CN113906078A - Fluorine-containing resin, active energy ray-curable composition, heat-curable composition, and cured product of the composition - Google Patents
Fluorine-containing resin, active energy ray-curable composition, heat-curable composition, and cured product of the composition Download PDFInfo
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- CN113906078A CN113906078A CN202080040897.4A CN202080040897A CN113906078A CN 113906078 A CN113906078 A CN 113906078A CN 202080040897 A CN202080040897 A CN 202080040897A CN 113906078 A CN113906078 A CN 113906078A
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- compound
- fluorine
- containing resin
- mass
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- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 66
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011737 fluorine Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 116
- 125000000524 functional group Chemical group 0.000 claims abstract description 41
- 125000001033 ether group Chemical group 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- -1 acrylate compound Chemical class 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 239000011342 resin composition Substances 0.000 claims description 19
- 125000005647 linker group Chemical group 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 150000004292 cyclic ethers Chemical group 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 125000003566 oxetanyl group Chemical group 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000463 material Substances 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
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- 125000003118 aryl group Chemical group 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 5
- 125000004450 alkenylene group Chemical group 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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Images
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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Abstract
Providing: a cationically polymerizable fluorine-containing resin which can provide a cured product having excellent antifouling properties and sliding properties. A fluorine-containing resin which is a copolymer having, as polymerization components, a compound (A) having a functional group capable of cationic polymerization and a radical polymerizable unsaturated group, and a compound (B) having a poly (perfluoroalkylene ether) chain and a radical polymerizable unsaturated group.
Description
Technical Field
The present invention relates to: a fluorine-containing resin, an active energy ray-curable composition, a heat-curable composition, and a cured product of the composition.
Background
Antifouling coatings for the purpose of stain resistance and/or scratch resistance are applied to screen surfaces of display devices such as liquid crystal displays, organic EL displays, and touch panels, and housing surfaces of terminals such as smart phones and notebook computers.
The above coating is typically formed as follows: the coating liquid containing a fluorine-containing resin is applied, and the coated surface is cured by irradiation with an active energy ray, heat treatment, or the like.
The above antifouling coating is used not only for the screen surface of a display device, but also for applications and application sites such as outdoor articles and automobile members. In the curing using active energy rays, radical polymerizable curing using a resin having an unsaturated polymerizable functional group and a radical generator is generally used (for example, patent document 1), and a fluorine-containing resin capable of using a curing method other than radical polymerizable curing is required as the application and the application site are expanded.
Documents of the prior art
Patent document
Patent document 1: international publication No. 12/002361
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide: a cationically polymerizable fluorine-containing resin which can provide a cured product having excellent antifouling properties and sliding properties.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: a fluororesin, which is a copolymer containing, as polymerization components, a compound (a) having a cationically polymerizable functional group and a radically polymerizable unsaturated group and a compound (B) having a poly (perfluoroalkylene ether) chain and a radically polymerizable unsaturated group, can be suitably used as a surface modifier, and a cured product obtained by cationically polymerizing a resin composition containing the fluororesin is excellent in stain resistance and sliding properties, and the present invention has been completed.
That is, the present invention relates to a fluorine-containing resin which is a copolymer having, as polymerization components, a compound (a) having a functional group capable of cationic polymerization and a radical polymerizable unsaturated group, and a compound (B) having a poly (perfluoroalkylene ether) chain and a radical polymerizable unsaturated group.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a cationically polymerizable fluorine-containing resin which can provide a cured product having excellent antifouling properties and sliding properties.
Drawings
FIG. 1 is a diagram showing an IR spectrum of a fluorine-containing resin obtained in Synthesis example 1.
FIG. 2 is a view showing a fluorine-containing resin obtained in Synthesis example 113Graph of C-NMR spectrum.
Detailed Description
Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out by appropriately changing the embodiments within a range not to impair the effects of the present invention.
[ fluorine-containing resin ]
The fluorine-containing resin of the present invention is a copolymer having, as polymerization components, a compound (a) having a functional group capable of cationic polymerization and a radical polymerizable unsaturated group, and a compound (B) having a poly (perfluoroalkylene ether) chain and a radical polymerizable unsaturated group.
The term "as a polymeric component" here means: the fluorine-containing resin of the present invention comprises, as essential reaction raw materials, a compound (A) having a functional group capable of cationic polymerization and a radically polymerizable unsaturated group, and a compound (B) having a poly (perfluoroalkylene ether) chain and a radically polymerizable unsaturated group.
The fluorine-containing resin of the present invention can exhibit high antifouling performance through a poly (perfluoroalkylene ether) chain, and can improve the durability of antifouling performance through a functional group capable of cationic polymerization.
Hereinafter, the polymerization component of the fluorine-containing resin will be described.
(Compound (A))
The compound (a) is a compound having a functional group capable of cationic polymerization and a radical polymerizable unsaturated group.
The fluorine-containing resin of the present invention can be cationically polymerized by the functional group capable of cationic polymerization of the compound (A).
Examples of the functional group capable of cationic polymerization which the compound (a) has include a cyclic ether group and the like.
Examples of the cyclic ether group as a functional group capable of cationic polymerization include an epoxy group and an oxetane group, and an epoxy group is preferable.
Examples of the radical polymerizable unsaturated group of the compound (a) include a group containing a vinyl group, and examples thereof include a (meth) acryloyl group, a (meth) acryloyloxy group, and a styryl group.
In addition, "(meth) acryloyl group" means: one or both of an acryloyl group and a methacryloyl group. The "(meth) acrylate" described later means: one or both of a methacrylate and an acrylate.
The compound (a) is preferably a (meth) acrylate compound having a functional group capable of cationic polymerization and/or a styrene compound having a functional group capable of cationic polymerization, and more preferably a compound represented by the following formula (a 1).
(in the aforementioned formula (a1),
Ra1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y is a group containing a cyclic ether structure. )
The group containing a cyclic ether structure of Y of the formula (a1) is, for example, a group containing an oxirane ring and/or an oxetane ring, preferably a group containing an oxirane ring and/or an oxetane ring at the terminal.
The compound represented by the formula (a1) is preferably a compound represented by the following formula (a 2).
(in the aforementioned formula (a1),
Ra1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ra2Is alkylene, arylene, or a 2-valent linking group formed by a combination of 2 or more selected from alkylene, arylene, and an ether bond (-O-).
Z is glycidyl, oxetanyl, alkyl oxetanyl having 4 to 10 carbon atoms or epoxycycloalkyl having 5 to 10 carbon atoms)
As Ra2Examples of the alkylene group of (b) include alkylene groups having 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic.
As Ra2The arylene group of (b) includes, for example, an arylene group having 6 to 18 carbon atoms, preferably an arylene group having 6 to 14 carbon atoms. The arylene group may be a single ring or a condensed ring. As Ra2Specific examples of the arylene group include phenylene and naphthylene.
Ra2The alkylene group and the arylene group in (a) may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like.
