TW202006084A - Fluorine-based copolymer, water-slidable surface modifier, curable resin composition, and water-slidable coating film - Google Patents

Abstract

Provided are: a fluorine-based copolymer, by which a surface having excellent water slidability can be obtained and which can be suitably used as a water-slidable surface modifier; a curable resin composition using the same; and a water-slidable coating film which is a cured product of this composition. Specifically, used are: a fluorine-based copolymer characterized by being a copolymer having, as essential raw materials, a polymerizable monomer (a1) having a fluorinated alkyl group represented by CnF2n+1-(where, n is 1 or 2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group; a water-slidable surface modifier comprising the same; a curable resin composition containing the same; and a cured coating film which is a cured product thereof.

Description

Fluorine-based copolymer, hydroplaning surface modifier, hardening resin composition, and hydroplaning coating film

The present invention relates to a coating film capable of forming a good water-skiing on a surface, a specific structure of a fluorine-based copolymer applicable as a water-skiing surface modifier, a curable resin composition using the same, and hardening of the composition Water-based coating film.

Based on its excellent leveling properties, water and oil repellency, fluorine-based surfactants or fluorine-based surface modifiers are widely used in various coating materials and surface modifiers. A cured film obtained by curing a curable resin composition blended with the fluorine-based surfactant or a fluorine-based surface modifier (hereinafter, sometimes referred to as "fluorine-based surfactant"). , Demonstrates excellent water repellent (oil repellent) properties. In general, in order to take advantage of the water and oil repellent properties of fluorine atoms, fluorine-based surfactants have a fluorinated hydrocarbon group in the structure of the compound, and further, they are in 1 molecule, in order to exhibit Compatible or hardenable, compounds with other structures are arranged, and various compounds can be provided according to the intended performance level or use method (for example, refer to Patent Documents 1 to 2).

In the modern living environment, most of the equipment, devices, and mechanical appliances that are expected or deemed necessary exist, and their types also involve automobile window glass, painted surfaces of automobiles, kitchen equipment, kitchen supplies, and kitchen equipment. Attached exhaust devices, bathing equipment, face washing equipment, medical facilities, medical machinery, mirrors, glasses, inkjet printer parts, etc. In addition, in the refrigerator heat exchanger or the outdoor unit of the air conditioner, and the heat pump heat exchanger of the EV vehicle orientation to be expanded in the future, water repellency is also required from the viewpoint of preventing icing and frost.

In the above-mentioned applications, the property of the attached water droplets to rapidly flow down due to gravity or the like (water skiing) is more required. That is, the water-repellent surface only shows that the water attached to it easily becomes water droplets, and large water droplets fall due to their own weight, but if the water-sliding property is weak, the water droplets will strongly adhere to the surface of the object, and even if the surface is inclined to vertical The situation does not fall. Such water droplets adhering to the surface stay as they are, which may cause various defects. For example, if the windshield of a car is in a state where a lot of water droplets are attached, the windshield is diffusely reflected by the light of a street lamp or the like, which may cause a bad situation that hinders the driver's view. In addition, if the material with low water-sliding property is used in an environment exposed to rainwater such as exterior decorative materials, traces of water flow (rainwater streaks) adhere to the surface, and it cannot be said that it is also excellent in pollution resistance. The lower the slip angle of the hydroplaning system, the better, but the relationship between the contact angle of the water and the slip angle is not seen, and a surface modifier that can balance both water repellency and hydroplaning is required.

[Prior Technical Literature] [Patent Literature]

Patent Literature 1 Japanese Patent Application Publication No. 2013-6928

Patent Literature 2 International Publication No. WO2012/002361

The problem to be solved by the present invention is to provide a fluorine-based copolymer, a curable resin composition using the same, and a water-based coating film of a cured product of the composition. The surface modifier of the surface.

The present inventors have devoted themselves to research and found that a copolymer can be used as a surface modifier to solve the above-mentioned problems, and finally completed the present invention. The copolymer has a fluorinated alkyl group containing a specific length and a polymerizable unsaturated group. The polymerizable monomer and the polymerizable monomer having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group are essential monomers.

That is, the present invention provides a fluorine-based copolymer, a water-based surface modifier using the same, a curable resin composition containing the same, and a water-based coating film of a cured product of the composition, which is characterized by the fluorine-based copolymer It is a polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group represented by C _n F _2n+1- (where n is 1 or 2), and has an alicyclic hydrocarbon skeleton and polymerizability Copolymers with unsaturated group polymerizable monomer (a2) as essential raw materials

Since the fluorine-based copolymer of the present invention is used as a surface modifier, a curable resin composition having excellent water slidability on a surface such as a coating film can be obtained. In applications requiring water slidability, various thermal curing systems and active energy can be selected Suitable for hardening systems such as wire hardening systems.

[Forms for carrying out the invention]

The fluorine-based copolymer of the present invention is characterized by a polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group represented by C _n F _2n+1- (where n is 1 or 2) and A copolymer having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group (a2) as a necessary raw material.

In the past, in order to achieve water and oil repellency, the more the number of carbon atoms to which the fluorine atoms are directly bonded, the better. On the other hand, due to concerns about the bioaccumulation of compounds with fluorinated alkyl groups, the upper limit of the number of carbon atoms Is 6. Therefore, for example, as in the aforementioned Patent Document 2, in order to increase the number of fluorine atoms in one molecule (that is, in order to increase the fluorine atom content rate), a fluorinated alkylene chain having an ether bond of about 2 to 3 carbon atoms is also provided The resulting compound has a perfluorinated alkyl ether chain.

However, as mentioned above, there is no correlation between water repellency and water repellency. Even if it is a water repellent surface, the water repellency is also poor, and there may remain white after water droplets, or the airborne substances contained in rainwater, etc., will become streaks and When remaining on the surface of the coating film, the current situation is that a curable resin composition containing a fluorine-based compound is used, which may not necessarily improve the water-sliding property.

Among them, it was found that a structure containing 1 or 2 carbon atoms directly bonded to a fluorine atom is used, that is, the compound has C _n F _2n+1- (but, n is 1 or 2) A compound having a fluorinated alkyl group and an alicyclic hydrocarbon skeleton in the compound significantly improves the hydroplaning of the coating film surface.

As the polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group represented by C _n F _2n+1- (where n is 1 or 2), as long as it has in the molecule The compound of the aforementioned fluorinated alkyl group and polymerizable unsaturated group can be used without particular limitation. As the fluorinated alkyl group, in particular, n is 1, from the viewpoint of obtaining a hardened product having more excellent water slidability. Moreover, the number of fluorinated alkyl groups represented by C _n F _2n+1- (n is 1 or 2) in one molecule is not particularly limited, and it is preferably in accordance with other properties required by the hardened product, for example Adjust the fluorine atom content rate according to the level of water repellency and surface smoothness.

Examples of the polymerizable unsaturated group included in the polymerizable monomer (a1) include (meth)acryloyl group, vinyl group, and maleimide group. Among these, from the viewpoint of easy availability of raw materials, ease of controlling compatibility with blending components in various curable resin compositions, or polymerization reactivity, it is preferably (meth)propylene Yaki. As the compound having this (meth)acryloyl group, for example, a monomer represented by the following general formula (1) or (2) is preferably exemplified. Moreover, the said polymerizable monomer (a1) system may use only 1 type, and may use 2 or more types together.

[In the above general formula (1)(2), R ¹ is a hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or -C _m H _2m -Rf (m is an integer of 1 to 8), Rf is a group represented by C _n F _2n+1 (however, n is 1 or 2), and X represents a group of any of the following formulas (X-1) to (X-10)].

-OC _m H _2m- (X-1)

-OCH ₂ CH ₂ OCH _2- (X-2)

[M in the above formula is an integer of 0-8, k is an integer of 0-8, and Rf is the same as the above].

Also, in the present invention, the so-called "(meth)acrylate" refers to one or both of methacrylate and acrylate, and the so-called "(meth)acrylic acid" refers to methacrylic acid One or both with acrylic.

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

烷、十氫萘、全氫茀、三環[5.2.1.0^2.6]癸烷、金剛烷、四環庚烷、五環十四烷、立方烷、螺[4.4]辛烷、環戊烯、環己烯、環庚烯、環辛烯、環癸烯、雙環[2.2.2]辛-2-烯、環己二烯、環庚二烯、環辛二烯、環庚三烯、環癸三烯、環辛四烯、降

烯、八氫萘、雙環[2.2.1]庚二烯、雙環[4.3.0]壬二烯、二環戊二烯、六氫蒽、螺[4.5]癸二烯等之脂環式烴骨架。 Examples of the alicyclic hydrocarbon skeleton include cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl and tri, which may be substituted with one or more substituents by arbitrary substituents. Cyclohexyl, drop

Alkane, decahydronaphthalene, perhydrofluorene, tricyclo[5.2.1.0 ^2.6 ]decane, adamantane, tetracycloheptane, pentacyclotetradecane, cubane, spiro[4.4]octane, cyclopentene, cyclo Hexene, cycloheptene, cyclooctene, cyclodecene, bicyclo[2.2.2]oct-2-ene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloheptatriene, cyclodecane Alkene, cyclooctatetraene, drop

Alicyclic hydrocarbon skeletons of ene, octahydronaphthalene, bicyclo[2.2.1]heptadiene, bicyclo[4.3.0]nonadiene, dicyclopentadiene, hexahydroanthracene, spiro[4.5]decadiene, etc. .

