CN112334501A - Fluorine-based copolymer, water-repellent surface modifier, curable resin composition, and water-repellent coating film - Google Patents
Fluorine-based copolymer, water-repellent surface modifier, curable resin composition, and water-repellent coating film Download PDFInfo
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Abstract
Provided are a fluorine-based copolymer which can give a surface having excellent water-slipping properties and can be suitably used as a water-slipping surface modifier, a curable resin composition using the same, and a cured product obtained therefromA water-repellent coating film of a cured product of the compound. Specifically, a fluorine-containing copolymer, a water-repellent surface modifier comprising the fluorine-containing copolymer, a curable resin composition comprising the fluorine-containing copolymer, and a cured coating film as a cured product of the curable resin composition are used, and the fluorine-containing copolymer is characterized by having CnF2n+1A polymerizable monomer (a1) containing a fluoroalkyl group represented by the general formula (1) or (2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) containing an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials.
Description
Technical Field
The present invention relates to a fluorine-based copolymer having a specific structure and suitably usable as a water-slipping surface modifier, which can form a coating film having good water-slipping properties on the surface, a curable resin composition using the same, and a water-slipping coating film as a cured product thereof.
Background
Fluorine-based surfactants and fluorine-based surface modifiers are widely used for various coating materials, surface modifiers and the like because of their excellent leveling properties, water and oil repellency and the like. A cured film obtained by curing a curable resin composition containing the fluorine-based surfactant or the fluorine-based surface modifier (hereinafter, these may be collectively referred to simply as "fluorine-based surfactant") exhibits excellent water (oil) repellency. Fluorine-based surfactants are generally compounds having a fluorocarbon group in the structure of the compound in order to utilize the water-and oil-repellent properties of a fluorine atom, and are compounds having another structure disposed in 1 molecule for exhibiting compatibility with a curable resin and curability, and various compounds can be provided according to the target performance level and the method of use (for example, see patent documents 1 to 2).
In modern living environments, there are many apparatuses, devices, and mechanical appliances that are required to have water repellency or water repellency, and the types thereof include automobile window glass, automobile painted surfaces, kitchen equipment, kitchen supplies, exhaust equipment attached to kitchen equipment, bath equipment, sink equipment, medical facilities, medical mechanical appliances, mirrors, glasses, ink jet printer components, and the like, and are extremely wide. Further, in heat pump heat exchangers for refrigerators, outdoor units of air conditioners, and EVs that will be developed in the future, water repellency is also required from the viewpoint of preventing freezing and frost formation.
In the above-mentioned applications, a property (water-slipping property) that the adhered water droplets flow down rapidly by gravity or the like is also required. That is, the water-repellent surface merely means that water attached thereto easily forms water droplets, large water droplets fall by their own weight, and if the water-repellency is poor, the water droplets are firmly attached to the surface of the object, and sometimes do not fall even if the surface is inclined to the vertical. Such water droplets adhering to the surface stay in this state, which may cause various problems. For example, a state in which a large number of water droplets are adhered to a windshield of an automobile has the following disadvantages: due to light from a street lamp or the like, the windshield undergoes diffuse reflection, obstructing the view of the driver. Further, when a material having poor water-sliding properties is used in an environment exposed to rainwater, such as an exterior material, water flow marks (rain marks) adhere to the surface, and the stain resistance is not necessarily excellent. The smaller the water slip angle, the better the water repellency, but the correlation between the water contact angle and the slip angle has not been confirmed, and a surface modifier that can achieve both water repellency and water repellency is required.
Documents of the prior art
Patent document
Patent document 1 Japanese patent laid-open publication No. 2013-6928
Patent document 2 International publication No. WO2012/002361
Disclosure of Invention
Problems to be solved by the invention
An object to be solved by the present invention is to provide a fluorine-based copolymer which can provide a surface having excellent water-repellency and can be suitably used as a surface modifier, a curable resin composition using the same, and a water-repellent coating film which is a cured product of the composition.
ForMeans for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that a copolymer comprising, as essential monomers, a polymerizable monomer having a fluoroalkyl group and a polymerizable unsaturated group of a specific length and a polymerizable monomer having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group becomes a surface modifier which solves the above problems, and have completed the present invention.
Namely, the present invention provides a fluorine-based copolymer, a water-repellent surface modifier using the same, a curable resin composition containing the same, and a water-repellent coating film which is a cured product of the composition, wherein the fluorine-based copolymer is characterized by having CnF2n+1A polymerizable monomer (a1) containing a fluoroalkyl group represented by the general formula (1) or (2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) containing an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the fluorine-based copolymer of the present invention as a surface modifier, a curable resin composition having excellent water-slipping property on the surface of a coating film or the like can be obtained, and various curing systems such as a thermosetting system and an active energy ray curing system can be selected and applied to applications requiring water-slipping property.
Detailed Description
The fluorine-based copolymer of the present invention is characterized in that it has CnF2n+1A polymerizable monomer (a1) containing a fluoroalkyl group represented by the general formula (1) or (2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) containing an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials.
Conventionally, it has been considered that the larger the number of carbon atoms to which fluorine atoms are directly bonded, the more preferable the water and oil repellency is exhibited, and on the other hand, the higher the number of carbon atoms is, the more the compound having a fluoroalkyl group is likely to be bio-accumulative, and the upper limit of the number of carbon atoms is generally set to 6. Therefore, as described in patent document 2, for example, a compound having a perfluoroalkylene ether chain in which fluoroalkylene chains having about 2 to 3 carbon atoms are linked by an ether bond is provided in order to increase the number of fluorine atoms in 1 molecule (that is, in order to increase the fluorine atom content).
However, as described above, no correlation is found between water repellency and water repellency, and even on a water-repellent surface, there is a possibility that water repellency is poor, white marks remain after dropping water, or streaks formed by substances in the air contained in rainwater or the like remain on the surface of a coating film.
In such a case, it has been found that the use of a compound having a structure in which the number of carbon atoms to which fluorine atoms are directly bonded is 1 or 2, that is, a compound having C in the compound, significantly improves the water-sliding property of the coating film surfacenF2n+1- (wherein n is 1 or 2) and has an alicyclic hydrocarbon skeleton in the compound.
Having C as a substituent for use in the present inventionnF2n+1The polymerizable monomer (a1) having a fluoroalkyl group and a polymerizable unsaturated group represented by the formula (1 or 2) is not particularly limited as long as it has the fluoroalkyl group and the polymerizable unsaturated group in the molecule. The fluoroalkyl group is particularly preferably n is 1 from the viewpoint of obtaining a cured product having more excellent water-slipping properties. Note that, 1 molecule contains CnF2n+1The number of fluoroalkyl groups (wherein n is 1 or 2) is not particularly limited, but the fluorine atom content is preferably adjusted according to other properties required for the cured product, for example, the level of water repellency and surface smoothness.
Examples of the polymerizable unsaturated group of the polymerizable monomer (a1) include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, (meth) acryloyl groups are preferable from the viewpoint of easy availability of raw materials, easy control of compatibility with various blending components in the curable resin composition, and good polymerization reactivity. Examples of the compound having a (meth) acryloyl group include monomers represented by the following general formula (1) or (2). The polymerizable monomer (a1) may be used alone or in combination of two or more.
[ in the above general formulae (1) and (2), R1Is a hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group or-CmH2m-Rf (m is an integer of 1 to 8), Rf is CnF2n+1(wherein n is 1 or 2), and X is any one of the following formulas (X-1) to (X-10). Angle (c)
-OCmH2m- (X-1)
-OCH2CH2OCH2- (X-2)
Wherein m is an integer of 0 to 8, k is an integer of 0 to 8, and Rf is the same as described above. Angle (c)
In the present invention, "(meth) acrylate" means either or both of methacrylate and acrylate, and "(meth) acrylic acid" means either or both of methacrylic acid and acrylic acid.
The polymerizable monomer (a2) used in the present invention has an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group.