Specific examples of the compound (A) include epoxy group-containing (meth) acrylate compounds such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, epoxycyclohexylmethyl (meth) acrylate and the like; oxetanyl group-containing (meth) acrylate compounds such as (3-ethyloxetan-3-yl) methyl acrylate; and mono (meth) acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether.
The compound (a) used as the polymerization component of the fluorine-containing resin of the present invention may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The compound (a) can be produced by a known method, and a commercially available product can be used.
Examples of commercially available products of the compound (a) include: SR-378 (manufactured by Sartomer Co., Ltd.) which is a commercially available glycidyl acrylate; lightester G (available from Kyoeisha chemical Co., Ltd.), Blemmer G (available from Nippon fat Co., Ltd.), SR-379 (available from Sartome Co., Ltd.), OXE-10, OXE-30 (available from Osaka organic chemical Co., Ltd.), Cyclomer M100 (available from Daicel Corporation), and the like are commercially available glycidyl methacrylate.
(Compound (B))
The compound (B) is a compound having a poly (perfluoroalkylene ether) chain and a radical polymerizable unsaturated group. The fluorine-containing resin of the present invention can exhibit antifouling properties through the poly (perfluoroalkylene ether) chain of the compound (B).
Examples of the poly (perfluoroalkylene ether) chain of the compound (B) include a linking group having a structure in which a 2-valent fluorinated hydrocarbon group having 1 to 3 carbon atoms and an oxygen atom are alternately linked.
As the poly (perfluoroalkylene ether) chain, a linking group represented by the following formula (X-1) may be mentioned.
(in the above formula (X-1),
each of the plurality of xs is independently a perfluoroalkylene group.
In the plural X, 2 or more kinds of perfluoroalkylene groups may be present in a random or block form.
n is the number of repeating units. n is, for example, 1 to 300, preferably 2 to 200, more preferably 3 to 100, further preferably 6 to 70, most preferably 12 to 50.
Examples of the perfluoroalkylene group as X include the following perfluoroalkylene groups (Y-1) to (Y-6).
Each X is independently preferably a perfluoromethylene group or a perfluoroethylene group, and more preferably a perfluoromethylene group is present together with a perfluoroethylene group, from the viewpoint of easy industrial availability.
When the perfluoromethylene group (a) and the perfluoroethylene group (b) are present together, the presence ratio (a/b) (ratio of the number of the units) is preferably 1/10 to 10/1, more preferably 3/10 to 10/3.
The total number of fluorine atoms contained in 1 poly (perfluoroalkylene ether) chain is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.
The radical polymerizable unsaturated group of the compound (B) is, for example, a group containing a vinyl group, and is preferably a group represented by the following formulae (U-1) to (U-5).
The compound (B) is preferably a compound having a radical polymerizable unsaturated group at both ends of a poly (perfluoroalkylene ether) chain.
Specific examples of the compound having a radical polymerizable unsaturated group at each end of a poly (perfluoroalkylene ether) chain include compounds represented by the following formulae (b1) to (b 13).
In the formulae (b1) to (b13), PFPE is a linking group represented by the formula (X-1).
The compound (B) used as the polymerization component of the fluorine-containing resin of the present invention may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the method for producing the compound (B) include the following methods: a method in which a compound having one hydroxyl group at each of both ends of a poly (perfluoroalkylene ether) chain is subjected to a dehydrochlorination reaction with (meth) acryloyl chloride; a method in which (meth) acrylic acid is subjected to a dehydration reaction; a method in which 2- (meth) acryloyloxyethyl isocyanate is urethanized; a method in which itaconic anhydride is subjected to esterification reaction; a method in which the compound is reacted with styrene having chloromethyl group in the presence of an alkali; a method in which a compound having one carboxyl group at each of both ends of a poly (perfluoroalkylene ether) chain is esterified with 4-hydroxybutylacrylate glycidyl ether; a method in which glycidyl (meth) acrylate is subjected to an esterification reaction; a method in which 2-hydroxyethyl (meth) acrylate is reacted with and introduced into a compound having one isocyanate group at each of both ends of a poly (perfluoroalkylene ether) chain; a method of reacting 2-hydroxyethyl (meth) acrylamide.
Among these, in terms of easy synthetic availability, a method of obtaining a compound having one hydroxyl group at each of both ends of a poly (perfluoroalkylene ether) chain by a dehydrochlorination reaction of (meth) acryloyl chloride and a method of obtaining a compound by a urethanization reaction of 2- (meth) acryloyloxyethyl isocyanate are particularly preferable.
(Compound (C))
The fluororesin of the present invention may be a copolymer having, as polymerization components, a compound (a) having a functional group capable of cationic polymerization and a radical polymerizable unsaturated group and a compound (B) having a poly (perfluoroalkylene ether) chain and a radical polymerizable unsaturated group, and compounds other than the compound (a) and the compound (B) may be used as polymerization components.
As the polymerization component other than the compound (a) and the compound (B), a compound (C) having 1 or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain (hereinafter, the functional group may be referred to as a "functional group") and a radical polymerizable unsaturated group is preferable.
By using the compound (C) having a functional group as a polymerization component, the following functions can be provided: the fluororesin of the present invention is imparted with higher antifouling performance, slidability, and/or improved compatibility with other resins to be mixed therewith.
Examples of the radical polymerizable unsaturated group of the compound (C) include a group containing a vinyl group, and examples thereof include a (meth) acryloyl group, a (meth) acryloyloxy group, and a styryl group.
The compound (C) is preferably a (meth) acrylate compound having a functional group and/or a styrene compound having a functional group.
Examples of the alkyl group having a functional group in the compound (C) include alkyl groups having 1 to 18 carbon atoms.
Specific examples of the compound (C) having an alkyl group as a functional group include: (meth) acrylic acids 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.
Examples of the hydroxyl group as the functional group of the compound (C) include hydroxyalkyl groups having 1 to 18 carbon atoms.
Specific examples of the compound (C) having a hydroxyalkyl group as a functional group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 4-hydroxystyrene.
Examples of the alicyclic hydrocarbon group having a functional group in the compound (C) include dicyclopentyl group, isobornyl group, and adamantyl group.
Specific examples of the compound (C) having an alicyclic hydrocarbon group as a functional group include dicyclopentyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like.
When the functional group is an adamantyl group, the compound (C) having an adamantyl group is preferably a compound represented by the following formula (C-ad).
(in the above-mentioned formula (C-ad),
Rc1is a hydrogen atom or a methyl group.
Rc2Is a single bond or an alkylene group having 1 to 8 carbon atoms.
Rc3Each independently a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic acid anhydride group.
Rc4Each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms.
n is an integer of 0 to 15. )
Specific examples of the compound (C) having an adamantyl group include the following.
Examples of the group containing a silicone chain as the functional group of the compound (C) include a group containing a siloxane structure represented by the following formula (S1), a group represented by the following formula (S2), and the like.