烷、降

烯等，特佳為金剛烷、二環戊烷、二環戊烯、降

烷、降

烯，金剛烷為最佳的骨架。 Among these, in view of the high hardness of the surface of the resulting coating film and the high change in water slidability and antifouling properties, those having a bridge structure are preferred, such as adamantane and perhydroindene. , Decahydronaphthalene, perhydrofluorene, perhydroanthracene, perhydrophenanthrene, dicyclopentane, dicyclopentene, perhydroacenaphthene, perhydrophalene

Alkane

Alkene, etc., especially adamantane, dicyclopentane, dicyclopentene,

Alkane

Enene and adamantane are the best skeletons.

Examples of the polymerizable unsaturated group include (meth)acryloyl group, vinyl group, maleimide group and the like. Among these, from the viewpoint of easy availability of raw materials, ease of controlling compatibility with blending components in various curable resin compositions, or polymerization reactivity, it is preferably (meth)propylene Yaki.

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

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

(In the formula, L represents a reactive functional group, X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group, or CF ₃ ).

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

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

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

As a more specific example of the polymerizable monomer represented by the general formula (a2-1), for example, the compounds shown below can be given.

In addition, as a more specific example of the polymerizable monomer represented by the general formula (a2-2), for example, the following compounds may be mentioned.

Among the polymerizable monomers having an adamantane skeleton and a (meth)acryloyl group, from the viewpoint of further improving the Tg of the coating film, the above formula (a2-1-1) and formula (a2 -1-3), (a2-1-5), (a2-1-7), (a2-2-1), (a2-2-2), (a2-2-3).

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

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

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

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

As a more specific example of the polymerizable monomer represented by the general formula (a2-3), for example, the compounds shown below can be given.

Among the polymerizable monomers having a dicyclopentane skeleton and a (meth)acryloyl group, from the viewpoint of further improving the Tg of the coating film, it is preferably represented by the aforementioned formula (a2-3-2) compound of.

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

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

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

In addition, in the compound represented by the aforementioned formula (a2-4), the (meth)acryloyl group may be bonded to any carbon atom in the dicyclopentene skeleton. In addition, in the general formula (a2-3), the hydrogen atom bonded to the carbon atom constituting the dicyclopentene skeleton 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 general formula (a2-4), for example, the compounds shown below may be mentioned.

Among the polymerizable monomers having a dicyclopentene skeleton and a (meth)acryloyl group, the above formula (a2-4-3), (( The compound shown in a2-4-4).

烷骨架與聚合性不飽和基之聚合性單體進行說明。 In the following, for the polymerizable monomer (a2) which can be preferably used in the present invention,

The polymerizable monomer of the alkyl skeleton and the polymerizable unsaturated group will be described.

烷骨架與(甲基)丙烯醯基之聚合性單體，例如可舉出下述式(a2-5)所示的化合物等。 As mentioned previously

Examples of the polymerizable monomer of the alkane skeleton and (meth)acryloyl group include compounds represented by the following formula (a2-5).

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

烷骨架中的任何碳原子。另外，上述通式(a2-5)中之鍵結於構成降

烷骨架的碳原子之氫原子，係其一部分或全部亦可被取代成氟原子、烷基等。 In addition, in the compound represented by the aforementioned formula (a2-5), the (meth)acryloyl group may be bonded to

Any carbon atom in the alkane skeleton. In addition, the bond in the above general formula (a2-5) is

Part or all of the hydrogen atoms of the carbon atoms of the alkane skeleton may be substituted with fluorine atoms, alkyl groups, or the like.

As a more specific example of the polymerizable monomer represented by the general formula (a2-5), for example, the compounds shown below can be given.

烷骨架與(甲基)丙烯醯基之聚合性單體之中，從能更提高塗膜的Tg之點來看，較佳為前述式(a2-5-3)、(a2-5-4)所示的化合物。 Yu Youjiang

Among the polymerizable monomers of alkane skeleton and (meth)acryloyl group, the above formula (a2-5-3), (a2-5-4 ).

烯骨架與聚合性不飽和基之聚合性單體進行說明。 In the following, for the polymerizable monomer (a2) which can be preferably used in the present invention,

The polymerizable monomer of the ethylenic skeleton and the polymerizable unsaturated group will be described.

烯骨架與(甲基)丙烯醯基之聚合性單體，例如可舉出下述式(a2-6)、(a2-7)所示的化合物等。 As mentioned previously

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

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

烯骨架中的任何碳原子。另外，上述通式(a2-6)中之鍵結於構成降

烯骨架的碳原子之氫原子，係其一部分或全部亦可被取代成氟原子、烷基等。 Furthermore, in the compound represented by the aforementioned formula (a2-6), the (meth)acryloyl group may be bonded to

Any carbon atom in the ene skeleton. In addition, the bond in the above general formula (a2-6) is

Part or all of the hydrogen atoms of the carbon atoms of the ene skeleton may be substituted with fluorine atoms, alkyl groups, or the like.

As a more specific example of the polymerizable monomer represented by the general formula (a2-6), for example, the following compounds may be mentioned.

烯骨架與(甲基)丙烯醯基之聚合性單體之中，從能更提高塗膜的Tg之點來看，較佳為前述式(a2-6-3)、(a2-6-4)所示的化合物。 Yu Youjiang

Among the polymerizable monomers of the ene skeleton and the (meth)acryloyl group, the above formula (a2-6-3) and (a2-6-4 ).

The fluorine-based copolymer of the present invention is as described above, and is characterized by a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group represented by C _n F _2n+1- (however, n is 1 or 2) ( a1) A copolymer having an alicyclic hydrocarbon skeleton and a polymerizable monomer (a2) having a polymerizable unsaturated group as essential raw materials. Here, the ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) is preferably a mass ratio in terms of obtaining a surface modifier having better compatibility with the curable resin composition in terms of mass ratio. It is the range of (a1): (a2)=5:95~95:5, more preferably the range of 10:90~90:10.

As a raw material for obtaining the fluorine-based copolymer of the present invention, the monomers copolymerizable with the aforementioned (a1) and (a2) may be used in combination as long as the effects of the present invention are not impaired. 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 alkyl groups having 1 to 18 carbon atoms. Based monomers, etc.

Examples of the polymerizable unsaturated group possessed by the other copolymerizable monomers include (meth)acryloyl group, vinyl group, maleimide group, etc. However, when the monomer (a1) and monomer When the polymerizable unsaturated group of the body (a2) is a (meth)acryloyl group, the polymerizable unsaturated group of other monomers is also preferably (methyl) from the viewpoint of good copolymerizability Acrylic.

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

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

Y ¹ and Y ² in the general formula (a3-1) are alkylene groups, but 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 ethylidene , The number of repeating units p is 1, m is 0, and Y ¹ is a propylene glycol residue of propylene, the number of repeating units is 1, m is 0, and Y ¹ is a butanediol residue of butylene, repeating The number of units p is an integer of 2 or more, q is 0, and Y ¹ is a polyethylene glycol residue of ethylidene group, the number of repeating units p is an integer of 2 or more, q is 0, and Y ¹ is of a propyl group Polypropylene glycol residue, the number of repeating units p and q are both integers of 1 or more, and Y ¹ or Y ² is ethylidene, and the other is the residue of a copolymer of ethylene oxide and propylene oxide of propylene Residues of polyalkylene glycol.

The degree of polymerization of the polyalkylene glycol in the aforementioned formula (a3-1), that is, the sum of p and q in the general formula (a3-1), is preferably in the range of 1 to 100, more preferably in the range of 2 to 80 , More preferably in the range of 3~50. In addition, the repeating unit containing Y ^{1 and} the repeating unit containing Y ² may be arranged in a disordered manner or in a block manner.

R ³ in the general formula (a3-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer becomes a mono(meth)acrylate of alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. When R ³ is 1 to 6 carbon atoms, it is not an alkyl The terminal of the (meth)acrylate of the mono(meth)acrylate of diol is blocked with an alkyl group having 1 to 6 carbon atoms.

