER PP-500", "BLEMMER PP-800", "BLEMMER 70PEP-350B", "BLEMMER 55PET-800", "BLEMMER 50POEP-800B", "BLEMMER 10PPB-500B", "BLEMMER NKH-5050" ", "BLEMMERAP-400", "BLEMMER AE-350", etc. These oxyalkylene group-containing monomers may be used alone or in combination of two or more.

As a monomer which has the said alkyl group, the monomer etc. which are represented by following general formula (a3-2) are mentioned, for example.

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

It should be noted that R ⁵ in the above general formula (a3-2) is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and the alkyl group may have aliphatic or aromatic Substituents such as hydrocarbon group, hydroxyl group, epoxy group, etc. Specific examples of the monomer represented by the above formula (a3-2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. , octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. ( C1-18 alkyl esters of meth)acrylic acid; unsaturated monomers containing epoxy groups such as glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether; (meth)acrylic acid, Carboxyl group-containing unsaturated monomers such as 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and itaconic acid, and the like. These alkyl group-containing monomers may be used alone or in combination of two or more.

When the above-mentioned various other monomers are used in combination with the above-mentioned monomers (a1) and (a2), it is possible to obtain a product that does not impair water slidability, and can also exhibit effects such as surface hardness and scratch resistance. From the viewpoint of the copolymer, the amount used is preferably in the range of 5 to 40 mol %, more preferably in the range of 5 to 30 mol %, relative to 100 mol of the total of the monomer (a1) and the monomer (a2). From the viewpoint of water slidability, it is most preferable not to use other monomers in combination.

For example, when the monomer (a1) and the monomer (a2) are allowed to coexist, or when other monomers used in combination according to need are also coexisted, living cationic polymerization, living anionic polymerization, living radical polymerization are preferred. The fluorine-based copolymer of the present invention is produced by living polymerization such as polymerization. In addition, living radical polymerization is particularly preferably used from the viewpoint of easy control of the polymerization reaction in these living polymerizations.

In the above-mentioned living radical polymerization, a dormant species whose end of the living polymerization is protected by an atom or an atomic group is allowed to reversibly generate a radical and react with a monomer, thereby performing a growth reaction. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation type radical polymerization (RAFT), radical polymerization via nitroxide (NMP), Radical Polymerization (TERP) etc. Which of these methods is used is not particularly limited, but the above-mentioned ATRP is preferable from the viewpoint of ease of control and the like. ATRP is polymerized using an organic halide or a halogenated sulfonyl compound as an initiator and a metal complex formed of a transition metal compound and a ligand as a catalyst.

As the polymerization initiator used in the above ATRP, an organic halogenated compound can be used. Specifically, 1-chloroethylbenzene and 1-bromoethylbenzene, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α,α'-dibromo Xylene, hexa(α-bromomethyl)benzene, 2-halogenated carboxylic acids having 1 to 6 carbon atoms (for example, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromo C1-C6 alkyl esters of isobutyric acid, etc.). In addition, as a more specific example of the C1-C6 alkyl ester of C1-C6 2-halogenated carboxylic acid, for example, methyl 2-chloropropionate and ethyl 2-chloropropionate can be mentioned. ester, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, etc.

The transition metal compound used in the above ATRP is represented by Mn ⁺ _Xn . Mn ⁺ as a transition metal can be selected from Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo0 , 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⁺ . In addition, X may be selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ) , trifluoromethanesulfonate, hexafluorophosphate, mesylate, arylsulfonate (preferably benzenesulfonate or tosylate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably, a carbon number of 1 to 10), and R ² represents a hydrogen atom, which may be substituted 1 to 5 times by halogen A linear or branched alkyl group (preferably a methyl group) having 1 to 6 carbon atoms (preferably substituted 1 to 3 times by fluorine or chlorine). In addition, n represents the formal charge on the metal, and is an integer of 0-7.

The above-mentioned transition metal complex is not particularly limited, and preferred transition metal complexes include transition metal complexes of Groups 7, 8, 9, 10, and 11, and more preferred transition metal complexes, A complex of 0-valent copper, mono-valent copper, bi-valent ruthenium, bi-valent iron, or bi-valent nickel can be mentioned.

Examples of the compound having a ligand capable of coordinative bonding with the transition metal include ligands including one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated to the transition metal through a σ bond. compounds, compounds having ligands capable of coordinating with transition metals via π bonds and containing two or more carbon atoms, and compounds having ligands capable of coordinating transition metals via μ bonds or η bonds.

Specific examples of the compound having the above-mentioned ligand include, for example, when the central metal is copper, 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, A complex of ligands such as polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine. In addition, examples of the divalent ruthenium complex include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, Dichloro(p-cymene)ruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridyl)ruthenium, dichlorotris(1,10-diazepine) Heterophenanthrene) ruthenium, carbonyl hydrochloride tris (triphenylphosphine) ruthenium, etc. Furthermore, as a divalent iron complex, a bistriphenylphosphine complex, a triazacyclononane complex, etc. are mentioned.

In addition, a solvent is preferably used in the above-mentioned living radical polymerization. Examples of the solvent to be used include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; diisopropyl ether, dimethoxyethane, diethylene glycol dimethyl ether, and the like. Ether-based solvents; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methanol, ethanol, isopropyl Alcohol-based solvents such as alcohols; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. In addition, for example, chlorofluorocarbons (especially carbon number 2 to 5), especially HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2 , 2,3,3-tetrachlorohexafluorobutane,), hexafluoroxylene, fluorine ethers, etc. In addition, these solvents may be used alone or in combination of two or more.

In the above-mentioned production method, it is preferable to subject the mixture of monomers to living radical polymerization in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinative bonding with the transition metal, and a solvent.

