WO2019142567A1 - Fluorine-containing active energy ray-curable composition and article - Google Patents
Fluorine-containing active energy ray-curable composition and article Download PDFInfo
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- WO2019142567A1 WO2019142567A1 PCT/JP2018/046108 JP2018046108W WO2019142567A1 WO 2019142567 A1 WO2019142567 A1 WO 2019142567A1 JP 2018046108 W JP2018046108 W JP 2018046108W WO 2019142567 A1 WO2019142567 A1 WO 2019142567A1
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- Prior art keywords
- fluorine
- meth
- group
- acrylic
- active energy
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 163
- 239000011737 fluorine Substances 0.000 title claims abstract description 159
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 150000001875 compounds Chemical class 0.000 claims abstract description 83
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 81
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 125000005647 linker group Chemical group 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 13
- -1 siloxane structure Chemical group 0.000 claims description 109
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 230000002940 repellent Effects 0.000 claims description 4
- 239000005871 repellent Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 3
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
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- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 4
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- 150000002222 fluorine compounds Chemical class 0.000 description 4
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
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- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
Definitions
- the present invention relates to a fluorine-containing active energy ray curable composition which is cured by ultraviolet light, electron beam or the like to impart excellent soil resistance to the surface, and an article having a cured product layer of the composition on the surface of a substrate.
- hard coating treatment is widely used generally as a means for protecting the surface of a resin molded product or the like. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded body and make it hard to be damaged.
- a material which comprises a hard-coat layer curable compositions by active energy rays, such as a thermosetting resin and ultraviolet-ray or electron beam curable resin, are used abundantly.
- Patent Document 1 Japanese Patent Application Laid-Open No. 6-211945 shows the production of a hard coat layer to which an antifouling property is imparted by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition. ing.
- the inventor of the present invention is promoting various developments as a fluorine compound capable of imparting antifouling properties to such a curable resin composition.
- JP-A-2010-53114 Patent Document 2
- JP-A-2010 A photocurable fluorine compound is proposed as disclosed in JP-A-138112 (Patent Document 3)
- JP-A-2010-285501 Patent Document 4
- the present invention has been made in view of the above circumstances, and provides a cured film capable of imparting stain resistance, in particular, excellent water and oil repellency, fingerprint adhesion prevention, fingerprint wiping and abrasion durability.
- An object of the present invention is to provide an active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.
- a cyclopolysiloxane structure is bonded to both ends of a perfluoropolyether group via a divalent linking group, to the above-mentioned cyclopolysiloxane structure.
- Fluorine-containing active energy ray curing comprising a fluorine compound having a structure in which a hydroxyl group through a divalent linking group and a (meth) acrylic group through a divalent linking group to the cyclopolysiloxane structure are respectively bonded
- the present invention is based on the finding that the adhesive composition, among various properties collectively referred to as anti-staining properties, is notable for fingerprint adhesion adhesion, fingerprint wiping properties, and wear resistance as a hard coat. It came to
- the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.
- a cyclopolysiloxane structure is bonded to both ends of a divalent perfluoropolyether group via a divalent linking group, and a hydroxy group bonded to the cyclopolysiloxane structure via a divalent linking group; It is characterized by containing a fluorine-containing compound (A) having a (meth) acrylic group bonded to a siloxane structure via a divalent linking group in any one or both of cyclopolysiloxane structures at both ends, respectively. Fluorine-containing active energy ray curable composition.
- the fluorine-containing compound (A) the molar ratio of (meth) acrylic group to hydroxyl group contained in the fluorine-containing compound (A) [(meth) acrylic group (mol) / hydroxyl group (mol)] is, as an average value, 0.
- a cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group via a divalent linking group, and a (meth) acryl bonded to the cyclopolysiloxane structure via a divalent linking group
- the fluorine-containing active energy ray curable composition according to 1 or 2 which contains a fluorine-containing compound (B) having a group and a structure having no hydroxyl group at both ends. 4.
- the fluorine-containing compound (A) is represented by the following general formula (1) X 1 -Z-Rf-Z-X 1 (1) [Wherein, R f represents the following formulas (2) to (5) (Wherein Y independently of one another is F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, provided that m + n is 2 to 200, and s is It is an integer of 0 to 6.
- Each repeating unit may be randomly combined.
- j is independently an integer of 1 to 3 and k is an integer of 1 to 200
- Y and j are the same as above, and p and q are each an integer of 0 to 200, provided that p + q is 2 to 200.
- Each repeating unit may be randomly bonded.
- t is an integer of 1 to 100
- a divalent perfluoropolyether group having a molecular weight of 500 ⁇ 30,000, X 1, independently of one another, the following formula (6)
- Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and includes a cyclic structure or a branched structure on the way] It may be the same or different.
- R 1 is the following formula (7) (Wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. , C is 1 or 2.) And a and b each represent an integer of 0 to 6, provided that a + b is 2 to 11. Each repeating unit may be randomly combined. ] And the sum of a and b in X 1 present in the molecule is 2 or more. Z is the following formula It is a bivalent organic group shown by either of. ] The fluorine-containing active energy ray curable composition according to any one of 1 to 4, which is represented by 6.
- the fluorine-containing active energy ray-curable composition according to any one of 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compound (A) or (B). 7.
- Active energy ray curable composition 7.
- Composition 9.
- the fluorine-containing active energy ray curable composition of the present invention is coated and cured on the surface of a substrate to obtain water repellency, oil repellency, stain resistance, slipperiness, low visibility of attached fingerprints, fingerprint wipes , Wear resistance can be provided.
- the fluorine-containing active energy ray-curable composition of the present invention has three or more valences (usually 3 to 12, preferably 3 to 8) via the divalent linking group at both ends of the divalent perfluoropolyether group. (More preferably trivalent to hexavalent) cyclopolysiloxane structure is bonded, and the cyclopolysiloxane structure has a hydroxyl group via a divalent linking group and a cyclopolysiloxane structure having a divalent linking group.
- the effect of making the fingerprint less noticeable by having the above-mentioned hydroxyl group is obtained, the curability is obtained by having the above-mentioned (meth) acrylic group, and the fluorine component showing antifouling property on the surface The effect of fixing is obtained.
- the ratio of the (meth) acrylic group to the hydroxyl group contained in the fluorine-containing compound (A) is particularly contained in the fluorine-containing compound (A) as an average value of the fluorine-containing compound (A) contained in the composition
- the molar ratio of (meth) acrylic group to hydroxyl group [(meth) acrylic group (mole) / hydroxyl group (mole)] is preferably 0.1 or more and 25 or less, and more preferably 0.15 or more and 19 or less
- the number is preferably 0.2 or more and 10 or less, more preferably 0.2 or more and 5 or less, and most preferably 0.2 or more and 2.5 or less.
- this molar ratio becomes larger than this, the effect of the hydroxyl group contained in the fluorine-containing compound (A) becomes small, and the difference in characteristics after curing with the fluorine-containing compound not containing a hydroxyl group becomes unclear.
- this molar ratio is smaller than this, the content of molecules having no (meth) acrylic group in the fluorine-containing compound (A) is increased, the solubility with a non-fluorinated acrylic compound is decreased, and coating is performed as a uniform plane. Processing may be difficult or curing failure may occur.
- Rf is a group of repeating units -CF 2 O- whose main structure is particularly shown below. -CF 2 CF 2 O- -CF 2 CF 2 CF 2 O- -CF (CF 3) CF 2 O- -CF 2 CF 2 CF 2 O- What consists of any one or several combination of these is preferable.
- a bonding portion to Z an initiator fragment at the time of construction of the main chain structure and a by-product structure can be mentioned.
- Rf is a divalent perfluoropolyether group having a molecular weight of 500 to 30,000, which is selected from among groups represented by the following formulas (2) to (5).
- Y independently of one another is F or CF 3
- r is an integer of 2 to 6
- m and n are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably 4 to It is an integer of 50, provided that m + n is 2 to 200, preferably 8 to 100, and s is an integer of 0 to 6.
- Each repeating unit may be randomly combined.)
- j is independently an integer of 1 to 3 and k is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 50).
- p and q are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, provided that p + q is 2 to 200
- t is an integer of 1 to 100, preferably an integer of 2 to 60, more preferably an integer of 4 to 40).
- Rf preferably has a molecular weight of 500 to 30,000, and particularly 1,500 to 10,000. If the molecular weight is too small, the compatibility with the non-fluorinated component in the composition may be too high, and the component (A) may not collect on the surface of the cured product (coating film) after coating. The compatibility with the non-fluorinated component in the product is too low, causing turbidity at the time of blending, generation of precipitation, increase in haze of cured product (coating film) after coating, loss of coating film, etc. May occur.
- the molecular weight can be determined, for example, as a polymethyl methacrylate equivalent value in gel permeation chromatography (GPC) analysis using various fluorine-containing solvents as a developing solvent, and usually, it is suitable to obtain as a number average molecular weight ,the same.).
- GPC gel permeation chromatography
- Z is a divalent organic group represented by any of the following formulas.
- X 1 is a group represented by the following Formula (6) independently of each other.
- Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and includes a cyclic structure or a branched structure on the way] It may be the same or different.
- R 1 is the following formula (7) (Wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms.
- Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and preferably 3 to 20 carbon atoms 20, particularly a divalent hydrocarbon group which may contain a bond selected from an ether bond having 3 to 12 carbon atoms, an ester bond, an amide bond and a urethane bond, and may contain a cyclic structure or a branched structure on the way They may be the same or different.
- R 1 is a (meth) acrylic group-containing group represented by the following Formula (7).
- R 2 is independently a hydrogen atom or a methyl group
- R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms.
- C is 1 or 2.
- R 2 is independently a hydrogen atom or a methyl group.
- R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms, particularly preferably 2 to 8 carbon atoms.
- a trivalent or more (usually a trivalent to 12 divalent, preferably a trivalent to octavalent, more preferably 3 to be linked to both ends of a divalent perfluoropolyether group A hydroxyl group bonded to a cyclopolysiloxane structure of ⁇ 6 via a divalent linking group and a (meth) acrylic group bonded to the cyclopolysiloxane structure via a divalent linking group are In one or both of the cyclopolysiloxane structures, one or more, preferably 1 to 6, more preferably 2 to 4, each independently having one or more, and in the above-mentioned formula (1), in the molecule
- the total of a corresponding to the total number of (meth) acrylic groups (that is, the total number of (meth) acrylic groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to
- the value of a + b is usually independently 2 to 11, preferably 2 to 7, more preferably 2 to 5, and as described above
- the sum of (a + b) values corresponding to the sum of the number of (meth) acrylic groups in the molecule and the number of hydroxyl groups (ie, (meth) in two X 1 groups present in the molecule The sum of the number of acrylic groups and the number of hydroxyl groups is usually 4 to 22, preferably 6 to 14, and more preferably 6 to 10.
- the compound which has a structure represented by following General formula (8) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
- X 1 , Z and R f are the same as the general formula (1), v is an integer of 1 to 4 and X 2 is independently represented by the following formula (9) It is a group.
- Q 1 and R 1 are as described above, d and e are each an integer of 0 to 3, preferably an integer of 1 to 3, and d + e is 1 to 10, preferably 1 to 6)
- Each repeating unit may be randomly combined.
- Rf ′ can be exemplified by the same as Rf described above, preferably —CF 2 O (CF 2 O) p ′ (CF 2 CF 2 O) q ′ CF 2 — (p ′ , Q ′ can exemplify the same as p and q described above).
- R 4 is a hydrogen atom or a (meth) acryl-containing group, and as the (meth) acryl-containing group, those shown below can be preferably exemplified.
- fluorine-containing compounds (A) for example. That is, an isocyanate compound containing a (meth) acrylic acid halide or a (meth) acrylic group, with a part of the hydroxyl groups of a compound (fluorinated alcohol compound) having a plurality of OH groups (hydroxy groups) at both ends of the fluoropolyether group
- the fluorine-containing compound (A) can be obtained by reacting with a reagent for introducing a (meth) acrylic group such as, etc. to partially introduce a (meth) acrylic group into the hydroxyl group.
- Examples of (meth) acrylic group introduction reagents include (meth) acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and isocyanate compounds (acrylic acid derivatives having an isocyanate group) containing (meth) acrylic groups shown below Can be illustrated.
- the amount of halogen atoms or isocyanate groups of the (meth) acrylic acid halide or the isocyanate compound containing (meth) acrylic groups Is preferably 0.1 ⁇ y / (xy) ⁇ 25, more preferably 0.15 ⁇ y / (xy) ⁇ 19, and particularly preferably 0.2 ⁇ y / ( xy) ⁇ 10, more preferably 0.2 ⁇ y / (xy) ⁇ 5, and most preferably 0.2 ⁇ y / (xy) ⁇ 2.5. All or any desired amount may be reacted. Also, a method of charging with the above ratio as y / (xy)> 25 and stopping without completing the reaction can be used, but in this case, it is necessary to stop the reaction surely by removing the reaction catalyst.
- any solvent which does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth) acrylic acid halide, or the isocyanate group of the (meth) acrylic group-containing isocyanate compound can be used without particular limitation Specifically, hydrocarbon solvents such as toluene, xylene and isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone And fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride; fluorine-modified ether solvents such as methyl perfluorobutyl
- the solvent may be removed by a known method such as evaporation under reduced pressure, or may be used as it is as a diluted solution according to the intended use.
- the amount of the solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of the reaction components. If the amount of solvent used is too high, there is a risk that the reaction rate may be significantly reduced.
- a polymerization inhibitor as needed.
- a polymerization inhibitor What is normally used as a polymerization inhibitor of an acryl compound can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butyl catechol, dibutyl hydroxytoluene and the like can be mentioned.
- the amount of the polymerization inhibitor to be used may be determined from the reaction conditions, the purification conditions after the reaction, and the final use conditions, and is not particularly limited, but usually 0.01 to 5, relative to the total mass of the reaction components 000 ppm, particularly preferably 0.1 to 500 ppm.
- the (meth) acrylic acid halide When the (meth) acrylic acid halide is reacted with the fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride and methacrylic acid chloride to produce an ester.
- the ester formation reaction is performed by dropping a (meth) acrylic acid halide while mixing and stirring the reaction intermediate (fluorinated alcohol compound) and an acid acceptor.
- an acid acceptor triethylamine, pyridine, urea and the like can be used.
- the use amount of the acid acceptor is desirably about 0.9 to 3 times the charged mole number of the (meth) acrylic acid halide. When the amount is too small, a large amount of untrapped acid remains, and when the amount is too large, removal of the excess acid acceptor becomes difficult.
- the dropwise addition of (meth) acrylic acid halide is carried out over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ° C. After that, stirring is continued for another 30 minutes to 10 hours.
- the fluorine-containing compound (A) according to the present invention is obtained by distilling off unreacted (meth) acrylic acid halide, a salt generated by the reaction, a reaction solvent and the like by a method such as adsorption or filtration washing. You can get
- an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth) acrylic acid halide.
- the (meth) acrylic acid esters formed can be removed in the same manner as the removal of the unreacted (meth) acrylic acid halide, but they can also be used as they are.
- an appropriate catalyst may be added to increase the rate of reaction.
- a catalyst for example, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dilaurate, tin dioctoate, etc., tetraisopropoxy titanium, tetra Titanates or titanium chelate compounds such as n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetona) titanium, titanium isopropoxy octylene glycol, zirconium tetraacetylacetonate, zirconium tributoxy monoacetyl Acetonate, zirconium monobutoxy acetylacetonate bis (ethyl)
- reaction rate is obtained by adding 0.01 to 5% by mass, preferably 0.05 to 3% by mass, of these catalysts based on the total mass of the fluorine-containing alcohol compound and the isocyanate compound containing a (meth) acrylic group. Can be increased.