In the aforementioned general formula (a3-1), a monomer having a poly(oxyalkylene) group composed of a plurality of oxyalkylene groups is preferable, and specific examples thereof include polypropylene glycol mono(meth)acrylate , Polyethylene glycol mono(meth)acrylate, Polytrimethylene glycol mono(meth)acrylate, Polytetramethylene glycol mono(meth)acrylate, Poly(ethylene glycol‧propylene glycol) Mono(meth)acrylate, polyethylene glycol‧polypropylene glycol mono(meth)acrylate, poly(ethylene glycol‧tetramethylene glycol) mono(meth)acrylate, polyethylene glycol‧poly Tetramethylene 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‧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) Base) acrylate, poly(propylene glycol‧trimethylene glycol) mono(meth)acrylate, polypropylene glycol‧polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol‧tetramethylene Methyl glycol) mono(meth)acrylate, polytrimethylene glycol‧polytetramethylene glycol mono(meth)acrylate, poly(butylene glycol‧trimethylene glycol) mono(meth Base) acrylate, polybutylene glycol‧polytrimethylene glycol mono(meth)acrylate, etc. In addition, "poly(ethylene glycol‧propylene glycol)" means a messy copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol•polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol. Other things are the same. In the present invention, when a monomer having an oxyalkylene group is used, from the viewpoint of obtaining a copolymer that has good compatibility with other components in the curable resin composition, polypropylene glycol mono(meth)acrylic acid is preferred Ester, polyethylene glycol mono(meth)acrylate, polyethylene glycol‧polypropylene glycol mono(meth)acrylate.

In addition, as a commercially available product of a monomer having an oxyalkylene group, for example, "NK Ester M-20G", "NK Ester M-40G", and "NK Ester M-90G" manufactured by Shin Nakamura Chemical Industry Co., Ltd. can be cited. '', ``NK Ester M-230G'', ``NK Ester AM-90G'', ``NK Ester AMP-10G'', ``NK Ester AMP-20G'', ``NK Ester AMP-60G'', ``NK Ester AMP-60G'', ``Nippon Oil Co., Ltd. Blemmer PE-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", "Blemmer AP-400", "Blemmer AE-350", etc. These single systems having an oxyalkylene group may be used alone or in combination of two or more.

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

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a hydrogen atom or a C1-C18 alkyl group having a linear, branched or cyclic structure).

In addition, R ⁵ in the general formula (a3-2) is a C 1-18 alkyl group having a linear, branched or cyclic structure, but the alkyl group may also have an aliphatic or aromatic group Substituents for hydrocarbyl, hydroxyl, epoxy, 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. Ester, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. ( Methacrylic acid C1-C18 alkyl esters, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and other epoxy-containing unsaturated monomers, (methyl ) Unsaturated monomers containing carboxyl groups such as acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, itaconic acid, etc. These single systems having an alkyl group may be used alone or in combination of two or more.

When used together with the aforementioned monomers (a1) and monomers (a2) and other monomers as described above, the amount used is 5 to 40 qualities relative to the total of 100 mol of the monomers (a1) and (a2) The range of mol%, but never impairs the water slidability, in addition, for example, a copolymer that can also exhibit the effects of surface hardness, scratch resistance, etc. is preferable, and the range of 5 to 30 mol% is more preferable. From the viewpoint of water slidability, it is best to not use other monomers.

The fluorine-based copolymer of the present invention is preferably, for example, a monomer (a1) and a monomer (a2) or other monomers used in combination as needed, by coexistence of them, by living cationic polymerization or living anionic polymerization or Manufactured by living polymerization such as living radical polymerization. In addition, among these living polymerizations, since it is easy to control the polymerization reaction, it is particularly preferable to use living radical polymerization.

In the aforementioned living radical polymerization, dormant species protected by atoms or atomic groups at the ends of living polymerizations reversibly generate free radicals and react with monomers, whereby the growth reaction proceeds. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cracking radical polymerization (RAFT), radical polymerization by nitroxide (NMP), use Free radical polymerization of organic tellurium (TERP), etc. There is no particular restriction on which method to use, but from the standpoint of ease of control, etc., the above-mentioned ATRP is preferred. The ATRP system uses an organic halide, a halogenated sulfonyl compound, or the like as an initiator, and uses a metal complex composed of a transition metal compound and a ligand as a catalyst to perform polymerization.

As the polymerization initiator used in the above ATRP, an organic halogenated compound can be used. Specifically, 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α,α'-dichloroxylene, α, α'-Dibromoxylene, tetrakis(α-bromomethyl)benzene, 2-halogenated carboxylic acid with 1 to 6 carbon atoms (such as 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid , 2-bromoisobutyric acid, etc.) C1-C6 alkyl esters, etc. In addition, as a more specific example of the C1-C6 alkyl ester of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, Methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, etc.

The transition metal compound is used in the above-described ATRP M ^{_n +} X ⁿ represents a person. The transition metal M ^{n+ can be} selected from Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ^{2 +} , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ . In addition, X may be selected from halogen atoms, alkoxy groups having 1 to 6 carbon atoms, (S0 ₄ ) _1/2 , (P0 ₄ ) _1/3 , (HP0 ₄ ) _1/2 , (H ₂ P0 ₄ ) , Trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or tosylate), SeR ¹ , CN and R ² COO group. Here, R ¹ represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ² represents a hydrogen atom, which may be substituted with halogen 1 to 5 A straight-chain or branched alkyl group having 1 to 6 carbon atoms (preferably methyl group) which is preferably substituted by fluorine or chlorine 1 to 3 times. Furthermore, n represents the formal charge on the metal and is an integer from 0 to 7.

The above-mentioned transition metal complex is not particularly limited, but as a preferred one, a group 7, 8, 9, 10, and 11 transition metal complex can be mentioned, and as a more preferable one, a zero-valent compound can be mentioned. Copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel complex.

As the compound having a ligand capable of coordinatively bonding with the above transition metal, there may be mentioned a compound having at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom which can coordinate with the transition metal through a σ bond Compounds with ligands, compounds with ligands containing 2 or more carbon atoms that can coordinate with transition metals through π bonds, and compounds with ligands that can coordinate with transition metals through μ bonds or η bonds .

二烯)釕、順二氯雙(2,2’-聯吡啶)釕、二氯參(1,10-啡啉)釕、羰基氯氫參(三苯基膦)釕等。再者，作為2價的鐵錯合物，可舉出雙三苯基膦錯合物、三氮雜環壬烷錯合物等。 As specific examples of the compound having the above ligand, for example, when the central metal is copper, there may be mentioned 2,2′-bipyridine and its derivatives, 1,10-morpholine and its derivatives, and tetramethyl Coordination complexes of ligands such as polyamines such as ethylenediamine, pentamethyldiethylenetriamine, and hexamethyl ginseng (2-aminoethyl)amine. Moreover, as a divalent ruthenium complex, dichloro ginseng (triphenylphosphine) ruthenium, dichloro ginseng (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium , Dichloro-p-isopropyltolueneruthenium, dichloro

Diene) ruthenium, cis-dichlorobis(2,2'-bipyridine) ruthenium, dichloro ginseng (1,10-morpholine) ruthenium, carbonyl chlorohydrogen ginseng (triphenylphosphine) ruthenium, etc. Furthermore, examples of the divalent iron complex include bistriphenylphosphine complex and triazacyclononane complex.

In addition, in the above-mentioned living radical polymerization, it is preferable to use a solvent. Examples of the solvent used include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; diisopropyl ether, dimethoxyethane, and diethylene glycol diacetate. Ether solvents such as methyl ether; halide solvents such as methylene chloride and dichloroethane; aromatic solvents such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol and isopropanol; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. Furthermore, within the range that does not impair the effects of the present invention, for example, chlorofluorinated hydrocarbons (especially carbon numbers 2 to 5), especially HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2,2,3,3-tetrachlorohexafluorobutane), hexafluoroxylene, fluorine-based ether, etc. In addition, these solvent systems may be used alone or in combination of two or more.

In the aforementioned manufacturing method, it is preferred to subject the mixture of monomers to active radicals in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinating with the transition metal, and a solvent polymerization.

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

In addition, when the copolymer of the present invention is produced by the aforementioned production method, in the copolymer, the metal due to the transition metal compound may remain. Therefore, when the surface modifier of the present invention is used in applications where metal residues cause problems, it is preferable to use activated alumina or the like to remove residual metals after the polymerization reaction.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably from 3000 to 50,000, more preferably from 10,000 to 30,000, particularly preferably from the viewpoint of being a surface modifier that can obtain a stronger coating film surface The range of 15000~20000. In addition, from the viewpoint of obtaining a surface with 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 particularly 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 the values of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as "GPC"). In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

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

Pipe Column: Tosoh Co., Ltd.'s protective pipe "HHR-H" (6.0mmI.D. × 4cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D. × 30cm) + ``TSK-GEL GMHHR-N'' (7.8mmI.D.×30cm) made by Tosoh Corporation + ``TSK-GEL GMHHR-N'' (7.8mmI.D.×30cm) made by Tosoh Corporation + Dong "TSK-GEL GMHHR-N" manufactured by Cao Co., Ltd. (7.8mmI.D.×30cm)

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

Data processing: "GPC-8020 type II data analysis version 4.30" manufactured by Tosoh Corporation

Measurement conditions: column temperature 40℃

Expand solvent Tetrahydrofuran (THF)

Flow rate 1.0ml/min

Sample: A tetrahydrofuran solution converted to 1.0% by mass in terms of resin solid content is filtered through a microfilter (5 μl).