The polymerization temperature in the 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-described production method, the metal derived from the above-described transition metal compound may remain in the copolymer. Therefore, when the surface modifier of the present invention is used for an application where metal residues cause problems, it is preferable to use activated alumina or the like to remove the remaining metals after the polymerization reaction.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably in the range of 3,000 to 50,000, more preferably in the range of 10,000 to 30,000, and even more preferably in the range of 15,000, from the viewpoint of being a surface modifier capable of obtaining a firmer coating film surface. ~20000 range. In addition, from the viewpoint of obtaining a surface having more uniform water slidability, the degree of dispersion (Mw/Mn) is preferably 1.50 or less, more preferably in the range of 1.00 to 1.50, and still more preferably in the range of 1.00 to 1.40.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured in terms of polystyrene by gel permeation chromatography (hereinafter simply referred to as "GPC".). In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

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

Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0mmI.D.×4cm) + Tosoh Co., Ltd. "TSK-GELGMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK- GEL GMHHR-N”(7.8mmI.D.×30cm)

Detector: ELSD ("ELSD2000" manufactured by Alltech Japan Co., Ltd.)

Data processing: Tosoh Corporation "GPC-8020 Type II Data Analysis Version No. 4.30"

Measurement conditions: column temperature 40°C

Developing solvent tetrahydrofuran (THF)

Flow rate 1.0ml/min

Sample: A sample (5 μl) obtained by filtering a 1.0 mass % tetrahydrofuran solution in terms of resin solid content with a microfilter.

Standard sample: The following monodisperse polystyrene with a known molecular weight was used based on the measurement guidelines of the above-mentioned "GPC-8020 Type II Data Analysis Version No. 4.30".

(monodisperse polystyrene)

Tosoh Corporation "A-500"

Tosoh Corporation "A-1000"

Tosoh Corporation "A-2500"

Tosoh Corporation "A-5000"

Tosoh Corporation "F-1"

Tosoh Corporation "F-2"

Tosoh Corporation "F-4"

Tosoh Corporation "F-10"

Tosoh Corporation "F-20"

Tosoh Corporation "F-40"

Tosoh Corporation "F-80"

Tosoh Corporation "F-128"

Tosoh Corporation "F-288"

Tosoh Corporation "F-550"

In addition, when reactive functional groups such as hydroxyl groups, isocyanate groups, epoxy groups, carboxyl groups, carboxyl halide groups, acid anhydride groups, etc. are contained in the copolymer of the present invention, that is, when copolymerization is performed using monomers containing these reactive functional groups, With these reactive functional groups, the fluorine-based copolymer of the present invention can be fixed to the surface of the coating film through a chemical bond with the curable resin when forming the curable resin composition described later. Therefore, from the viewpoint of maintaining the long-term performance of water slidability Departure is preferred. Furthermore, active energy ray-curable groups can also be introduced into the surface modifier using these reactive functional groups.

It does not specifically limit as a method to make the said reactive functional group contained in the copolymer of this invention, The monomer which has these reactive functional groups is used as the said monomer (a1), the said monomer (a2) is mentioned. Method: A method of using a monomer having these reactive functional groups in combination as another monomer to be used in combination with the monomers (a1) and (a2).

Examples of the monomer having the above reactive functional group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate ) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-(2-hydroxyethyl)(meth)propylene Amide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropane(meth)acrylate Hydroxyl-containing unsaturated monomers such as esters, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth)acrylates containing terminal hydroxyl groups; Isocyanate group-containing unsaturated monomers such as 2-(meth)acryloyloxyethyl isocyanate and 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate; glycidyl methacrylate , 4-hydroxybutyl acrylate glycidyl ether and other epoxy-containing unsaturated monomers; (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyl Carboxyl-containing unsaturated monomers such as oxyethyl phthalic acid and itaconic acid; carboxylic acid anhydrides with unsaturated double bonds such as maleic anhydride and itaconic anhydride. These monomers may be used alone or in combination of two or more.

The reactive functional group can be introduced into the obtained copolymer by adding these monomers having reactive functional groups to the reaction system at the same time as the above-mentioned monomers (a1) and (a2), and copolymerizing them by the above-mentioned polymerization method.

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

For example, in the case of a copolymer having a hydroxyl group, the above-mentioned monomers having an isocyanate group, glycidyl group, carboxyl group, acid anhydride group, etc. which can react therewith 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 and the copolymer are reacted, conditions under which the active energy ray-curable functional group does not react is preferable. It needs to be carried out in an organic solvent.

Specifically, when reacting a hydroxyl group and an isocyanate group, it is preferable to use p-methoxyphenol, hydroquinone, 2,6-di-tert-butyl-4-methylphenol, etc. as a polymerization inhibitor, and use dilaurate dilaurate as a polymerization inhibitor. A method in which butyltin, dibutyltin diacetate, tin octoate, zinc octoate, etc. are used as urethane reaction catalysts at a reaction temperature of 40 to 120°C, particularly 60 to 90°C.

In addition, when reacting a glycidyl group with a carboxyl group, it is preferable to use p-methoxyphenol, hydroquinone, 2,6-di-tert-butyl-4-methylphenol, etc. as a polymerization inhibitor, and use a tertiary agent such as triethylamine. Amines, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, and quaternary phosphines such as tetrabutylphosphine chloride are used as esterification catalysts at a reaction temperature of 80 to 150 °C, especially 100 °C. The reaction was carried out at -120°C.

The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and ethyl acetate. Ester, butyl acetate, propylene glycol monomethyl ether acetate, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane , toluene, xylene, etc. These can be appropriately selected in consideration of boiling point and compatibility.

The fluorine atom content in the fluorine-based copolymer of the present invention is preferably in the range of 5 to 40 wt%, more preferably in the range of 5 to 30 wt%, and further Preferably it is the range of 5 to 25 wt%. 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 varies depending on the type of curable resin to be combined, the coating method, the target film thickness, etc., from the viewpoint of high water slidability and good leveling on the coating film surface From the viewpoint, 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 100 parts by mass of the solid content in the composition.