(in the aforementioned formulae (S-1) and (S-2),
Rc5each independently is an alkyl group having 1 to 18 carbon atoms or a phenyl group.
n is the number of repeating units and is an integer of 1 to 200. )
Specific examples of the compound (C) having a group containing a silicone chain as a functional group include compounds represented by the following formulae (C-si1) to (C-si 8).
(in the formulae (c-si1) to (c-si8),
m is an integer of 1 to 6.
n is an integer of 0 to 250 independently.
Rc5Each independently is an alkyl group having 1 to 18 carbon atoms or a phenyl group.
Rc6Each independently is a hydrogen atom or a methyl group. )
As the compound (C) having a group containing an organosilicon chain, commercially available compounds can be used, and examples thereof include Silaplane FM-0711, Silaplane FM-0721K, Silaplane FM-0725 and Silaplane TM-0701T (all of JNC Co., Ltd.).
When the functional group is a polyoxyalkylene chain-containing group, the compound (C) having a polyoxyalkylene chain-containing group is preferably a compound represented by the following formula (C-pae1) or (C-pae 2).
(in the aforementioned formulae (C-pae1) and (C-pae2),
Rc7each independently is a hydrogen atom or a methyl group.
Rc8Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
p is an integer of 0 or more, q is an integer of 0 or more, r is an integer of 0 or more, and p + q + r is an integer of 1 or more.
X, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms. )
As the compound (C) having a group containing a polyoxyalkylene chain, commercially available compounds can be used, and examples thereof include: blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50PEP-300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Blemmer 10PPB-500 APB-500B, Blemmer 10 (manufactured by Japan oil & fats & oils); blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer AOEP-800B, Blemmer PLE-200, Blemmer ALE-800, Blemmer 400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer AKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer 70ANEP-550 (above, manufactured by Nippon oil Co., Ltd.), Lighter MC, Lightester 130MA, Lightest MA, BO 42A-32, BO-LIGHT ACRYLATE MTG A, B-800B, Blemmer PLEMmer PLE-200, Blemmer ALE-200, Blemmer PNEP series, Blemmer NAP series, B-32, BO 32A, BO E-7A, and the like, LIGHT ACRYLATE DPM-A, LIGHT ACRYLATE P-200A, LIGHT ACRYLATE NP-4EA and LIGHT ACRYLATE NP-8EA (Kyoeisha chemical Co., Ltd.).
The compound (C) used as the polymerization component of the fluorine-containing resin of the present invention may be used alone in 1 kind or in combination of 2 or more kinds.
[ Process for producing fluorine-containing resin ]
The fluorine-containing resin of the present invention can be produced, for example, by polymerizing the compound (a), the compound (B), and optionally the compound (C) in an organic solvent using a radical polymerization initiator.
The organic solvent used for producing the fluorine-containing resin of the present invention may be suitably selected in consideration of boiling point, compatibility between polymerization components, and polymerizability, and ketones, esters, amides, sulfoxides, ethers, and hydrocarbons are preferable. In addition, a halogen-based organic solvent in which a part or all of hydrogen atoms contained in the structure of the organic solvent is substituted by halogen may be used.
Specific examples of the organic solvent include 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, chloroform, 1, 3-bis (trifluoromethyl) benzene, and the like.
Examples of the radical polymerization initiator used for producing the fluorine-containing resin of the present invention include peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, and the like.
In addition to the above-mentioned radical polymerization initiator, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid, or the like may be used as necessary.
The amount of the compound (B) used in the polymerization is, for example, 1 to 100 parts by mass, preferably 5 to 90 parts by mass, more preferably 10 to 75 parts by mass, and still more preferably 20 to 70 parts by mass, based on 100 parts by mass of the compound (A).
When the amount of the compound (B) is 1 to 100 parts by mass based on 100 parts by mass of the compound (A), compatibility with the solvent and/or other resin of the resulting fluorine-containing resin can be ensured.
When the compound (C) is used, the amount of the compound (C) used in the polymerization may be suitably set to, for example, 10 to 300 parts by mass, preferably 15 to 250 parts by mass, more preferably 30 to 200 parts by mass, and still more preferably 30 to 150 parts by mass, based on 100 parts by mass of the compound (A).
The fluorine-containing resin of the present invention is preferably a copolymer comprising a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (B1).
In the copolymer, the structural unit represented by the formula (a1) is a structural unit derived from the compound (a), and the structural unit represented by the formula (B1) is a structural unit derived from the compound (B).
(in the aforementioned formulae (A1) and (B1),
Ra1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ra2Is a linking group having a valence of 2.
Y is a group containing a cyclic ether structure.
Each of the plurality of xs is independently a perfluoroalkylene group.
a and b are each independently the number of repeating units. )
As Ra2A linking group having a valence of 2, e.g. alkylene, alkenylene, arylene, heterocyclic group, -O-, -S-, -NRN1-、-CO-、-CS-、-SO2A linking group having a valence of 2 formed by or a combination thereof. Here, RN1Is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
Examples of the alkylene group include a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, and the like.
The alkenylene group includes an alkenylene group having 2 to 10 carbon atoms, and preferably an alkenylene group having 2 to 8 carbon atoms.
The arylene group is preferably an arylene group having 6 to 18 carbon atoms, and more preferably an arylene group having 6 to 14 carbon atoms. The arylene group is a single ring or a condensed ring, preferably a single ring or a condensed ring having a condensed number of 2 to 8, more preferably a single ring or a condensed ring having a condensed number of 2 to 4. Specifically, phenylene, naphthylene and the like can be exemplified.
The heterocyclic group includes a hetero alicyclic group containing a hetero atom in an alicyclic group and an aromatic heterocyclic group containing a hetero atom in an aromatic cyclic group. The heterocyclic group may be a single ring or a condensed ring. Specific examples of the heterocyclic ring include an oxirane ring, an oxacyclohexane ring, a sulfane ring, an oxazole ring, a thiophene ring, a thianthrene ring, a furan ring, a pyran ring, an isobenzofuran ring, a chromene ring, a xanthene ring, a phenoxazine ring, a pyrrole ring, a pyrazole ring, an isothiazole ring, an isoxazole ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an isoindoline ring, an indole ring, an indazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a phthalazine ring, a naphthyridine ring, a quinazoline ring, a cinnoline ring, a pteridine ring, a carbazole ring, a carboline ring, a phenanthrene ring, an acridine ring, a pyrimidine ring, an o-phenanthroline ring, a phthalazine ring, a phenethylhydrazine ring, a phenoxazine ring, a furazan ring, and the like, and a group corresponding to 2 valences of these heterocyclic rings is preferable as the heterocyclic group.
RN1The alkyl group (b) may be linear, branched or cyclic. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. The cyclic alkyl group may be monocyclic or polycyclic. The cyclic alkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, and more preferably a substituted or unsubstituted cycloalkyl group having 4 to 14 carbon atoms.