Examples of the alicyclic hydrocarbon skeleton include cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl (dicyclohexyl), tricyclohexyl (tricyclohexyl), norbornane, decalin, perhydrofluorene, tricyclo [5.2.1.0 ] naphthalene, which may be mono-or polysubstituted with an optional substituent2.6]Decane, adamantane, tetracycloheptane, diamantane, cubane, spiro [4.4 ]]Octane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, bicyclo [2.2.2]Octa-2-ene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloheptatriene, cyclodecatriene, cyclooctatetraene, norbornene, octahydronaphthalene, bicyclo [2.2.1]Heptadiene, bicyclo [ alpha ], [ alpha4.3.0]Nonadiene, dicyclopentadiene, hexahydroanthracene, spiro [4.5 ]]An alicyclic hydrocarbon skeleton such as decadiene.
Among these, a skeleton having a bridged structure is preferable from the viewpoint of high hardness of the surface of the obtained coating film and higher water-repellency and anti-contamination properties, and for example, adamantane, perhydroindene, decahydronaphthalene, perhydrofluorene, perhydroanthracene, perhydrophenanthrene, dicyclopentane, dicyclopentene, perhydroacenaphthylene, perhydrophenalene, norbornane, norbornene and the like are preferable, and adamantane, dicyclopentane, dicyclopentene, norbornane, norbornene are particularly preferable, and adamantane is the most preferable skeleton.
Examples of the polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, (meth) acryloyl groups are preferable from the viewpoint of easy availability of raw materials, easy control of compatibility with various blending components in the curable resin composition, and good polymerization reactivity.
Hereinafter, a polymerizable monomer having an adamantane skeleton and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (a2) in the present invention will be described.
Examples of the polymerizable monomer having an adamantane skeleton and a (meth) acryloyl group include compounds represented by the following formulae (a2-1) and (a 2-2).
(wherein L represents a reactive functional group, X and Y represent a 2-valent organic group or a single bond, and R represents a hydrogen atom, a methyl group or CF3。)
Examples of the reactive functional group include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. Among them, a hydroxyl group is preferable from the viewpoint of obtaining a surface modifier having good compatibility with the curable resin composition or easily introducing an active energy ray-curable group into the obtained copolymer.
The binding site between the organic group having the reactive functional group represented by-X-L in the general formula (a2-1) and Y may be bonded to any carbon atom in the adamantane skeleton, and may have 2 or more-X-L groups. Further, hydrogen atoms bonded to carbon atoms constituting the adamantane skeleton may be partially or entirely substituted with fluorine atoms, alkyl groups, or the like. In the general formula (a2-1), X and Y are a 2-valent organic group or a single bond, and examples of the 2-valent organic group include alkylene groups having 1 to 8 carbon atoms such as methylene, propyl, and isopropylidene.
In the compound represented by the above formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantane skeleton. In addition, the hydrogen atoms bonded to the carbon atoms constituting the adamantane skeleton in the above general formula (a2-1) may be partially or wholly substituted with fluorine atoms, alkyl groups, or the like.
More specific examples of the polymerizable monomer represented by the general formula (a2-1) include the following compounds.
Further, as more specific examples of the polymerizable monomer represented by the general formula (a2-2), for example, the following compounds can be mentioned.
Among the polymerizable monomers having an adamantane skeleton and a (meth) acryloyl group, the compounds represented by the above-mentioned formulae (a2-1-1), formulae (a2-1-3), (a2-1-5), (a2-1-7), (a2-2-1), (a2-2-2), and (a2-2-3) are more preferable from the viewpoint of further improving the Tg of the coating film.
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 (a 2-3).
(wherein R represents a hydrogen atom, a methyl group or CF)3。)
In the compound represented by the above formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentane skeleton. In the general formula (a2-3), the hydrogen atoms bonded to the carbon atoms constituting the cyclopentane skeleton may be partially or entirely substituted with fluorine atoms, alkyl groups, or the like.
More specific examples of the polymerizable monomer represented by the general formula (a2-3) include the following compounds.
Among the polymerizable monomers having a dicyclopentane skeleton and a (meth) acryloyl group, the compound represented by the above formula (a2-3-2) is preferable in that the Tg of the coating film can be further increased.
Hereinafter, a polymerizable monomer having a dicyclopentenyl 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 dicyclopentenyl skeleton and a (meth) acryloyl group include compounds represented by the following formula (a 2-4).
(wherein R represents a hydrogen atom, a methyl group or CF)3。)
In the compound represented by the above formula (a2-4), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentenyl skeleton. In the general formula (a2-3), the hydrogen atoms bonded to the carbon atoms constituting the dicyclopentenyl skeleton may be partially or entirely substituted with fluorine atoms, alkyl groups, or the like.
More specific examples of the polymerizable monomer represented by the general formula (a2-4) include the following compounds.
Among the polymerizable monomers having a dicyclopentene skeleton and a (meth) acryloyl group, the compound represented by the above formula (a2-4-3) (a2-4-4) is preferable in that Tg of the coating film can be further increased.
Hereinafter, a polymerizable monomer having a norbornane skeleton and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (a2) in the present invention will be described.
Examples of the polymerizable monomer having a norbornane skeleton and a (meth) acryloyl group include compounds represented by the following formula (a 2-5).
(wherein R represents a hydrogen atom, a methyl group or CF)3。)
In the compound represented by the above formula (a2-5), the (meth) acryloyl group may be bonded to any carbon atom in the norbornane skeleton. In addition, the hydrogen atoms bonded to the carbon atoms constituting the norbornane skeleton in the general formula (a2-5) may be partially or wholly replaced with fluorine atoms, alkyl groups, or the like.
More specific examples of the polymerizable monomer represented by the general formula (a2-5) include the following compounds.
Among the polymerizable monomers having a norbornane skeleton and a (meth) acryloyl group, the compounds represented by the above formula (a2-5-3) (a2-5-4) are preferable in terms of further improving the Tg of the coating film.
Hereinafter, a polymerizable monomer having a norbornene skeleton and a polymerizable unsaturated group which can be preferably used as the polymerizable monomer (a2) in the present invention will be described.
Examples of the polymerizable monomer having a norbornene skeleton and a (meth) acryloyl group include compounds represented by the following formulae (a2-6) and (a 2-7).
(wherein R represents a hydrogen atom, a methyl group or CF)3。)
In the compound represented by the above formula (a2-6), the (meth) acryloyl group may be bonded to any carbon atom in the norbornene skeleton. In addition, the hydrogen atoms bonded to the carbon atoms constituting the norbornene skeleton in the above general formula (a2-6) may be partially or entirely substituted with fluorine atoms, alkyl groups, or the like.
More specific examples of the polymerizable monomer represented by the general formula (a2-6) include the following compounds.
Among the polymerizable monomers having a norbornene skeleton and a (meth) acryloyl group, the compounds represented by the above formulae (a2-6-3) and (a2-6-4) are preferable in that Tg of the coating film can be further increased.
As described above, the fluorine-containing copolymer of the present invention is characterized in that it has CnF2n+1A polymerizable monomer (a1) containing a fluoroalkyl group represented by the general formula (1) or (2) and a polymerizable unsaturated group, and a polymerizable monomer (a2) containing an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group as essential raw materials. The surface modification is more compatible with the curable resin compositionFrom the viewpoint of the agent, the ratio of the polymerizable monomer (a1) to the polymerizable monomer (a2) is preferably (a 1): (a2) 5: 95-95: 5, more preferably 10: 90-90: 10, in the above range.
As the raw material used for obtaining the fluorine-based copolymer of the present invention, a monomer copolymerizable with the above (a1) and (a2) may be used in combination within a range not impairing the effects of the present invention. Examples of the 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 monomers having a branched alkyl group having 1 to 18 carbon atoms.
Examples of the polymerizable unsaturated group contained in the other copolymerizable monomer include a (meth) acryloyl group, a vinyl group, and a maleimide group, and when the polymerizable unsaturated group contained in the monomer (a1) and the monomer (a2) is a (meth) acryloyl group, the polymerizable unsaturated group contained in the other monomer is preferably a (meth) acryloyl group from the viewpoint of favorable copolymerizability.