As the curable resin composition, for example, for paint applications, petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, oil-based vehicle paints, etc. Coatings using natural resins; phenolic resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amino resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyurethane resin coatings, organic Silicone resin paints, fluororesin paints, and other paints using synthetic resins, etc.

Moreover, in addition to the composition for coating materials exemplified above, the fluorine-based copolymer of the present invention can be used in an active energy ray-curable composition. At this time, as described above, the use of a copolymer in which an active energy ray-curable group is 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, and therefore the water slidability is improved. It is also excellent in long-term stability, and is preferable from this point. The 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-mentioned active energy ray-curable resin and active energy ray-curable monomer may be used alone or in combination.

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

The urethane (meth)acrylate resin used here includes a urethane bond obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth)acrylate compound and (meth)acryloyl resins, etc.

As said aliphatic polyisocyanate compound, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, deca methylene diisocyanate, for example Diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecanediisocyanate, 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, cyclohexyl diisocyanate, etc. In addition, as the aromatic polyisocyanate compound, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, toluidine diisocyanate, p-phenylene diisocyanate and the like.

Examples of the hydroxyl group-containing acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 4-Hydroxybutyl, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, hydroxy Mono(meth)acrylates of glycols such as neopentyl glycol mono(meth)acrylate valerate; trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane (methylolpropane) (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl Mono(meth)acrylate or di(meth)acrylate of trihydric alcohols such as isocyanurate, or a hydroxyl group-containing monoacrylate obtained by modifying a part of these alcoholic hydroxyl groups with ε-caprolactone and di(meth)acrylate; pentaerythritol tri(meth)acrylate, di(trimethylol)propane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. have monofunctional hydroxyl and Trifunctional or higher (meth)acryloyl compounds, or hydroxyl-containing polyfunctional (meth)acrylates obtained by further modifying the compounds with ε-caprolactone; dipropylene glycol mono(meth)acrylates , (meth)acrylate compounds with oxyalkylene chains such as diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc.; (Meth)acrylates having an oxyalkylene chain with a block structure, such as polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. Compounds; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate and other oxyalkylenes with random structures (meth)acrylate compounds of the base chain, etc.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and a hydroxyl group-containing acrylate compound can be carried out, for example, by a conventional method in the presence of a urethanization catalyst. Specific examples of the carbamate catalyst that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; Organotin compounds such as butyltin, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and tin octoate; organometallic compounds such as zinc octoate.

Among these urethane acrylate resins, it is particularly preferable to combine an aliphatic polyisocyanate compound with a hydroxyl-containing (methyl) ) resin obtained by reacting an acrylate compound.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of an α,β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and diols, and is referred to as an α,β-unsaturated polyester resin. As a saturated dibasic acid or its acid anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and these esters etc. are mentioned. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, internal Methylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and their esters, etc. As aliphatic or alicyclic saturated dibasic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and their esters can be mentioned Wait. The glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2- Di-(4-hydroxypropoxydiphenyl)propane etc., and oxides, such as ethylene oxide and propylene oxide, can also be used similarly.

Next, as epoxy vinyl ester resin, epoxy resins, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, can be mentioned. Resin obtained by reacting the epoxy group with (meth)acrylic acid.

Moreover, as a maleimide group containing resin, the bifunctional maleimide obtained by urethane-forming N-hydroxyethylmaleimide and isophorone diisocyanate can be mentioned. Carbamate compound, bifunctional maleimide ester compound obtained by esterification of maleimide acetic acid and polytetramethylene glycol, tetracyclic tetracyclic maleimide caproic acid and pentaerythritol A tetrafunctional maleimide ester compound obtained by esterifying an oxyethane adduct, a polyfunctional maleimide ester compound obtained by esterifying maleimidoacetic acid and a polyhydric alcohol compound, and the like. These active energy ray-curable resins may be used alone or in combination of two or more.

Examples of the active energy ray-curable monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, number average Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4- Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxypivalate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane Di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dicyclopentenyl(meth)acrylate, methyl(meth)acrylate, propyl(meth)acrylate, (meth)acrylic acid Butyl ester, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, ( Aliphatic alkyl esters of (meth)acrylates such as lauryl meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; glycerin (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-butoxyethyl (meth)acrylate Esters, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane , 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol ( meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxy polypropylene glycol (meth)acrylate base) acrylate, polybutadiene (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polystyryl Ethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylate ) isobornyl acrylate, methoxylated cyclodecatriene (meth)acrylate, phenyl (meth)acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide Laminide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecyl Maleimide Amine, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2- Maleimidoethyl-propyl carbonate, N-ethyl-(2-maleimidoethyl)carbamate, N,N-hexamethylenebismaleimide, poly Propylene glycol-bis(3-maleimidopropyl) ether, bis(2-maleimidoethyl) carbonate, 1,4-dimaleimide cyclohexane and other maleimides class etc.

Among these, from the viewpoint of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetrakis Bifunctional or higher polyfunctional (meth)acrylates such as (meth)acrylates. These active energy ray-curable monomers may be used alone or in combination of two or more.

After the active energy ray-curable composition is applied to a substrate, a cured coating film can be formed by irradiating the active energy ray. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When forming a cured coating film by irradiating ultraviolet rays as an active energy ray, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve curability. In addition, 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, the curing process is rapid even without using a photopolymerization initiator or photosensitizer, so there is no need to add a photopolymerization initiator. agent, photosensitizer.

As said photoinitiator, an intramolecular cleavage type photoinitiator and a hydrogen abstraction type photoinitiator are mentioned. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 1 -(4-Isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-Hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butanone and other acetophenone compounds;

Benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoins; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis(2,4,6-trimethyl) acyl phosphine oxide compounds such as phenyl benzoyl)-phenyl phosphine oxide; benzil, methyl phenyl glyoxylate and the like.