- the above reaction is carried out at a temperature of 0 to 120 ° C., preferably 10 to 70 ° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of (meth) acrylic groups may occur as a side reaction.
- the fluorine-containing compound (A) according to the present invention can be obtained by distilling off unreacted isocyanate compound, reaction solvent and the like by adsorption, filtration washing and the like.
- an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound.
- the generated urethane (meth) acrylates can be removed in the same manner as the unreacted isocyanate compound, but can also be used as it is.
- the precursor unreacted fluoropolyether is a by-product in the production of the fluorine-containing compound (A), such as the introduction ratio of (meth) acrylic groups.
- the fluorine-containing compound (A) such as the introduction ratio of (meth) acrylic groups.
- a compound having a plurality of alcohols at both ends of the group may remain, it may be contained.
- a compound in which all (meth) acrylic groups are introduced into hydroxyl groups may be generated, but this may be considered to correspond to the fluorine-containing compound (B) described later.
- a cyclopolysiloxane structure is formed via a divalent linking group at both ends of the fluorine-containing compound (A) and the perfluoropolyether group.
- a fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (B) having a structure which is bonded and a (meth) acrylic group via a divalent linking group is bonded to the cyclopolysiloxane structure and does not contain a hydroxyl group Can be shown.
- a fluorine-containing compound (B) the compound which has a structure represented by following General formula (10) can be illustrated.
- X 3 -Z-Rf-Z-X 3 (10) [Wherein, R f and Z are as defined above.
- X 3 independently of each other, represented by the following formula (11) (Wherein, Q 1 and R 1 are the same as above.
- F is an integer of 2 to 11, preferably an integer of 2 to 7, more preferably an integer of 2 to 5.
- Each repeating unit is a random bond It may be done.
- the compound which has a structure represented by following General formula (12) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
- Rf, Z, X 3 is the same as the general formula (10), w is an integer of 0 ⁇ 5, X 4, independently of one another, represented by the following formula (13) It is a group.
- Q 1 and R 1 are the same as above, and g is an integer of 1 or more, preferably an integer of 1 to 7, more preferably an integer of 2 to 3.
- Each repeating unit is randomly bonded May be
- a fluorine-containing compound (B) the following can be illustrated. (Wherein, Rf ′ is the same as above, and R 5 is a (meth) acrylic-containing group).
- Such a fluorine-containing compound (B) is a halogen atom or isocyanate of the (meth) acrylic group introduction reagent with respect to the total x moles of hydroxyl groups of the fluorine-containing alcohol compound in the method of synthesizing the fluorine-containing compound (A) exemplified above. It can be obtained by charging the base weight y mole at a ratio of x ⁇ y and reacting all the hydroxyl groups.
- the fluorine-containing compound (A) and the fluorine-containing compound (B) can be adjusted by adjusting the content rates thereof.
- the same effect as changing the ratio of (meth) acrylic group to hydroxyl group can be obtained by itself.
- the average value of the entire fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the composition The molar ratio of the total of (meth) acrylic groups contained in (F) to (meth) acrylic groups contained in the fluorine-containing compound (B) [total (mol) of (meth) acrylic groups / hydroxyl group (mol)] is 0. It is preferably 2 or more and 19 or less, more preferably 0.3 or more and 10 or less, and still more preferably 0.4 or more and 5 or less.
- the total number of moles of (meth) acrylic groups contained in the fluorine-containing compound (A) contained in the system is N aA
- the total number of moles of hydroxyl groups is N aH
- (meth) acrylics contained in the fluorine-containing compound (B) It is desirable that 0.2 ⁇ (N aA + N bA ) / N aH ⁇ 19, where N bA is the total number of moles of groups. If it is larger than this range, the difference in properties with the fluorine-containing compound (B) alone will not be clear, and if smaller than this range, the solubility with non-fluorinated acrylic compounds will be reduced, and uniform at the concentration necessary for expression of properties. Coating becomes difficult.
- the fluorine-containing active energy ray curable composition can be used only as the fluorine-containing compound (A) alone and as a mixture of the fluorine-containing compound (A) and the fluorine-containing compound (B), but the fluorine-containing compound (A) Any compound that can be mixed and cured with the fluorine compound (B) can be used.
- a compound specifically, it does not correspond to the fluorine-containing compounds (A) and (B), preferably contains no fluorine atom in the molecule (non-fluorinated), contains a urethane bond in the molecule
- the acrylic compound (C) which is not or contained can be mentioned.
- acrylic compound (C) examples include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, ethylene oxide modified with isocyanuric acid, di (meth) acrylate, Isocyanuric acid EO modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2 , 2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ester 2) 2- to 6-
- urethane (meth) acrylates those obtained by reacting polyisocyanate with (meth) acrylate having hydroxyl group, those obtained by reacting polyisocyanate with polyester of terminal diol with (meth) acrylate having hydroxyl group, It is also possible to use one obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate obtained by reacting a polyol with an excess of diisocyanate.
- non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond having one or more (meth) acrylic groups in one molecule and no hydroxyl group in one molecule, and one molecule
- Non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond having three or more (meth) acrylic groups and one or more hydroxyl groups in one, and one urethane compound having a urethane bond in the molecule
- component (C) one type may be used alone, or two or more types may be used in combination. Moreover, you may mix
- the fluorine-containing active energy ray curable composition of this invention can be made into the curable composition which is easy to be hardened
- the photopolymerization initiator of the component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, and preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-one (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ -(4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-dip
- the fluorine-containing active energy ray curable composition which is one of the embodiments of the present invention comprises the component (A), and the surface after curing is such as water and oil repellency, stain resistance, fingerprint resistance, and wear resistance. It is essential to impart properties, and the compounding amount of each component is appropriately determined according to the desired water repellency, oil repellency, solubility of the composition, coating conditions, curing conditions, hardness of the obtained article, etc.
- the blending amount in the case of blending the (B) component is the sum of the (meth) acrylic groups contained in the (A) component and the (B) component with respect to the hydroxyl group contained in the (A) component. It is preferable to mix
- blending (C) component is not restrict
- the amount is preferably 0.1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, and particularly preferably 5 to 800 parts by mass, per 1 part by mass. If the amount of the component (C) is too small, the expected coating properties and cured product properties may not be obtained by the blending of the component (C). If the amount is too large, the antifouling properties expected of the component (A) are obtained. It may not be possible.
- the blending amount in the case of blending the component (D) is preferably 0.1 to 10 parts by mass when the total amount of the components (A), (B) and (C) component is 100 parts by mass, Particularly preferably, it is 0.5 to 5 parts by mass. If the amount of the component (D) is too small, curing defects may occur and expected cured product properties may not be obtained. If the amount is too large, defects may occur on the surface of the cured material or turbidity may occur on the cured material. , And may become strong.
- the fluorine-containing active energy ray curable composition of the present invention may be one obtained by adding the component (A) or the components (A) and (B) to such a commercial product.
- Commercially available hard coating agents include, for example, Arakawa Chemical Industries, Ltd. “Beam Set”, Ohashi Chemical Industries, Ltd. “Eubik”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd. “Cashew UV”, JSR Co., Ltd. "Desorite”, Dainichi Seika Kogyo Co., Ltd. "Seika Beam”, Nippon Gohsei Kagaku Co., Ltd.
- the fluorine-containing active energy ray-curable composition of the present invention further comprises, according to the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a heat resistant stabilizer, oxidation Inhibitors, surfactants, colorants, fillers and the like can also be blended.
- an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, and heat stability Agents, antioxidants, surfactants, colorants, fillers and the like can be blended.
- various inorganic fine particles such as reactive non-reactive hollow and solid silica fine particles may be blended to improve various properties such as film strength, scratch resistance and transparency, and to improve characteristics such as adjustment of refractive index. Good.
- alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, etc .; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK) And ketones such as cyclohexanone; dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), ethers such as propylene glycol monomethyl ether acetate; ethyl acetate, Esters such as propyl acetate, butyl acetate and cyclohexyl acetate, m-xylene hexafluoride, benzoto Fluorine-modified
- the organic solvents may be used alone or in combination of two or more. Although the amount of the organic solvent used is not particularly limited, it is preferably 50 to 10,000 parts by mass, particularly 80 to 1,000 parts by mass, with respect to 100 parts by mass in total of the components (A) to (C). preferable.
- polymerization inhibitors such as, antistatic agents, antifoaming agents, viscosity regulators, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers according to the present invention may be used. It can be used without particular limitation as long as the purpose is not impaired.
- the curing method of the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, and component (A) alone, component (A) and component (B), component (A) and component (C), or (A)
- the composition containing the component (B) and the component (C) may be suitably diluted with a solvent, and the composition applied may be cured by active energy rays such as an electron beam, but further photopolymerization of the component (D) When it contains an initiator, it can be cured by ultraviolet light.
- UV irradiation can be carried out in air, but in order to prevent the inhibition of curing by oxygen, it is preferable to suppress the oxygen concentration to 5,000 ppm or less, and inert gases such as nitrogen, carbon dioxide, argon etc. Curing under an atmosphere is particularly preferred.
- (C) component and other additives can be mix
- any substrate can be used as long as the fluorine-containing active energy ray curable composition layer of the present invention adheres or adheres after curing. It can also be applied on top, but in particular resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate , Cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone , Mention may be made of polyether ether ketone, polyether sulfone, Mention may be made of polyether ether ketone, polyether sulfone, polyether
- a film substrate When applied to a film substrate, it may have a structure in which an adhesive is applied to the surface opposite to that on which the fluorine-containing active energy ray curable composition layer is applied and formed, and further protects the adhesive
- a mold release film may be disposed.
- the film substrate may be a substrate consisting only of the resin film mentioned above, but in order to improve the adhesion with the fluorine-containing active energy ray curable composition of the present invention, the resin It may be a film substrate provided with a primer layer on the film.
- the primer layer include those made of polyester resins, urethane resins, acrylic resins and the like.
- the fluorine-containing active energy ray curable composition of the present invention may be coated and cured on a curable / uncured curable composition layer that does not fall under the present invention.
- the fluorine-containing active energy ray curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic properties, and deformation prevention properties such as curl.
- the surface of the resin film is subjected to surface roughening treatment by corona blasting, solvent treatment, etc., corona discharge treatment, chromic acid treatment
- the treatment can also be performed by flame treatment, hot air treatment, ozone / ultraviolet radiation treatment, oxidation treatment or the like.
- the method for applying the fluorine-containing active energy ray-curable composition of the present invention to the above-mentioned substrate or article is not particularly limited.
- roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating Known coating methods such as spin coating, bar coating and screen printing can be used.
- the coating film is irradiated with active energy rays to cure it.
- active energy ray an electron beam, an ultraviolet ray, or the like can be used, but the ultraviolet ray is particularly preferable.
- the ultraviolet light source a mercury lamp, a metal halide lamp, and an LED lamp are preferable.
- the amount of UV irradiation is too small, the uncured component will remain, and if too much, the coating film and the substrate may deteriorate, so 10 to 10,000 mJ / cm 2 , especially 100 to 4,000 mJ / cm. It is desirable to be in the range of 2 .
- the irradiation atmosphere is replaced with an inert gas containing no oxygen molecule such as nitrogen, carbon dioxide, argon, etc.
- the coated surface is covered with a protective layer having releasability, and it is opposite to the coated surface of the substrate You may irradiate an ultraviolet-ray from the side.
- the coating and substrate are heated by an arbitrary method such as infrared rays or a hot air drying furnace before and during ultraviolet irradiation. It is also good.
- the thickness of the cured product layer of the fluorine-containing active energy ray-curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 ⁇ m, particularly preferably 0.05 to 200 ⁇ m.
- the cured product layer of the fluorine-containing active energy ray-curable composition of the present invention thus obtained has an angle formed between the liquid surface and the solid surface after 2 seconds of 2 ⁇ L droplets of ion exchanged water coming into contact with the liquid.
- Static water contact angle measured by 100 ° C or more, in particular 105 ° or more
- it can be a water and oil repellent surface having an angle of 60 ° or more, particularly 65 ° or more.
- the cured product layer of the fluorine-containing active energy ray curable composition of the present invention is a layer having a thickness of 10 nm or more on average with respect to the total surface area of the cured product layer.
- the amount is Further, it is preferable that no unreacted (meth) acrylic group remain on the surface of the cured product layer, and therefore, it is desirable that the cured product layer be cured under an inert gas atmosphere such as nitrogen or carbon dioxide.
- the fluorine-containing active energy ray curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and the water and oil repellency, stain resistance, slipperiness, and abrasion resistance on the surface of an article It is possible to form a cured resin layer having excellent properties.
- the present invention provides an article having a cured film obtained by applying the above-mentioned fluorine-containing active energy ray curable composition of the present invention to the surface and curing the composition.
- the fluorine-containing active energy ray curable composition of the present invention when used, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of a substrate (article).
- it is useful for imparting water repellency, oil repellency and stain resistance to the surface of an acrylic hard coat.
- the fluorine-containing active energy ray-curable composition of the present invention is a substrate (article) which may be contaminated with human fat, cosmetics, etc. by human contact, with human fat, mechanical oil, etc. of workers.
- An antifouling coating film or a protective film can be provided on the surface of a process material film or the like used inside a machine that may be contaminated.
- the cured film (cured resin layer) formed by using the fluorine-containing active energy ray curable composition of the present invention is a tablet computer, a notebook PC, a portable (communication) information terminal such as a mobile phone or a smartphone, a digital media player , Housings for various devices such as e-book readers, watch-type and glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, Various flat panel displays such as CRT and toner type display, display operation equipment surface such as TV screen, various optical films used in these, exterior of car, glossy surface of piano or furniture, marble etc Architectural stone surface, decoration building materials around water such as toilet, bath, washroom, etc., protective glass for art display, show window, showcase, cover for photo frame, watch, glass for automobile window, window glass for train, aircraft etc. It is useful as a coating film and surface protective film of transparent glass or transparent plastic (acrylic, polycarbonate etc.) members such as
- various devices having a display input device that performs operations on the screen with a human finger or palm such as a touch panel display
- a touch panel display for example, tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, smart watches , Digital media player, e-book reader, digital photo frame, game machine, digital camera, digital video camera, GPS display recording device, navigation device for cars etc., control panel for cars etc, automatic cash withdrawal depositor, cash automatic Useful as surface protection films for various controllers such as payment machines, vending machines, digital signage (electronic signs), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices A.
- the cured film formed of the fluorine-containing active energy ray curable composition of the present invention is an optical recording medium such as a magneto-optical disc or an optical disc; spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticulars It is also useful as a surface protective film of optical components and optical devices such as lenses, Fresnel lenses, antireflective films, lenses for various cameras, protective filters for various lenses, optical fibers and optical couplers.
- the fluorine-containing active energy ray curable composition of the present invention is water repellent by arranging the perfluoropolyether structure of the fluorine-containing compound (A) according to the present invention on the surface of an article to be aimed Essential to impart excellent properties such as oil repellency, slipperiness, stain resistance, fingerprint inconspicuousness, fingerprint wiping resistance, abrasion resistance, low refractive index characteristics, solvent resistance, chemical resistance, etc. .
- the fluorine-containing active energy ray curable composition of the present invention when compounded and prepared, in addition to the fluorine-containing compound (A) according to the present invention, when combining various compounds in the above-mentioned main curable composition
- reactive hollow silica hollow silica having no reactive group
- polyfunctional acrylic compound film strength and scratch resistance.
- the combination of the polyfunctional acrylic compound having 6 or more functions and the acrylic compound having 3 or less functional is used. What to do can be easily inferred from the knowledge of the known acrylic curable composition formulation.