Examples of the monomer having an oxyalkylene group include monomers represented by the following general formula (a 3-1).
(in the formula, R2Is a hydrogen atom or a methyl group, Y1X and Y2Each independently an alkylene group, p and q each independently an integer of 0 or 1 or more, and the sum of p and q is 1 or more, R3Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
Y in the above general formula (a3-1)1And Y2Is an alkylene group, and the alkylene group also includes a type having a substituent. as-O- (Y)1O)n-(Y2Specific examples of the moiety O) m-include: the number of repeating units p is 1, m is 0, and Y1A glycol residue which is ethylene; the number of repeating units p is 1, m is 0, and Y1A propylene glycol residue that is propylene; the number of repeating units p is 1, m is 0, and Y1A butanediol residue that is butylene; repeating sheetThe number of elements p is an integer of 2 or more, q is 0, and Y1A polyethylene glycol residue which is ethylene; the number p of repeating units is an integer of 2 or more, q is 0, and Y1Polypropylene glycol residues which are propylene groups; the numbers p and q of the repeating units are integers of 1 or more, and Y1Or Y2A residue of a polyalkylene glycol such as a residue of a copolymer of ethylene oxide and propylene oxide, which is an ethylene group and the other is a propylene group.
The polymerization degree of the polyalkylene glycol of the formula (a3-1), i.e., the sum of p and q in the general formula (a3-1), is preferably in the range of 1 to 100, more preferably in the range of 2 to 80, and still more preferably in the range of 3 to 50. It should be noted that the composition contains Y1And contains Y2The repeating units (2) may be arranged in a random or block form.
R in the above general formula (a3-1)3Is hydrogen or alkyl having 1 to 6 carbon atoms. R3When hydrogen is used, the monomer is a mono (meth) acrylate of an alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, or the like, R3And a monomer in which the terminal of the non- (meth) acrylate in the mono (meth) acrylate to be an alkylene glycol is blocked with an alkyl group having 1 to 6 carbon atoms when the monomer is an alkyl group having 1 to 6 carbon atoms.
In the above general formula (a3-1), a monomer having a poly (oxyalkylene) group containing 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-polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, polypropylene glycol-polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol-butylene glycol) mono (meth) acrylate, polypropylene glycol-tetramethylene 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, poly (ethylene glycol-trimethylene glycol) mono (meth) acrylate, polyethylene glycol-polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol-trimethylene glycol) mono (meth) acrylate, polypropylene glycol-polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol-tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol-polytetramethylene glycol mono (meth) acrylate, poly (butylene glycol-trimethylene glycol) mono (meth) acrylate, Polytetramethylene glycol and polytrimethylene glycol mono (meth) acrylate. The term "poly (ethylene glycol-propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and the term "polyethylene glycol-polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol. The same applies to other substances. In the present invention, when the monomer having an oxyalkylene group is used, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate are preferable from the viewpoint of obtaining a copolymer having good compatibility with other components in the curable resin composition.
Further, examples of commercially available products of the oxyalkylene group-containing monomer include: "NK ESTER M-20G", "NK ESTER M-40G", "NK ESTER M-90G", "NK ESTER M-230G", "NK ESTER AM-90G", "NK ESTER AMP-10G", "NK ESTER AMP-20G", "NK ESTER AMP-60G", manufactured by Xinzhongcun chemical industry Co., Ltd; "BLEMMER PE-90", "BLEMMER PE-200", "BLEMMER PE-350", "BLEMMER PME-100", "BLEMMER PME-200", "BLEMMER PME-400", "BLEMMER PME-4000", "BLEMER PP-1000", "BLEMER PP-500", "BLEMER PP-800", "BLEMER 70 PEP-350B", "BLEMER 55 PET-800", "BLEMER 50 POEP-800B", "BLEMER 10 PPB-500B", "BLEMER NKH-5050", "BLEMER AP-400", "BLEMER AE-350", and the like, manufactured by Nissan oil Co. These oxyalkylene group-containing monomers 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 (a 3-2).
(in the formula, R4Is a hydrogen atom or a methyl group, R5Is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. )
R in the above general formula (a3-2)5The alkyl group is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and the alkyl group may have a substituent such as an aliphatic or aromatic hydrocarbon group, a hydroxyl group or an epoxy group. Specific examples of the monomer represented by the formula (a3-2) include alkyl esters having 1 to 18 carbon atoms of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; unsaturated monomers containing epoxy groups such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; and carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, and itaconic acid. These monomers having an alkyl group may be used alone or in combination of two or more.
When the various other monomers are used in combination with the monomer (a1) and the monomer (a2), the amount of the monomer used is preferably in the range of 5 to 40 mol%, more preferably in the range of 5 to 30 mol%, based on 100mol of the total of the monomer (a1) and the monomer (a2), from the viewpoint of obtaining a copolymer which does not impair water-sliding properties and can also exhibit effects such as surface hardness and scratch resistance. From the viewpoint of water-slipping property, it is most preferable not to use other monomers in combination.
For example, when the monomer (a1) and the monomer (a2) are present together or when another monomer used in combination as needed is present together, the fluorine-based copolymer of the present invention is preferably produced by living polymerization such as living cationic polymerization, living anionic polymerization, and living radical polymerization. In addition, living radical polymerization is particularly preferably used from the viewpoint of easy control of the polymerization reaction in these living polymerizations.
In the living radical polymerization, a dormant species whose living polymerization end is protected by an atom or an atomic group is reversibly generated as a radical and reacts with a monomer to cause a growth reaction. Examples of such living radical polymerization include Atom Transfer Radical Polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), radical polymerization by Nitroxide (NMP), and radical polymerization using organotellurium (TERP). Any of these methods is not particularly limited, and the ATRP is preferred in view of ease of control and the like. ATRP is a polymerization method in which an organic halide, a halogenated sulfonyl compound, or the like is used as an initiator, and a metal complex composed of a transition metal compound and a ligand is used as a catalyst.
As the polymerization initiator used in the ATRP, an organic halogenated compound can be used. Specific examples thereof include alkyl esters having 1 to 6 carbon atoms of 1-chloroethylbenzene, 1-bromoethylbenzene, chloroform, carbon tetrachloride, 2-chloropropionitrile, α '-dichloroxylene, α' -dibromoxylene, hexa (. α -bromomethyl) benzene, and 2-halocarboxylic acids having 1 to 6 carbon atoms (for example, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.). More specific examples of the alkyl ester having 1 to 6 carbon atoms of the 2-halogenocarboxylic acid having 1 to 6 carbon atoms include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.
The transition metal compound used in the above ATRP is Mn+XnThe substances shown. M as transition metaln+Can be selected from Cu+、Cu2+、Fe2+、Fe3+、Ru2+、Ru3+、Cr2+、Cr3+、Mo0、Mo+、Mo2+、Mo3+、W2+、W3+、Rh3+、Rh4+、Co+、Co2 +、Re2+、Re3+、Ni0、Ni+、Mn3+、Mn4+、V2+、V3+、Zn+、Zn2+、Au+、Au2+、Ag+And Ag2+Group (d) of (a). X is selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and (SO)4)1/2、(PO4)1/3、(HPO4)1/2、(H2PO4) Triflate, hexafluorophosphate, mesylate, arylsulfonate (preferably benzenesulfonate or tosylate), SeR1CN and R2COO. Herein, R is1Represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), R2Represents a hydrogen atom, a straight or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with a halogen (preferably 1 to 3 times with fluorine or chlorine). In addition, n represents formal charge on the metal and is an integer of 0 to 7.
The transition metal complex is not particularly limited, and preferable transition metal complexes include transition metal complexes of groups 7,8, 9,10 and 11, and more preferable transition metal complexes include complexes of 0-valent copper, 1-valent copper, 2-valent ruthenium, 2-valent iron or 2-valent nickel.