As the above-mentioned hydrogen abstraction type photopolymerization initiator, for example, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxydibenzophenone, etc. may be mentioned. Benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl Benzophenone-based compounds such as ketone, 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2 ,4-diethylthioxanthone, 2,4-dichlorothioxanthone and other thioxanthone compounds; Michler's ketone, 4,4'-diethylaminobenzophenone and other aminobenzophenone compounds Compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc.

Among the above-mentioned photopolymerization initiators, 1-hydroxycyclohexylbenzene is preferred from the viewpoint of being excellent in compatibility with the above-mentioned active energy ray-curable resin and active energy ray-curable monomer in the active energy ray-curable coating composition. ketones and benzophenones, particularly preferably 1-hydroxycyclohexyl phenyl ketone. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiouronium-p- Sulfur compounds such as tosylate, etc.

The amount of these photopolymerization initiators and photosensitizers used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.3 to 7 parts by mass.

In addition, in the above coating composition, various additives can be appropriately added as required, such as: organic solvents; colorants such as pigments, dyes, and carbon; silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, oxide Inorganic powders such as calcium and calcium carbonate; higher fatty acids, acrylic resins, phenolic resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyamide resins , polycarbonate resin, petroleum resin, fluororesin (PTFE (polytetrafluoroethylene), etc.), polyethylene, polypropylene and other resin fine powder; antistatic agent, viscosity modifier, light stabilizer, weather stabilizer, Heat-resistant stabilizer, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity regulator, dispersant, dispersion stabilizer, thickener, anti-settling agent, silicone series or hydrocarbon-based surfactants, etc.

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

In addition, the coating method of the above-mentioned composition varies depending on the application, and examples thereof include the use of a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, and a curtain coater. , Coating methods of anastomosis coater, spray coater, Wheeler coater, spin coater, dipping, screen printing, spray coating, applicator, bar coater, electrostatic coating, etc.; Or molding methods using various molds, etc.

In addition, the fluorine-based copolymer of the present invention can also be used for resist applications. The resist application includes the fluorine-based copolymer of the present invention and a photoresist, and the photoresist may contain (1) an alkali-soluble resin, (2) a radiation-sensitive substance (photosensitive substance), (3) Solvent, and (4) other additives used as needed.

As said (1) alkali-soluble resin, the resin soluble to the alkaline solution which is a developing solution used at the time of patterning a resist is mentioned, for example. Examples of the above-mentioned alkali-soluble resin include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, phloroglucinol, and hydroquinone, and alkyl-substituted or halogen-substituted aromatic compounds thereof. At least one of the family compounds is condensed with aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde, etc. Novolak resin, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, α-methyl vinyl phenol and other vinyl polymers or copolymers of phenolic compounds and their halogen-substituted compounds, acrylic or methacrylic polymers or copolymers such as acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate, polyvinyl alcohol, and further Modified resins in which radiation-sensitive groups such as a quinonediazide group, a naphthoquinone azide group, an aromatic azide group, and an aromatic cinnamoyl group are introduced into a part of the hydroxyl groups of the above-mentioned various resins. These alkali-soluble resins may be used alone or in combination of two or more.

Furthermore, as the above-mentioned alkali-soluble resin, a urethane resin containing acidic groups such as carboxylic acid and sulfonic acid in the molecule can be used, and this urethane resin can also be used in combination with the above-mentioned alkali-soluble resin .

(2) The radiation-sensitive substance (photosensitive substance) may be mixed with the above-mentioned alkali-soluble resin and irradiated with ultraviolet rays, extreme ultraviolet rays, excimer laser light, X-rays, electron beams, ion rays, molecular rays, γ rays, etc. On the other hand, those that change the solubility of the alkali-soluble resin in the developing solution can be used.

Examples of the radiation-sensitive substance include quinonediazide-based compounds, diazonium-based compounds, diazide-based compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, Organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds described in Japanese Patent Laid-Open No. 59-152, and the like.

Examples of the quinonediazide-based compound include 1,2-benzoquinone azide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, and 1,2-naphthoquinone Diazide-5-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide-5-sulfonate, and 1,2-benzoquinoneazide Nitrogen-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,1-naphthoquinonediazide-4-sulfonyl Acid chlorides, sulfonyl chlorides of quinonediazide derivatives such as 2,1-naphthoquinonediazide-5-sulfonyl chloride, etc.

As the above-mentioned diazo compound, for example, salts of condensates of p-diazodianiline and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the above-mentioned The diazo resin inorganic salt of the reaction product of the condensate, the diazo resin organic salt which is the reaction product of the said condensate and a sulfonic acid, as described in the specification of USP 3,300,309, etc. are mentioned.

As said azide compound and diazide compound, the azide chalcone acid, the diazide benzylidene methylcyclohexanone and the azide azide described in Japanese Unexamined Patent Publication No. Sho 58-203438 can be mentioned, for example. Cinnamyl acetophenones, aromatic azide compounds or aromatic diazide compounds described in Journal of the Chemical Society of Japan No. 12, p1708-1714 (1983).

As the above-mentioned halogenated organic compound, for example, any halogenated organic compound can be used, and specific examples thereof include halogen-containing oxadiazole-based compounds, halogen-containing triazine-based compounds, halogen-containing acetophenone-based compounds, Halogen-containing benzophenone-based compounds, halogen-containing sulfoxide-based compounds, halogen-containing sulfone-based compounds, halogen-containing thiazole-based compounds, halogen-containing oxazole-based compounds, halogen-containing triazole-based compounds, halogen-containing 2-pyrone-based compounds Compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, other halogen-containing heterocyclic compounds, various compounds such as hydrocarbon sulfur-based halide (Sulfenylhalide)-based compounds, and further for example, 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-dibromobisphenol A) Propyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromobenzene) compounds used as halogen-based flame retardants, such as yl) propane, compounds used as organochlorine-based pesticides such as dichlorophenyltrichloroethane, and the like.