- an appropriate coating film thickness is obtained to prevent interference fringes. Adjusting the thickness of the film substrate to make it easy to suppress curling, or adjusting the elastic modulus of the substrate film to cure the coating of the fluorine-containing active energy ray curable composition Of suppressing the deformation of the coating film and cracking of the coating film, etc. is to perform screening work based on the combination of the existing conditions according to the respective characteristics, and can be easily achieved by the combination of the existing techniques .
- Synthesis Example 2 Synthesis of Fluorine-Containing Acrylic Compound (A-2) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was 2.64 g (0.0187 mol). 48.0 g of a fluorine-containing acrylic compound (A-2) which is a pale yellow highly viscous substance having a hydroxyl group content of 0.5 was obtained.
- Synthesis Example 3 Synthesis of Fluorine-Containing Acrylic Compound (A-3) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was changed to 7.50 g (0.0532 mol). 52.8 g of a fluorine-containing acrylic compound (A-3), which is a pale yellow highly viscous substance having a hydroxyl content of 19 was obtained.
- C-1) pentaerythritol triacrylate (number of acrylic groups in molecule: 3 and number of hydroxyl groups: 1)
- C-2) dipentaerythritol pentaacrylate (number of acrylic groups in molecule: 5, hydroxyl number: 1) / dipentaerythritol hexaacrylate (number of acrylic groups in molecule: 6, hydroxyl number: 0)
- Mixture C-3): Shin-Nakamura Chemical Co., Ltd. Multifunctional urethane acrylate "U-6 LPA" (number of acrylic groups in molecule: 6 or more)
- C-4) Negami Industrial Co., Ltd.
- Multifunctional Urethane Acrylate “UN-3320HS” (Number of Acrylic Groups in Molecule: 6 or More)
- D-1 1-hydroxy-cyclohexyl-phenyl-ketone
- D-2 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ - 2-Methyl-propan-1-one
- S-1 methyl ethyl ketone
- S-3) propylene glycol monomethyl ether
- S-4 2-propanol
- Examples 1 to 7 using the fluorine-containing active energy ray-curable composition of the present invention, which contains the fluorine-containing acrylic compounds (A-1) to (A-4), are Excellent in water repellency, oil repellency, abrasion resistance, fingerprint inconspicuousness, fingerprint wipeability, magic repellence, and magic wipeability. Further, Comparative Example 1 using a fluorine-containing active energy ray-curable composition obtained by mixing the fluorine-containing acrylic compounds (B-1) and (B-2) without containing the fluorine-containing acrylic compound (A) The sample No. 4 is inferior in abrasion resistance to the examples corresponding to these, and fingerprints stand out.
- Example 5 comparison using a non-fluorine active energy ray-curable composition containing neither fluorine-containing acrylic compounds (A-1) to (A-4) nor fluorine-containing acrylic compounds (B-1) and (B-2) Example 5 is inferior to the said Example in water repellency, oil repellency, abrasion resistance, the ease of wiping off of a fingerprint, magic repellence, and magic wiping off.
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Abstract
A fluorine-containing active energy ray-curable composition which is characterized by containing a fluorine-containing compound (A) wherein: a cyclopolysiloxane structure is bonded to each end of a divalent perfluoropolyether group via a divalent linking group; and a hydroxyl group that is bonded to the cyclopolysiloxane structure via a divalent linking group and a (meth)acrylic group that is bonded to the cyclopolysiloxane structure via a divalent linking group are respectively bonded to one or both of the cyclopolysiloxane structures at both ends. This fluorine-containing active energy ray-curable composition enables the achievement of a cured coating film which is capable of providing excellent antifouling properties, in particular, excellent water/oil repellency, fingerprint accumulation preventing properties and fingerprint wiping-off properties, and excellent durability in terms of wear.
Description
本発明は、紫外線や電子線等により硬化し、優れた防汚性を表面に付与する含フッ素活性エネルギー線硬化性組成物、並びにこの組成物の硬化物層を基材表面に有する物品に関する。
The present invention relates to a fluorine-containing active energy ray curable composition which is cured by ultraviolet light, electron beam or the like to impart excellent soil resistance to the surface, and an article having a cured product layer of the composition on the surface of a substrate.
従来、樹脂成形体等の表面を保護する手段として、ハードコート処理が広く一般に用いられている。これは成形体の表面に硬質の硬化樹脂層（ハードコート層）を形成し、傷つき難くするものである。ハードコート層を構成する材料としては、熱硬化性樹脂や紫外線もしくは電子線硬化性樹脂など活性エネルギー線による硬化性組成物が多く使用されている。
Conventionally, hard coating treatment is widely used generally as a means for protecting the surface of a resin molded product or the like. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded body and make it hard to be damaged. As a material which comprises a hard-coat layer, curable compositions by active energy rays, such as a thermosetting resin and ultraviolet-ray or electron beam curable resin, are used abundantly.
一方、樹脂成形品の利用分野の拡大や高付加価値化の流れに伴い、硬化樹脂層（ハードコート層）に対する高機能化の要望が高まっており、その一つとして、ハードコート層への防汚性の付与が求められている。これはハードコート層の表面に撥水性、撥油性などの性質を付与することにより、汚れ難く、あるいは汚れても容易に取り除くことができるようにするものである。
On the other hand, with the expansion of the field of application of resin molded products and the trend toward higher added value, there is a growing demand for higher functionality for the cured resin layer (hard coat layer), one of which is the prevention of hard coat layer It is required to give stains. This is to make the surface of the hard coat layer resistant to soiling or easily soiled by giving properties such as water repellency and oil repellency to the surface.
ハードコート層に防汚性を付与する方法としては、一旦形成されたハードコート層表面に含フッ素防汚剤を塗工及び／又は定着させる方法が広く用いられているが、含フッ素硬化性成分を硬化前の硬化樹脂組成物に添加し、これを塗布硬化させることでハードコート層の形成と防汚性の付与を同時に行う方法についても検討されてきた。例えば、特開平６－２１１９４５号公報（特許文献１）には、アクリル系の硬化性樹脂組成物にフルオロアルキルアクリレートを添加、硬化させることで防汚性を付与したハードコート層の製造が示されている。
As a method of imparting antifouling properties to the hard coat layer, a method of coating and / or fixing a fluorine-containing antifouling agent on the surface of the hard coat layer once formed is widely used. A method of simultaneously forming a hard coat layer and imparting antifouling properties by adding it to a cured resin composition before curing and coating and curing it has also been studied. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) shows the production of a hard coat layer to which an antifouling property is imparted by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition. ing.
本発明者は、このような硬化性樹脂組成物に防汚性を付与できるフッ素化合物として、様々な開発を進めており、例えば、特開２０１０－５３１１４号公報（特許文献２）、特開２０１０－１３８１１２号公報（特許文献３）、特開２０１０－２８５５０１号公報（特許文献４）に示す光硬化可能なフッ素化合物を提案している。
The inventor of the present invention is promoting various developments as a fluorine compound capable of imparting antifouling properties to such a curable resin composition. For example, JP-A-2010-53114 (Patent Document 2), JP-A-2010 A photocurable fluorine compound is proposed as disclosed in JP-A-138112 (Patent Document 3) and JP-A-2010-285501 (Patent Document 4).
一方、ハードコートの機能性の向上が求められている中で、人が素手で触る機会のある装置、例えば、スマートフォン、タブレットＰＣ、デジタルサイネージ、ナビゲーションシステムやコンソールなどの自動車の車載タッチパネルディスプレイ、家庭用大型ＴＶ、ＰＣ用ディスプレイの用途においては、特に防汚性と総称される中でも、指紋の付着が目立たないこと、指紋の拭き取り性に優れること、更にハードコートとして摩耗の耐久性に優れることといった特性がますます強く求められてきている。このため、これらの特徴について従来よりも優れた特性を付与できる活性エネルギー線硬化性組成物が常に求められている。
On the other hand, while there is a demand for improvement in the functionality of hard coats, devices that people have the opportunity to touch with their bare hands, such as smartphones, tablet PCs, digital signage, car touch panel displays for automobiles such as navigation systems and consoles, homes In applications for large-screen TVs and PCs, particularly when it is generally referred to as stain resistance, fingerprint adhesion is inconspicuous, fingerprint wiping properties are excellent, and as hard coats, wear durability is excellent. Characteristics are increasingly sought after. For this reason, there is always a need for an active energy ray curable composition that can impart superior characteristics to the prior art with respect to these characteristics.
本発明は、上記事情に鑑みなされたもので、防汚性、特には優れた撥水撥油性、指紋付着防止性、指紋拭き取り性及び摩耗耐久性を付与することができる硬化被膜を与える含フッ素活性エネルギー線硬化性組成物、及びこの組成物の硬化物層を基材表面に有する物品を提供することを目的とする。
The present invention has been made in view of the above circumstances, and provides a cured film capable of imparting stain resistance, in particular, excellent water and oil repellency, fingerprint adhesion prevention, fingerprint wiping and abrasion durability. An object of the present invention is to provide an active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、パーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介した水酸基と、前記シクロポリシロキサン構造に２価の連結基を介した（メタ）アクリル基とが、それぞれ結合した構造を有するフッ素化合物を含有する含フッ素活性エネルギー線硬化性組成物が、防汚性と総称される諸特性の中でも、指紋の付着の目立ちにくさ、指紋の拭き取り性に優れ、更にハードコートとして摩耗の耐久性に優れることを見出し、本発明をなすに至った。
As a result of intensive studies to achieve the above object, the inventor of the present invention has found that a cyclopolysiloxane structure is bonded to both ends of a perfluoropolyether group via a divalent linking group, to the above-mentioned cyclopolysiloxane structure. Fluorine-containing active energy ray curing comprising a fluorine compound having a structure in which a hydroxyl group through a divalent linking group and a (meth) acrylic group through a divalent linking group to the cyclopolysiloxane structure are respectively bonded The present invention is based on the finding that the adhesive composition, among various properties collectively referred to as anti-staining properties, is notable for fingerprint adhesion adhesion, fingerprint wiping properties, and wear resistance as a hard coat. It came to
従って、本発明は、下記の含フッ素活性エネルギー線硬化性組成物及び該組成物の硬化物層を基材表面に有する物品を提供する。
１．
２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した水酸基と、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基とを、それぞれ両末端のシクロポリシロキサン構造のいずれか一方又は両方に有する含フッ素化合物（Ａ）を含有することを特徴とする含フッ素活性エネルギー線硬化性組成物。
２．
含フッ素化合物（Ａ）において、含フッ素化合物（Ａ）中に含まれる水酸基に対する（メタ）アクリル基のモル比［（メタ）アクリル基（モル）／水酸基（モル）］が、平均値として０．１以上２５以下である１に記載の含フッ素活性エネルギー線硬化性組成物。
３．
更に、２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基を有し、かつ、水酸基を有さない構造を両末端に有する含フッ素化合物（Ｂ）を含むものである１又は２に記載の含フッ素活性エネルギー線硬化性組成物。
４．
組成物全体に含まれる平均値として、組成物中の含フッ素化合物（Ａ）に含まれる水酸基に対する含フッ素化合物（Ａ）に含まれる（メタ）アクリル基と含フッ素化合物（Ｂ）に含まれる（メタ）アクリル基の合計のモル比［（メタ）アクリル基の合計（モル）／水酸基（モル）］が、０．１以上２５以下である３に記載の含フッ素活性エネルギー線硬化性組成物。
５．
含フッ素化合物（Ａ）が、下記一般式（１）
Ｘ1－Ｚ－Ｒｆ－Ｚ－Ｘ1 （１）
［式中、Ｒｆは下記式（２）～（５）
（式中、Ｙは互いに独立にＦ又はＣＦ3であり、ｒは２～６の整数であり、ｍ、ｎはそれぞれ０～２００の整数であり、但しｍ＋ｎは２～２００であり、ｓは０～６の整数である。各繰り返し単位はランダムに結合されていてもよい。）
（式中、ｊは独立に１～３の整数であり、ｋは１～２００の整数である。）
（式中、Ｙ、ｊは上記と同じであり、ｐ、ｑはそれぞれ０～２００の整数であり、但しｐ＋ｑは２～２００である。各繰り返し単位はランダムに結合されていてもよい。）
（式中、ｔは１～１００の整数である。）
で表される基から選ばれる、分子量５００～３０，０００の２価のパーフルオロポリエーテル基であり、Ｘ1は互いに独立に、下記式（６）
〔式中、Ｑ1は炭素数３～２０のエーテル結合、エステル結合、アミド結合及びウレタン結合から選ばれる結合を含んでいてもよい２価の連結基であり、途中環状構造や分岐構造を含んでいてもよく、それぞれ同一でも異なっていてもよい。Ｒ1は下記式（７）
（式中、Ｒ2は独立に、水素原子又はメチル基であり、Ｒ3は炭素数１～１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の連結基であり、ｃは１又は２である。）
で表される（メタ）アクリル基含有基であり、ａ及びｂはそれぞれ０～６の整数であり、但しａ＋ｂは２～１１である。各繰り返し単位はランダムに結合されていてもよい。〕
で表される基であり、分子中に存在するＸ1中のａ、ｂの合計はそれぞれ２以上である。Ｚは下記式
のいずれかで示される２価の有機基である。］
で表されるものである１～４のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
６．
更に、含フッ素化合物（Ａ）、（Ｂ）以外のアクリル化合物（Ｃ）を含む１～５のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
７．
アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基を有し、かつ分子中に水酸基を有さない非フッ素化多官能（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
８．
アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基と１個以上の水酸基を有する非フッ素化多官能（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
９．
アクリル化合物（Ｃ）が、分子中にウレタン結合を有し、１分子中に６個以上の（メタ）アクリル基を有する非フッ素化多官能ウレタン（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
１０．
更に、（Ｄ）光重合開始剤を含む１～９のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
１１．
１～１０のいずれかに記載の含フッ素活性エネルギー線硬化性組成物の硬化被膜を表面に有し、水接触角１０５°以上の撥水性表面を有する物品。 Accordingly, the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.
1.
A cyclopolysiloxane structure is bonded to both ends of a divalent perfluoropolyether group via a divalent linking group, and a hydroxy group bonded to the cyclopolysiloxane structure via a divalent linking group; It is characterized by containing a fluorine-containing compound (A) having a (meth) acrylic group bonded to a siloxane structure via a divalent linking group in any one or both of cyclopolysiloxane structures at both ends, respectively. Fluorine-containing active energy ray curable composition.
2.
In the fluorine-containing compound (A), the molar ratio of (meth) acrylic group to hydroxyl group contained in the fluorine-containing compound (A) [(meth) acrylic group (mol) / hydroxyl group (mol)] is, as an average value, 0. The fluorine-containing active energy ray curable composition according to 1, which is 1 or more and 25 or less.
3.
Furthermore, a cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group via a divalent linking group, and a (meth) acryl bonded to the cyclopolysiloxane structure via a divalent linking group The fluorine-containing active energy ray curable composition according to 1 or 2, which contains a fluorine-containing compound (B) having a group and a structure having no hydroxyl group at both ends.
4.
The (meth) acrylic group contained in the fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the fluorine-containing compound (A) with respect to the hydroxyl group contained in the fluorine-containing compound (A) in the composition 3. The fluorine-containing active energy ray-curable composition according to 3, wherein the molar ratio [total of (meth) acrylic groups (mol) / hydroxyl group (mol)] of total of acrylic groups is 0.1 or more and 25 or less.
5.