As RN1The aryl group of (1) is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 14 carbon atoms. As RN1Specific examples of the aryl group include phenyl and naphthyl.
As RN1The aralkyl group of (2) is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms.
Form Ra2Alkylene, alkenylene, arylene and heterocyclic groups of a linking group of valency 2, and RN1The alkyl group, aryl group and aralkyl group of (a) may further have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), a hydroxyl group, a carboxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloyl groupOxy, amide, acyl, aralkyl, and the like.
Examples of the group having a cyclic ether structure including Y include a cyclic ether group, preferably an epoxy group and an oxetane group, and more preferably an epoxy group.
The structural unit represented by the formula (A1) is preferably a structural unit represented by the following formula (A1-1).
(in the above formula (A1-1),
Ra1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ra3Is alkylene, arylene, or a 2-valent linking group formed by a combination of 2 or more selected from alkylene, arylene, and an ether bond (-O-).
Y1Is a cyclic ether group.
a is the number of repeating units. )
The structural unit represented by formula (B1) corresponds to the linking group represented by formula (X-1) of compound (B).
The preferable mode of the structural unit represented by the formula (B1) is the same as the preferable mode of the linking group represented by the formula (X-1).
The ratio of the structural unit represented by the formula (a1) to the structural unit represented by the formula (B1) in the fluororesin of the present invention is, for example, (a 1): (B1) 100: 0.1 to 100: 100. preferably (a 1): (B1) 100: 1-100: 75. more preferably 100: 1-100: 50. further preferably 100: 1-100: 30. most preferably 100: 1-100: 15.
the ratio of the formulae (A1) and (B1) can be determined, for example1HNMR spectrum was obtained. The copolymer may be a block copolymer or a random copolymer.
The fluorine-containing resin of the present invention preferably further contains a structural unit represented by the following formula (C1).
The structural unit represented by formula (C1) is a structural unit derived from compound (C).
(in the aforementioned formula (C1),
Rc1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Rc2Is a linking group having a valence of 2.
Z is a group containing 1 or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain.
c is the number of repeating units. )
As Rc2The 2-valent linking group of (1) may be bonded to Ra2The same 2-valent linking group.
The functional group of Z is preferably a hydroxyalkyl group, a hydroxyphenyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, or a group containing a silicone chain, more preferably a hydroxyalkyl group, an isobornyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dicyclopentyl group, a substituted or unsubstituted dicyclopentenyl group, or a group containing a polyoxyalkylene chain and a group containing a polyalkylsiloxane, and most preferably a hydroxyalkyl group, a substituted or unsubstituted adamantyl group, a polyalkylene ether group, or a polyalkylsiloxane.
The amount of the structural unit represented by the formula (C1) in the fluororesin of the present invention is not particularly limited, and may be set as appropriate.
The number average molecular weight (Mn) of the fluorine-containing resin of the present invention is preferably in the range of 500 to 20000, more preferably 1200 to 10000.
The weight average molecular weight (Mw) of the fluorine-containing resin of the present invention is preferably in the range of 2000 to 100000, more preferably in the range of 3000 to 50000.
The number average molecular weight and the weight average molecular weight are values obtained in terms of polystyrene measured by gel permeation chromatography (hereinafter, sometimes referred to as "GPC"). The GPC measurement conditions were those described in examples.
[ resin composition ]
The resin composition containing the fluorine-containing resin of the present invention has a functional group capable of cationic polymerization, and therefore can be cationic polymerized by further containing a photoacid generator or a thermal acid generator. The composition of the present invention can form an active energy ray-curable resin composition by containing a photoacid generator, and the composition of the present invention can form a heat-curable resin composition by containing a thermal acid generator.
Cationic polymerization is not hindered by curing by oxygen unlike radical polymerization, and is polymerization simultaneously with ring opening, so that volume shrinkage during curing is small and deterioration in performance of the resulting cured product can be suppressed.
The photoacid generator is a compound that generates an acid upon irradiation with active energy rays such as visible light, ultraviolet light, X-rays, and electron beams, and examples thereof include a compound in which the cation moiety is a complex ion such as a sulfonium salt, a bisazo onium salt, an ammonium salt, an iodonium salt, a thioxanthone onium salt, a selenium onium salt, and an iron complex salt, and the anion moiety is a chloride ion (Cl-), a bromide ion (Br-), and a tetrafluoroborate (BF-)4-) hexafluorophosphate (PF)6-) hexafluoroantimonate (SbF)6-), hexafluoroarsenate (AsF)6-) hexachloroantimonate (SbCl)6-) and the like.
Commercially available photo-acid generators include, for example, CD1010 (Sartomer Co.), WPAG-281, WPAG-336, WPAG-367, WPI-113 (Wako pure chemical industries, Ltd., supra), IPTX, CI-5102, CI-2855 (Kodak Co., Ltd., Japan), UVI-6970, UVI-6974 (Union Carbide Corporation, supra), Rhodoxsil Photonitiator 2074(Rhone-Poulenc Co., Ltd.), IRGACURE 250(BASF Japan Ltd.), SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (ADEKA Corporation, supra), CPI-100P, CPI-101A, CPI-210S, CPI-300PG (San-Aptd.) (Sant Ltd.).
The thermal acid generator is a compound which generates an acid by heat, and examples thereof include complex ions such as sulfonium salt, bisazo onium salt, ammonium salt, phosphonium salt, iodonium salt and sulfoxonium salt as a cation portion and chloride ions (Cl) as an anion portion-) Bromine ion (Br)-) Etc. in combinationThe produced onium salt type acid generator.
As the thermal acid generator, there can be used, for example, CI-2624, CI-2855 (described above by Kazada Co., Ltd.), SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-145, SI-150, SI-160, SI-180L (described above by Sanxin chemical Co., Ltd.), TA-90, TA-100, TA-120, TA-160, IK-1, IK-2 (described above by San-Apro Ltd.), Adeka Opton CP-66, Adeka Opton CP-77 (described above by ADEKA Co., Ltd.), and the like.
The content of the photo-acid generator or the thermal acid generator is preferably in the range of, for example, 0.01 to 0.1 parts by mass per 100 parts by mass of the fluorine-containing resin.
The composition comprising the fluorine-containing resin of the present invention may further comprise a base monomer.