As said organic acid ester, a carboxylate, a sulfonate etc. are mentioned, for example. Moreover, as said organic acid amide, a carboxylic acid amide, a sulfonic acid amide, etc. are mentioned. Furthermore, as an organic acid imide, a carboxylic acid imide, a sulfonic acid imide, etc. are mentioned. These radiation-sensitive substances may be used alone or in combination of two or more.

(3) As the solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; methanol, ethanol, normal Propanol, isopropanol, n-butanol, isobutanol, tert-butanol, amyl alcohol, heptanol, octanol, nonanol, decanol and other alcohols; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Dioxane and other ethers;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and other alcohol ethers; ethyl formate, propyl formate, butyl formate, Methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate , propyl butyrate, ethyl lactate, butyl lactate and other esters, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2 -Monocarboxylates such as methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate;

Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol Propylene glycols such as monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethylene glycol Diethylene glycols such as methyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene, Freon solvents, HCFC, HFC; fully fluorinated solvents such as perfluorooctane Aromatics such as dimethylacetamide, toluene, xylene, etc.; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone, etc., published the book "Solvent Pocket Handbook" (Organic The solvent described in the Society of Synthetic Chemistry, Ohmsha, Ltd.). These solvents may be used alone or in combination of two or more.

Examples of coating methods for preparing the composition for resist use include spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, and gravure coating. The composition is filtered with a filter to remove solid impurities before coating.

Examples of active energy rays for curing the above-mentioned composition prepared for resist use include active energy rays such as light, electron beams, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, fluorescent lamps for ultraviolet light, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps, Ultraviolet rays using natural light or the like as a light source, or electron beams using scanning-type or curtain-type electron beam accelerators, etc. In addition, when hardening with an electron beam, it is not necessary to mix|blend a polymerization initiator.

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

Example

The present invention will be described in further detail below with reference to Examples and Comparative Examples. In the example, unless otherwise stated, parts and % are the basis of the amount of substances.

Synthesis Example 1

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 to the flask substituted with nitrogen, and the solution was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (1). As a result of measuring the molecular weight of the copolymer (1) by GPC, the weight average molecular weight (Mw) was 15,200 and the number average molecular weight (Mn) was 12,100.

Synthesis Example 2

86 parts by mass of methyl ethyl ketone, 36 parts by mass of cyclohexyl methacrylate, and 24 parts by mass of 2,2,2-trifluoroethyl methacrylate were put into a nitrogen-substituted flask as solvents, and the mixture was heated at 25° C. under a nitrogen stream. Stir for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (2). As a result of measuring the molecular weight of the copolymer (2) by GPC, the weight average molecular weight (Mw) was 12,300 and the number average molecular weight (Mn) was 9,500.

Synthesis Example 3

68 parts by mass of methyl ethyl ketone, 32 parts by mass of isobornyl methacrylate, and 16 parts by mass of 2,2,2-trifluoroethyl methacrylate were put into a nitrogen-substituted flask as solvents, and the mixture was heated at 25° C. under nitrogen flow. Stir for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (3). As a result of measuring the molecular weight of the copolymer (3) by GPC, the weight average molecular weight (Mw) was 9,800 and the number average molecular weight (Mn) was 7,800.

Synthesis Example 4

95 parts by mass of methyl ethyl ketone, 44 parts by mass of dicyclopentyl methacrylate, and 22 parts by mass of 2,2,2-trifluoroethyl methacrylate were added as solvents to the flask substituted with nitrogen, and the solution was heated at 25°C under nitrogen. Stir under flow for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (4). As a result of measuring the molecular weight of the copolymer (4) by GPC, the weight average molecular weight (Mw) was 13,500 and the number average molecular weight (Mn) was 10,500.

Synthesis Example 5

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 to the nitrogen-substituted flask, Stir at 25°C under nitrogen flow for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 g of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (5). As a result of measuring the molecular weight of the copolymer (5) by GPC, the weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,700.

Synthesis Example 6

84 parts by mass of methyl ethyl ketone, 34 parts by mass of 1-adamantyl methacrylate, and 24 parts by mass of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate were added to the nitrogen-substituted flask as solvents. parts by mass, and stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (6). As a result of measuring the molecular weight of the copolymer (6) by GPC, the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,500.

Synthesis Example 7

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

Synthesis Example 8

108 parts by mass of methyl ethyl ketone, 53 parts by mass of 1-adamantyl methacrylate, and 27 parts by mass of 2,2,2-trifluoroethyl methacrylate were added as solvents to the flask substituted with nitrogen, and the mixture was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 6.2 parts by mass of 2,2'-bipyridine 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 nitrogen flow. To the obtained reaction product, 30 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (8). As a result of measuring the molecular weight of the copolymer (8) by GPC, the weight average molecular weight (Mw) was 5,200 and the number average molecular weight (Mn) was 4,200.

Synthesis Example 9

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 to the flask substituted with nitrogen, and the mixture was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 1.1 parts by mass of 2,2'-bipyridine and 0.3 parts by mass of cuprous chloride were added, and the temperature was raised to 60°C. Then, 0.68 part by mass of ethyl 2-bromoisobutyrate was added, and the reaction was carried out at 60°C for 12 hours under nitrogen flow. To the obtained reaction product, 5.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (9). As a result of measuring the molecular weight of the copolymer (9) by GPC, the weight average molecular weight (Mw) was 22,100 and the number average molecular weight (Mn) was 18,200.