The fluorine-containing compound (A) is represented by the following general formula (1)
X 1 -Z-Rf-Z-X 1 (1)
[Wherein, R f represents the following formulas (2) to (5)
(Wherein Y independently of one another is F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, provided that m + n is 2 to 200, and s is It is an integer of 0 to 6. Each repeating unit may be randomly combined.)
(Wherein, j is independently an integer of 1 to 3 and k is an integer of 1 to 200)
(Wherein Y and j are the same as above, and p and q are each an integer of 0 to 200, provided that p + q is 2 to 200. Each repeating unit may be randomly bonded.)
(In the formula, t is an integer of 1 to 100)
In selected from the groups represented, a divalent perfluoropolyether group having a molecular weight of 500 ~ 30,000, X 1, independently of one another, the following formula (6)
[Wherein, Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and includes a cyclic structure or a branched structure on the way] It may be the same or different. R 1 is the following formula (7)
(Wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. , C is 1 or 2.)
And a and b each represent an integer of 0 to 6, provided that a + b is 2 to 11. Each repeating unit may be randomly combined. ]
And the sum of a and b in X 1 present in the molecule is 2 or more. Z is the following formula
It is a bivalent organic group shown by either of. ]
The fluorine-containing active energy ray curable composition according to any one of 1 to 4, which is represented by
6.
Further, the fluorine-containing active energy ray-curable composition according to any one of 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compound (A) or (B).
7.
The fluorine-containing compound according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acrylic groups in one molecule and no hydroxyl group in the molecule. Active energy ray curable composition.
8.
The fluorine-containing active energy ray curability according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acrylic groups and one or more hydroxyl groups in one molecule. Composition.
9.
The fluorine-containing activity according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in the molecule and having 6 or more (meth) acrylic groups in one molecule Energy ray curable composition.
10.
Furthermore, the fluorine-containing active energy ray-curable composition according to any one of 1 to 9, further comprising (D) a photopolymerization initiator.
11.
An article having a cured coating of the fluorine-containing active energy ray-curable composition according to any one of 1 to 10 on the surface and having a water repellent surface having a water contact angle of 105 ° or more.
１．
２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した水酸基と、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基とを、それぞれ両末端のシクロポリシロキサン構造のいずれか一方又は両方に有する含フッ素化合物（Ａ）を含有することを特徴とする含フッ素活性エネルギー線硬化性組成物。
２．
含フッ素化合物（Ａ）において、含フッ素化合物（Ａ）中に含まれる水酸基に対する（メタ）アクリル基のモル比［（メタ）アクリル基（モル）／水酸基（モル）］が、平均値として０．１以上２５以下である１に記載の含フッ素活性エネルギー線硬化性組成物。
３．
更に、２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基を有し、かつ、水酸基を有さない構造を両末端に有する含フッ素化合物（Ｂ）を含むものである１又は２に記載の含フッ素活性エネルギー線硬化性組成物。
４．
組成物全体に含まれる平均値として、組成物中の含フッ素化合物（Ａ）に含まれる水酸基に対する含フッ素化合物（Ａ）に含まれる（メタ）アクリル基と含フッ素化合物（Ｂ）に含まれる（メタ）アクリル基の合計のモル比［（メタ）アクリル基の合計（モル）／水酸基（モル）］が、０．１以上２５以下である３に記載の含フッ素活性エネルギー線硬化性組成物。
５．
含フッ素化合物（Ａ）が、下記一般式（１）
Ｘ1－Ｚ－Ｒｆ－Ｚ－Ｘ1 （１）
［式中、Ｒｆは下記式（２）～（５）
で表される基から選ばれる、分子量５００～３０，０００の２価のパーフルオロポリエーテル基であり、Ｘ1は互いに独立に、下記式（６）
で表される（メタ）アクリル基含有基であり、ａ及びｂはそれぞれ０～６の整数であり、但しａ＋ｂは２～１１である。各繰り返し単位はランダムに結合されていてもよい。〕
で表される基であり、分子中に存在するＸ1中のａ、ｂの合計はそれぞれ２以上である。Ｚは下記式
で表されるものである１～４のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
６．
更に、含フッ素化合物（Ａ）、（Ｂ）以外のアクリル化合物（Ｃ）を含む１～５のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
７．
アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基を有し、かつ分子中に水酸基を有さない非フッ素化多官能（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
８．
アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基と１個以上の水酸基を有する非フッ素化多官能（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
９．
アクリル化合物（Ｃ）が、分子中にウレタン結合を有し、１分子中に６個以上の（メタ）アクリル基を有する非フッ素化多官能ウレタン（メタ）アクリレートである６に記載の含フッ素活性エネルギー線硬化性組成物。
１０．
更に、（Ｄ）光重合開始剤を含む１～９のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
１１．
１～１０のいずれかに記載の含フッ素活性エネルギー線硬化性組成物の硬化被膜を表面に有し、水接触角１０５°以上の撥水性表面を有する物品。 Accordingly, the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.
1.
A cyclopolysiloxane structure is bonded to both ends of a divalent perfluoropolyether group via a divalent linking group, and a hydroxy group bonded to the cyclopolysiloxane structure via a divalent linking group; It is characterized by containing a fluorine-containing compound (A) having a (meth) acrylic group bonded to a siloxane structure via a divalent linking group in any one or both of cyclopolysiloxane structures at both ends, respectively. Fluorine-containing active energy ray curable composition.
2.
In the fluorine-containing compound (A), the molar ratio of (meth) acrylic group to hydroxyl group contained in the fluorine-containing compound (A) [(meth) acrylic group (mol) / hydroxyl group (mol)] is, as an average value, 0. The fluorine-containing active energy ray curable composition according to 1, which is 1 or more and 25 or less.
3.
Furthermore, a cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group via a divalent linking group, and a (meth) acryl bonded to the cyclopolysiloxane structure via a divalent linking group The fluorine-containing active energy ray curable composition according to 1 or 2, which contains a fluorine-containing compound (B) having a group and a structure having no hydroxyl group at both ends.
4.
The (meth) acrylic group contained in the fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the fluorine-containing compound (A) with respect to the hydroxyl group contained in the fluorine-containing compound (A) in the composition 3. The fluorine-containing active energy ray-curable composition according to 3, wherein the molar ratio [total of (meth) acrylic groups (mol) / hydroxyl group (mol)] of total of acrylic groups is 0.1 or more and 25 or less.
5.
The fluorine-containing compound (A) is represented by the following general formula (1)
X 1 -Z-Rf-Z-X 1 (1)
[Wherein, R f represents the following formulas (2) to (5)
In selected from the groups represented, a divalent perfluoropolyether group having a molecular weight of 500 ~ 30,000, X 1, independently of one another, the following formula (6)
And a and b each represent an integer of 0 to 6, provided that a + b is 2 to 11. Each repeating unit may be randomly combined. ]
And the sum of a and b in X 1 present in the molecule is 2 or more. Z is the following formula
The fluorine-containing active energy ray curable composition according to any one of 1 to 4, which is represented by
6.
Further, the fluorine-containing active energy ray-curable composition according to any one of 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compound (A) or (B).
7.
The fluorine-containing compound according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acrylic groups in one molecule and no hydroxyl group in the molecule. Active energy ray curable composition.
8.
The fluorine-containing active energy ray curability according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acrylic groups and one or more hydroxyl groups in one molecule. Composition.
9.
The fluorine-containing activity according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in the molecule and having 6 or more (meth) acrylic groups in one molecule Energy ray curable composition.
10.
Furthermore, the fluorine-containing active energy ray-curable composition according to any one of 1 to 9, further comprising (D) a photopolymerization initiator.
11.
An article having a cured coating of the fluorine-containing active energy ray-curable composition according to any one of 1 to 10 on the surface and having a water repellent surface having a water contact angle of 105 ° or more.
本発明の含フッ素活性エネルギー線硬化性組成物は、基材の表面に塗工硬化させることで、撥水性、撥油性、防汚性、すべり性、付着指紋の低視認性、指紋の拭き取り性、耐摩耗性を付与することができる。
The fluorine-containing active energy ray curable composition of the present invention is coated and cured on the surface of a substrate to obtain water repellency, oil repellency, stain resistance, slipperiness, low visibility of attached fingerprints, fingerprint wipes , Wear resistance can be provided.
本発明の含フッ素活性エネルギー線硬化性組成物は、２価のパーフルオロポリエーテル基の両末端に２価の連結基を介して３価以上（通常、３～１２価、好ましくは３～８価、より好ましくは３～６価）のシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介した水酸基と、前記シクロポリシロキサン構造に２価の連結基を介した（メタ）アクリル基とが、両末端のシクロポリシロキサン構造のいずれか一方又は両方にそれぞれ１個以上結合した構造を有する含フッ素化合物（Ａ）を含有することを特徴とする。含フッ素化合物（Ａ）において、上記水酸基を有することにより指紋が目立ちにくくなるという効果が得られ、上記（メタ）アクリル基を有することにより硬化性が得られ、表面に防汚性を示すフッ素成分が固定されるという効果が得られるものである。
The fluorine-containing active energy ray-curable composition of the present invention has three or more valences (usually 3 to 12, preferably 3 to 8) via the divalent linking group at both ends of the divalent perfluoropolyether group. (More preferably trivalent to hexavalent) cyclopolysiloxane structure is bonded, and the cyclopolysiloxane structure has a hydroxyl group via a divalent linking group and a cyclopolysiloxane structure having a divalent linking group. A fluorine-containing compound (A) having a structure in which one or more (meth) acrylic groups are bonded to one or both of the cyclopolysiloxane structures at both ends, is included. In the fluorine-containing compound (A), the effect of making the fingerprint less noticeable by having the above-mentioned hydroxyl group is obtained, the curability is obtained by having the above-mentioned (meth) acrylic group, and the fluorine component showing antifouling property on the surface The effect of fixing is obtained.
含フッ素化合物（Ａ）中に含まれる（メタ）アクリル基と水酸基の比率は、特に、組成物中に含まれる含フッ素化合物（Ａ）の平均値として、含フッ素化合物（Ａ）中に含まれる水酸基に対する（メタ）アクリル基のモル比［（メタ）アクリル基（モル）／水酸基（モル）］が、０．１以上２５以下であることが好ましく、０．１５以上１９以下であることがより好ましく、０．２以上１０以下であることが特に好ましく、０．２以上５以下であることが更に好ましく、０．２以上２．５以下であることが最も好ましい。このモル比がこれよりも大きくなると含フッ素化合物（Ａ）中に含まれる水酸基の効果が小さくなり、水酸基を含まない含フッ素化合物との硬化後の特性の差が明確でなくなる。このモル比がこれより小さくなると含フッ素化合物（Ａ）のうち（メタ）アクリル基を持たない分子の含有量が多くなり、非フッ素のアクリル化合物との溶解性が低下し、均一な平面として塗工が困難になったり、硬化不良が発生したりする場合がある。
The ratio of the (meth) acrylic group to the hydroxyl group contained in the fluorine-containing compound (A) is particularly contained in the fluorine-containing compound (A) as an average value of the fluorine-containing compound (A) contained in the composition The molar ratio of (meth) acrylic group to hydroxyl group [(meth) acrylic group (mole) / hydroxyl group (mole)] is preferably 0.1 or more and 25 or less, and more preferably 0.15 or more and 19 or less The number is preferably 0.2 or more and 10 or less, more preferably 0.2 or more and 5 or less, and most preferably 0.2 or more and 2.5 or less. When this molar ratio becomes larger than this, the effect of the hydroxyl group contained in the fluorine-containing compound (A) becomes small, and the difference in characteristics after curing with the fluorine-containing compound not containing a hydroxyl group becomes unclear. When this molar ratio is smaller than this, the content of molecules having no (meth) acrylic group in the fluorine-containing compound (A) is increased, the solubility with a non-fluorinated acrylic compound is decreased, and coating is performed as a uniform plane. Processing may be difficult or curing failure may occur.
含フッ素化合物（Ａ）として、具体的には、下記一般式（１）で表される構造を有する化合物が例示できる。
Ｘ1－Ｚ－Ｒｆ－Ｚ－Ｘ1 （１） Specifically as a fluorine-containing compound (A), the compound which has a structure represented by following General formula (1) can be illustrated.
X 1 -Z-Rf-Z-X 1 (1)
Ｘ1－Ｚ－Ｒｆ－Ｚ－Ｘ1 （１） Specifically as a fluorine-containing compound (A), the compound which has a structure represented by following General formula (1) can be illustrated.
X 1 -Z-Rf-Z-X 1 (1)
式（１）中、Ｒｆは、特に主な構造が以下に示す繰り返し単位群
－ＣＦ2Ｏ－
－ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ（ＣＦ3）ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
のいずれか一つ又は複数の組み合わせからなるものが好ましい。ここで、主な構造に該当しない部分としては、Ｚとの結合部分、主鎖構造構築時の開始剤断片や副生成構造が挙げられる。 In the formula (1), Rf is a group of repeating units -CF 2 O- whose main structure is particularly shown below.
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3) CF 2 O-
-CF 2 CF 2 CF 2 CF 2 O-
What consists of any one or several combination of these is preferable. Here, as a portion which does not correspond to the main structure, a bonding portion to Z, an initiator fragment at the time of construction of the main chain structure and a by-product structure can be mentioned.
－ＣＦ2Ｏ－
－ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ（ＣＦ3）ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
のいずれか一つ又は複数の組み合わせからなるものが好ましい。ここで、主な構造に該当しない部分としては、Ｚとの結合部分、主鎖構造構築時の開始剤断片や副生成構造が挙げられる。 In the formula (1), Rf is a group of repeating units -CF 2 O- whose main structure is particularly shown below.
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3) CF 2 O-
-CF 2 CF 2 CF 2 CF 2 O-
What consists of any one or several combination of these is preferable. Here, as a portion which does not correspond to the main structure, a bonding portion to Z, an initiator fragment at the time of construction of the main chain structure and a by-product structure can be mentioned.
Ｒｆとしては、中でも下記式（２）～（５）で表される基から選ばれる、分子量５００～３０，０００の２価のパーフルオロポリエーテル基であるものが好ましい。
（式中、Ｙは互いに独立にＦ又はＣＦ3であり、ｒは２～６の整数であり、ｍ、ｎはそれぞれ０～２００の整数、好ましくは１～１００の整数、より好ましくは４～５０の整数であり、但しｍ＋ｎは２～２００、好ましくは８～１００であり、ｓは０～６の整数である。各繰り返し単位はランダムに結合されていてもよい。）
（式中、ｊは独立に１～３の整数であり、ｋは１～２００の整数、好ましくは２～１００の整数、より好ましくは４～５０の整数である。）
（式中、Ｙ、ｊは上記と同じであり、ｐ、ｑはそれぞれ０～２００の整数、好ましくは１～１００の整数、より好ましくは４～５０の整数であり、但しｐ＋ｑは２～２００、好ましくは８～１００である。各繰り返し単位はランダムに結合されていてもよい。）
（式中、ｔは１～１００の整数、好ましくは２～６０の整数、より好ましくは４～４０の整数である。）
Among them, preferred as Rf is a divalent perfluoropolyether group having a molecular weight of 500 to 30,000, which is selected from among groups represented by the following formulas (2) to (5).
(Wherein Y independently of one another is F or CF 3 , r is an integer of 2 to 6, m and n are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably 4 to It is an integer of 50, provided that m + n is 2 to 200, preferably 8 to 100, and s is an integer of 0 to 6. Each repeating unit may be randomly combined.)
(Wherein, j is independently an integer of 1 to 3 and k is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 50).
(Wherein Y and j are the same as above, p and q are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, provided that p + q is 2 to 200) , Preferably 8 to 100. Each repeating unit may be randomly bonded.)
(Wherein t is an integer of 1 to 100, preferably an integer of 2 to 60, more preferably an integer of 4 to 40).