Examples of the compound having a ligand coordinately bonded to the transition metal include a compound having a ligand containing 1 or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms, which is coordinately bonded to the transition metal via a sigma bond, a compound having a ligand containing 2 or more carbon atoms, which is coordinately bonded to the transition metal via a pi bond, and a compound having a ligand which is coordinately bonded to the transition metal via a μ bond or an η bond.
Specific examples of the compound having the ligand include, for example, complexes with ligands such as 2, 2' -bipyridine and derivatives thereof, 1, 10-phenanthroline and derivatives thereof, and polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris (2-aminoethyl) amine, in the case where the central metal is copper. Examples of the 2-valent ruthenium complex include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlororuthenium, dichloro (p-cymene) ruthenium, dichloro (norbornadiene) ruthenium, cis-dichlorobis (2, 2' -bipyridine) ruthenium, dichlorotris (1, 10-phenanthroline) ruthenium, and carbonylchlorohydroxytris (triphenylphosphine) ruthenium. Further, examples of the 2-valent iron complex include a bis-triphenylphosphine complex and a triazacyclononane complex.
In addition, a solvent is preferably used in the living radical polymerization. Examples of the solvent used include: ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane and diethylene glycol dimethyl ether; halogen-based solvents such as methylene chloride and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. For example, chlorofluorocarbons (particularly, those having 2 to 5 carbon atoms), particularly HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316(2,2,3, 3-tetrachlorohexafluorobutane), hexafluoroxylene, fluorine-based ethers, and the like can be used within a range not to impair the effects of the present invention. These solvents may be used alone or in combination of two or more.
In the above production method, it is preferable that the living radical polymerization is performed on a mixture of monomers in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand coordinately bound to the transition metal, and a solvent.
The polymerization temperature in living radical polymerization is preferably in the range of room temperature to 120 ℃.
In addition, when the copolymer of the present invention is produced by the above production method, a metal derived from the above transition metal compound may remain in the copolymer. Therefore, when the surface modifier of the present invention is used in applications where metal residues cause problems, it is preferable to remove the residual metal after the polymerization reaction using activated alumina or the like.
The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 3000 to 50000, more preferably 10000 to 30000, and still more preferably 15000 to 20000, from the viewpoint of providing a surface modifier which can provide a more firm coating film surface. The dispersion (Mw/Mn) is preferably 1.50 or less, more preferably 1.00 to 1.50, and still more preferably 1.00 to 1.40, from the viewpoint of obtaining a surface having more uniform water-repellency.
Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography (hereinafter simply referred to as "GPC") and converted to polystyrene. The measurement conditions of GPC are as follows.
[ GPC measurement conditions ]
A measuring device: HLC-8220GPC manufactured by Tosoh corporation,
Column: "HHR-H" manufactured by Tosoh corporation (6.0 mmI.D.. times.4 cm), "TSK-GEL GMHHR-N" manufactured by Tosoh corporation (7.8 mmI.D.. times.30 cm) ("TSK-GEL GMHHR-N" manufactured by Tosoh corporation (7.8 mmI.D.. times.30 cm)
A detector: ELSD (ALLTECH JAPAN "ELSD 2000" manufactured by JUSH)
Data processing: "GPC-8020 type II data analysis version number 4.30" manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran (THF) as developing solvent
Flow rate 1.0 ml/min
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of resin solid content) was filtered through a microfilter to obtain a sample (5. mu.l).
Standard sample: based on the above-mentioned guidelines for the determination of "GPC-8020 type II data analysis version number 4.30", the following monodisperse polystyrenes of known molecular weight were used.
(monodisperse polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
F-288, Tosoh corporation "
"F-550" made by Tosoh corporation "
When the copolymer of the present invention contains reactive functional groups such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group, that is, when copolymerization is carried out using monomers containing these reactive functional groups, the fluorine-based copolymer of the present invention can be fixed to the surface of the coating film by chemical bonding with a curable resin when forming a curable resin composition described later, and therefore, the copolymer is preferable from the viewpoint of maintaining long-term performance of the water-slipping property. Further, an active energy ray-curable group can be introduced into the surface modifier by using these reactive functional groups.
The method for including the reactive functional group in the copolymer of the present invention is not particularly limited, and examples thereof include: a method of using a monomer having these reactive functional groups as the monomer (a1) or the monomer (a 2); a method of using a monomer having these reactive functional groups in combination as another monomer used in combination with the monomers (a1) and (a 2).
Examples of the monomer having the reactive functional group include: hydroxyl group-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and lactone-modified (meth) acrylate containing a terminal hydroxyl group; isocyanate group-containing unsaturated monomers such as 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate; epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, and itaconic acid; and carboxylic acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. These monomers may be used alone or in combination of two or more.
These monomers having a reactive functional group can be introduced into the resulting copolymer by adding them to the reaction system together with the monomer (a1) and the monomer (a2) and copolymerizing them by the above polymerization method.
Further, the reactive functional group-containing copolymer obtained by the copolymerization reaction is reacted with a compound having a group capable of reacting with the reactive functional group and an active energy ray-curable group, whereby an active energy ray-curable group can be introduced into the side chain of the copolymer, and an active energy ray-curable surface modifier can be obtained.
For example, in the case of a copolymer having a hydroxyl group, the above-mentioned monomer having an isocyanate group, a glycidyl group, a carboxyl group, an acid anhydride group, or the like, which is capable of reacting therewith, may be reacted, in the case of a copolymer having a carboxyl group, the monomer having a glycidyl group and a hydroxyl group may be reacted, and in the case of a copolymer having an isocyanate group, the monomer having a hydroxyl group may be reacted.
When the monomer and the copolymer are reacted, the active energy ray-curable functional group is preferably not reacted, and for example, the reaction can be carried out in an organic solvent in the presence of a catalyst and a polymerization inhibitor, if necessary, while adjusting the temperature to a range of 30 to 120 ℃.
Specifically, when a hydroxyl group and an isocyanate group are reacted, a method of reacting p-methoxyphenol, hydroquinone, 2, 6-di-t-butyl-4-methylphenol, or the like as a polymerization inhibitor and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, or the like as a carbamation reaction catalyst at a reaction temperature of 40 to 120 ℃, particularly 60 to 90 ℃, is preferable.
In the reaction of a glycidyl group with a carboxyl group, it is preferable to use p-methoxyphenol, hydroquinone, 2, 6-di-t-butyl-4-methylphenol, etc. as a polymerization inhibitor, tertiary amines such as triethylamine, quaternary amines such as tetramethylammonium chloride, etc., tertiary phosphines such as triphenylphosphine, etc. as an esterification catalyst, and to carry out the reaction at a reaction temperature of 80 to 150 ℃, particularly 100 to 120 ℃.
The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, and the like are exemplified. These may be suitably selected in consideration of boiling point and compatibility.
The fluorine atom content in the fluorine-based copolymer of the present invention is preferably in the range of 5 to 40 wt%, more preferably in the range of 5 to 30 wt%, and even more preferably in the range of 5 to 25 wt%, from the viewpoint of a good balance between leveling property and water-slipping property. The fluorine atom content can be measured by combustion ion chromatography.
The curable resin composition of the present invention contains the fluorine-based copolymer of the present invention. The content of the fluorine-based copolymer in the curable resin composition varies depending on the type of the curable resin to be combined, the coating method, the target film thickness, and the like, and is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the solid content in the composition, from the viewpoints of high water-sliding property and good leveling property of the coating film surface.
Examples of the curable resin composition include coating materials using natural resins such as petroleum resin coating materials, shellac coating materials, rosin coating materials, cellulose coating materials, rubber coating materials, paint coating materials, cashew resin coating materials, and oily vehicle coating materials; and coatings using synthetic resins such as phenol resin coatings, alkyd resin coatings, unsaturated polyester resin coatings, amino resin coatings, epoxy resin coatings, vinyl resin coatings, acrylic resin coatings, polyurethane resin coatings, silicone resin coatings, and fluororesin coatings.