Examples of the base monomer include:
3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, bis- (3, 4-epoxycyclohexyl) adipate, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexanone-methyl-dioxane, bis- (2, 3-epoxycyclopentyl) ether, 2-ethylhexyl diglycol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, compounds having an epoxy group such as propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like;
compounds having an oxetane ring such as 3, 3-dimethyloxetane, 2-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane and the like;
lactone compounds such as beta-propiolactone, gamma-butyrolactone, epsilon-caprolactone and sigma-valerolactone;
cyclic carbonate compounds such as ethylene carbonate, propylene carbonate, and butylene carbonate;
polyglycidyl ether compounds of aliphatic polyhydric alcohols having 4 or more hydroxyl groups in 1 molecule, such as sorbitol polyglycidyl ethers (DENACOL EX-611, DENACOL EX-612, DENACOL EX-614B, DENACOL EX-622: all manufactured by Nagase ChemeteX Corporation), pentaerythritol polyglycidyl ether (DENACOL EX-411: manufactured by Nagase ChemeteX Corporation), and the like;
a polyglycidyl ether compound of a polyether polyol obtained by adding one or two or more alkylene oxides to an aliphatic polyol having 4 or more hydroxyl groups in 1 molecule;
a polyglycidyl ether compound of a polyether alcohol obtained by adding alkylene oxide to a phenol having 4 or more hydroxyl groups in 1 molecule;
compounds having one or two or more epoxy groups or oxetanyl groups, such as aliphatic polycarboxylic acid derivatives having 4 or more carboxyl groups in 1 molecule, e.g., butane tetracarboxylic acid tetra (3, 4-epoxycyclohexylmethyl) modified with e-caprolactone (Epolide GT-401: manufactured by Daicel Corporation) or ethane tetracarboxylic acid tetra (3, 4-epoxycyclohexylmethyl) ester;
a condensation reaction product of 3-ethyl-3-oxetanemethanol and a condensation product of a silanetetraol (ARONE OXETANE OXT-191 (average condensation degree of the condensation product of silanetetraol 5): Toyo chemical Co., Ltd.);
and compounds having one or more epoxy groups or oxetane groups, which are derivatives of silanetriol or silantetraol or polycondensates thereof.
The composition containing the fluorine-containing resin of the present invention preferably contains an organic solvent, because the viscosity of the composition can be adjusted and the thickness of the resulting coating film can be adjusted.
Examples of the organic solvent 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 organic solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The composition containing the fluorine-containing resin of the present invention may contain, within a range not impairing the effects of the present invention: various particles such as PTFE (polytetrafluoroethylene) particles, polyethylene particles, polypropylene particles, carbon particles, titanium oxide particles, aluminum oxide particles, copper particles, and silica particles; polymerization initiators, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, mold release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, surfactants, and the like.
[ cured product ]
Since the cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention is excellent in stain resistance and sliding properties, it is possible to impart stain resistance and sliding properties to the surface of an article by applying the composition to the surface of the article and curing the composition, and it is possible to form an article which is less likely to be stained or scratched.
The cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention is excellent in antifouling property and sliding property, and therefore, can be suitably used as a protective film (hard coat layer) or a resist material for displays such as liquid crystal displays and OLED displays.
As the use of microwaves having extremely short wavelengths is advanced due to the advancement of wireless communication systems, the necessity of replacing the housing of a smartphone with a housing made of metal or plastic is also increased in order to prevent the attenuation of the microwaves, but a plastic hard coat layer formed of a cured product of the composition of the present invention can impart excellent antifouling properties and sliding properties (scratch resistance) to the surface of the housing of a smartphone made of plastic.
When a protective film for a display is formed from a cured product obtained by curing the active energy ray-curable resin composition of the present invention or the thermosetting resin composition of the present invention, the thickness of the protective film may be, for example, 1 to 200 μm, preferably 1 to 100 μm, and more preferably 1 to 70 μm. Since cationic polymerizable curing is free of curing inhibition by oxygen and less in curing shrinkage than radical polymerizable curing, the film thickness can be increased to increase the hardness of the film.
Examples
The present invention will be specifically described below with reference to examples and comparative examples.
The IR spectrum of the obtained fluorine-containing polymerizable resin,13The measurement conditions of C-NMR spectrum and GPC are as follows.
[ IR Spectrometry conditions ]
The resin solution obtained in the example was measured by the KBr method using the following apparatus.
The device comprises the following steps: "FT/IR-6100" manufactured by Nippon spectral Co., Ltd "
[13C-NMR spectroscopic measurement conditions]
The device comprises the following steps: JNM-ECA500 manufactured by Japan electronic Co., Ltd "
Solvent: acetone-d6
[ GPC measurement conditions ]
A measuring device: HLC-8220GPC, manufactured by Tosoh corporation "
Column: "HHR-H" protective column manufactured by Tosoh corporation (6.0 mmI.D.. times.4 cm)
+ Tosoh corporation "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm)
+ Tosoh corporation "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm)
+ Tosoh corporation "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm)
+ Tosoh corporation "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm)
A detector: evaporative light scattering Detector (ELSD 2000, manufactured by Alltech Japan K.K.)
Data processing: "GPC-8020 model II data analysis version 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 solid content) was filtered through a microfilter (5. mu.l).
Standard sample: the following monodisperse polystyrene having a known molecular weight was used according to the manual for measurement of "GPC-8020 model II data analysis version 4.30" described above.
(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 "
Synthesis example 1
Into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (b-1), 20 parts by mass of diisopropyl ether as a solvent, 0.02 part by mass of p-methoxyphenol as a polymerization inhibitor and 3.1 parts by mass of triethylamine as a neutralizer were charged, and 2.7 parts by mass of acryloyl chloride was added dropwise over 1 hour while keeping the flask at 10 ℃ under stirring under an air stream.
After the completion of the dropwise addition, the mixture was stirred at 10 ℃ for 1 hour, heated and stirred at 30 ℃ for 1 hour, then heated to 50 ℃ and stirred for 10 hours, thereby carrying out the reaction. The obtained reaction solution was confirmed to have disappeared methacryloyl chloride by gas chromatography measurement.
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms was 46 on average.
The number average molecular weight based on GPC was 1500. )
Subsequently, 40 parts by mass of diisopropyl ether as a solvent and 80 parts by mass of ion-exchanged water were added to the reaction mixture, and the mixture was stirred, allowed to stand, and then the separated water layer was removed, followed by repeating washing 3 times. To the reaction solution after washing, 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 reaction solution, and the dehydrating agent was filtered off.
Then, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (B-1) (hereinafter, referred to as "compound (B-1)").
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms was 46 on average. )
Synthesis example 2
Into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the formula (b-1), 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 neutralizer 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 flask at 10 ℃.
After the completion of the dropwise addition, the mixture was stirred at 10 ℃ for 1 hour, heated and stirred at 30 ℃ for 1 hour, then heated to 50 ℃ and stirred for 10 hours, thereby carrying out the reaction. The obtained reaction solution was confirmed to have disappeared methacryloyl chloride by gas chromatography measurement.
Subsequently, 70 parts by mass of diisopropyl ether as a solvent and 80 parts by mass of ion-exchanged water were added to the reaction mixture, and the mixture was stirred, allowed to stand, and then the separated water layer was removed, followed by repeating washing 3 times. To the reaction solution after washing, 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 reaction solution, and the dehydrating agent was filtered off.
Then, the solvent was distilled off under reduced pressure to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (B-2) (hereinafter, referred to as "compound (B-2)").