Comparative Synthesis Example 1

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 put into a nitrogen-substituted flask as solvents, and the mixture was heated at 25°C under nitrogen flow. Stir for 1 hour. Next, 1.8 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (10). As a result of measuring the molecular weight of the copolymer (10) by GPC, the weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 12,300.

Comparative Synthesis Example 2

95 parts by mass of methyl ethyl ketone, 37 parts by mass of tert-butyl methacrylate, and 29 parts by mass of 2,2,2-trifluoroethyl methacrylate were put into a nitrogen-substituted flask as solvents, and the mixture was heated at 25° C. under a nitrogen stream. Stir for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (11). As a result of measuring the molecular weight of the copolymer (11) by GPC, the weight average molecular weight (Mw) was 13,100 and the number average molecular weight (Mn) was 10,800.

Comparative Synthesis Example 3

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 to the flask substituted with nitrogen, and the mixture was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 1.9 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (12). As a result of measuring the molecular weight of the copolymer (12) by GPC, the weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 11,700.

Comparative Synthesis Example 4

109 parts by mass of methyl ethyl ketone, 33 parts by mass of 1-adamantyl methacrylate, 3, 3, 4, 4, 5, 5, 6, 6, 7, methacrylic acid, 3, 3, 4, 4, 5, 5, 6, 6, 7, 43 parts by mass of 7,8,8,8-tridecafluorooctyl ester was stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (13). As a result of measuring the molecular weight of the copolymer (13) by GPC, the weight average molecular weight (Mw) was 15,400 and the number average molecular weight (Mn) was 12,300.

Synthesis Example 10

55 parts by mass of methyl ethyl ketone, 55 parts by mass of 2-propanol, 51 parts by mass of 3-hydroxy-1-adamantyl methacrylate, and 2,2,2-methacrylic acid 2,2,2- 24 parts by mass of trifluoroethyl ester was stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60°C. Then, 1.2 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 g of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (14). As a result of measuring the molecular weight of this copolymer (14) by GPC, the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,100.

Synthesis Example 11

45 parts by mass of methyl ethyl ketone, 45 parts by mass of 2-propanol, 20 parts by mass of 1-adamantyl methacrylate, and 22 parts by mass of 3-hydroxy-1-adamantyl methacrylate were added to the flask substituted with nitrogen as solvents. Parts by mass and 21 parts by mass of 2,2,2-trifluoroethyl methacrylate were stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine and 0.5 parts by mass of cuprous chloride were added, and the temperature was raised to 60°C. Then, 1.2 mass parts of ethyl 2-bromoisobutyrate was added, and it was made to react at 60 degreeC under nitrogen flow for 12 hours. Next, 9.03 g of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (15). As a result of measuring the molecular weight of this copolymer (15) by GPC, the weight average molecular weight (Mw) was 12,600 and the number average molecular weight (Mn) was 10,100.

Synthesis Example 12

47 parts by mass of methyl ethyl ketone, 47 parts by mass of 2-propanol, 25 parts by mass of 1-adamantyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, methane 26 parts by mass of 2,2,2-trifluoroethyl base acrylate was stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (16). As a result of measuring the molecular weight of this copolymer (16) by GPC, the weight average molecular weight (Mw) was 13,800 and the number average molecular weight (Mn) was 10,700.

Comparative Synthesis Example 5

55 parts by mass of methyl ethyl ketone, 55 parts by mass of 2-propanol, 34 parts by mass of 3-hydroxy-1-adamantyl methacrylate, 3,3,4, methacrylic acid, 41 parts by mass of 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester was stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (17). As a result of measuring the molecular weight of this copolymer (17) by GPC, the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 12,100.

Comparative Synthesis Example 6

43 parts by mass of methyl ethyl ketone, 43 parts by mass of 2-propanol, 19 parts by mass of 2-hydroxyethyl methacrylate, 3, 3, 4, 4, 5, 3, 3, 4, 4, 5, 41 parts by mass of 5,6,6,7,7,8,8,8-tridecafluorooctyl ester was stirred for 1 hour at 25°C under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (18). As a result of measuring the molecular weight of this copolymer (18) by GPC, the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,700.

Comparative Synthesis Example 7

56 parts by mass of methyl ethyl ketone, 56 parts by mass of 2-propanol, 60 parts by mass of polyoxypropylene chain-containing methacrylate, and 2,2,2-methacrylic acid were added to the nitrogen-substituted flask as solvents. 18 parts by mass of trifluoroethyl ester was stirred at 25°C for 1 hour under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (19). As a result of measuring the molecular weight of the copolymer (19) by GPC, the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,900.

Comparative Synthesis Example 8

55 parts by mass of methyl ethyl ketone, 55 parts by mass of 2-propanol, 42 parts by mass of polyoxypropylene chain-containing methacrylate, 3, 3, 4, 4, 33 parts by mass of 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester was stirred for 1 hour at 25°C under nitrogen flow. Next, 1.9 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. Next, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (20). As a result of measuring the molecular weight of the copolymer (20) by GPC, the weight average molecular weight (Mw) was 15,100 and the number average molecular weight (Mn) was 11,800.

Synthesis Example 13

In a flask subjected to dry air replacement, 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 added as 0.03 mass part of tin octoate as a urethanization catalyst, and 0.04 mass part of p-methoxyphenol as a polymerization inhibitor, were heated up to 75 degreeC. Under a dry air atmosphere, 30 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as "AOI") was added dropwise 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 3 hours. In addition, the completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and disappearance of absorption of the isocyanate group. Next, PGMEA dilution was performed, and the PGMEA solution containing the copolymer (21) of 20 mass % was obtained. As a result of measuring the molecular weight of the copolymer (21) by GPC, the weight average molecular weight was 19,900 and the number average molecular weight was 17,600.