In addition to the above-described exemplary coating compositions, the fluorine-based copolymer of the present invention can be used in an active energy ray-curable composition. In this case, as described above, it is preferable to use a copolymer in which an active energy ray-curable group is introduced into a side chain of a copolymer used as a surface modifier, because the modifier can be firmly fixed to the surface of the coating film, and the long-term stability of the water-slipping property is also excellent. The active energy ray-curable composition contains an active energy ray-curable resin or an active energy ray-curable monomer as its main component. The active energy ray-curable resin and the active energy ray-curable monomer may be used alone or in combination.
Examples of the active energy ray-curable resin include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, acrylic (meth) acrylate resins, maleimide group-containing resins, and the like, and urethane (meth) acrylate resins are particularly preferable from the viewpoint of transparency, low shrinkage, and the like.
The urethane (meth) acrylate resin used here includes: and resins having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound.
Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, and the like, Cyclohexyl diisocyanate and the like, and examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate and the like.
Examples of the hydroxyl group-containing acrylate compound include mono (meth) acrylates of dihydric alcohols such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 5-pentanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neopentyl glycol mono (meth) acrylate, and the like; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate and other trihydric mono (meth) acrylate, or hydroxyl group-containing mono-and di (meth) acrylates obtained by modifying a part of these alcoholic hydroxyl groups with e-caprolactone; a compound having a 1-functional hydroxyl group and a (meth) acryloyl group having 3 or more functional groups, such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, or a hydroxyl group-containing polyfunctional (meth) acrylate obtained by modifying the compound with e-caprolactone; (meth) acrylate compounds having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate; (meth) acrylate compounds having an oxyalkylene chain with a block structure, such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; and (meth) acrylate compounds having an oxyalkylene chain of a random structure, such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate.
The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxyl group-containing acrylate compound can be carried out by a conventional method, for example, in the presence of a urethane-forming catalyst. Specific examples of the urethanization catalyst that can be used herein include: amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate and the like; organic metal compounds such as zinc octoate.
Among these urethane acrylate resins, a resin obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound is particularly preferable in view of excellent transparency of the cured coating film, good sensitivity to active energy rays, and excellent curability.
The unsaturated polyester resin is a curable resin obtained by polycondensation of an α, β -unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a diol, and examples of the α, β -unsaturated dibasic acid or an anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halophthalic anhydride, and esters thereof. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Examples of the glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 3-butanediol, 1, 4-butanediol, 2-methylpropane-1, 3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, bisphenol a, hydrogenated bisphenol a, ethylene glycol carbonate, 2-bis- (4-hydroxypropoxydiphenyl) propane, and oxides such as ethylene oxide and propylene oxide can be used in the same manner.
Next, as the epoxy vinyl ester resin, there can be mentioned: resins obtained by reacting (meth) acrylic acid with epoxy groups of epoxy resins such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins.
In addition, as the maleimide group-containing resin, there can be mentioned: a 2-functional maleimide carbamate compound obtained by carbamating N-hydroxyethylmaleimide and isophorone diisocyanate, a 2-functional maleimide ester compound obtained by esterifying maleimidoacetic acid and polytetramethylene glycol, a 4-functional maleimide ester compound obtained by esterifying a tetracyclooxirane adduct of maleimidocaproic acid and pentaerythritol, a polyfunctional maleimide ester compound obtained by esterifying maleimidoacetic acid and a polyol compound, and the like. These active energy ray-curable resins may be used alone or in combination of two or more.
Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having a number average molecular weight in the range of 150 to 1000, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having a number average molecular weight in the range of 150 to 1000, neopentyl glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol a di (meth) acrylate, and the like, Aliphatic alkyl (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ - (meth) acryloyloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, glycidyl (, Phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrene ethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2-maleimidoethyl) carbamate, N-hexamethylenebismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1, and maleimides such as 4-bismaleimidocyclohexane.
Among these, 2 or more functional polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate are particularly preferable from the viewpoint of excellent hardness of the cured coating film. These active energy ray-curable monomers may be used alone, or two or more of them may be used in combination.
The active energy ray-curable composition can be applied to a substrate and then irradiated with an active energy ray to form a cured coating film. The active energy rays are ionizing radiation rays such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When a cured coating film is formed by irradiation with ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve curability. Further, a photosensitizer may be added as necessary to improve curability. On the other hand, when ionizing radiation such as electron beam, α -ray, β -ray, or γ -ray is used, the curing is rapid without using a photopolymerization initiator or a photosensitizer, and therefore, it is not necessary to add a photopolymerization initiator or a photosensitizer in particular.
Examples of the photopolymerization initiator include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, acetophenone compounds such as 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;
benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like; acylphosphine oxide-based compounds such as 2,4, 6-trimethylbenzoin diphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; benzil, methylphenylglyoxylate, and the like.
Examples of the hydrogen abstraction-type photopolymerization initiator include benzophenone-based compounds such as benzophenone, methyl-4-phenylbenzophenone o benzoylbenzoate, 4,4 ' -dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, acrylated benzophenone, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 3,3 ' -dimethyl-4-methoxybenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone; aminobenzophenone-based compounds such as Michler's ketone and 4, 4' -diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, and the like.
Among the photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable, 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. These photopolymerization initiators may be used alone or in combination of two or more.
Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiouronium-p-toluenesulfonate.
The amounts of the photopolymerization initiator and the photosensitizer used are preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.3 to 7 parts by mass, based on 100 parts by mass of nonvolatile components in the active energy ray-curable composition.
In addition, in the above-mentioned coating composition, various additives such as: an organic solvent; colorants such as pigments, dyes, and charcoal; inorganic powders such as silica, titanium oxide, zinc oxide, alumina, zirconia, calcium oxide, and calcium carbonate; various resin fine powders such as higher fatty acids, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, polyamide resins, polycarbonate resins, petroleum resins, fluorine resins (PTFE (polytetrafluoroethylene) and the like), polyethylene, polypropylene and the like; antistatic agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss control agents, mold release agents, compatibilizers, conductivity control agents, dispersants, dispersion stabilizers, thickeners, anti-settling agents, silicone-based or hydrocarbon-based surfactants, and the like.
The organic solvent is useful for appropriately adjusting the solution viscosity of the coating composition, and particularly, is easy to adjust the film thickness for thin film coating. Examples of the organic solvent usable herein include: aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tert-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone, or two or more of them may be used in combination.
The coating method of the composition varies depending on the application, and examples thereof include: coating methods using a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a spray coater, a Wheeler coater, a spin coater, dipping, screen printing, spraying, an applicator, a bar coater, electrostatic painting, and the like; or a molding method using various molds.
The fluorine-based copolymer of the present invention can also be used for a resist. The fluorine-based copolymer of the present invention and a photoresist are used for a resist, and the photoresist may contain (1) an alkali-soluble resin, (2) a radiation-sensitive substance (photosensitive substance), (3) a solvent, and (4) other additives used as needed.
Examples of the alkali-soluble resin (1) include: a resin soluble in an alkaline solution as a developer used for patterning a resist. Examples of the alkali-soluble resin include novolak resins, o-vinylphenol and m-vinylphenol obtained by condensing at least one aromatic hydroxy compound selected from phenol, cresol, xylenol, resorcinol, phloroglucinol and hydroquinone, and alkyl-substituted or halogen-substituted aromatic compounds thereof with an aldehyde compound such as formaldehyde, acetaldehyde and benzaldehyde, examples of the resin include polymers or copolymers of a vinylphenol compound such as vinylphenol or α -methylvinylphenol and halogen-substituted compounds thereof, acrylic or methacrylic polymers or copolymers such as acrylic acid, methacrylic acid and hydroxyethyl (meth) acrylate, polyvinyl alcohol, and modified resins obtained by introducing a radiation-sensitive group such as a quinonediazide group, a naphthoquinonediazide group, an aromatic azide group and an aromatic cinnamoyl group into a part of hydroxyl groups of the above-mentioned resins. These alkali-soluble resins may be used alone, or two or more kinds may be used in combination.
Further, as the alkali-soluble resin, a urethane resin containing an acid group such as a carboxylic acid or a sulfonic acid in the molecule may be used, or the urethane resin may be used in combination with the alkali-soluble resin.