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms was 46 on average. )
Synthesis example 3
Into a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, 200 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the formula (b-1), 123.4 parts by mass of p-chloromethyl styrene, 0.06 part by mass of p-methoxyphenol, 32.3 parts by mass of a50 mass% aqueous solution of benzyltriethylammonium chloride and 1.35 parts by mass of potassium iodide were charged, and stirring was started under an air stream, and 9.2 parts by mass of a 49 mass% aqueous solution of sodium hydroxide was added dropwise over 2 hours while keeping the temperature in the flask at 45 ℃.
After completion of the dropwise addition, the mixture was stirred at 60 ℃ for 1 hour, 37.1 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 4 hours, and then the reaction was further carried out for 15 hours.
After the reaction, the salt produced was filtered off, the filtrate was allowed to stand, and the supernatant was removed. Further, 500mL of water was added thereto, and washing was performed 3 times. After washing with water, the mixture was further washed 3 times with 500mL of methanol. To the reaction solution after washing, 0.06 part by mass of p-methoxyphenol and 0.2 part by mass of 3, 5-di-t-butyl-4-hydroxytoluene (hereinafter, abbreviated as "BHT") as polymerization inhibitors were added, and while concentrating the mixture in a water bath set at 45 ℃ and a rotary evaporator, methanol was distilled off to obtain a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (B-3) and styrene groups located at both ends thereof (hereinafter, abbreviated as "compound (B-3)").
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and the number of fluorine atoms was 46 on average. )
Synthesis example 4
A reaction was carried out in the same manner as in Synthesis example 3 except that a compound represented by the following formula (B-2) was used in place of the above formula (B-1), thereby obtaining a compound represented by the following formula (B-4).
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 19 perfluoromethylene groups, an average of 19 perfluoroethylene groups, and an average number of fluorine atoms of 114.
The number average molecular weight based on GPC was 4000. )
(in the formula, wherein,
each of a plurality of X is independently a perfluoromethylene group or a perfluoroethylene group, present in every 1 molecule: an average of 19 perfluoromethylene groups, an average of 19 perfluoroethylene groups, and an average number of fluorine atoms of 114. )
[ production of fluororesin ]
Synthesis example 1
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was charged, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Subsequently, 3 kinds of dropping liquids, i.e., a liquid containing 36 parts by mass of the compound having a poly (perfluoroalkylene ether) chain (B-1) prepared in Synthesis example 1, a monomer solution containing 144 parts by mass of glycidyl methacrylate and 327 parts by mass of butyl acetate as a solvent, and an initiator solution containing 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent were attached to respective dropping apparatuses, and were dropped over 2 hours while maintaining the flask interior at 105 ℃.
After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction mixture to dilute the mixture, and the mixture was filtered to obtain a 20 mass% butyl acetate solution containing a fluorine-containing resin having a cationically polymerizable group (P1).
The molecular weight of the resulting fluororesin (P1) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2700 and the weight average molecular weight was 6500.
The structure of the resulting fluorine-containing resin (P1) was determined from the sum of the IR spectrum and the13C-NMR spectrum was confirmed. The results of the IR spectra are shown in FIG. 1 for13The results of the C-NMR spectrum are shown in FIG. 2.
Synthesis example 2
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was charged, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Next, 36 parts by mass of the compound having a poly (perfluoroalkylene ether) chain (B-2) prepared in synthesis example 1,3 kinds of dropping solutions of a monomer solution in which 72 parts by mass of glycidyl methacrylate, 72 parts by mass of 2-hydroxypropyl methacrylate, and 327 parts by mass of butyl acetate as a solvent were mixed, and an initiator solution in which 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent were mixed were attached to respective dropping apparatuses, and the dropping solution was dropped over 2 hours while maintaining the flask interior at 105 ℃.
After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction mixture to dilute the mixture, and the mixture was filtered to obtain a 20 mass% butyl acetate solution containing a fluorine-containing resin having a cationically polymerizable group (P2).
The molecular weight of the resulting fluororesin (P2) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 1400 and the weight average molecular weight was 4000.
Synthesis example 3
A fluororesin (P3) having a cationically polymerizable group was obtained by polymerizing the monomer solution of formula (C-1) in the same manner as in Synthesis example 2 except that a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain was used in place of 2-hydroxypropyl methacrylate as a hydroxyl group-containing monomer, and a monomer solution prepared by mixing 126 parts by mass of glycidyl methacrylate, 18 parts by mass of a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain of formula (C-1) and 327 parts by mass of butyl acetate as a solvent was used as the monomer solution.
The molecular weight of the resulting fluororesin (P3) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2800 and the weight average molecular weight was 8000.
(wherein n is 65 on average.)
Synthesis example 4
A fluorine-containing resin (P4) having a cationically polymerizable group was obtained by polymerizing the monomer in the same manner as in Synthesis example 2, except that polypropylene glycol monomethacrylate ("Blemmer PP-1000" manufactured by Nichikoku corporation, hydroxyl value 382, number of repeating units of propylene oxide unit: average 6) as a monomer having a hydroxyl group and a polyoxyalkylene chain was used in place of 2-hydroxypropyl methacrylate as a hydroxyl monomer.
The molecular weight of the resulting fluororesin (P4) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2200 and the weight average molecular weight was 5300.
Synthesis example 5
Polymerization was carried out in the same manner as in Synthesis example 2 except that the compound (B-3) prepared in Synthesis example 3 was used in place of the compound (B-1) and 2-methyl-2-adamantyl methacrylate as an adamantyl monomer was used in place of 2-hydroxypropyl methacrylate as a hydroxyl monomer to obtain a fluorine-containing resin (P5) having a cationically polymerizable group.
The molecular weight of the resulting fluororesin (P5) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 1500 and the weight average molecular weight was 4400.
Synthesis example 6
Polymerization was carried out in the same manner as in synthesis example 1 except for using the compound (B-4) prepared in synthesis example 4 in place of the compound (B-1) and using 1, 3-bis (trifluoromethyl) benzene in place of butyl acetate as a solvent, thereby obtaining a fluorine-containing resin (P6) having a cationically polymerizable group.
The molecular weight of the resulting fluororesin (P6) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 1600 and the weight average molecular weight was 10000.
Synthesis of comparative example 1
In a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, 210.5 parts by mass of methyl isobutyl ketone as a solvent was charged, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Then, 42.1 parts by mass of the compound having a poly (perfluoroalkylene ether) chain (B-1) obtained in Synthesis example 1, 168.4 parts by mass of a monomer solution in which polypropylene glycol monomethacrylate ("Blemmer PP-1000" manufactured by Nichikoku K.K., hydroxyl value 382, number of repeating units of propylene oxide units: average 6) and 109.3 parts by mass of methyl isobutyl ketone as a solvent were mixed, and 3 dropping solutions in which 31.6 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 71.2 parts by mass of methyl isobutyl ketone as a solvent were mixed were each attached to each dropping device, and dropped over 2 hours while maintaining the flask interior at 105 ℃.