Ｒｆとしては、中でも式（２）及び（４）で表される構造が好ましい。
また、Ｒｆは、分子量が５００～３０，０００、特に１，５００～１０，０００であることが好ましい。分子量が小さすぎると組成物中の非フッ素化成分との相溶性が高くなり過ぎ、塗工後の硬化物（塗膜）の表面に（Ａ）成分が集まらなくなる場合があり、大きすぎると組成物中の非フッ素化成分との相溶性が低すぎて、配合時の濁り、沈殿の発生や塗工後の硬化物（塗膜）のヘイズの上昇、塗膜の欠損等、平滑性の低下などが発生する場合がある。なお、分子量は、例えば、各種含フッ素溶媒を展開溶媒としたゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリメチルメタクリレート換算値として求めることができ、通常、数量平均分子量として求めることが好適である（以下、同じ。）。 Among them, structures represented by formulas (2) and (4) are preferable as Rf.
Also, Rf preferably has a molecular weight of 500 to 30,000, and particularly 1,500 to 10,000. If the molecular weight is too small, the compatibility with the non-fluorinated component in the composition may be too high, and the component (A) may not collect on the surface of the cured product (coating film) after coating. The compatibility with the non-fluorinated component in the product is too low, causing turbidity at the time of blending, generation of precipitation, increase in haze of cured product (coating film) after coating, loss of coating film, etc. May occur. The molecular weight can be determined, for example, as a polymethyl methacrylate equivalent value in gel permeation chromatography (GPC) analysis using various fluorine-containing solvents as a developing solvent, and usually, it is suitable to obtain as a number average molecular weight ,the same.).
また、Ｒｆは、分子量が５００～３０，０００、特に１，５００～１０，０００であることが好ましい。分子量が小さすぎると組成物中の非フッ素化成分との相溶性が高くなり過ぎ、塗工後の硬化物（塗膜）の表面に（Ａ）成分が集まらなくなる場合があり、大きすぎると組成物中の非フッ素化成分との相溶性が低すぎて、配合時の濁り、沈殿の発生や塗工後の硬化物（塗膜）のヘイズの上昇、塗膜の欠損等、平滑性の低下などが発生する場合がある。なお、分子量は、例えば、各種含フッ素溶媒を展開溶媒としたゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリメチルメタクリレート換算値として求めることができ、通常、数量平均分子量として求めることが好適である（以下、同じ。）。 Among them, structures represented by formulas (2) and (4) are preferable as Rf.
Also, Rf preferably has a molecular weight of 500 to 30,000, and particularly 1,500 to 10,000. If the molecular weight is too small, the compatibility with the non-fluorinated component in the composition may be too high, and the component (A) may not collect on the surface of the cured product (coating film) after coating. The compatibility with the non-fluorinated component in the product is too low, causing turbidity at the time of blending, generation of precipitation, increase in haze of cured product (coating film) after coating, loss of coating film, etc. May occur. The molecular weight can be determined, for example, as a polymethyl methacrylate equivalent value in gel permeation chromatography (GPC) analysis using various fluorine-containing solvents as a developing solvent, and usually, it is suitable to obtain as a number average molecular weight ,the same.).
一般式（１）において、Ｚは下記式のいずれかで示される２価の有機基である。
In the general formula (1), Z is a divalent organic group represented by any of the following formulas.
Ｚとしては、中でも、
が特に好ましい。
Especially as Z,
Is particularly preferred.
式（１）において、Ｘ1は互いに独立に、下記式（６）で表される基である。
〔式中、Ｑ1は炭素数３～２０のエーテル結合、エステル結合、アミド結合及びウレタン結合から選ばれる結合を含んでいてもよい２価の連結基であり、途中環状構造や分岐構造を含んでいてもよく、それぞれ同一でも異なっていてもよい。Ｒ1は下記式（７）
（式中、Ｒ2は独立に、水素原子又はメチル基であり、Ｒ3は炭素数１～１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の連結基であり、ｃは１又は２である。）
で表される（メタ）アクリル基含有基である。ａ及びｂはそれぞれ０～６、好ましくは１～６、より好ましくは２～４の整数であり、但しａ＋ｂは２～１１、好ましくは２～７、より好ましくは２～５である。各繰り返し単位はランダムに結合されていてもよい。なお、式（１）において、分子中に存在するＸ1中のａ、ｂの合計はそれぞれ２以上である。〕 In Formula (1), X 1 is a group represented by the following Formula (6) independently of each other.
[Wherein, Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and includes a cyclic structure or a branched structure on the way] It may be the same or different. R 1 is the following formula (7)
(Wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. , C is 1 or 2.)
(Meth) acrylic group-containing group represented by Each of a and b is an integer of 0 to 6, preferably 1 to 6, and more preferably 2 to 4, provided that a + b is 2 to 11, preferably 2 to 7, and more preferably 2 to 5. Each repeating unit may be randomly combined. In Formula (1), the sum of a and b in X 1 present in the molecule is 2 or more. ]
で表される（メタ）アクリル基含有基である。ａ及びｂはそれぞれ０～６、好ましくは１～６、より好ましくは２～４の整数であり、但しａ＋ｂは２～１１、好ましくは２～７、より好ましくは２～５である。各繰り返し単位はランダムに結合されていてもよい。なお、式（１）において、分子中に存在するＸ1中のａ、ｂの合計はそれぞれ２以上である。〕 In Formula (1), X 1 is a group represented by the following Formula (6) independently of each other.
(Meth) acrylic group-containing group represented by Each of a and b is an integer of 0 to 6, preferably 1 to 6, and more preferably 2 to 4, provided that a + b is 2 to 11, preferably 2 to 7, and more preferably 2 to 5. Each repeating unit may be randomly combined. In Formula (1), the sum of a and b in X 1 present in the molecule is 2 or more. ]
式（６）において、Ｑ1は炭素数３～２０のエーテル結合、エステル結合、アミド結合及びウレタン結合から選ばれる結合を含んでいてもよい２価の連結基であり、好ましくは炭素数３～２０、特に炭素数３～１２のエーテル結合、エステル結合、アミド結合及びウレタン結合から選ばれる結合を含んでいてもよい２価の炭化水素基であり、途中環状構造や分岐構造を含んでいてもよく、それぞれ同一でも異なっていてもよい。
In the formula (6), Q 1 is a divalent linking group which may contain a bond selected from an ether bond having 3 to 20 carbon atoms, an ester bond, an amide bond and a urethane bond, and preferably 3 to 20 carbon atoms 20, particularly a divalent hydrocarbon group which may contain a bond selected from an ether bond having 3 to 12 carbon atoms, an ester bond, an amide bond and a urethane bond, and may contain a cyclic structure or a branched structure on the way They may be the same or different.
Ｑ1としては、中でも以下のいずれかの構造が好ましい。
－ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－［ＣＨ2ＣＨ（ＣＨ3）Ｏ］z－ＣＨ2ＣＨ（ＣＨ3）－
（式中、ｚは０～１０の整数である。）
Among them, one of the following structures is preferable as Q 1 .
-CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 -O-CH 2 CH 2-
-CH 2 CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2-
-CH 2 CH 2 CH 2 -O- CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -
-[CH 2 CH (CH 3 ) O] z -CH 2 CH (CH 3 )-
(In the formula, z is an integer of 0 to 10)
－ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－
－［ＣＨ2ＣＨ（ＣＨ3）Ｏ］z－ＣＨ2ＣＨ（ＣＨ3）－
-CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 -O-CH 2 CH 2-
-CH 2 CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2-
-CH 2 CH 2 CH 2 -O- CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -
-[CH 2 CH (CH 3 ) O] z -CH 2 CH (CH 3 )-
式（６）において、Ｒ1は下記式（７）で表される（メタ）アクリル基含有基である。
（式中、Ｒ2は独立に、水素原子又はメチル基であり、Ｒ3は炭素数１～１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の連結基であり、ｃは１又は２である。）
In Formula (6), R 1 is a (meth) acrylic group-containing group represented by the following Formula (7).
(Wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms. , C is 1 or 2.)
式（７）において、Ｒ2は独立に、水素原子又はメチル基である。
また、Ｒ3は炭素数１～１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の連結基であり、好ましくは炭素数１～１８、特に炭素数２～８のエーテル結合及び／又はエステル結合を含んでいてもよい２価の炭化水素基、特にはアルキレン基であり、例えば、下記式で表されるものが好ましい。
－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
ｃは１又は２であり、１が好ましい。 In formula (7), R 2 is independently a hydrogen atom or a methyl group.
R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms, particularly preferably 2 to 8 carbon atoms. A divalent hydrocarbon group which may contain an ether bond and / or an ester bond, in particular an alkylene group, for example, one represented by the following formula is preferable.
-CH 2 CH 2-
-CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2-
c is 1 or 2, preferably 1.
また、Ｒ3は炭素数１～１８のエーテル結合及び／又はエステル結合を含んでいてもよい２価もしくは３価の連結基であり、好ましくは炭素数１～１８、特に炭素数２～８のエーテル結合及び／又はエステル結合を含んでいてもよい２価の炭化水素基、特にはアルキレン基であり、例えば、下記式で表されるものが好ましい。
－ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－
ｃは１又は２であり、１が好ましい。 In formula (7), R 2 is independently a hydrogen atom or a methyl group.
R 3 is a divalent or trivalent linking group which may contain an ether bond and / or an ester bond having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms, particularly preferably 2 to 8 carbon atoms. A divalent hydrocarbon group which may contain an ether bond and / or an ester bond, in particular an alkylene group, for example, one represented by the following formula is preferable.
-CH 2 CH 2-
-CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 CH 2-
-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2-
-CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2-
c is 1 or 2, preferably 1.
なお、本発明に係る含フッ素化合物（Ａ）において、２価のパーフルオロポリエーテル基の両末端に連結する３価以上（通常、３～１２価、好ましくは３～８価、より好ましくは３～６価）のシクロポリシロキサン構造に２価の連結基を介して結合した水酸基と、該シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基は、該両末端のシクロポリシロキサン構造のいずれか一方又は両方に、それぞれ独立に、１個以上、好ましくは１～６個、より好ましくは２～４個有するものであり、上述した式（１）において、分子中の上記（メタ）アクリル基数の合計に相当するａの合計（即ち、両末端のシクロポリシロキサン構造中の（メタ）アクリル基数の合計）は１以上、好ましくは１～１２、より好ましくは２～８、更に好ましくは４～６であり、分子中の上記水酸基数の合計に相当するｂの合計（即ち、両末端のシクロポリシロキサン構造中の水酸基数の合計）は１以上、好ましくは１～１２、より好ましくは２～８、更に好ましくは４～６である。
また、上述した式（６）で示される各シクロポリシロキサン構造中において、ａ＋ｂの値はそれぞれ独立に、通常、２～１１、好ましくは２～７、より好ましくは２～５であり、上述した式（１）において、分子中の上記（メタ）アクリル基数と上記水酸基数との合計に相当する（ａ＋ｂ）値の合計（即ち、分子中に存在する２個のＸ1基中の（メタ）アクリル基数と上記水酸基数との合計）は、通常、４～２２、好ましくは６～１４、より好ましくは６～１０である。 In the fluorine-containing compound (A) according to the present invention, a trivalent or more (usually a trivalent to 12 divalent, preferably a trivalent to octavalent, more preferably 3 to be linked to both ends of a divalent perfluoropolyether group A hydroxyl group bonded to a cyclopolysiloxane structure of ~ 6 via a divalent linking group and a (meth) acrylic group bonded to the cyclopolysiloxane structure via a divalent linking group are In one or both of the cyclopolysiloxane structures, one or more, preferably 1 to 6, more preferably 2 to 4, each independently having one or more, and in the above-mentioned formula (1), in the molecule The total of a corresponding to the total number of (meth) acrylic groups (that is, the total number of (meth) acrylic groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8 , And the sum of b corresponding to the sum of the number of hydroxyl groups in the molecule (ie, the sum of the number of hydroxyl groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, More preferably, it is 2 to 8, further preferably 4 to 6.
Further, in each cyclopolysiloxane structure represented by the above-mentioned formula (6), the value of a + b is usually independently 2 to 11, preferably 2 to 7, more preferably 2 to 5, and as described above In Formula (1), the sum of (a + b) values corresponding to the sum of the number of (meth) acrylic groups in the molecule and the number of hydroxyl groups (ie, (meth) in two X 1 groups present in the molecule The sum of the number of acrylic groups and the number of hydroxyl groups is usually 4 to 22, preferably 6 to 14, and more preferably 6 to 10.
また、上述した式（６）で示される各シクロポリシロキサン構造中において、ａ＋ｂの値はそれぞれ独立に、通常、２～１１、好ましくは２～７、より好ましくは２～５であり、上述した式（１）において、分子中の上記（メタ）アクリル基数と上記水酸基数との合計に相当する（ａ＋ｂ）値の合計（即ち、分子中に存在する２個のＸ1基中の（メタ）アクリル基数と上記水酸基数との合計）は、通常、４～２２、好ましくは６～１４、より好ましくは６～１０である。 In the fluorine-containing compound (A) according to the present invention, a trivalent or more (usually a trivalent to 12 divalent, preferably a trivalent to octavalent, more preferably 3 to be linked to both ends of a divalent perfluoropolyether group A hydroxyl group bonded to a cyclopolysiloxane structure of ~ 6 via a divalent linking group and a (meth) acrylic group bonded to the cyclopolysiloxane structure via a divalent linking group are In one or both of the cyclopolysiloxane structures, one or more, preferably 1 to 6, more preferably 2 to 4, each independently having one or more, and in the above-mentioned formula (1), in the molecule The total of a corresponding to the total number of (meth) acrylic groups (that is, the total number of (meth) acrylic groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8 , And the sum of b corresponding to the sum of the number of hydroxyl groups in the molecule (ie, the sum of the number of hydroxyl groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, More preferably, it is 2 to 8, further preferably 4 to 6.
Further, in each cyclopolysiloxane structure represented by the above-mentioned formula (6), the value of a + b is usually independently 2 to 11, preferably 2 to 7, more preferably 2 to 5, and as described above In Formula (1), the sum of (a + b) values corresponding to the sum of the number of (meth) acrylic groups in the molecule and the number of hydroxyl groups (ie, (meth) in two X 1 groups present in the molecule The sum of the number of acrylic groups and the number of hydroxyl groups is usually 4 to 22, preferably 6 to 14, and more preferably 6 to 10.
また含フッ素化合物（Ａ）の製造を行う際に、下記一般式（８）で表される構造を有する化合物が副生する場合があり、これらは蒸留、抽出、分取クロマトグラフ等の各種の手段により除去してもよいが、そのまま含んだものも使用できる。
Ｘ1－［Ｚ－Ｒｆ－Ｚ－Ｘ2］v－Ｚ－Ｒｆ－Ｚ－Ｘ1 （８） Moreover, when manufacturing a fluorine-containing compound (A), the compound which has a structure represented by following General formula (8) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
X 1- [Z-Rf-Z-X 2 ] v -Z-Rf-Z-X 1 (8)
Ｘ1－［Ｚ－Ｒｆ－Ｚ－Ｘ2］v－Ｚ－Ｒｆ－Ｚ－Ｘ1 （８） Moreover, when manufacturing a fluorine-containing compound (A), the compound which has a structure represented by following General formula (8) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
X 1- [Z-Rf-Z-X 2 ] v -Z-Rf-Z-X 1 (8)
一般式（８）において、Ｘ1、Ｚ、Ｒｆは一般式（１）と同じであり、ｖは１～４の整数であり、Ｘ2は互いに独立に、下記式（９）で表される基である。
（式中、Ｑ1、Ｒ1は上記の通りであり、ｄ、ｅはそれぞれ０～３の整数、好ましくは１～３の整数であり、かつｄ＋ｅは１～１０、好ましくは１～６の整数である。各繰り返し単位はランダムに結合されていてもよい。）
In the general formula (8), X 1 , Z and R f are the same as the general formula (1), v is an integer of 1 to 4 and X 2 is independently represented by the following formula (9) It is a group.