Standard sample: According to the aforementioned "GPC-8020 Type II Data Analysis Version 4.30" measurement manual, the following monodisperse polystyrene with known molecular weight is used.

(Monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

"F-288" manufactured by Tosoh Corporation

"F-550" manufactured by Tosoh Corporation

In addition, in the copolymer of the present invention, when a reactive functional group including a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxyhalo group, an acid anhydride group, etc. is included, that is, when using such a reactive functional group In the case of copolymerization of functional group monomers, since these reactive functional groups can be utilized, when becoming a curable resin composition described later, the fluorine system of the present invention is chemically bonded to the curable resin by chemical bonding The copolymer is fixed to the surface of its coating film, so it is more preferable from the viewpoint of maintaining the long-term performance of the water slidability. Furthermore, these reactive functional groups may be used to introduce active energy ray-curable groups into the surface modifier.

The method of making the copolymer of the present invention contain the above-mentioned reactive functional group is not particularly limited, and examples thereof include the above-mentioned monomer (a1) and the above-mentioned monomer (a2), which also have these reactive functions A method of using a monomer having a reactive functional group as the other monomer used in combination with the monomers (a1) and (a2).

Examples of the monomer having the aforementioned reactive functional group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and Group) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, N-(2-hydroxyethyl) (methyl) Acrylamide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-phenoxypropion Hydroxyl-containing unsaturated monomers such as esters, 2-(meth)acryloxyethyl-2-hydroxyethyl phthalate, lactone containing terminal hydroxyl groups modified (meth)acrylate ; 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate and other unsaturated monomers containing isocyanate groups; methacrylic acid ring Oxypropyl ester, 4-hydroxybutyl acrylate epoxypropyl ether and other unsaturated monomers containing epoxy groups; (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, 2- (Meth) acryloxyethyl phthalic acid, itaconic acid and other unsaturated monomers containing a carboxyl group; maleic anhydride, itaconic anhydride and other carboxylic acid anhydrides having unsaturated double bonds and the like. These single systems may use only 1 type, or may use 2 or more types together.

These single systems with reactive functional groups can be copolymerized by the aforementioned polymerization method by adding the aforementioned monomer (a1) and the aforementioned monomer (a2) to the reaction system at the same time. Reactive functional groups are introduced into the product.

Furthermore, for the copolymer having a reactive functional group obtained by the copolymerization reaction, by reacting a compound having a group capable of reacting with the reactive functional group and an active energy ray-curable group, it can be on the side of the copolymer The active energy ray hardening group is introduced into the chain to obtain an active energy ray hardening surface modifier.

For example, in the case of a copolymer having a hydroxyl group, the aforementioned monomer having an isocyanate group, a glycidyl group, a carboxyl group, and an acid anhydride group that can react with it can be reacted. In the case of a copolymer having an isocyanate group, a monomer having an epoxy group and a hydroxyl group reacts, and a monomer having a hydroxyl group can be reacted.

When reacting the monomer with the copolymer, it is preferred that the active energy ray-hardenable functional group does not react, for example, the temperature condition can be adjusted to a range of 30 to 120°C in the presence of a catalyst or a polymerization inhibitor , If necessary, in an organic solvent.

Specifically, when reacting a hydroxyl group with an isocyanate group, it is preferable to use p-methoxyphenol, hydroquinone, 2,6-di-tertiarybutyl-4-methylphenol, etc. as a polymerization inhibitor, and use dilaurel Dibutyltin acid, dibutyltin diacetate, tin octoate, zinc octoate, etc. are used as the carbamate reaction catalyst at the reaction temperature of 40~120℃, especially 60~90℃.

Moreover, when reacting an epoxypropyl group with a carboxyl group, it is preferable to use p-methoxyphenol, hydroquinone, 2,6-di-tertiary butyl-4-methylphenol, etc. as a polymerization inhibitor, and use triethyl Tertiary amines such as amines, quaternary amines such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. are used as esterification catalysts. React at a reaction temperature of 80 to 150°C, especially 100 to 120°C.

烷、甲苯、二甲苯等。此等只要考慮沸點、相溶性而適宜選擇即可。 The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfonamides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethy Ethyl ether, diisopropyl ether, tetrahydrofuran, di

Alkanes, toluene, xylene, etc. These may be appropriately selected in consideration of boiling point and compatibility.

From the viewpoint of a better balance between good leveling properties and hydroplaning, the fluorine atom content of 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% , Particularly preferably in the range of 5~25wt%. In addition, the fluorine atom content rate can be measured by combustion ion chromatography.

The curable resin composition of the present invention includes 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 the curable resin to be combined, the coating method, and the intended film thickness, etc., but from the high water-sliding property, the leveling property of the coating film surface is also From a good viewpoint, it is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the solid content in the composition.

Examples of the curable resin composition include, for example, paints such as petroleum resin paints, shellac paints, rosin paints, cellulose paints, rubber paints, paint paints, cashew resin paints, and oily paints. Natural resin coatings such as vehicle fluid coatings; use phenol resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amine-based resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyaminomethan Synthetic resin coatings such as ester resin coatings, polysiloxane resin coatings, fluororesin coatings, etc.

In addition to the above-described exemplified paint composition, the fluorine-based copolymer of the present invention can also be used in the active energy ray-curable composition. At this time, as described above, if an active energy ray-curable group is introduced into the side chain of the copolymer used as a surface modifier, the modifier can be firmly fixed to the surface of the coating film, so the The long-term performance stability is also preferable. This active energy ray-curable composition contains an active energy ray-curable resin or an active energy ray-curable monomer as its main component. In addition, the aforementioned active energy ray-curable resin and the active energy ray-curable single system may be used alone, but it may be used in combination.

Examples of the active energy ray-curable resins include urethane (meth)acrylate resins, unsaturated polyester resins, epoxy (meth)acrylate resins, and polyester (meth)acrylate resins. Acrylic (meth)acrylate resins, resins containing maleimide groups, etc., but especially from the viewpoint of transparency or low shrinkage, etc., urethane (meth)acrylate resins are preferred .

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

烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化甲苯二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯、環己基二異氰酸酯等，另外，作為芳香族聚異氰酸酯化合物，可舉出甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯、1,5-萘二異氰酸酯、聯甲苯胺二異氰酸酯、對伸苯基二異氰酸酯等。 Examples of the aforementioned aliphatic polyisocyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and decamethylene Diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate , 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate,

Alkyl diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate, etc. In addition, as an aromatic polyisocyanate compound , Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, p-phenylene diisocyanate, etc. are mentioned.

Examples of the aforementioned hydroxy-containing acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth) 4-Hydroxybutyl acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, hydroxyl Mono(meth)acrylates of dihydric alcohols such as trimethylacetic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxylated trimethylol Propane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyl Mono- or di(meth)acrylates of trihydric alcohols such as ethyl triisocyanate, or mono- and di(methyl)-containing hydroxy groups modified by ε-caprolactone Acrylic esters; Neopentaerythritol tri (meth) acrylate, bistrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. have 1 functional hydroxyl group and 3 (Meth)acryloyl compound with more than functional, or polyfunctional (meth)acrylate containing hydroxyl group modified by ε-caprolactone; dipropylene glycol mono(meth)acrylate, di Ethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc. (meth)acrylate compounds with oxyalkylene chains; polyethylene Alcohol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. (meth)acrylate compounds having a block structure of the oxyalkylene chain; poly(ethylene di) Alcohol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, etc. (meth)acrylic acid chain having a messy structure Ester compounds, etc.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with a hydroxyl-containing acrylate compound can be carried out by a common method in the presence of a urethane-based catalyst, for example. The carbamate catalysts that can be used here specifically include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; triphenylphosphine, triethylphosphine Phosphines; organic tin compounds such as dibutyltin dilaurate, octin tin trilaurate, octin tin diacetate, dibutyltin diacetate, tin octoate; organic metal compounds such as zinc octoate.