As the radiation sensitive substance (photosensitive substance) of (2), any substance can be used as long as it changes the solubility of the alkali-soluble resin in the developer by mixing with the alkali-soluble resin and irradiating with ultraviolet rays, far ultraviolet rays, excimer laser, X-rays, electron beams, ion rays, molecular rays, γ rays, or the like.
Examples of the radiation-sensitive substance include: quinone diazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly (alkylene sulfone) compounds described in Japanese unexamined patent publication No. Sho 59-152.
Examples of the quinonediazide-based compound include: and sulfonyl chlorides of quinone diazide derivatives such as 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, and 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, and 2, 1-naphthoquinone diazide-5-sulfonyl chloride.
Examples of the diazo compound include: salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, inorganic salts of diazoresins which are reaction products of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the above condensates, organic salts of diazoresins which are reaction products of the above condensates with sulfonic acids as described in specification of USP3,300,309, and the like.
Examples of the azide compound and the diazide compound include: azidochalcone, diazidobenzylidenemethylcyclohexanone, and azidocinnamylidenephenylacetophenone, which are described in Japanese patent laid-open publication No. 58-203438, and aromatic azide compounds or aromatic diazide compounds, which are described in Japanese chemical Association No.12, p1708-1714 (1983).
Examples of the halogenated organic compound include halogenated compounds of organic compounds, and specific examples thereof include various compounds such as halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, and mercapto halide (Sulfenyl halide) compounds, and further include tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, tetrabromomethane, and sulfur halide (Sulfenyl halide) compounds, Compounds used as halogen flame retardants such as hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol a, tetrabromobisphenol a, bis (bromoethyl ether) tetrabromobisphenol a, bis (chloroethyl ether) tetrachlorobisphenol a, tris (2, 3-dibromopropyl) isocyanurate, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxyethoxy-3, 5-dibromophenyl) propane, and compounds used as organochlorine pesticides such as dichlorophenyl trichloroethane.
Examples of the organic acid ester include carboxylic acid esters and sulfonic acid esters. Examples of the organic acid amide include carboxylic acid amides and sulfonic acid amides. Further, examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. These radiation-sensitive substances may be used alone or in combination of two or more.
Examples of the solvent (3) include: ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone, etc.; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, heptanol, octanol, nonanol, decanol and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane;
alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; esters such as 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, and butyl lactate, and monocarboxylic acid esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate;
cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene, freon solvents, HCFC, HFC and the like; fully fluorinated solvents such as perfluorooctane, and aromatic solvents such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide and N-methylpyrrolidone, and solvents described in "solvent pocket handbook" (edited by the society for organic synthetic chemistry, Ohmsha, Ltd.) in published books. These solvents may be used alone, or two or more of them may be used in combination.
As a coating method of the composition for the resist application, there are methods such as spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, gravure coating, and the like, and the composition may be filtered by a filter before coating to remove solid impurities.
Examples of the active energy ray for curing the composition for resist use include active energy rays such as light, electron beam, and radiation. Specific examples of the energy source and the curing device include a germicidal lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium-pressure or high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, ultraviolet rays using natural light or the like as a light source, and electron beams using a scanning type or curtain type electron beam accelerator. When curing is performed by electron beam, it is not necessary to add a polymerization initiator.
Among these active energy rays, ultraviolet rays are particularly preferable. Further, irradiation in an inert gas atmosphere such as nitrogen is preferable because the surface curability of the coating film is improved. If necessary, heat may be used in combination as an energy source, and curing may be performed by active energy rays and then heat treatment may be performed.
Examples
The present invention will be described in further detail below with reference to examples and comparative examples. In the examples, parts and% are based on the amount of the substance unless otherwise specified.
Synthesis example 1
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 50 parts by mass of 1-adamantane methacrylate, and 25 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (1). The molecular weight of the copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 15,200, and the number average molecular weight (Mn) was 12,100.
Synthesis example 2
To the flask purged with nitrogen, 86 parts by mass of methyl ethyl ketone, 36 parts by mass of cyclohexyl methacrylate, and 24 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (2). The molecular weight of the copolymer (2) was measured by GPC, and it was found that the weight-average molecular weight (Mw) was 12,300 and the number-average molecular weight (Mn) was 9,500.
Synthesis example 3
To the flask purged with nitrogen, 68 parts by mass of methyl ethyl ketone, 32 parts by mass of isobornyl methacrylate, and 16 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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 weight average molecular weight (Mw) was 9,800 and the number average molecular weight (Mn) was 7,800.
Synthesis example 4
To the flask purged with nitrogen, 95 parts by mass of methyl ethyl ketone, 44 parts by mass of dicyclopentyl methacrylate, and 22 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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, and the weight average molecular weight (Mw) was 13,500 and the number average molecular weight (Mn) was 10,500.
Synthesis example 5
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 45 parts by mass of 1-adamantane methacrylate, and 30 parts by mass of 2,2,3,3, 3-pentafluoropropyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0g of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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 weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,700.
Synthesis example 6
To the flask purged with nitrogen, 84 parts by mass of methyl ethyl ketone, 34 parts by mass of 1-adamantane methacrylate, and 24 parts by mass of 1,1,1,3,3, 3-hexafluoroisopropyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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, and the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,500.
Synthesis example 7
To the flask purged with nitrogen were added 110 parts by mass of methyl ethyl ketone and 50 parts by mass of 1-adamantane methacrylate as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Subsequently, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, the temperature was raised to 60 ℃, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the reaction was carried out for 12 hours. Then, 25 parts by mass of 2,2, 2-trifluoroethyl methacrylate was added thereto, and the reaction was continued for 12 hours. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (7). The molecular weight of the copolymer (7) was measured by GPC, and the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 11,500.
Synthesis example 8
To the flask purged with nitrogen, 108 parts by mass of methyl ethyl ketone, 53 parts by mass of 1-adamantane methacrylate, and 27 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 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 ℃. Then, 3.9 parts by mass of ethyl 2-bromoisobutyrate was added thereto, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. To the obtained reaction product, 30 parts by mass of activated alumina was added and stirred. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (8). As a result of measuring the molecular weight of the copolymer (8) by GPC, the weight average molecular weight (Mw) was 5,200 and the number average molecular weight (Mn) was 4,200.
Synthesis example 9
To the flask purged with nitrogen, 92 parts by mass of methyl ethyl ketone, 42 parts by mass of 1-adamantane methacrylate, and 21 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 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 ℃. Thereafter, 0.68 part by mass of ethyl 2-bromoisobutyrate was added thereto, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. To the obtained reaction product, 5.0 parts by mass of activated alumina was added and stirred. After filtering off 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 it was found that the weight-average molecular weight (Mw) was 22,100 and the number-average molecular weight (Mn) was 18,200.
Comparative Synthesis example 1
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 50 parts by mass of isodecyl methacrylate, and 25 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (10). The molecular weight of the copolymer (10) was measured by GPC, and the weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 12,300.
Comparative Synthesis example 2
To the flask purged with nitrogen, 95 parts by mass of methyl ethyl ketone, 37 parts by mass of t-butyl methacrylate, and 29 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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, and the weight average molecular weight (Mw) was 13,100 and the number average molecular weight (Mn) was 10,800.
Comparative Synthesis example 3
To the flask purged with nitrogen, 104 parts by mass of methyl ethyl ketone, 36 parts by mass of 1-adamantane methacrylate, and 36 parts by mass of 2- (perfluorobutyl) ethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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 weight average molecular weight (Mw) was 14,600 and the number average molecular weight (Mn) was 11,700.
Comparative Synthesis example 4
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 33 parts by mass of 1-adamantane ester methacrylate, and 43 parts by mass of 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ester as a solvent were added, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (13). The molecular weight of the copolymer (13) was measured by GPC, and it was found that the weight-average molecular weight (Mw) was 15,400 and the number-average molecular weight (Mn) was 12,300.