(Wherein, Q 1 and R 1 are as described above, d and e are each an integer of 0 to 3, preferably an integer of 1 to 3, and d + e is 1 to 10, preferably 1 to 6) Each repeating unit may be randomly combined.)
含フッ素化合物（Ａ）の好ましい構造として、具体的には、以下のものを例示することができる。
［式中、Ｒｆ’は上述したＲｆと同様のものを例示することができ、好ましくは、－ＣＦ2Ｏ（ＣＦ2Ｏ）p’（ＣＦ2ＣＦ2Ｏ）q’ＣＦ2－（ｐ’、ｑ’は上述したｐ、ｑと同様のものを例示することができる。）である。Ｒ4は水素原子又は（メタ）アクリル含有基であり、分子中に含まれるＲ4としての水素原子の数をｎH、（メタ）アクリル含有基の数をｎAとした時に、ｎH、ｎAはそれぞれ１～５の整数であり、それぞれの分子についてｎH＋ｎA＝６である。］
Specifically as a preferable structure of a fluorine-containing compound (A), the following can be illustrated.
[Wherein, Rf ′ can be exemplified by the same as Rf described above, preferably —CF 2 O (CF 2 O) p ′ (CF 2 CF 2 O) q ′ CF 2 — (p ′ , Q ′ can exemplify the same as p and q described above). R 4 is a hydrogen atom or a (meth) acryl-containing group, and when the number of hydrogen atoms as R 4 contained in the molecule is n H and the number of (meth) acryl-containing groups is n A , n H , n A is an integer of 1 to 5, and n H + n A = 6 for each molecule. ]
ここで、Ｒ4は水素原子又は（メタ）アクリル含有基であり、（メタ）アクリル含有基として、好ましくは下記に示すものが例示できる。
ＣＨ2＝ＣＨＣＯ－
ＣＨ2＝Ｃ（ＣＨ3）ＣＯ－
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
［ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2］2ＣＨ（ＣＨ3）－ＮＨ－ＣＯ－
また、含フッ素化合物（Ａ）１分子中に含まれるＲ4としての水素原子の数をｎH、（メタ）アクリル含有基の数をｎAとした時に、ｎH、ｎAはそれぞれ１～５の整数であり、それぞれの分子についてｎH＋ｎA＝６である。 Here, R 4 is a hydrogen atom or a (meth) acryl-containing group, and as the (meth) acryl-containing group, those shown below can be preferably exemplified.
CH 2 = CHCO-
CH 2 = C (CH 3 ) CO-
CH 2 = CHCOOCH 2 CH 2 -NH-CO-
CH 2 = CCH 3 COOCH 2 CH 2 -NH-CO-
CH 2 = CCH 3 COOCH 2 CH 2 OCH 2 CH 2 -NH-CO-
[CH 2 = CCH 3 COOCH 2 ] 2 CH (CH 3 ) -NH-CO-
When the number of hydrogen atoms as R 4 contained in one molecule of the fluorine-containing compound (A) is n H and the number of (meth) acryl-containing groups is n A , n H and n A each are 1 to It is an integer of 5 and n H + n A = 6 for each molecule.
ＣＨ2＝ＣＨＣＯ－
ＣＨ2＝Ｃ（ＣＨ3）ＣＯ－
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－ＮＨ－ＣＯ－
［ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2］2ＣＨ（ＣＨ3）－ＮＨ－ＣＯ－
また、含フッ素化合物（Ａ）１分子中に含まれるＲ4としての水素原子の数をｎH、（メタ）アクリル含有基の数をｎAとした時に、ｎH、ｎAはそれぞれ１～５の整数であり、それぞれの分子についてｎH＋ｎA＝６である。 Here, R 4 is a hydrogen atom or a (meth) acryl-containing group, and as the (meth) acryl-containing group, those shown below can be preferably exemplified.
CH 2 = CHCO-
CH 2 = C (CH 3 ) CO-
CH 2 = CHCOOCH 2 CH 2 -NH-CO-
CH 2 = CCH 3 COOCH 2 CH 2 -NH-CO-
CH 2 = CCH 3 COOCH 2 CH 2 OCH 2 CH 2 -NH-CO-
[CH 2 = CCH 3 COOCH 2 ] 2 CH (CH 3 ) -NH-CO-
When the number of hydrogen atoms as R 4 contained in one molecule of the fluorine-containing compound (A) is n H and the number of (meth) acryl-containing groups is n A , n H and n A each are 1 to It is an integer of 5 and n H + n A = 6 for each molecule.
本発明に係る含フッ素化合物（Ａ）は、いかなる製造方法を用いてもその効果は変わらないが、例えば、以下のような方法において製造することが好ましい。即ち、フルオロポリエーテル基の両末端にＯＨ基（水酸基）を複数有する化合物（含フッ素アルコール化合物）の水酸基の一部を、（メタ）アクリル酸ハライドや、（メタ）アクリル基を含有するイソシアネート化合物等の（メタ）アクリル基導入試薬と反応させて、該水酸基部分に（メタ）アクリル基を部分的に導入することにより、含フッ素化合物（Ａ）を得ることができる。
Although the effect does not change even if it uses any manufacturing method, it is preferable to manufacture the following fluorine-containing compounds (A), for example. That is, an isocyanate compound containing a (meth) acrylic acid halide or a (meth) acrylic group, with a part of the hydroxyl groups of a compound (fluorinated alcohol compound) having a plurality of OH groups (hydroxy groups) at both ends of the fluoropolyether group The fluorine-containing compound (A) can be obtained by reacting with a reagent for introducing a (meth) acrylic group such as, etc. to partially introduce a (meth) acrylic group into the hydroxyl group.
ここで、含フッ素化合物（Ａ）の前駆体となるフルオロポリエーテル基の両末端にＯＨ基を複数有する化合物（含フッ素アルコール化合物）として、具体的には、以下に示すものが挙げられる。
（式中、Ｒｆ’は上記と同じである。）
Here, specific examples of the compound (fluorinated alcohol compound) having a plurality of OH groups at both ends of the fluoropolyether group to be a precursor of the fluorinated compound (A) may be mentioned.
(Wherein, R f 'is the same as above.)
（メタ）アクリル基導入試薬としては、アクリル酸クロリド、メタクリル酸クロリド等の（メタ）アクリル酸ハライド、及び下記に示す（メタ）アクリル基を含有するイソシアネート化合物（イソシアネート基を有するアクリル酸誘導体）等を例示することができる。
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
［ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2］2ＣＨ（ＣＨ3）－Ｎ＝Ｃ＝Ｏ Examples of (meth) acrylic group introduction reagents include (meth) acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and isocyanate compounds (acrylic acid derivatives having an isocyanate group) containing (meth) acrylic groups shown below Can be illustrated.
CH 2 = CHCOOCH 2 CH 2 -N = C = O
CH 2 = CCH 3 COOCH 2 CH 2 -N = C = O
CH 2 CCCH 3 COOCH 2 CH 2 OCH 2 CH 2 -NCC = O
[CH 2 CCCH 3 COOCH 2 ] 2 CH (CH 3 ) -NCC = O
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2－Ｎ＝Ｃ＝Ｏ
［ＣＨ2＝ＣＣＨ3ＣＯＯＣＨ2］2ＣＨ（ＣＨ3）－Ｎ＝Ｃ＝Ｏ Examples of (meth) acrylic group introduction reagents include (meth) acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and isocyanate compounds (acrylic acid derivatives having an isocyanate group) containing (meth) acrylic groups shown below Can be illustrated.
CH 2 = CHCOOCH 2 CH 2 -N = C = O
CH 2 = CCH 3 COOCH 2 CH 2 -N = C = O
CH 2 CCCH 3 COOCH 2 CH 2 OCH 2 CH 2 -NCC = O
[CH 2 CCCH 3 COOCH 2 ] 2 CH (CH 3 ) -NCC = O
これらの（メタ）アクリル酸ハライドあるいは（メタ）アクリル基を含有するイソシアネート化合物は、含フッ素アルコール化合物の水酸基量の合計に対して過剰とならない必要量を仕込み、反応させる方法が好ましい。具体的には、反応系中の、含フッ素アルコール化合物の水酸基量の合計をｘモルとした場合、（メタ）アクリル酸ハライドあるいは（メタ）アクリル基を含有するイソシアネート化合物のハロゲン原子あるいはイソシアネート基量をｙモルとした場合、好ましくは０．１≦ｙ／（ｘ－ｙ）≦２５、より好ましくは０．１５≦ｙ／（ｘ－ｙ）≦１９、特に好ましくは０．２≦ｙ／（ｘ－ｙ）≦１０、更に好ましくは０．２≦ｙ／（ｘ－ｙ）≦５、最も好ましくは０．２≦ｙ／（ｘ－ｙ）≦２．５となる比率で仕込み、これを全て又は望ましい量で反応させればよい。また、上記比率をｙ／（ｘ－ｙ）＞２５として仕込み、反応を完結させずに停止させる方法も使用できるが、この場合は反応触媒の除去等により反応を確実に停止させる必要がある。
It is preferable to charge the (meth) acrylic acid halide or (meth) acrylic group-containing isocyanate compound in a necessary amount so as not to be excessive with respect to the total of the hydroxyl group content of the fluorine-containing alcohol compound, and to react. Specifically, when the total amount of hydroxyl groups of the fluorine-containing alcohol compound in the reaction system is x mol, the amount of halogen atoms or isocyanate groups of the (meth) acrylic acid halide or the isocyanate compound containing (meth) acrylic groups Is preferably 0.1 ≦ y / (xy) ≦ 25, more preferably 0.15 ≦ y / (xy) ≦ 19, and particularly preferably 0.2 ≦ y / ( xy) ≦ 10, more preferably 0.2 ≦ y / (xy) ≦ 5, and most preferably 0.2 ≦ y / (xy) ≦ 2.5. All or any desired amount may be reacted. Also, a method of charging with the above ratio as y / (xy)> 25 and stopping without completing the reaction can be used, but in this case, it is necessary to stop the reaction surely by removing the reaction catalyst.
これらの反応は、必要に応じて適当な溶剤で希釈して反応を行ってもよい。このような溶剤としては、含フッ素アルコール化合物の水酸基、（メタ）アクリル酸ハライドのハロゲン原子、（メタ）アクリル基を含有するイソシアネート化合物のイソシアネート基と反応しない溶剤であれば特に制限なく用いることができ、具体的には、トルエン、キシレン、イソオクタンなどの炭化水素系溶剤、テトラヒドロフラン、ジイソプロピルエーテル、ジブチルエーテル等のエーテル系溶剤、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等のフッ素変性芳香族炭化水素系溶剤、メチルパーフルオロブチルエーテル等のフッ素変性エーテル系溶剤などが挙げられる。この溶剤は、反応後に減圧留去等の公知の手法で除去してもよく、目的の用途に応じてそのまま希釈溶液として使用してもよい。溶剤の使用量は特に限定されないが、反応成分の全合計質量に対して１０倍以下が好ましい。溶媒の使用量が多すぎると、反応速度が大幅に低下する危険がある。
These reactions may be carried out by diluting with an appropriate solvent, if necessary. As such solvent, any solvent which does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth) acrylic acid halide, or the isocyanate group of the (meth) acrylic group-containing isocyanate compound can be used without particular limitation Specifically, hydrocarbon solvents such as toluene, xylene and isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone And fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride; fluorine-modified ether solvents such as methyl perfluorobutyl ether; and the like. After the reaction, the solvent may be removed by a known method such as evaporation under reduced pressure, or may be used as it is as a diluted solution according to the intended use. The amount of the solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of the reaction components. If the amount of solvent used is too high, there is a risk that the reaction rate may be significantly reduced.
また、反応の際には、必要に応じて重合禁止剤を添加してもよい。重合禁止剤としては特に制限はないが、通常、アクリル化合物の重合禁止剤として用いられるものを用いることができる。具体的には、ヒドロキノン、ヒドロキノンモノメチルエーテル、４－ｔｅｒｔ－ブチルカテコール、ジブチルヒドロキシトルエン等を挙げることができる。重合禁止剤の使用量は反応条件、反応後の精製条件、最終的な使用条件から決定すればよく、特に制限はされないが、通常、反応成分の全合計質量に対して０．０１～５，０００ｐｐｍ、特に好ましくは０．１～５００ｐｐｍである。
Moreover, in the case of reaction, you may add a polymerization inhibitor as needed. Although there is no restriction | limiting in particular as a polymerization inhibitor, What is normally used as a polymerization inhibitor of an acryl compound can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butyl catechol, dibutyl hydroxytoluene and the like can be mentioned. The amount of the polymerization inhibitor to be used may be determined from the reaction conditions, the purification conditions after the reaction, and the final use conditions, and is not particularly limited, but usually 0.01 to 5, relative to the total mass of the reaction components 000 ppm, particularly preferably 0.1 to 500 ppm.
含フッ素アルコール化合物に、（メタ）アクリル酸ハライドを反応させる場合、特にアクリル酸クロリド、メタクリル酸クロリドを反応させて、エステルを生成することが好ましい。該エステル生成反応は、上記反応中間体（含フッ素アルコール化合物）、受酸剤を混合攪拌しながら（メタ）アクリル酸ハライドを滴下して行う。受酸剤はトリエチルアミン、ピリジン、尿素などが使用できる。受酸剤の使用量は、（メタ）アクリル酸ハライドの仕込みモル数に対して０．９～３倍程度が望ましい。少なすぎるとトラップされない酸が多く残存することになり、多すぎると余剰となる受酸剤の除去が困難になる。
When the (meth) acrylic acid halide is reacted with the fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride and methacrylic acid chloride to produce an ester. The ester formation reaction is performed by dropping a (meth) acrylic acid halide while mixing and stirring the reaction intermediate (fluorinated alcohol compound) and an acid acceptor. As an acid acceptor, triethylamine, pyridine, urea and the like can be used. The use amount of the acid acceptor is desirably about 0.9 to 3 times the charged mole number of the (meth) acrylic acid halide. When the amount is too small, a large amount of untrapped acid remains, and when the amount is too large, removal of the excess acid acceptor becomes difficult.
（メタ）アクリル酸ハライドの滴下は、反応混合物の温度を０～３５℃に維持し、２０～６０分かけて行う。その後、更に３０分～１０時間攪拌を継続する。反応終了後、未反応の（メタ）アクリル酸ハライド、反応により発生した塩及び反応溶媒等を留去、吸着、濾過洗浄等の方法で除去することで、本発明に係る含フッ素化合物（Ａ）を得ることができる。
The dropwise addition of (meth) acrylic acid halide is carried out over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ° C. After that, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the fluorine-containing compound (A) according to the present invention is obtained by distilling off unreacted (meth) acrylic acid halide, a salt generated by the reaction, a reaction solvent and the like by a method such as adsorption or filtration washing. You can get
また、反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応の（メタ）アクリル酸ハライドをエステル化してもよい。生成した（メタ）アクリル酸エステル類は、未反応の（メタ）アクリル酸ハライド除去と同様の方法で除去できるが、残存させたまま使用することもできる。
In addition, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth) acrylic acid halide. The (meth) acrylic acid esters formed can be removed in the same manner as the removal of the unreacted (meth) acrylic acid halide, but they can also be used as they are.