After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours and cooled to room temperature. To the reaction mixture, methyl isobutyl ketone was added for dilution, followed by filtration to obtain a methyl isobutyl ketone solution containing 20 mass% of a fluorine-containing resin (Q1).
The molecular weight of the fluorine-containing resin (Q1) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2400 and the weight average molecular weight was 5700.
Synthesis comparative example 2
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 128.3 parts by mass of methyl isobutyl ketone as a solvent was charged, and the temperature was raised to 90 ℃ while stirring under a nitrogen gas flow. Subsequently, 2 kinds of dropping solutions of a monomer solution in which 30.4 parts by mass of 2- (perfluorohexyl) ethyl acrylate, 65.8 parts by mass of glycidyl methacrylate, and 76.9 parts by mass of methyl isobutyl ketone as a solvent were mixed, and an initiator solution in which 5.8 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 19.2 parts by mass of methyl isobutyl ketone as a solvent were mixed were attached to each dropping device, and the dropping solution was dropped over 2 hours while maintaining the flask interior at 90 ℃.
After the completion of the dropwise addition, the mixture was stirred at 90 ℃ for 10 hours and cooled to room temperature. To the reaction mixture, methyl isobutyl ketone was added for dilution, followed by filtration to obtain a methyl isobutyl ketone solution containing 20 mass% of a fluorine-containing resin (Q2).
The molecular weight of the fluorine-containing resin (Q2) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2300 and the weight average molecular weight was 5000.
Comparative Synthesis example 3
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 180 parts by mass of butyl acetate as a solvent was charged, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Next, 3 kinds of dropping solutions of a monomer solution in which 36 parts by mass of a single terminal methacryloyl group-containing monomer having a polydimethylsiloxane chain represented by the above formula (C-1) was mixed with 144 parts by mass of glycidyl methacrylate and 327 parts by mass of butyl acetate as a solvent, and an initiator solution in which 27 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 33 parts by mass of butyl acetate as a solvent were mixed were attached to respective dropping apparatuses, and the dropping solution was dropped over 2 hours while maintaining the flask interior at 105 ℃.
After the completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours and cooled to room temperature. Butyl acetate was added to the reaction mixture for dilution, followed by filtration to obtain a butyl acetate solution containing 20 mass% of the fluorine-containing resin (Q3).
The molecular weight of the fluorine-containing resin (Q3) was measured by GPC (molecular weight in terms of polystyrene), and as a result, the number average molecular weight was 2300 and the weight average molecular weight was 6000.
[ preparation and evaluation of resin composition ]
Example 1
40 parts by mass of pentaerythritol polyglycidyl ether ("DENACOL EX-411" manufactured by NAGASE CHEMTEX CORPORATION), 2 parts by mass of a butyl acetate solution containing 20% by mass of a fluorine-containing resin (P1) prepared in Synthesis example 1, 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (CPI-210S manufactured by San-Apro Ltd.) as a photoacid generator, 24 parts by mass of toluene as a solvent, 12 parts by mass of 2-propanol, 12 parts by mass of ethyl acetate, and 12 parts by mass of propylene glycol monomethyl ether were mixed and dissolved to obtain a resin composition.
The obtained resin composition was applied to a 188 μm thick PET film using a bar coater No.13, and then dried at 60 ℃ for 5 minutes using a dryer to volatilize the solvent. Curing with an ultraviolet curing apparatus (under nitrogen atmosphere, using a high pressure mercury lamp, ultraviolet irradiation dose 25kJ/m2) The coating film on the PET film was cured to form a hard coat layer having a thickness of 10 μm on the PET film.
The following evaluation was performed on the obtained PET film having a hard coat layer. The results are shown in Table 1.
(evaluation of Water repellency)
A droplet of ultrapure water (3. mu.L) was dropped on the hard coat layer using a contact angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku Co., Ltd.) to measure the contact angle of the droplet. The contact angle was measured 5 times, and the average value of 5 times was taken as the contact angle of the hard coat layer surface.
(oil repellency evaluation)
A3. mu.L drop of n-decane was dropped on the hard coat layer using a contact angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku Co., Ltd.), and the contact angle of the drop was measured. The contact angle was measured 5 times, and the average value of 5 times was taken as the contact angle of the hard coat layer surface.
(evaluation of antifouling Property)
The surface of the hard coat layer was marked with a felt pen (Magic ink large blue, manufactured by temple, western chemical industries) to visually observe the adhesion state of the ink on the surface of the hard coat layer, and the adhesion of the smudge-proof substance to the hard coat layer was evaluated in accordance with the following criteria.
Very good: ink spherical repulsion
O: the ink did not resist spherical repulsion and linear repulsion occurred (line width was less than 50% of the nib width)
And (delta): the ink did not form spherical repulsion and linear repulsion occurred (line width was 50% or more and less than 100% of the pen tip width)
X: the ink being applied cleanly to the surface without repelling it at all
After the above-described anti-stain adhesion test, the adhered ink tissue was wiped off, and then the line was drawn again at the same position on the surface of the hard coat layer with a felt pen, and the adhered ink tissue was wiped off, and this operation was repeated. The number of times of wiping of contaminants until the ink was not repelled on the surface of the hard coat layer was evaluated.
Note that, when this operation is performed 10 times at maximum, and the hard coat layer also repels ink after wiping the adhered ink 10 times, the evaluation result is denoted as "> 10".
(evaluation of slidability)
Using a dynamic friction coefficient measuring apparatus ("Tribogear TYPE: 38", manufactured by Xindong scientific Co., Ltd.) to
Ball indenter, load 100g, traveling speedThe coefficient of dynamic friction of the surface of the hard coat layer was measured at a degree of 300 mm/min. The measurement was performed 3 times, and the average of the 3 times was taken as the coefficient of dynamic friction of the hard coat surface.
Examples 2 to 6 and comparative examples 1 to 4
A resin composition was prepared and evaluated in the same manner as in example 1, except that the fluorine-containing resin shown in table 1 was used instead of the fluororesin (P1). The results are shown in Table 1.
In comparative example 4, no fluorine-containing resin was used.
[ Table 1]
Example 7
40 parts by mass of pentaerythritol polyglycidyl ether ("DENACOL EX-411" manufactured by NAGASE CHEMTEX CORPORATION), 2 parts by mass of a butyl acetate solution containing 20% by mass of a fluorine-containing resin (P1) prepared in Synthesis example 1, 2 parts by mass of an aromatic sulfonium antimony hexafluoride salt (SAN-AID SI-60L manufactured by shin-Kogyo Co., Ltd.) as a thermal acid generator, 24 parts by mass of toluene as a solvent, 12 parts by mass of 2-propanol, 12 parts by mass of ethyl acetate, and 12 parts by mass of propylene glycol monomethyl ether were mixed and dissolved to obtain a resin composition.