Synthesis Example 14

In a flask subjected to dry air replacement, 66 parts by mass of the copolymer (16) obtained in Synthesis Example 15 was dissolved in 66 parts by mass of PGMEA, and 0.02 parts by mass of tin octoate as a urethanization catalyst was added as a polymerization inhibitor. 0.03 parts by mass of p-methoxyphenol as the agent, and the temperature was raised to 75°C. Under a dry air atmosphere, 16 parts by mass of AOI was added dropwise 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 3 hours. In addition, the completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and disappearance of absorption of the isocyanate group. Next, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of the copolymer (22). As a result of measuring the molecular weight of the copolymer (22) by GPC, the weight average molecular weight was 15,900 and the number average molecular weight was 13,700.

Comparative Synthesis Example 9

In a flask subjected to dry air replacement, 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 octoate as a urethanization catalyst was added as a resistance 0.04 mass part of p-methoxyphenol of the polymerization agent was heated up to 75 degreeC. Under a dry air atmosphere, 20 parts by mass of AOI was added dropwise 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 3 hours. In addition, the completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and disappearance of absorption of the isocyanate group. Next, PGMEA dilution was performed, and the PGMEA solution containing the copolymer (23) of 20 mass % was obtained. As a result of measuring the molecular weight of the copolymer (23) by GPC, the weight average molecular weight was 17,100 and the number average molecular weight was 13,400.

Comparative Synthesis Example 10

In a flask subjected to dry air replacement, 60 parts by mass of the copolymer (18) obtained in Comparative Synthesis Example 6 was dissolved in 60 parts by mass of PGMEA, and 0.02 parts by mass of tin octoate as a urethanization catalyst was added as a resistance 0.03 mass part of p-methoxyphenol of the polymerization agent was heated up to 75 degreeC. Under a dry air atmosphere, 21 parts by mass of AOI was added dropwise 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 3 hours. In addition, the completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and disappearance of absorption of the isocyanate group. Next, PGMEA dilution was performed, and the PGMEA solution containing the copolymer (24) of 20 mass % was obtained. As a result of measuring the molecular weight of the copolymer (24) by GPC, the weight average molecular weight was 17,000 and the number average molecular weight was 13,300.

Comparative Synthesis Example 11

In a flask subjected to dry air replacement, 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 paraformaldehyde as a polymerization inhibitor were added 0.006 parts by mass of oxyphenol and 3.3 parts by mass of triethylamine as a neutralizing agent were stirred under an air flow, and 3.1 parts by mass of methacryloyl chloride was added dropwise over 2 hours while maintaining the inside of the flask at 10°C. After completion of the dropwise addition, the reaction was carried out by stirring at 10° C. for 1 hour, heating up and stirring at 30° C. for 1 hour, and then raising the temperature to 50° C. and stirring for 10 hours. The disappearance of methacryloyl chloride was confirmed by gas chromatography. Next, washing was repeated three times by a method of adding 70 parts by mass of diisopropyl ether as a solvent, mixing 80 parts by mass of ion-exchanged water, stirring, and then standing to separate and remove the aqueous layer. Next, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor and 8 parts by mass of magnesium sulfate as a dehydrating agent were added and left to stand for 1 day to completely dehydrate, and then the dehydrating agent was filtered off.

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

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

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

Comparative Synthesis Example 12

100 parts by mass of methyl isobutyl ketone as a solvent was put into the nitrogen-substituted flask, and the temperature was raised to 95° C. while stirring under nitrogen gas flow. 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 were dissolved in methyl isobutyl A monomer solution containing 120 parts by mass of ketone, and a polymerization initiator solution prepared by dissolving 10.5 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator in 80 parts by mass of methyl isobutyl ketone These three kinds of dripping liquids were set in the respective dripping devices, and were dripped over 3 hours while maintaining the inside of the flask at 95°C. After completion of the dropwise addition, the mixture was stirred at 95° C. for 5 hours and then at 105° C. for 2 hours, after which 262.1 parts by mass of the solvent was distilled off under reduced pressure to obtain a solution of the copolymer (26).

Next, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octoate as a urethanization catalyst were added to the polymer (25) solution obtained as described above, and stirring was started under an air flow. , 29.9 parts by mass of AOI was added dropwise over 1 hour while maintaining at 75°C. 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. The disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 362 parts by mass of methyl isobutyl ketone was added to obtain 20% by mass containing Methyl isobutyl ketone solution of fluoropolymer resin (26).

Sliding angle determination using cured coating films

The slip angle of water was measured, and the evaluation of the slip angle of the coating film surface was performed. In addition, in the evaluation of sliding property, DM-500 made by Kyowa Interface Science Co., Ltd. was used. 50 μL of water droplets were dropped on the substrate, the base 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 slip angle. The measurement was performed five times, and the average value was used as the value of the slip angle.

<Evaluation using UV-curable coating film>

125 parts by mass of ultraviolet curable urethane acrylate resin ("UNIDIC 17-806" manufactured by DIC Corporation; 80 mass % butyl acetate solution for resin component), 1-hydroxycyclohexyl as a photopolymerization initiator 5 parts by mass of phenyl ketone (“IRGACURE 184” manufactured by BASF JAPAN Co., Ltd.), 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether were mixed, It melt|dissolved and obtained the base resin composition of an active energy ray-curable composition. To 268 parts by mass of the obtained base resin composition, 1 part by mass of the compound obtained in the synthesis example was added, and the mixture was uniformly mixed to obtain an active energy ray-curable composition. Next, the active energy ray-curable composition was applied to a glass plate having a thickness of 1 mm and a length of 7 cm×width of 7 cm with a spin coater, and then left to stand in a dryer at 60° C. for 5 minutes to volatilize the solvent. Then, the dried coating film was irradiated with ultraviolet rays using an ultraviolet curing apparatus (in a nitrogen atmosphere, a high-pressure mercury lamp, and an ultraviolet irradiation dose of 2 kJ/m ² ) to obtain a cured coating film. Then, the slip angle of the obtained coating film was measured.