Among these urethane acrylate resins, especially those obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl-containing (meth)acrylate compound, the cured coating film is excellent in transparency and is active against It is preferable that the sensitivity of the energy ray is good and the curability is excellent.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α,β-unsaturated dibasic acid or its anhydride, aromatic saturated dibasic acid or its anhydride and glycol, as α,β -Unsaturated dibasic acids or anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As the aromatic saturated dibasic acid or its anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, Inner methylene tetrahydrophthalic anhydride, halogenated phthalic anhydride and these esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and the like Of esters, etc. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 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 and the like, and oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

Next, examples of the epoxy resin include epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. The epoxy group, (meth) acrylic acid is obtained by the reaction.

Moreover, as a resin containing a maleimide group, a bifunctional maleimide obtained by carbamating N-hydroxyethyl maleimide and isophorone diisocyanate can be mentioned. Aminocarbamate compounds, bifunctional maleimide compounds obtained by esterifying maleimide acetic acid and polytetramethylene glycol, maleimide caproic acid and neopentyl A tetrafunctional maleimide ester compound obtained by esterifying the tetraethylene oxide adduct of tetraol, and a multifunctional maleimide obtained by esterifying maleimide acetic acid and a polyol compound Aminoester compounds, etc. These active energy ray-curable resin systems may be used alone or in combination of two or more.

酯、甲氧基化環癸三烯(甲基)丙烯酸酯、(甲基)丙烯酸苯酯；馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-丁基馬來醯亞胺、N-己基馬來醯亞胺、N-辛基馬來醯亞胺、N-十二基馬來醯亞胺、N-硬脂基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、2-馬來醯亞胺乙基-乙基碳酸酯、2-馬來醯亞胺乙基-丙基碳酸酯、N-乙基-(2-馬來醯亞胺乙基)胺甲酸酯、N,N-六亞甲基雙馬來醯亞胺、聚丙二醇-雙(3-馬來醯亞胺丙基)醚、雙(2-馬來醯亞胺乙基)碳酸酯、1,4-二馬來醯亞胺環己烷等之馬來醯亞胺類等。 Examples of the active energy ray-curable monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and quantity. Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, average molecular weight in the range of 150-1000 Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4 with a number average molecular weight in the range of 150-1000 -Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, bisphenol A di (Meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentaerythritol tetra (Meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate Ester, propyl (meth)acrylate, butyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (A (Meth)acrylic acid, such as decyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Alkyl esters, glycerol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth) ) Allyl acrylate, 2-butoxyethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino) (meth)acrylate Ethyl acetate, γ-(meth)acryl propyl propyl trimethoxy silane, 2-methoxy ethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, Phenoxy dipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, poly Ethylene glycol-polybutylene glycol (meth)acrylate, polystyrene ethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dimethacrylate (meth)acrylate Cyclopentyl ester, dicyclopentenyl (meth)acrylate, iso(meth)acrylate

Ester, methoxylated cyclodectriene (meth)acrylate, phenyl (meth)acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide , N-propyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, N-dodecyl maleimide , N-stearyl maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimide ethyl-ethyl carbonate, 2-maleimide Laimide ethyl-propyl carbonate, N-ethyl-(2-maleimide ethyl) carbamate, N,N-hexamethylene bismaleimide, polypropylene glycol -Maleimide such as bis(3-maleimidepropyl) ether, bis(2-maleimideethyl) carbonate, 1,4-dimaleimidecyclohexane Class etc.

Among these, especially from the viewpoint of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, neopentyl alcohol tri(meth)acrylate, and dineopentyl are preferred Multifunctional (meth)acrylates of more than two functions, such as tetraol hexa(meth)acrylate and neopentyltetraol (meth)acrylate. These active energy ray-curable single systems may be used alone or in combination of two or more.

After the active energy ray hardening type composition is applied to the substrate, the active energy ray can be irradiated to form a cured coating film. The so-called active energy line refers to free radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiated with ultraviolet rays as an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve the curability. In addition, if necessary, a photosensitizer may be further added to improve the hardenability. On the other hand, when free radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it can be hardened quickly without using a photopolymerization initiator or photosensitizer, so no special addition of photopolymerization is required Starter or light sensitizer.

啉基(4-硫代甲基苯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮等之苯乙酮系化合物； Examples of the aforementioned photopolymerization initiator include an intramolecular cleavage type photopolymerization initiator and a hydrogen extraction type photopolymerization initiator. Examples of the intramolecular cleavage-type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and benzyl dimethyl condensate. Ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl ) Ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-

Porphyrinyl (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-

Acetophenone-based compounds such as phenylphenyl)-butanone;

Benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoins; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis(2,4, 6-trimethylbenzyl)-phenylphosphine oxide and other acylphosphine oxide-based compounds; diphenyl ethyl ketone, methyl phenyl glyoxylate, etc.

Examples of the aforementioned hydrogen-trapping photopolymerization initiator include diphenyl ketone, o-benzoyl benzoic acid methyl-4-phenyl diphenyl ketone, and 4,4'-dichlorodiphenyl Ketone, hydroxydiphenyl ketone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetra (tertiary butyl (Peroxycarbonyl) diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone and other diphenyl ketone compounds; 2-isopropyl thioxanthone, 2,4-di Thioxanthone-based compounds such as methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Michelinone, 4,4'-diethylaminodi Amino diphenyl ketone compounds such as phenyl ketone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc.

Among the above photopolymerization initiators, from the viewpoint of excellent compatibility with the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition, it is preferably 1 -Hydroxycyclohexyl phenyl ketone and diphenyl ketone, particularly preferably 1-hydroxycyclohexyl phenyl ketone. These photopolymerization initiator systems 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-benzyl isosulfide. Sulfur compounds such as ureonium-p-toluenesulfonate, etc.

The use amount of these photopolymerization initiators and photosensitizers is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of nonvolatile components in the active energy ray-curable composition. %, particularly preferably 0.3 to 7 parts by mass.

In addition, in the above coating composition, organic solvents can be suitably added as needed; colorants such as pigments, dyes, and carbon; silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate, etc. Inorganic powder; higher fatty acid, acrylic resin, phenol resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate Resin, petroleum resin, fluororesin (PTFE (polytetrafluoroethylene), etc.), polyethylene, polypropylene and other resin fine powder; antistatic agent, viscosity adjuster, light stabilizer, weather stabilizer, heat stabilizer, Antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, mold release agents, dissolving agents, conductivity modifiers, dispersants, dispersion stabilizers, tackifiers, anti-settling agents, polysiloxanes or hydrocarbons Various additives such as surfactants.

The aforementioned organic solvent is useful for appropriately adjusting the solution viscosity of the above-mentioned coating composition, and in particular for film coating, the film thickness can be easily adjusted. Examples of organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ethyl acetate and propylene glycol monomethyl ether ethyl Esters such as acid esters; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. These solvent systems 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, but for example, a gravure coater, a roll coater, a corner coater, a knife coater, an air knife coater, a curtain coater, a kiss Coating methods such as coaters, spray coaters, wheel coaters, spin coaters, dipping, screen printing, spraying, applicators, bar coaters, electrostatic coating, etc., or forming methods using various molds Wait.

In addition, the fluorine-based copolymer of the present invention can also be used for resist applications. In the use of resist, it contains the fluorine-based copolymer of the present invention and a photoresist. The photoresist may include (1) alkali-soluble resin, (2) radiation-sensitive substance (photosensitive substance), (3) solvent and (4) Other additives as needed.

Examples of the aforementioned (1) alkali-soluble resin include resins that are soluble in the alkaline solution of the developer used in the patterning of the resist. Examples of the aforementioned alkali-soluble resins include, for example, substitution of aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, resorcinol, and hydroquinone, and these alkyl groups or halogens Novolac resin obtained by condensing at least one aldehyde compound selected from substituted aromatic compounds and formaldehyde, acetaldehyde, benzaldehyde, etc., o-vinylphenol, m-vinylphenol, p-vinylphenol, α-methyl Polymers or copolymers of vinylphenol compounds such as vinylphenol and halogen-substituted compounds, acrylic or methacrylic polymers or copolymers of acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, etc. Substances, through the introduction of polyvinyl alcohol, and part of the hydroxyl groups of the above various resins, the introduction of radioactive groups such as quinonediazide groups, naphthoquinone azide groups, aromatic azide groups, aromatic cassia acetyl groups, etc. Quality resin, etc. These alkali-soluble resins may be used alone or in combination of two or more.

In addition, as the alkali-soluble resin, an urethane resin containing an acid group such as carboxylic acid or sulfonic acid in the molecule can be used, and the urethane resin can be used in combination with the above-mentioned alkali-soluble resin. Use together.

As the (2) radioactive sensitive substance (photosensitive substance), as long as it is irradiated with ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, gamma rays by mixing with the above alkali-soluble resin It is possible to use substances that change the solubility of the alkali-soluble resin in the developer.

Examples of the radiation-sensitive substance include quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, and organic acid esters. Compounds, organic acid amide compounds, organic acid amide imine compounds, and poly(olefin sulfone) compounds described in Japanese Patent Laid-Open No. 59-152, etc.