Synthesis example 10
Into the flask purged with nitrogen, 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as solvents, 51 parts by mass of 3-hydroxy-1-adamantane ester methacrylate and 24 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0g of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (14). The molecular weight of the copolymer (14) was measured by GPC, and the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,100.
Synthesis example 11
To the flask purged with nitrogen, 45 parts by mass of methyl ethyl ketone and 45 parts by mass of 2-propanol as solvents, 20 parts by mass of 1-adamantane ester methacrylate, 22 parts by mass of 3-hydroxy-1-adamantane ester methacrylate, and 21 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.03g of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (15). The molecular weight of the copolymer (15) was measured by GPC, and the weight average molecular weight (Mw) was 12,600 and the number average molecular weight (Mn) was 10,100.
Synthesis example 12
To the flask purged with nitrogen, 47 parts by mass of methyl ethyl ketone and 47 parts by mass of 2-propanol as solvents, 25 parts by mass of 1-adamantane ester methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, and 26 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (16). The molecular weight of the copolymer (16) was measured by GPC, and the weight average molecular weight (Mw) was 13,800 and the number average molecular weight (Mn) was 10,700.
Comparative Synthesis example 5
Into the flask purged with nitrogen gas were charged 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as solvents, 34 parts by mass of 3-hydroxy-1-adamantane ester methacrylate, and 41 parts by mass of 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ester methacrylate, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (17). The molecular weight of the copolymer (17) was measured by GPC, and the weight average molecular weight (Mw) was 15,300 and the number average molecular weight (Mn) was 12,100.
Comparative Synthesis example 6
To the flask purged with nitrogen, 43 parts by mass of methyl ethyl ketone and 43 parts by mass of 2-propanol as solvents, 19 parts by mass of 2-hydroxyethyl methacrylate, and 41 parts by mass of octyl methacrylate 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ester were added, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (18). The molecular weight of the copolymer (18) was measured by GPC, and the weight average molecular weight (Mw) was 11,500 and the number average molecular weight (Mn) was 9,700.
Comparative Synthesis example 7
To a flask purged with nitrogen, 56 parts by mass of methyl ethyl ketone and 56 parts by mass of 2-propanol as solvents, 60 parts by mass of a polyoxypropylene chain-containing methacrylate and 18 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain copolymer (19). The molecular weight of the copolymer (19) was measured by GPC, and the weight average molecular weight (Mw) was 15,800 and the number average molecular weight (Mn) was 12,900.
Comparative Synthesis example 8
Into the flask purged with nitrogen gas were charged 55 parts by mass of methyl ethyl ketone and 55 parts by mass of 2-propanol as solvents, 42 parts by mass of methacrylic acid ester having a polyoxypropylene chain, and 33 parts by mass of octyl methacrylate 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl ester, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.9 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. Then, 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (20). The molecular weight of the copolymer (20) was measured by GPC, and the weight average molecular weight (Mw) was 15,100 and the number average molecular weight (Mn) was 11,800.
Synthesis example 13
In a flask 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 part by mass of tin octylate as a urethane-forming catalyst and 0.04 part by mass of p-methoxyphenol as a polymerization inhibitor were added to the solution, and the temperature was raised to 75 ℃. Under a dry air atmosphere, 30 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as "AOI") was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 75 ℃ for 1 hour, and then heated to 80 ℃ and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and the disappearance of the absorption of the isocyanate group. Subsequently, PGMEA dilution was performed to obtain a PGMEA solution containing 20 mass% of the copolymer (21). The molecular weight of the copolymer (21) was measured by GPC, and the weight average molecular weight was 19,900, and the number average molecular weight was 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, 0.02 part by mass of tin octylate as a urethane-forming catalyst and 0.03 part by mass of p-methoxyphenol as a polymerization inhibitor were added, and the temperature was raised to 75 ℃. Under a dry air atmosphere, 16 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 75 ℃ for 1 hour, and then heated to 80 ℃ and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and the disappearance of the absorption of the isocyanate group. Subsequently, PGMEA dilution was performed to obtain a PGMEA solution containing 20 mass% of the copolymer (22). The molecular weight of the copolymer (22) was measured by GPC, and 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 PGMEA, 0.03 part by mass of tin octylate as a urethane-forming catalyst and 0.04 part by mass of p-methoxyphenol as a polymerization inhibitor were added, and the temperature was raised to 75 ℃. 20 parts by mass of AOI was added dropwise over 1 hour in a dry air atmosphere. After completion of the dropwise addition, the mixture was stirred at 75 ℃ for 1 hour, and then heated to 80 ℃ and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and the disappearance of the absorption of the isocyanate group. Subsequently, PGMEA dilution was performed to obtain a PGMEA solution containing 20 mass% of the copolymer (23). The molecular weight of the copolymer (23) was measured by GPC, and the weight average molecular weight was 17,100, and the number average molecular weight was 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 PGMEA, 0.02 part by mass of tin octylate as a urethane-forming catalyst and 0.03 part by mass of p-methoxyphenol as a polymerization inhibitor were added, and the temperature was raised to 75 ℃. In a dry air atmosphere, 21 parts by mass of AOI was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 75 ℃ for 1 hour, and then heated to 80 ℃ and stirred for 3 hours. The completion of the reaction was confirmed by measuring the IR spectrum of the reaction product and the disappearance of the absorption of the isocyanate group. Subsequently, PGMEA dilution was performed to obtain a PGMEA solution containing 20 mass% of the copolymer (24). The molecular weight of the copolymer (24) was measured by GPC, and the weight average molecular weight was 17,000 and the number average molecular weight was 13,300.
Comparative Synthesis example 11
In a flask subjected to dry air replacement, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends, 10 parts by mass of diisopropyl ether as a solvent, 0.006 part by mass of p-methoxyphenol as a polymerization inhibitor, and 3.3 parts by mass of triethylamine as a neutralizing agent, represented by the following formula, were charged, and stirring was started under an air stream, and 3.1 parts by mass of methacryloyl chloride was added dropwise over 2 hours while keeping the temperature in the flask at 10 ℃. After completion of the dropwise addition, the reaction was carried out by stirring at 10 ℃ for 1 hour, raising the temperature and stirring at 30 ℃ for 1 hour, and then raising the temperature to 50 ℃ and stirring for 10 hours, and disappearance of methacryloyl chloride was confirmed by gas chromatography measurement. Next, washing was repeated 3 times by the following method: after adding 70 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then the mixture was allowed to stand to separate and remove an aqueous layer. Subsequently, 0.02 part by mass of p-methoxyphenol as a polymerization inhibitor and 8 parts by mass of magnesium sulfate as a dehydrating agent were added, and the mixture was allowed to stand for 1 day to completely dehydrate the mixture, and then the dehydrating agent was filtered off.
(wherein X is a perfluoromethylene group and a perfluoroethylene group, an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per 1 molecule, and the average number of fluorine atoms is 46. further, the number average molecular weight by GPC is 1,500.)
Then, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula.
(wherein X represents a perfluoromethylene group or a perfluoroethylene group, and the average number of fluorine atoms is 46: the average number of perfluoromethylene groups or 8 perfluoroethylene groups per 1 molecule.)
Comparative Synthesis example 12
100 parts by mass of methyl isobutyl ketone as a solvent was added to the flask purged with nitrogen, and the temperature was raised to 95 ℃ while stirring the mixture under a nitrogen stream. Subsequently, 3 kinds of dropping solutions of 20 parts by mass of the compound having a poly (perfluoroalkylene ether) chain obtained in comparative synthesis example 11, 50.1 parts by mass of 3-hydroxy-1-adamantane methacrylate dissolved in 120 parts by mass of methyl isobutyl ketone, and 10.5 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator dissolved in 80 parts by mass of methyl isobutyl ketone were set in respective dropping devices, and the dropping was performed for 3 hours while keeping the flask at 95 ℃. After completion of the dropwise addition, the mixture was stirred at 95 ℃ for 5 hours and then at 105 ℃ for 2 hours, and 262.1 parts by mass of the solvent was distilled off under reduced pressure to obtain a solution of the copolymer (26).