含フッ素アルコール化合物に、（メタ）アクリル基を含有するイソシアネート化合物を反応させる場合には、含フッ素アルコール化合物と（メタ）アクリル基を含有するイソシアネート化合物を必要に応じて溶媒とともに攪拌し、反応を進行させる。
When a fluorine-containing alcohol compound is reacted with an isocyanate compound containing a (meth) acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing a (meth) acrylic group are optionally stirred with a solvent, and the reaction is carried out Let go.
この反応において、反応の速度を増加するために適切な触媒を加えてもよい。触媒としては、例えば、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート、ジオクチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ジオクテート、ジオクタン酸第１錫などのアルキル錫エステル化合物、テトライソプロポキシチタン、テトラｎ－ブトキシチタン、テトラキス（２－エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナ）チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス（エチルアセトアセテート）、ジルコニウムジブトキシビス（エチルアセトアセテート）、ジルコニウムテトラアセチルアセトネート、ジルコニウムキレート化合物等が例示される。これらはその１種に限定されず、２種もしくはそれ以上の混合物として使用できるが、特に環境への影響が低いチタン化合物、ジルコニウム化合物の使用が好ましい。
これらの触媒を、含フッ素アルコール化合物と（メタ）アクリル基を含有するイソシアネート化合物の総質量に対して、０．０１～５質量％、好ましくは０．０５～３質量％加えることにより、反応速度を増加させることができる。 In this reaction, an appropriate catalyst may be added to increase the rate of reaction. As a catalyst, for example, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dilaurate, tin dioctoate, etc., tetraisopropoxy titanium, tetra Titanates or titanium chelate compounds such as n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetona) titanium, titanium isopropoxy octylene glycol, zirconium tetraacetylacetonate, zirconium tributoxy monoacetyl Acetonate, zirconium monobutoxy acetylacetonate bis (ethyl acetoacetate), zirconium dibutoxy bis (ethyl acetoacetate) G), zirconium tetra acetylacetonate, zirconium chelate compound and the like. These are not limited to one type, and can be used as a mixture of two or more types, but the use of titanium compounds and zirconium compounds having particularly low environmental impact is preferable.
The reaction rate is obtained by adding 0.01 to 5% by mass, preferably 0.05 to 3% by mass, of these catalysts based on the total mass of the fluorine-containing alcohol compound and the isocyanate compound containing a (meth) acrylic group. Can be increased.
これらの触媒を、含フッ素アルコール化合物と（メタ）アクリル基を含有するイソシアネート化合物の総質量に対して、０．０１～５質量％、好ましくは０．０５～３質量％加えることにより、反応速度を増加させることができる。 In this reaction, an appropriate catalyst may be added to increase the rate of reaction. As a catalyst, for example, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dilaurate, tin dioctoate, etc., tetraisopropoxy titanium, tetra Titanates or titanium chelate compounds such as n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetona) titanium, titanium isopropoxy octylene glycol, zirconium tetraacetylacetonate, zirconium tributoxy monoacetyl Acetonate, zirconium monobutoxy acetylacetonate bis (ethyl acetoacetate), zirconium dibutoxy bis (ethyl acetoacetate) G), zirconium tetra acetylacetonate, zirconium chelate compound and the like. These are not limited to one type, and can be used as a mixture of two or more types, but the use of titanium compounds and zirconium compounds having particularly low environmental impact is preferable.
The reaction rate is obtained by adding 0.01 to 5% by mass, preferably 0.05 to 3% by mass, of these catalysts based on the total mass of the fluorine-containing alcohol compound and the isocyanate compound containing a (meth) acrylic group. Can be increased.
上記反応は０～１２０℃、好ましくは１０～７０℃の温度で、１分～５００時間、好ましくは１０分～４８時間行う。反応温度が低すぎると反応速度が遅くなりすぎる場合があり、反応温度が高すぎると副反応として（メタ）アクリル基の重合が起きてしまう可能性がある。
反応終了後、未反応のイソシアネート化合物及び反応溶媒等を留去、吸着、濾過洗浄等の方法で除去することで本発明に係る含フッ素化合物（Ａ）を得ることができる。 The above reaction is carried out at a temperature of 0 to 120 ° C., preferably 10 to 70 ° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of (meth) acrylic groups may occur as a side reaction.
After completion of the reaction, the fluorine-containing compound (A) according to the present invention can be obtained by distilling off unreacted isocyanate compound, reaction solvent and the like by adsorption, filtration washing and the like.
反応終了後、未反応のイソシアネート化合物及び反応溶媒等を留去、吸着、濾過洗浄等の方法で除去することで本発明に係る含フッ素化合物（Ａ）を得ることができる。 The above reaction is carried out at a temperature of 0 to 120 ° C., preferably 10 to 70 ° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of (meth) acrylic groups may occur as a side reaction.
After completion of the reaction, the fluorine-containing compound (A) according to the present invention can be obtained by distilling off unreacted isocyanate compound, reaction solvent and the like by adsorption, filtration washing and the like.
また反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応のイソシアネート化合物とウレタン結合を形成させてもよい。生成したウレタン（メタ）アクリレート類は、未反応のイソシアネート化合物と同様の方法で除去できるが、残存させたまま使用することもできる。
When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The generated urethane (meth) acrylates can be removed in the same manner as the unreacted isocyanate compound, but can also be used as it is.
また、本発明の含フッ素活性エネルギー線硬化性組成物において、含フッ素化合物（Ａ）の製造において副生する、（メタ）アクリル基の導入比率などの要因により、前駆体未反応のフルオロポリエーテル基の両末端に複数のアルコールを有する化合物が残存する可能性があるが、これを含有していてもよい。また水酸基に全て（メタ）アクリル基が導入された化合物も発生する可能性があるが、これについては後述する含フッ素化合物（Ｂ）に相当すると考えてよい。
Also, in the fluorine-containing active energy ray curable composition of the present invention, the precursor unreacted fluoropolyether is a by-product in the production of the fluorine-containing compound (A), such as the introduction ratio of (meth) acrylic groups. Although a compound having a plurality of alcohols at both ends of the group may remain, it may be contained. There is also a possibility that a compound in which all (meth) acrylic groups are introduced into hydroxyl groups may be generated, but this may be considered to correspond to the fluorine-containing compound (B) described later.
本発明の含フッ素活性エネルギー線硬化性組成物のもう一つの構成法として、含フッ素化合物（Ａ）、及びパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介した（メタ）アクリル基が結合し、水酸基を含まない構造を有する含フッ素化合物（Ｂ）を含む含フッ素活性エネルギー線硬化性組成物を示すことができる。
As another construction method of the fluorine-containing active energy ray-curable composition of the present invention, a cyclopolysiloxane structure is formed via a divalent linking group at both ends of the fluorine-containing compound (A) and the perfluoropolyether group. A fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (B) having a structure which is bonded and a (meth) acrylic group via a divalent linking group is bonded to the cyclopolysiloxane structure and does not contain a hydroxyl group Can be shown.
含フッ素化合物（Ｂ）として、具体的には、下記一般式（１０）で表される構造を有する化合物が例示できる。
Ｘ3－Ｚ－Ｒｆ－Ｚ－Ｘ3 （１０）
［式中、Ｒｆ、Ｚは上記と同じである。Ｘ3は互いに独立に、下記式（１１）
（式中、Ｑ1、Ｒ1は上記と同じである。ｆは２～１１の整数、好ましくは２～７の整数、より好ましくは２～５の整数である。各繰り返し単位はランダムに結合されていてもよい。）
で表される基である。］ Specifically as a fluorine-containing compound (B), the compound which has a structure represented by following General formula (10) can be illustrated.
X 3 -Z-Rf-Z-X 3 (10)
[Wherein, R f and Z are as defined above. X 3 independently of each other, represented by the following formula (11)
(Wherein, Q 1 and R 1 are the same as above. F is an integer of 2 to 11, preferably an integer of 2 to 7, more preferably an integer of 2 to 5. Each repeating unit is a random bond) It may be done.)
Is a group represented by ]
Ｘ3－Ｚ－Ｒｆ－Ｚ－Ｘ3 （１０）
［式中、Ｒｆ、Ｚは上記と同じである。Ｘ3は互いに独立に、下記式（１１）
で表される基である。］ Specifically as a fluorine-containing compound (B), the compound which has a structure represented by following General formula (10) can be illustrated.
X 3 -Z-Rf-Z-X 3 (10)
[Wherein, R f and Z are as defined above. X 3 independently of each other, represented by the following formula (11)
Is a group represented by ]
また含フッ素化合物（Ｂ）の製造を行う際に、下記一般式（１２）で表される構造を有する化合物が副生する場合があり、これらは蒸留、抽出、分取クロマトグラフ等の各種の手段により除去してもよいが、そのまま含んだものも使用できる。
Ｘ3－［Ｚ－Ｒｆ－Ｚ－Ｘ4］w－Ｚ－Ｒｆ－Ｚ－Ｘ3 （１２） Moreover, when manufacturing a fluorine-containing compound (B), the compound which has a structure represented by following General formula (12) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
X 3- [Z-Rf-Z-X 4 ] w- Z-Rf-Z-X 3 (12)
Ｘ3－［Ｚ－Ｒｆ－Ｚ－Ｘ4］w－Ｚ－Ｒｆ－Ｚ－Ｘ3 （１２） Moreover, when manufacturing a fluorine-containing compound (B), the compound which has a structure represented by following General formula (12) may byproduce, and these may be various things, such as distillation, extraction, a preparative chromatograph, etc. Although it may remove by means, what was included as it is can also be used.
X 3- [Z-Rf-Z-X 4 ] w- Z-Rf-Z-X 3 (12)
一般式（１２）において、Ｒｆ、Ｚ、Ｘ3は一般式（１０）と同じであり、ｗは０～５の整数であり、Ｘ4は互いに独立に、下記式（１３）で表される基である。
（式中、Ｑ1、Ｒ1は上記と同じであり、ｇは１以上の整数、好ましくは１～７の整数、より好ましくは２～３の整数である。各繰り返し単位はランダムに結合されていてもよい。）
In the general formula (12), Rf, Z, X 3 is the same as the general formula (10), w is an integer of 0 ~ 5, X 4, independently of one another, represented by the following formula (13) It is a group.
(Wherein, Q 1 and R 1 are the same as above, and g is an integer of 1 or more, preferably an integer of 1 to 7, more preferably an integer of 2 to 3. Each repeating unit is randomly bonded May be
即ち、含フッ素化合物（Ｂ）は、一般式（１）において示される化合物のうち、Ｘ1においてｂ＝０である化合物を示すことができる。
含フッ素化合物（Ｂ）の好ましい構造として、具体的には、以下のものを例示することができる。
（式中、Ｒｆ’は上記と同じであり、Ｒ5は（メタ）アクリル含有基である。）
That is, the fluorine-containing compound (B), among the compounds represented in the general formula (1) may indicate the compound is b = 0 in X 1.
Specifically as a preferable structure of a fluorine-containing compound (B), the following can be illustrated.
(Wherein, Rf ′ is the same as above, and R 5 is a (meth) acrylic-containing group).
含フッ素化合物（Ｂ）の好ましい構造として、具体的には、以下のものを例示することができる。
Specifically as a preferable structure of a fluorine-containing compound (B), the following can be illustrated.
ここで、Ｒ5の（メタ）アクリル含有基としては、Ｒ4で例示した（メタ）アクリル含有基と同様のものが例示できる。
Here, the (meth) acryl-containing group R 5, exemplified in R 4 (meth) similar to the acrylic-containing group can be exemplified.
このような含フッ素化合物（Ｂ）は、前に例示した含フッ素化合物（Ａ）の合成法において、含フッ素アルコール化合物の水酸基量の合計ｘモルに対する（メタ）アクリル基導入試薬のハロゲン原子あるいはイソシアネート基量ｙモルをｘ＜ｙとなる比率で仕込み、水酸基を全て反応させることにより得ることができる。
Such a fluorine-containing compound (B) is a halogen atom or isocyanate of the (meth) acrylic group introduction reagent with respect to the total x moles of hydroxyl groups of the fluorine-containing alcohol compound in the method of synthesizing the fluorine-containing compound (A) exemplified above. It can be obtained by charging the base weight y mole at a ratio of x <y and reacting all the hydroxyl groups.
本発明における含フッ素化合物（Ａ）と含フッ素化合物（Ｂ）を併用する形態においては、含フッ素化合物（Ａ）と含フッ素化合物（Ｂ）の含有率を調整することで、含フッ素化合物（Ａ）単体で（メタ）アクリル基と水酸基の比率を変化させるのと同様の効果を得ることができる。この場合、組成物中に含まれる含フッ素化合物（Ａ）、含フッ素化合物（Ｂ）全体の平均値として、組成物中の含フッ素化合物（Ａ）に含まれる水酸基に対する含フッ素化合物（Ａ）中に含まれる（メタ）アクリル基と含フッ素化合物（Ｂ）中に含まれる（メタ）アクリル基の合計のモル比［（メタ）アクリル基の合計（モル）／水酸基（モル）］が、０．２以上１９以下であることが好ましく、０．３以上１０以下であることがより好ましく、０．４以上５以下であることが更に好ましい。即ち系内に含まれる含フッ素化合物（Ａ）に含まれる（メタ）アクリル基の合計モル数をＮaA、水酸基の合計モル数をＮaH、含フッ素化合物（Ｂ）に含まれる（メタ）アクリル基の合計モル数をＮbA、とした時に、０．２≦（ＮaA＋ＮbA）／ＮaH≦１９であることが望ましい。
これよりも大きくなると含フッ素化合物（Ｂ）単体との特性の差が明確でなくなり、これより小さくなると非フッ素のアクリル化合物との溶解性が低下し、特性の発現に必要な濃度での均一な塗工が困難になる。 In the embodiment where the fluorine-containing compound (A) and the fluorine-containing compound (B) are used in combination in the present invention, the fluorine-containing compound (A) and the fluorine-containing compound (B) can be adjusted by adjusting the content rates thereof. The same effect as changing the ratio of (meth) acrylic group to hydroxyl group can be obtained by itself. In this case, in the fluorine-containing compound (A) to the hydroxyl group contained in the fluorine-containing compound (A) in the composition, the average value of the entire fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the composition The molar ratio of the total of (meth) acrylic groups contained in (F) to (meth) acrylic groups contained in the fluorine-containing compound (B) [total (mol) of (meth) acrylic groups / hydroxyl group (mol)] is 0. It is preferably 2 or more and 19 or less, more preferably 0.3 or more and 10 or less, and still more preferably 0.4 or more and 5 or less. That is, the total number of moles of (meth) acrylic groups contained in the fluorine-containing compound (A) contained in the system is N aA , the total number of moles of hydroxyl groups is N aH , and (meth) acrylics contained in the fluorine-containing compound (B) It is desirable that 0.2 ≦ (N aA + N bA ) / N aH ≦ 19, where N bA is the total number of moles of groups.
If it is larger than this range, the difference in properties with the fluorine-containing compound (B) alone will not be clear, and if smaller than this range, the solubility with non-fluorinated acrylic compounds will be reduced, and uniform at the concentration necessary for expression of properties. Coating becomes difficult.