Examples of the quinonediazide-based compounds 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-benzoquinone Nitrogen-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,1-naphthoquinonediazide- 4-sulfonyl chloride, 2,1-naphthoquinonediazide-5-sulfonyl chloride and other quinonediazide derivatives such as sulfonyl chloride.

Examples of the aforementioned diazo compound include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate, or periodate and the above The reactive biological diazo resin inorganic salt of the condensate is, for example, the diazo resin organic salt of the reaction product of the above condensate and sulfonic acid described in USP 3,300,309.

Examples of the azide compound and diazide compound include azide chalcone acid, diazidebenzylidenemethylcyclohexanone, and azide as described in Japanese Patent Laid-Open No. 58-203438. Cinnamyl acetophenones, aromatic azide compounds, aromatic diazide compounds, etc. described in Japanese Chemical Society Journal No. 12, p1708-1714 (1983).

二唑系化合物、含有鹵素的三

系化合物、含有鹵素的苯乙酮系化合物、含有鹵素的二苯基酮系化合物、含有鹵素的亞碸系化合物、含有鹵素的碸系化合物、含有鹵素的噻唑系化合物、含有鹵素的

唑系化合物、含有鹵素的三唑系化合物、含有鹵素的2-哌哢系化合物、含有鹵素的脂肪族烴系化合物、含有鹵素的芳香族烴系化合物、其它含有鹵素的雜環狀化合物、次磺醯基鹵系化合物等之各種化合物，再者例如參(2,3-二溴丙基)磷酸酯、參(2,3-二溴-3-氯丙基)磷酸酯、氯四溴甲烷、六氯苯、六溴苯、六溴環十二烷、六溴聯苯、三溴苯基烯丙基醚、四氯雙酚A、四溴雙酚A、雙(溴乙基醚)四溴雙酚A、雙(氯乙基醚)四氯雙酚A、參(2,3-二溴丙基)三聚異氰酸酯、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基乙氧基-3,5-二溴苯基)丙烷等之作為鹵素系阻燃劑使用的化合物、二氯苯基三氯乙烷等之作為有機氯系農藥使用的化合物等。 As the halogenated organic compound, for example, it can be used as long as it is a halide of an organic compound, but as a specific example, a halogen-containing

Diazole compounds, halogen-containing three

Compounds, halogen-containing acetophenone-based compounds, halogen-containing diphenyl ketone-based compounds, halogen-containing sulfonium-based compounds, halogen-containing benzene-based compounds, halogen-containing benzene-based compounds, halogen-containing thiazole-based compounds, halogen-containing

Azole compounds, halogen-containing triazole compounds, halogen-containing 2-piperidine compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, Various compounds such as sulfonyl halides, and ginseng (2,3-dibromopropyl) phosphate, ginseng (2,3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, Hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether) tetrabromo Bisphenol A, bis(chloroethyl ether) tetrachlorobisphenol A, ginseng (2,3-dibromopropyl) tripolyisocyanate, 2,2-bis(4-hydroxy-3,5-dibromophenyl) ) Propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane and other compounds used as halogen flame retardants, dichlorophenyl trichloroethane and other compounds as organic Compounds used in chlorine-based pesticides.

Examples of the organic acid esters include carboxylic acid esters and sulfonic acid esters. In addition, examples of the above-mentioned organic acid amides include carboxylic acid amides, sulfonic acid amides, and the like. In addition, examples of the organic acid amide imine include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances can be used alone or in combination of two or more.

烷等之醚類； Examples of the solvent (3) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone. ; Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, pentanol, heptanol, octanol, nonanol, decanol and other alcohols; ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, two

Ethers such as alkanes;

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

Cyclosulfate esters of Cyclosulfoacetate, Methyl Cyclosulfoacetate, Ethyl Cyclosulfoacetate, Propyl Cyclosulfoacetate, Butyl Cyclosulfoacetate; Propylene glycol such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether, diethyl ether Diethylene glycols such as glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; trichloroethylene, chlorofluorocarbon solvents , HCFC, HFC and other halogenated hydrocarbons; fully fluorinated solvents like perfluorooctane, aromatics such as toluene and xylene; dimethylacetamide, dimethylformamide, N-methyl Solvents such as polar solvents such as ethyl acetamide and N-methylpyrrolidone, etc., and published in the book "Solvent Pocket Manual" (Organic Synthetic Chemistry Association, OHM Co., Ltd.). These solvent systems may be used alone or in combination of two or more.

The coating method of the composition adjusted to the resist application includes spin coating, roll coating, dip coating, spray coating, doctor blade coating, slit coating, curtain coating, gravure coating, etc. The filter filters the composition to remove solid impurities.

Examples of the active energy rays for curing the composition adjusted to the resist application include active energy rays such as light, electron rays, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arc, xenon lamps, high-pressure mercury lamps for photocopying, medium-pressure or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halogen lamps, Natural light, etc. are ultraviolet rays of the light source, or scanning type, curtain type electron beam accelerator electron beam, etc. Also, when it is hardened with an electron wire, it is not necessary to blend a polymerization initiator.

Among these active energy rays, ultraviolet rays are particularly preferred. In addition, when irradiated in an inert gas environment such as nitrogen, the surface hardenability of the coating film is increased, which is preferable. In addition, if necessary, heat can be used as an energy source together with active energy rays for hardening and heat treatment.

[Example]

Examples and comparative examples are given below to explain the present invention in more detail. In the example, as long as it is not specified in advance, the parts and% are based on the material quality.

Synthesis Example 1

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 50 parts by mass of 1-adamantyl methacrylate, and 25 parts by mass of 2,2,2-trifluoroethane methacrylate The ester was stirred 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (1). The molecular weight of the copolymer (1) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,200 and a number average molecular weight (Mn) of 12,100.

Synthesis Example 2

In a flask replaced with nitrogen, 86 parts by mass of methyl ethyl ketone as a solvent, 36 parts by mass of cyclohexyl methacrylate, and 24 parts by mass of 2,2,2-trifluoroethyl methacrylate were added, Stir 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (2). The molecular weight of the copolymer (2) was measured by GPC, and the result was a weight average molecular weight (Mw) of 12,300 and a number average molecular weight (Mn) of 9,500.

Synthesis Example 3

酯、16質量份的甲基丙烯酸 2,2,2-三氟乙酯，在25℃、氮氣流下攪拌1小時。接著，添加1.9質量份的2,2’-聯吡啶、0.5質量份的氯化亞銅，升溫至60℃。然後，添加1.2質量份的2-溴異丁酸乙酯，於氮氣流下，在60℃反應12小時。於所得之反應物中，添加9.0質量份的活性氧化鋁並攪拌。過濾活性氧化鋁後，減壓餾去溶劑而得到共聚物(3)。以GPC測定共聚物(3)的分子量，結果為重量平均分子量(Mw)9,800、數量平均分子量(Mn)7,800。 In a flask replaced with nitrogen, add 68 parts by mass of methyl ethyl ketone as a solvent, 32 parts by mass of methacrylic acid

The ester and 16 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 parts by mass of ethyl 2-bromoisobutyrate was added and reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (3). The molecular weight of the copolymer (3) was measured by GPC, and the result was a weight average molecular weight (Mw) of 9,800 and a number average molecular weight (Mn) of 7,800.

Synthesis Example 4

In a flask replaced with nitrogen, add 95 parts by mass of methyl ethyl ketone as a solvent, 44 parts by mass of dicyclopentyl methacrylate, and 22 parts by mass of 2,2,2-trifluoroethyl methacrylate , Stir 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (4). The molecular weight of the copolymer (4) was measured by GPC. As a result, the weight average molecular weight (Mw) was 13,500 and the number average molecular weight (Mn) was 10,500.

Synthesis Example 5

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 45 parts by mass of 1-adamantyl methacrylate, and 30 parts by mass of methacrylic acid 2,2,3,3,3 -Pentafluoropropyl ester, stirred 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 reacted at 60°C for 12 hours under a nitrogen stream. To the resulting reaction product, 9.0 g of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (5). The molecular weight of the copolymer (5) was measured by GPC, and the result was a weight average molecular weight (Mw) of 14,800 and a number average molecular weight (Mn) of 11,700.

Synthesis Example 6

In a flask replaced with nitrogen, 84 parts by mass of methyl ethyl ketone as a solvent, 34 parts by mass of 1-adamantyl methacrylate, and 24 parts by mass of methacrylic acid 1,1,1,3,3 were added , 3-Hexafluoroisopropyl ester, 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (6). The molecular weight of the copolymer (6) was measured by GPC. As a result, the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,500.