[Table 1]

Copolymer Water slide angle (°) Synthesis Example 1 (1) 14 Synthesis Example 2 (2) 19 Synthesis Example 3 (3) 17 Synthesis Example 4 (4) 18 Synthesis Example 5 (5) 19 Synthesis Example 6 (6) 18 Synthesis Example 7 (7) 17 Synthesis Example 8 (8) 15 Synthesis Example 9 (9) 15 Synthesis Example 13 (twenty one) 17 Synthesis Example 14 (twenty two) 18 Comparative Example 1 (10) 33 Comparative Example 2 (11) 37 Comparative Example 3 (12) 32 Comparative Example 4 (13) 35 Comparative Example 9 (twenty three) 37 Comparative Example 10 (twenty four) 38 Comparative Example 12 (26) 42

<Evaluation of coating film by thermosetting>

100 parts by mass of CERANATE SSA-500 manufactured by DIC Co., Ltd., 186 parts by mass of BURNOCK DN-980, and 0.1 mass % of the compounds obtained above were added in a solid content ratio, and diluted to 40% with butyl acetate to obtain Prepare the solution. 1 mL of the prepared solution was applied to a glass substrate with a thickness of 1 mm and a length of 15 cm×width of 7 cm with a 6 mil applicator. After that, it was dried at 23°C for 7 days to prepare a coating film, and the slip angle was measured.

[Table 2]

Copolymer Water slide angle (°) Synthesis Example 10 (14) 17 Synthesis Example 11 (15) 18 Synthesis Example 12 (16) 20 Comparative Example 5 (17) 27 Comparative Example 6 (18) 38 Comparative Example 7 (19) 45 Comparative Example 8 (20) 47

Comparative Synthesis Example 13

109 parts by mass of methyl ethyl ketone and 75 parts by mass of 2,2,2-trifluoroethyl methacrylate were added as solvents to the nitrogen-substituted flask, and the mixture was stirred at 25° C. under nitrogen flow for 1 hour. Next, 1.8 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (27). As a result of measuring the molecular weight of the copolymer (27) by GPC, the weight average molecular weight (Mw) was 15,100 and the number average molecular weight (Mn) was 11,600.

Synthesis Example 15

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 to the flask substituted with nitrogen, and the mixture was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 1.8 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (28). As a result of measuring the molecular weight of the copolymer (28) by GPC, the weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,800.

Synthesis Example 16

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 to the flask substituted with nitrogen, and the mixture was heated at 25° C. Stir under nitrogen flow for 1 hour. Next, 1.8 parts by mass of 2,2'-bipyridine 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 the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (29). As a result of measuring the molecular weight of the copolymer (29) by GPC, the weight average molecular weight (Mw) was 15,500 and the number average molecular weight (Mn) was 12,400.

Comparative Synthesis Example 14

110 parts by mass of methyl ethyl ketone and 75 parts by mass of 1-adamantyl methacrylate were added to the nitrogen-substituted flask as solvents, and the mixture was stirred at 25° C. under a nitrogen stream for 1 hour. Next, 1.8 parts by mass of 2,2'-bipyridine 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 reaction was carried out at 60° C. for 12 hours under nitrogen flow. To the obtained reaction product, 9.0 parts by mass of activated alumina was added and stirred. After the activated alumina was filtered off, the solvent was distilled off under reduced pressure to obtain a copolymer (30). As a result of measuring the molecular weight of the copolymer (30) by GPC, the weight average molecular weight (Mw) was 15,200 and the number average molecular weight (Mn) was 11,600.

[table 3]

Claims (7)

1. A water-sliding coating film, which is a cured film of a curable resin composition containing a fluorine-based copolymer and a curable resin, The content of the fluorine-based copolymer is 0.001 to 10 parts by mass with respect to 100 parts by mass of the solid content in the curable resin composition, The fluorine-based copolymer is a polymerizable monomer (a1) represented by the following general formula (1) or (2), and a polymerizable monomer having an alicyclic hydrocarbon skeleton and a (meth)acryloyl group ( a2) Copolymers as essential raw materials, The ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) is (a1):(a2)=5:95 to 40:60 in terms of mass ratio, The curable resin is selected from urethane (meth)acrylate resin, unsaturated polyester resin, epoxy (meth)acrylate resin, polyester (meth)acrylate resin, acrylic (meth)acrylate resin. active energy ray-curable resin of at least one of acrylate resin and maleimide group-containing resin,

In the general formulas (1) and (2), R ¹ is hydrogen atom, halogen atom, methyl group, cyano group, phenyl group, benzyl group or -C _m H _2m -Rf, and Rf is C _n F _2n+1 In the group shown, X represents any one of the following formulae (X-1) to (X-10), in -C _m H _2m -Rf, m is an integer of 1 to 8, and in C _n In F _2n+1 , n is 1 or 2, -OC _m H _2m - (X-1) -OCH ₂ CH ₂ OCH ₂ - (X-2)

In the formula, m is an integer of 1 to 8, k is an integer of 0 to 8, and Rf is the same as described above. 2 . The water slidable coating film according to claim 1 , wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is a bridged cyclic hydrocarbon skeleton. 3 . The water slidable coating film according to claim 1 or 2, wherein the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the fluorine-based copolymer is in the range of 1.00 to 1.40. The water slidable coating film according to claim 1 or 2, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, or a dicyclopentene ring , norbornane ring or norbornene ring. The water slidable coating film according to claim 1 or 2, wherein the polymerizable monomer (a2) further has a hydroxyl group. 6 . The water-sliding coating film according to claim 1 , wherein the fluorine-based copolymer further has an active energy ray-curable group. 7 . 7. The water-sliding coating film according to claim 1 or 2, wherein the fluorine-based copolymer is a random copolymer.