Subsequently, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethane-forming catalyst were added to the polymer (25) solution obtained above, and then stirring was started under an air current, and 29.9 parts by mass of AOI was added dropwise over 1 hour while maintaining 75 ℃. After completion of the dropwise addition, the mixture was stirred at 75 ℃ for 1 hour, then heated to 80 ℃ and stirred for 4 hours, and then, after confirming disappearance of the isocyanate group by IR spectrum measurement, 362 parts by mass of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 20% by mass of the fluorine-containing polymerizable resin (26).
Slip angle determination using cured coating film
The slip angle of the water was measured to evaluate the slip angle of the coating film surface. For the evaluation of the slidability, DM-500, manufactured by Kyowa interface science, Inc., was used. 50 μ L of water droplets were dropped on the substrate, the base was tilted at a speed of 2 °/second, and the angle at which the water droplets started to move was defined as the value of the landing angle. The measurement was performed 5 times, and the average value was defined as the value of the slip angle.
< evaluation of Using UV-curable coating film >
A base resin composition of an active energy ray-curable composition was obtained by mixing and dissolving 125 parts by mass of an ultraviolet-curable urethane acrylate resin (UNIDIC 17-806 manufactured by DIC Co., Ltd.; a butyl acetate solution having a resin component of 80% by mass), 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184 manufactured by BASF JAPAN Co., Ltd.) as a photopolymerization initiator, 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether. 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. Subsequently, the active energy ray-curable composition was applied to a glass plate having a length of 7cm × a width of 7cm and a thickness of 1mm by a spin coater, and then the resultant was left in a drier at 60 ℃ for 5 minutes to volatilize the solvent. Then, the resultant was cured by an ultraviolet curing apparatus (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation dose of 2kJ/m2) The dried coating film was irradiated with ultraviolet rays to obtain a cured coating film. Then, the slip angle of the obtained coating film was measured.
[ Table 1]
| Copolymer | Water slide falling angle (°) | |
| Synthesis example 1 | (1) | 14 |
| Synthesis example 2 | (2) | 19 |
| Synthesis example 3 | (3) | 17 |
| Synthesis example 4 | (4) | 18 |
| Synthesis example 5 | (5) | 19 |
| Synthesis example 6 | (6) | 18 |
| Synthesis example 7 | (7) | 17 |
| Synthesis example 8 | (8) | 15 |
| Synthesis example 9 | (9) | 15 |
| Synthesis example 13 | (21) | 17 |
| Synthesis example 14 | (22) | 18 |
| Comparative example 1 | (10) | 33 |
| Comparative example 2 | (11) | 37 |
| Comparative example 3 | (12) | 32 |
| Comparative example 4 | (13) | 35 |
| Comparative example 9 | (23) | 37 |
| Comparative example 10 | (24) | 38 |
| Comparative example 12 | (26) | 42 |
< evaluation of coating film by Heat curing >
A solution was prepared by adding CERANATE SSA-500100 parts by mass, BURNOCK DN-980186 parts by mass, and 0.1% by mass in terms of solid content of the compound obtained above, and diluting the resulting mixture with butyl acetate to 40%. 1mL of the preparation solution was applied to a glass substrate having a thickness of 1mm and a length of 15 cm. times.a width of 7cm with a 6mil applicator. Thereafter, the film was dried at 23 ℃ for 7 days to prepare a coating film, and the slip angle was measured.
[ Table 2]
| Copolymer | Water slide falling angle (°) | |
| Synthesis example 10 | (14) | 17 |
| Synthesis example 11 | (15) | 18 |
| Synthesis example 12 | (16) | 20 |
| Comparative example 5 | (17) | 27 |
| Comparative example 6 | (18) | 38 |
| Comparative example 7 | (19) | 45 |
| Comparative example 8 | (20) | 47 |
Comparative Synthesis example 13
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone and 75 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (27). The molecular weight of the copolymer (27) was measured by GPC, and it was found that the weight-average molecular weight (Mw) was 15,100 and the number-average molecular weight (Mn) was 11,600.
Synthesis example 15
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 9.5 parts by mass of 1-adamantane methacrylate and 65 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer (28). The molecular weight of the copolymer (28) was measured by GPC, and the weight average molecular weight (Mw) was 14,800 and the number average molecular weight (Mn) was 11,800.
Synthesis example 16
To the flask purged with nitrogen, 109 parts by mass of methyl ethyl ketone, 69 parts by mass of 1-adamantane methacrylate and 5.9 parts by mass of 2,2, 2-trifluoroethyl methacrylate were added as solvents, and the mixture was stirred at 25 ℃ under a nitrogen stream for 1 hour. Then, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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 weight average molecular weight (Mw) was 15,500 and the number average molecular weight (Mn) was 12,400.
Comparative Synthesis example 14
To the flask purged with nitrogen were added 110 parts by mass of methyl ethyl ketone and 75 parts by mass of 1-adamantane methacrylate as solvents, and the mixture was stirred at 25 ℃ for 1 hour under a nitrogen stream. Then, 1.8 parts by mass of 2, 2' -bipyridine and 0.5 part by mass of cuprous chloride were added, and the temperature was raised to 60 ℃. Thereafter, 1.2 parts by mass of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 60 ℃ for 12 hours under a nitrogen stream. 9.0 parts by mass of activated alumina was added to the obtained reaction product, followed by stirring. After filtering off 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 weight average molecular weight (Mw) was 15,200, and the number average molecular weight (Mn) was 11,600.
[ Table 3]
Claims (11)
1. A fluorine-containing copolymer characterized in that it is a copolymer having CnF2n+1A polymerizable monomer (a1) having a fluoroalkyl group and a polymerizable unsaturated group, and a polymerizable monomer (a2) having an alicyclic hydrocarbon skeleton and a polymerizable unsaturated group, wherein C is a copolymer obtained by using, as essential raw materialsnF2n+1In-n is 1 or 2.
2. The fluorine-based copolymer according to claim 1, wherein the alicyclic hydrocarbon skeleton in the polymerizable monomer (a2) is a bridged hydrocarbon skeleton.
3. The fluorine-based copolymer according to claim 1 or 2, wherein the copolymer has a ratio of weight average molecular weight Mw to number average molecular weight Mn Mw/Mn in the range of 1.00 to 1.40.
4. 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 norbornane ring or a norbornene ring.
5. 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 general formulas (1) and (2), R1Is a hydrogen atom, a halogen atom, a methyl group, a cyano group, a phenyl group, a benzyl group or-CmH2m-Rf, Rf being CnF2n+1Wherein X represents any one of the following formulae (X-1) to (X-10) and is represented by the formula-CmH2min-Rf, m is an integer of 1 to 8, in CnF2n+1In the formula (I), n is 1 or 2,
-OCmH2m- (X-1)
-OCH2CH2OCH2- (X-2)
in the formula, m is an integer of 1 to 8, k is an integer of 0 to 8, and Rf is the same as above.
6. The fluorine-based copolymer according to any one of claims 1 to 5, wherein the polymerizable monomer (a2) further has a hydroxyl group.
7. The fluorine-based copolymer according to any one of claims 1 to 5, wherein the copolymer further has an active energy ray-curable group.
8. The fluorine-based copolymer according to any one of claims 1 to 7, wherein the copolymer is a random copolymer.
9. A slippery surface modifier comprising the copolymer according to any one of claims 1 to 8.
10. A curable resin composition comprising the fluorine-based copolymer according to any one of claims 1 to 8 and a curable resin.
11. A water-repellent coating film which is a cured film of the curable resin composition according to claim 10.
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- 2019-06-11 JP JP2020527363A patent/JP6908193B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6908193B2 (en) | 2021-07-21 |
| WO2020004000A1 (en) | 2020-01-02 |
| KR102761339B1 (en) | 2025-02-04 |
| CN112334501B (en) | 2022-09-27 |
| KR20210021955A (en) | 2021-03-02 |
| TWI783153B (en) | 2022-11-11 |
| JPWO2020004000A1 (en) | 2021-02-15 |
| TW202006084A (en) | 2020-02-01 |
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