Synthesis Example 7

In a flask replaced with nitrogen, 110 parts by mass of methyl ethyl ketone as a solvent and 50 parts by mass of 1-adamantyl methacrylate were added, and the mixture was stirred at 25° C. for 1 hour under a nitrogen flow. 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, and 1.2 parts by mass of ethyl 2-bromoisobutyrate was added to react for 12 hours. Then, 25 parts by mass of 2,2,2-trifluoroethyl methacrylate was added and reacted for 12 hours. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (7). The molecular weight of the copolymer (7) was measured by GPC. As a result, the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 11,500.

Synthesis Example 8

In a flask replaced with nitrogen, 108 parts by mass of methyl ethyl ketone as a solvent, 53 parts by mass of 1-adamantyl methacrylate, and 27 parts by mass of 2,2,2-trifluoroethyl methacrylate The ester was stirred at 25°C 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (8). The molecular weight of the copolymer (8) was measured by GPC, and the result was a weight average molecular weight (Mw) of 5,200 and a number average molecular weight (Mn) of 4,200.

Synthesis Example 9

In a flask replaced with nitrogen, add 92 parts by mass of methyl ethyl ketone as a solvent, 42 parts by mass of 1-adamantyl methacrylate, and 21 parts by mass of 2,2,2-trifluoroethane methacrylate The ester was stirred at 25°C 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 parts by mass of ethyl 2-bromoisobutyrate was added and reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 5.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (9). The molecular weight of the copolymer (9) was measured by GPC, and the result was a weight average molecular weight (Mw) of 22,100 and a number average molecular weight (Mn) of 18,200.

Comparative Synthesis Example 1

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 50 parts by mass of isodecyl methacrylate, and 25 parts by mass of 2,2,2-trifluoroethyl methacrylate. Stir for 1 hour at 25°C under nitrogen flow. 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (10). The molecular weight of the copolymer (10) was measured by GPC, and the result was a weight average molecular weight (Mw) of 14,600 and a number average molecular weight (Mn) of 12,300.

Comparative Synthesis Example 2

In a flask replaced with nitrogen, add 95 parts by mass of methyl ethyl ketone as a solvent, 37 parts by mass of tertiary butyl methacrylate, and 29 parts by mass of 2,2,2-trifluoroethyl methacrylate , Stir 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (11). The molecular weight of the copolymer (11) was measured by GPC. As a result, the weight average molecular weight (Mw) was 13,100 and the number average molecular weight (Mn) was 10,800.

Comparative Synthesis Example 3

In a flask replaced with nitrogen, add 104 parts by mass of methyl ethyl ketone as a solvent, 36 parts by mass of 1-adamantyl methacrylate, and 36 parts by mass of 2-(perfluorobutyl) methacrylate The ester was stirred 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (12). The molecular weight of the copolymer (12) was measured by GPC, and the result was a weight average molecular weight (Mw) of 14,600 and a number average molecular weight (Mn) of 11,700.

Comparative Synthesis Example 4

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 33 parts by mass of 1-adamantyl methacrylate, and 43 parts by mass of methacrylic acid 3,3,4,4,5 ,5,6,6,7,7,8,8,8-dodecylfluorooctyl ester, stirred at 25 ℃ 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (13). The molecular weight of the copolymer (13) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,400 and a number average molecular weight (Mn) of 12,300.

Synthesis Example 10

In a flask replaced with nitrogen, add 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as a solvent, 51 parts by mass of 3-hydroxy-1-adamantanyl methacrylate, 24 parts by mass The 2,2,2-trifluoroethyl methacrylate 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 reacted under a nitrogen stream at 60°C for 12 hours. Next, 9.0 g of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (14). The molecular weight of this copolymer (14) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,800 and a number average molecular weight (Mn) of 12,100.

Synthesis Example 11

In a flask replaced with nitrogen, add 45 parts by mass of methyl ethyl ketone and 45 parts by mass of 2-propanol as a solvent, 20 parts by mass of 1-adamantyl methacrylate, 22 parts by mass of methacrylic acid 3-Hydroxy-1-adamantyl ester and 21 parts by mass of 2,2,2-trifluoroethyl methacrylate were stirred at 25°C for 1 hour under a nitrogen stream. 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 reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.03 g of activated alumina was added to the resulting reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (15). The molecular weight of this copolymer (15) was measured by GPC, and the result was a weight average molecular weight (Mw) of 12,600 and a number average molecular weight (Mn) of 10,100.

Synthesis Example 12

In a flask replaced with nitrogen, add 47 parts by mass of methyl ethyl ketone and 47 parts by mass of 2-propanol as a solvent, 25 parts by mass of 1-adamantyl methacrylate, and 15 parts by mass of methacrylic acid 2-Hydroxyethyl ester and 26 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 parts by mass of ethyl 2-bromoisobutyrate was added and reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (16). The molecular weight of this copolymer (16) was measured by GPC, and the result was a weight average molecular weight (Mw) of 13,800 and a number average molecular weight (Mn) of 10,700.

Comparative Synthesis Example 5

In a flask replaced with nitrogen, add 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as a solvent, 34 parts by mass of 3-hydroxy-1-adamantanyl methacrylate, 41 parts by mass The methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecylfluorooctyl ester was stirred 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 reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (17). The molecular weight of this copolymer (17) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,300 and a number average molecular weight (Mn) of 12,100.

Comparative Synthesis Example 6

In a flask replaced with nitrogen, add 43 parts by mass of methyl ethyl ketone and 43 parts by mass of 2-propanol as a solvent, 19 parts by mass of 2-hydroxyethyl methacrylate, 41 parts by mass of methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-dodecylfluorooctyl ester, 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 reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (18). The molecular weight of this copolymer (18) was measured by GPC, and the result was a weight average molecular weight (Mw) of 11,500 and a number average molecular weight (Mn) of 9,700.

Comparative Synthesis Example 7

In a flask replaced with nitrogen, add 56 parts by mass of methyl ethyl ketone and 56 parts by mass of 2-propanol as a solvent, 60 parts by mass of methacrylate containing a polypropylene oxide chain, and 18 parts by mass of 2,2,2-Trifluoroethyl methacrylate 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 reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (19). The molecular weight of this copolymer (19) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,800 and a number average molecular weight (Mn) of 12,900.

【0164】 Comparative Synthesis Example 8

In a flask replaced with nitrogen, add 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as a solvent, 42 parts by mass of methacrylate containing a polypropylene oxide chain, and 33 parts by mass of 3,3,4,4,5,5,6,6,7,7,8,8,8-8-dodecylfluorooctyl methacrylate 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 reacted at 60°C for 12 hours under a nitrogen stream. Next, 9.0 parts by mass of activated alumina was added to the obtained reactant and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (20). The molecular weight of this copolymer (20) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,100 and a number average molecular weight (Mn) of 11,800.

Synthesis Example 13

In a flask replaced with dry air, 75 parts by mass of the copolymer (14) obtained in Synthesis Example 10 was dissolved in 75 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), and 0.03 was added Mass parts of tin octoate as a urethane catalyst and 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor were heated to 75°C. In an environment under dry air, 30 parts by mass of 2-propenyloxyethyl isocyanate (hereinafter abbreviated as "AOI") was dropped over 1 hour. After the dropping, the mixture was stirred at 75°C for 1 hour, and then heated to 80°C and stirred for 3 hours. In addition, the end of the reaction was confirmed by the disappearance of the isocyanate group measured by the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of copolymer (21). The molecular weight of this copolymer (21) was measured by GPC, and the result was a weight average molecular weight of 19,900 and a number average molecular weight of 17,600.

Synthesis Example 14

In a flask replaced with dry air, 66 parts by mass of the copolymer (16) obtained in Synthesis Example 15 was dissolved in 66 parts by mass of PGMEA, and 0.02 parts by mass of tin octoate as a carbamate catalyst, 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor was heated to 75°C. Under dry air, 16 parts by mass of AOI was dropped in 1 hour. After the dropping, the mixture was stirred at 75°C for 1 hour, and then heated to 80°C and stirred for 3 hours. In addition, the end of the reaction was confirmed by the disappearance of the isocyanate group measured by the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of copolymer (22). The molecular weight of this copolymer (22) was measured by GPC. As a result, the weight average molecular weight was 15,900 and the number average molecular weight was 13,700.

Comparative Synthesis Example 9

In a flask replaced with dry air, 75 parts by mass of the copolymer (17) obtained in Comparative Synthesis Example 5 was dissolved in 75 parts by mass of Propy PGMEA, and 0.03 parts by mass of octanoic acid as a urethane-based catalyst was added Tin and 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor were heated to 75°C. In an environment under dry air, 20 parts by mass of AOI was dropped in 1 hour. After the dropping, the mixture was stirred at 75°C for 1 hour, and then heated to 80°C and stirred for 3 hours. In addition, the end of the reaction was confirmed by the disappearance of the isocyanate group measured by the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of copolymer (23). The molecular weight of this copolymer (23) was measured by GPC, and the result was a weight average molecular weight of 17,100 and a number average molecular weight of 13,400.