The obtained resin composition was applied to a glass plate having a thickness of 2mm by using a bar coater No.13, and then dried at 60 ℃ for 5 minutes by a dryer to volatilize the solvent. The coating film on the glass plate was cured by heating at 90 ℃ for 90 minutes to form a hard coat layer having a thickness of 7 μm on the glass plate.
The glass plate having the hard coat layer obtained was evaluated in the same manner as in example 1. As a result, the water contact angle was 109 °, the dodecane contact angle was 59 °, and the dynamic friction coefficient was 0.16. From the results, it was found that the same antifouling property and sliding property can be obtained even when a thermal acid generator is used instead of the photoacid generator.
Claims (14)
1. A fluorine-containing resin which is a copolymer having, as polymerization components, a compound A having a functional group capable of cationic polymerization and a radically polymerizable unsaturated group, and a compound B having a poly (perfluoroalkylene ether) chain and a radically polymerizable unsaturated group.
2. The fluorine-containing resin according to claim 1, wherein the radical polymerizable unsaturated group is a vinyl group.
3. The fluorine-containing resin according to claim 1 or2, wherein the compound a is a (meth) acrylate compound having a functional group capable of cationic polymerization and/or a styrene compound having a functional group capable of cationic polymerization.
4. The fluorine-containing resin according to any one of claims 1 to 3, wherein the compound A is a (meth) acrylate compound having a functional group capable of cationic polymerization.
5. The fluorine-containing resin according to any one of claims 1 to 4, wherein the functional group capable of cationic polymerization is a cyclic ether group.
6. The fluorine-containing resin according to any one of claims 1 to 5, wherein the functional group capable of cationic polymerization is an epoxy group or an oxetanyl group.
7. The fluorine-containing resin according to any one of claims 1 to 6, wherein the compound B is a compound having a poly (perfluoroalkylene ether) chain and having a (meth) acryloyl group and/or a styryl group.
8. The fluorine-containing resin according to any one of claims 1 to 7, wherein a compound C having 1 or more kinds of functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain, and a radical polymerizable unsaturated group is contained as the polymerization component.
9. The fluorine-containing resin according to claim 1, which comprises a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1),
in the formulae (A1) and (B1),
Ra1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Ra2is a linking group having a valence of 2,
y is a group containing a cyclic ether structure,
each of a plurality of X is independently a perfluoroalkylene group,
a and b are each independently the number of repeating units.
10. The fluorine-containing resin according to claim 9, which has a structural unit represented by the following formula (C1),
in the formula (C1), the metal oxide,
Rc1is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Rc2is a linking group having a valence of 2,
z is a group containing 1 or more functional groups selected from the group consisting of a hydroxyl group, an alkyl group, an alicyclic hydrocarbon group, a group containing a polyoxyalkylene chain, and a group containing a silicone chain,
c is the number of repeating units.
11. An active energy ray-curable resin composition comprising: the fluorine-containing resin and the photoacid generator according to any one of claims 1 to 10.
12. A heat-curable resin composition comprising: the fluorine-containing resin according to any one of claims 1 to 10, and a thermal acid generator.
13. A cured product of the composition according to claim 11 or 12.
14. The cured product according to claim 13, which is a protective film for a display, a plastic hard coat layer, or a resist material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-106117 | 2019-06-06 | ||
| JP2019106117 | 2019-06-06 | ||
| PCT/JP2020/021521 WO2020246409A1 (en) | 2019-06-06 | 2020-06-01 | Fluororesin, active energy ray-curable composition, thermosetting composition, and cured products of compositions |
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| CN113906078A true CN113906078A (en) | 2022-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080040897.4A Pending CN113906078A (en) | 2019-06-06 | 2020-06-01 | Fluorine-containing resin, active energy ray-curable composition, heat-curable composition, and cured product of the composition |
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| Country | Link |
|---|---|
| JP (1) | JP6989055B2 (en) |
| KR (1) | KR20210151878A (en) |
| CN (1) | CN113906078A (en) |
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| WO (1) | WO2020246409A1 (en) |
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| WO2013024764A1 (en) * | 2011-08-12 | 2013-02-21 | ダイキン工業株式会社 | Liquid-repellent curable ink composition |
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| WO2015025835A1 (en) * | 2013-08-23 | 2015-02-26 | Dic株式会社 | Multilayer film, optical element, polarizing plate and image display device |
| JP2015120861A (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Surfactant composition, coating composition, and resist composition |
| CN110121515A (en) * | 2016-12-26 | 2019-08-13 | Dic株式会社 | Fluorine-containing active energy ray curable resin, surfactant, active energy ray-curable resin composition and cured coating film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5255104B2 (en) | 2011-10-03 | 2013-08-07 | Ｔｈｋ株式会社 | Roller retainer for guide device and guide device using the same |
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2020
- 2020-06-01 JP JP2021524827A patent/JP6989055B2/en active Active
- 2020-06-01 CN CN202080040897.4A patent/CN113906078A/en active Pending
- 2020-06-01 KR KR1020217036277A patent/KR20210151878A/en not_active Application Discontinuation
- 2020-06-01 WO PCT/JP2020/021521 patent/WO2020246409A1/en active Application Filing
- 2020-06-04 TW TW109118756A patent/TW202112855A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885815A (en) * | 2009-05-14 | 2010-11-17 | Dic株式会社 | Fluorine-containing polymerizable polymer and active energy ray-curable composition using the same |
| JP2011074248A (en) * | 2009-09-30 | 2011-04-14 | Dic Corp | Fluorine-containing curable resin, active energy beam curable type coating composition, and cured article of the same |
| JP2011184517A (en) * | 2010-03-05 | 2011-09-22 | Daikin Industries Ltd | Liquid-repellent resist composition |
| CN102532432A (en) * | 2010-09-30 | 2012-07-04 | Dic株式会社 | Fluorine-containing polymerizable resin, active energy ray-curable composition using the same and cured product thereof |
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| WO2013024764A1 (en) * | 2011-08-12 | 2013-02-21 | ダイキン工業株式会社 | Liquid-repellent curable ink composition |
| JP2013095776A (en) * | 2011-10-28 | 2013-05-20 | Dic Corp | Fluorine-containing polymerizable resin, active-energy ray-curable composition including the same, and cured product obtained therefrom |
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| JP2015120861A (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Surfactant composition, coating composition, and resist composition |
| CN110121515A (en) * | 2016-12-26 | 2019-08-13 | Dic株式会社 | Fluorine-containing active energy ray curable resin, surfactant, active energy ray-curable resin composition and cured coating film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210151878A (en) | 2021-12-14 |
| TW202112855A (en) | 2021-04-01 |
| WO2020246409A1 (en) | 2020-12-10 |
| JPWO2020246409A1 (en) | 2021-10-21 |
| JP6989055B2 (en) | 2022-01-05 |
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