Comparative Synthesis Example 10

In a flask replaced with dry air, 60 parts by mass of the copolymer (18) obtained in Comparative Synthesis Example 6 was dissolved in 60 parts by mass of Propy PGMEA, and 0.02 parts by mass of octanoic acid as a carbamate catalyst was added Tin and 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor were heated to 75°C. In an environment under dry air, 21 mass parts of AOI was dropped in 1 hour. After the dropping, the mixture was stirred at 75°C for 1 hour, and then heated to 80°C and stirred for 3 hours. In addition, the end of the reaction was confirmed by the disappearance of the isocyanate group measured by the IR spectrum of the reactant. Next, PGMEA was diluted to obtain a PGMEA solution containing 20% by mass of copolymer (24). The molecular weight of this copolymer (24) was measured by GPC. As a result, the weight average molecular weight was 17,000 and the number average molecular weight was 13,300.

Comparative Synthesis Example 11

In a flask replaced with dry air, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula, 10 parts by mass of diisopropyl ether as a solvent, and 0.006 parts by mass as a polymerization inhibitor P-methoxyphenol and 3.3 parts by mass of triethylamine as a neutralizing agent, stirring was started under an air flow, and while maintaining the flask at 10°C, 3.1 parts by mass of methacryloyl chloride was dropped over 2 hours . After completion of the dripping, the mixture was stirred at 10°C for 1 hour, heated to 30°C for 1 hour, then heated to 50°C, stirred for 10 hours to carry out a reaction, measured by gas chromatography to confirm the disappearance of methacrylic acid chloride. Next, after adding 70 parts by mass of diisopropyl ether as a solvent, the washing was repeated three times by mixing and stirring 80 parts by mass of ion-exchanged water, and then standing to separate and remove the water layer. Next, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor was added, 8 parts by mass of magnesium sulfate as a dehydrating agent was added, and after standing for one day to completely dehydrate, the dehydrating agent was filtered and separated.

(In the formula, X is perfluoromethylene and perfluoroethylidene, per molecule, perfluoromethylene is an average of 7, perfluoroethylidene is an average of 8 exist, the number of fluorine atoms is Average 46. The number average molecular weight determined by GPC is 1,500).

Next, by distilling off the solvent under reduced pressure, a compound having a poly(perfluoroalkyl ether) chain represented by the following formula is obtained.

(In the formula, X is perfluoromethylene and perfluoroethylidene, per molecule, perfluoromethylene is an average of 7, perfluoroethylidene is an average of 8 exist, the number of fluorine atoms is Average 46).

Comparative Synthesis Example 12

In a flask replaced with nitrogen, 100 parts by mass of methyl isobutyl ketone as a solvent was added, and the temperature was raised to 95°C while stirring under a nitrogen flow. Next, 20 parts by mass of the compound having a poly(perfluoroalkyl ether) chain obtained in Comparative Synthesis Example 11 and 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate were dissolved in 120 parts by mass of The monomer solution in methyl isobutyl ketone and 10.5 parts by mass of tertiary butyl peroxy-2-ethylhexanoate as a polymerization initiator are dissolved in 80 parts by mass of methyl isobutyl ketone The three kinds of dripping liquids of the polymerization initiator solution were set in the respective dripping devices, and the dripping liquid was simultaneously dripped for 3 hours while keeping the inside of the flask at 95°C. After completion of the dropping, the mixture was stirred at 95°C for 5 hours and then at 105°C for 2 hours, and then 262.1 parts by mass of the solvent was distilled off under reduced pressure to obtain a solution of copolymer (26).

Next, to the polymer (25) solution obtained above, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octoate as a carbamate catalyst were started under the air flow While stirring, 29.9 parts by mass of AOI was dropped over 1 hour while maintaining 75°C. After the dripping was completed, after stirring at 75°C for 1 hour, the temperature was raised to 80°C and stirred for 4 hours. The IR spectrum measurement confirmed the disappearance of the isocyanate group, and 362 parts by mass of methyl isobutyl ketone was added to obtain Methyl isobutyl ketone solution of fluoropolymer resin (26).

Determination of slip angle of hardened coating

The evaluation of the slip angle of the surface of the coating film was performed by measuring the slip angle of water. In addition, DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used for the evaluation of sliding properties. Drop 50 μL of water droplets on the substrate, tilt the stage at a rate of 2°/sec, and take the angle at which the water droplets begin to move as the value of the slip angle. The measurement is performed 5 times, and the average value is taken.

<Evaluation of UV-cured coating film>

125 parts by mass of UV-curable urethane acrylate resin ("Unidic 17-806" manufactured by DIC Corporation; resin component 80% by mass of butyl acetate solution), 5 parts by mass as a photopolymerization initiator 1-hydroxycyclohexyl 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 And dissolve the propylene glycol monomethyl ether to obtain the basic resin composition of the 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 mixed uniformly to obtain an active energy ray-curable composition. Next, this active energy ray-curable composition was applied on a glass plate having a thickness of 1 mm and a length of 7 cm and a width of 7 cm with a spin coater, and then placed in a dryer at 60° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was irradiated with ultraviolet rays using an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, and an ultraviolet irradiation amount of ² kJ/m ² ) to obtain a cured coating film. Then, the slip angle of the obtained coating film was measured.

Table 1

<Evaluation of Thermosetting Coating>

The compound obtained by adding 100 parts by mass of Ceranate SSA-500 manufactured by DIC Corporation, 186 parts by mass of Burnock DN-980, and 0.1% by mass in terms of solid content was diluted with butyl acetate to prepare 40% Solution. Using a 6 mil applicator, apply 1 mL of the prepared solution to a glass substrate with a thickness of 1 mm and a length of 15 cm and a width of 7 cm. Then, it was dried at 23°C for 7 days to prepare a coating film, and the slip angle was measured.

Table 2

Comparative Synthesis Example 13

In a flask replaced with nitrogen, 109 parts by mass of methyl ethyl ketone as a solvent and 75 parts by mass of 2,2,2-trifluoroethyl methacrylate were added, and stirred at 25°C for 1 hour under a nitrogen flow. 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (27). The molecular weight of the copolymer (27) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,100 and a number average molecular weight (Mn) of 11,600.

Synthesis Example 15

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 9.5 parts by mass of 1-adamantyl methacrylate, and 65 parts by mass of 2,2,2-trifluoroethane methacrylate The ester 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (28). The molecular weight of the copolymer (28) was measured by GPC, and the result was a weight average molecular weight (Mw) of 14,800 and a number average molecular weight (Mn) of 11,800.

Synthesis Example 16

In a flask replaced with nitrogen, add 109 parts by mass of methyl ethyl ketone as a solvent, 69 parts by mass of 1-adamantyl methacrylate, and 5.9 parts by mass of 2,2,2-trifluoroethyl methacrylate The ester 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (29). The molecular weight of the copolymer (29) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,500 and a number average molecular weight (Mn) of 12,400.

Comparative Synthesis Example 14

In a flask replaced with nitrogen, 110 parts by mass of methyl ethyl ketone as a solvent and 75 parts by mass of 1-adamantyl methacrylate were added, and the mixture was stirred at 25° C. for 1 hour under a nitrogen flow. 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 reacted at 60°C for 12 hours under a nitrogen stream. To the obtained reactant, 9.0 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (30). The molecular weight of the copolymer (30) was measured by GPC, and the result was a weight average molecular weight (Mw) of 15,200 and a number average molecular weight (Mn) of 11,600.

table 3

Claims (11)

A fluorine-based copolymer characterized by a copolymer which uses polymerizable monomer (a1) and polymerizable monomer (a2) as essential raw materials, The polymerizable monomer (a1) has a fluorinated alkyl group represented by C _n F _2n+1- (where n is 1 or 2) and a polymerizable unsaturated group, The polymerizable monomer (a2) has an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group. The fluorine-based copolymer according to claim 1, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is a bridged cyclic hydrocarbon skeleton. The fluorine-based copolymer according to claim 1 or 2, wherein the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn) of the copolymer is in the range of 1.00 to 1.40. The fluorine-based copolymer according to any one of claims 1 to 3, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a drop

Alkane ring

Ene ring. The fluorine-based copolymer according to any one of claims 1 to 4, wherein the polymerizable monomer (a1) is a monomer represented by the following general formula (1) or (2);

[In the above general formula (1)(2), R ¹ is a hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or -C _m H _2m -Rf (m is an integer of 1 to 8), Rf is a group represented by C _n F _2n+1 (however, n is 1 or 2), X represents a group of any of the following formulas (X-1) to (X-10)]; -OC _m H _2m- (X-1) -OCH ₂ CH ₂ OCH _2- (X-2)

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