これよりも大きくなると含フッ素化合物（Ｂ）単体との特性の差が明確でなくなり、これより小さくなると非フッ素のアクリル化合物との溶解性が低下し、特性の発現に必要な濃度での均一な塗工が困難になる。 In the embodiment where the fluorine-containing compound (A) and the fluorine-containing compound (B) are used in combination in the present invention, the fluorine-containing compound (A) and the fluorine-containing compound (B) can be adjusted by adjusting the content rates thereof. The same effect as changing the ratio of (meth) acrylic group to hydroxyl group can be obtained by itself. In this case, in the fluorine-containing compound (A) to the hydroxyl group contained in the fluorine-containing compound (A) in the composition, the average value of the entire fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the composition The molar ratio of the total of (meth) acrylic groups contained in (F) to (meth) acrylic groups contained in the fluorine-containing compound (B) [total (mol) of (meth) acrylic groups / hydroxyl group (mol)] is 0. It is preferably 2 or more and 19 or less, more preferably 0.3 or more and 10 or less, and still more preferably 0.4 or more and 5 or less. That is, the total number of moles of (meth) acrylic groups contained in the fluorine-containing compound (A) contained in the system is N aA , the total number of moles of hydroxyl groups is N aH , and (meth) acrylics contained in the fluorine-containing compound (B) It is desirable that 0.2 ≦ (N aA + N bA ) / N aH ≦ 19, where N bA is the total number of moles of groups.
If it is larger than this range, the difference in properties with the fluorine-containing compound (B) alone will not be clear, and if smaller than this range, the solubility with non-fluorinated acrylic compounds will be reduced, and uniform at the concentration necessary for expression of properties. Coating becomes difficult.
含フッ素活性エネルギー線硬化性組成物は、含フッ素化合物（Ａ）単体、及び含フッ素化合物（Ａ）と含フッ素化合物（Ｂ）の混合物のみとしても使用できるが、含フッ素化合物（Ａ）及び含フッ素化合物（Ｂ）と混合、硬化可能であれば、いかなるものであっても使用することができる。このような配合物として、具体的には、含フッ素化合物（Ａ）、（Ｂ）に該当しない、好ましくは分子中にフッ素原子を含有しない（非フッ素化の）、分子中にウレタン結合を含有又は非含有の、アクリル化合物（Ｃ）を挙げることができる。このアクリル化合物（Ｃ）としては、例えば、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキシド変性ジ（メタ）アクリレート、イソシアヌル酸ＥＯ変性トリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、フタル酸水素－（２，２，２－トリ－（メタ）アクリロイルオキシメチル）エチル、グリセロールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート等の２～６官能の（メタ）アクリル化合物、これらの（メタ）アクリル化合物のエチレンオキシド、プロピレンオキシド、エピクロルヒドリン、脂肪酸、アルキル変性品、エポキシ樹脂に（メタ）アクリル酸を付加させて得られるエポキシ（メタ）アクリレート類、及びアクリル酸エステル共重合体の側鎖に（メタ）アクリロイル基を導入した共重合体等を含むものが挙げられる。
The fluorine-containing active energy ray curable composition can be used only as the fluorine-containing compound (A) alone and as a mixture of the fluorine-containing compound (A) and the fluorine-containing compound (B), but the fluorine-containing compound (A) Any compound that can be mixed and cured with the fluorine compound (B) can be used. As such a compound, specifically, it does not correspond to the fluorine-containing compounds (A) and (B), preferably contains no fluorine atom in the molecule (non-fluorinated), contains a urethane bond in the molecule The acrylic compound (C) which is not or contained can be mentioned. Examples of the acrylic compound (C) include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, ethylene oxide modified with isocyanuric acid, di (meth) acrylate, Isocyanuric acid EO modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2 , 2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ester 2) 2- to 6-functional (meth) acrylic compounds such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, ethylene oxide of these (meth) acrylic compounds, Propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy (meth) acrylates obtained by adding (meth) acrylic acid to epoxy resin, and (meth) acryloyl group introduced into the side chain of acrylic ester copolymer Include those containing the copolymer and the like.
また、ウレタン（メタ）アクリレート類、ポリイソシアネートに水酸基を有する（メタ）アクリレートを反応させて得られるもの、ポリイソシアネートと末端ジオールのポリエステルに水酸基を有する（メタ）アクリレートを反応させて得られるもの、ポリオールに過剰のジイソシアネートと反応させて得られるポリイソシアネートに、水酸基を有する（メタ）アクリレートを反応させて得られるものを使用することもできる。中でも、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシ－３－アクリロイロキシプロピルメタクリレート、及びペンタエリスリトールトリ（メタ）アクリレートから選ばれる水酸基を有する（メタ）アクリレートと、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、メチレンビス（４－シクロヘキシルイソシアネート）、２－メチル－１，３－ジイソシアナトシクロヘキサン、２－メチル－１，５－ジイソシアナトシクロヘキサン及びジフェニルメタンジイソシアネートから選ばれるポリイソシアネートを反応させたウレタン（メタ）アクリレート類が好ましい。
Also, urethane (meth) acrylates, those obtained by reacting polyisocyanate with (meth) acrylate having hydroxyl group, those obtained by reacting polyisocyanate with polyester of terminal diol with (meth) acrylate having hydroxyl group, It is also possible to use one obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate obtained by reacting a polyol with an excess of diisocyanate. Among them, (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol tri (meth) acrylate, hexamethylene diisocyanate, isophorone diisocyanate, Tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylene bis (4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 Urethane (meth) acrylates which are obtained by reacting polyisocyanates selected from -diisocyanatocyclohexane and diphenylmethane diisocyanate are preferred.
中でも特に、１分子中に３個以上の（メタ）アクリル基を有し、かつ分子中に水酸基を有さない、ウレタン結合含有又は非含有の、非フッ素化多官能（メタ）アクリレート、１分子中に３個以上の（メタ）アクリル基と１個以上の水酸基を有する、ウレタン結合含有又は非含有の、非フッ素化多官能（メタ）アクリレート、及び分子中にウレタン結合を有し、１分子中に６個以上の（メタ）アクリル基を有する非フッ素化多官能ウレタン（メタ）アクリレートのいずれか又は２種類以上の組み合わせを含んだものが好ましい。
（Ｃ）成分は、１種単独で使用しても２種以上を併用してもよい。また組成物の物性調整のためフッ素化、非フッ素化の１官能の（メタ）アクリレート類を配合してもよい。 In particular, non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond, having one or more (meth) acrylic groups in one molecule and no hydroxyl group in one molecule, and one molecule Non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond having three or more (meth) acrylic groups and one or more hydroxyl groups in one, and one urethane compound having a urethane bond in the molecule It is preferable to contain one or a combination of two or more kinds of non-fluorinated polyfunctional urethane (meth) acrylates having 6 or more (meth) acrylic groups.
As the component (C), one type may be used alone, or two or more types may be used in combination. Moreover, you may mix | blend fluorinated and non-fluorinated monofunctional (meth) acrylates for physical-property adjustment of a composition.
（Ｃ）成分は、１種単独で使用しても２種以上を併用してもよい。また組成物の物性調整のためフッ素化、非フッ素化の１官能の（メタ）アクリレート類を配合してもよい。 In particular, non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond, having one or more (meth) acrylic groups in one molecule and no hydroxyl group in one molecule, and one molecule Non-fluorinated polyfunctional (meth) acrylate containing or not containing a urethane bond having three or more (meth) acrylic groups and one or more hydroxyl groups in one, and one urethane compound having a urethane bond in the molecule It is preferable to contain one or a combination of two or more kinds of non-fluorinated polyfunctional urethane (meth) acrylates having 6 or more (meth) acrylic groups.
As the component (C), one type may be used alone, or two or more types may be used in combination. Moreover, you may mix | blend fluorinated and non-fluorinated monofunctional (meth) acrylates for physical-property adjustment of a composition.
また、本発明の含フッ素活性エネルギー線硬化性組成物は、（Ｄ）成分として光重合開始剤を含有することで、活性エネルギー線の中でも紫外線によって硬化しやすい硬化性組成物とすることができる。（Ｄ）成分の光重合開始剤は、紫外線照射によりアクリル化合物を硬化させることができるものであれば特に限定されないが、好ましくは、例えば、アセトフェノン、ベンゾフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、１，２－オクタンジオン－１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、エタノン－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン等が挙げられ、これらは１種単独で使用しても２種以上を併用してもよい。
Moreover, the fluorine-containing active energy ray curable composition of this invention can be made into the curable composition which is easy to be hardened | cured by an ultraviolet-ray among the active energy rays by containing a photoinitiator as (D) component. . The photopolymerization initiator of the component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, and preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-one (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ -(4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octane Dion-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and the like. These may be used alone or in combination of two or more.
本発明の実施形態の一つである含フッ素活性エネルギー線硬化性組成物は、（Ａ）成分を含み、硬化後の表面に撥水撥油性、防汚性、耐指紋性、摩耗耐久性といった特性を付与することがその本質であり、各成分の配合量は、所望する撥水性、撥油性、組成物の溶解性、塗工条件、硬化条件、得られる物品の硬度等に応じて適宜決定すればよく、
（Ａ）成分単独、
（Ａ）成分と（Ｂ）成分、
（Ａ）成分と（Ｃ）成分、
（Ａ）成分と（Ｄ）成分、
（Ａ）成分と（Ｂ）成分と（Ｃ）成分、
（Ａ）成分と（Ｃ）成分と（Ｄ）成分、
（Ａ）成分と（Ｂ）成分と（Ｃ）成分と（Ｄ）成分、
及びこれらそれぞれに、必要に応じて後述するその他添加剤を加えたいずれの組み合わせでも使用できるが、中でも好適なのは、（Ａ）成分と（Ｂ）成分と（Ｃ）成分と（Ｄ）成分を含む組成物である。 The fluorine-containing active energy ray curable composition which is one of the embodiments of the present invention comprises the component (A), and the surface after curing is such as water and oil repellency, stain resistance, fingerprint resistance, and wear resistance. It is essential to impart properties, and the compounding amount of each component is appropriately determined according to the desired water repellency, oil repellency, solubility of the composition, coating conditions, curing conditions, hardness of the obtained article, etc. Just do
(A) component alone,
(A) component and (B) component,
(A) component and (C) component,
(A) component and (D) component,
(A) component, (B) component and (C) component,
(A) component, (C) component and (D) component,
(A) component, (B) component, (C) component and (D) component,
And although it is possible to use any combination of these and any of the other additives described later if necessary, among them, preferred ones include (A) component, (B) component, (C) component and (D) component. It is a composition.
（Ａ）成分単独、
（Ａ）成分と（Ｂ）成分、
（Ａ）成分と（Ｃ）成分、
（Ａ）成分と（Ｄ）成分、
（Ａ）成分と（Ｂ）成分と（Ｃ）成分、
（Ａ）成分と（Ｃ）成分と（Ｄ）成分、
（Ａ）成分と（Ｂ）成分と（Ｃ）成分と（Ｄ）成分、
及びこれらそれぞれに、必要に応じて後述するその他添加剤を加えたいずれの組み合わせでも使用できるが、中でも好適なのは、（Ａ）成分と（Ｂ）成分と（Ｃ）成分と（Ｄ）成分を含む組成物である。 The fluorine-containing active energy ray curable composition which is one of the embodiments of the present invention comprises the component (A), and the surface after curing is such as water and oil repellency, stain resistance, fingerprint resistance, and wear resistance. It is essential to impart properties, and the compounding amount of each component is appropriately determined according to the desired water repellency, oil repellency, solubility of the composition, coating conditions, curing conditions, hardness of the obtained article, etc. Just do
(A) component alone,
(A) component and (B) component,
(A) component and (C) component,
(A) component and (D) component,
(A) component, (B) component and (C) component,
(A) component, (C) component and (D) component,
(A) component, (B) component, (C) component and (D) component,
And although it is possible to use any combination of these and any of the other additives described later if necessary, among them, preferred ones include (A) component, (B) component, (C) component and (D) component. It is a composition.
このとき、（Ｂ）成分を配合する場合の配合量は、上述したように、（Ａ）成分に含まれる水酸基に対する（Ａ）成分と（Ｂ）成分に含まれる（メタ）アクリル基の合計のモル比［（メタ）アクリル基の合計（モル）／水酸基（モル）］が、０．２以上１９以下となる量で配合することが好ましい。
（Ｃ）成分を配合する場合の配合量は特に制限されないが、（Ａ）成分と（Ｂ）成分の合計に対する比率で考えることが望ましく、例えば（Ａ）成分と（Ｂ）成分の合計量を１質量部とした時に、０．１～１０，０００質量部が好ましく、より好ましくは１～１，０００質量部、特に好ましくは５～８００質量部である。（Ｃ）成分が少なすぎると（Ｃ）成分の配合により期待される塗工特性、硬化物特性が得られない場合があり、多すぎると、（Ａ）成分に期待される防汚特性が得られない場合がある。
更に、（Ｄ）成分を配合する場合の配合量は、（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計量を１００質量部とした時に、０．１～１０質量部が好ましく、特に好ましくは０．５～５質量部である。（Ｄ）成分が少なすぎると硬化不良が発生し、期待される硬化物特性が得られない場合があり、多すぎると、硬化物表面に欠損が発生したり、硬化物に濁りが発生したり、着色が強くなったりする場合がある。 At this time, as described above, the blending amount in the case of blending the (B) component is the sum of the (meth) acrylic groups contained in the (A) component and the (B) component with respect to the hydroxyl group contained in the (A) component. It is preferable to mix | blend in molar ratio [total (mol) of a (meth) acryl group / hydroxyl group (mol)] to be 0.2 or more and 19 or less.
Although the compounding quantity in particular in mix | blending (C) component is not restrict | limited, It is desirable to consider by the ratio with respect to the sum total of (A) component and (B) component, for example, the total amount of (A) component and (B) component The amount is preferably 0.1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, and particularly preferably 5 to 800 parts by mass, per 1 part by mass. If the amount of the component (C) is too small, the expected coating properties and cured product properties may not be obtained by the blending of the component (C). If the amount is too large, the antifouling properties expected of the component (A) are obtained. It may not be possible.
Furthermore, the blending amount in the case of blending the component (D) is preferably 0.1 to 10 parts by mass when the total amount of the components (A), (B) and (C) component is 100 parts by mass, Particularly preferably, it is 0.5 to 5 parts by mass. If the amount of the component (D) is too small, curing defects may occur and expected cured product properties may not be obtained. If the amount is too large, defects may occur on the surface of the cured material or turbidity may occur on the cured material. , And may become strong.
（Ｃ）成分を配合する場合の配合量は特に制限されないが、（Ａ）成分と（Ｂ）成分の合計に対する比率で考えることが望ましく、例えば（Ａ）成分と（Ｂ）成分の合計量を１質量部とした時に、０．１～１０，０００質量部が好ましく、より好ましくは１～１，０００質量部、特に好ましくは５～８００質量部である。（Ｃ）成分が少なすぎると（Ｃ）成分の配合により期待される塗工特性、硬化物特性が得られない場合があり、多すぎると、（Ａ）成分に期待される防汚特性が得られない場合がある。
更に、（Ｄ）成分を配合する場合の配合量は、（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計量を１００質量部とした時に、０．１～１０質量部が好ましく、特に好ましくは０．５～５質量部である。（Ｄ）成分が少なすぎると硬化不良が発生し、期待される硬化物特性が得られない場合があり、多すぎると、硬化物表面に欠損が発生したり、硬化物に濁りが発生したり、着色が強くなったりする場合がある。 At this time, as described above, the blending amount in the case of blending the (B) component is the sum of the (meth) acrylic groups contained in the (A) component and the (B) component with respect to the hydroxyl group contained in the (A) component. It is preferable to mix | blend in molar ratio [total (mol) of a (meth) acryl group / hydroxyl group (mol)] to be 0.2 or more and 19 or less.
Although the compounding quantity in particular in mix | blending (C) component is not restrict | limited, It is desirable to consider by the ratio with respect to the sum total of (A) component and (B) component, for example, the total amount of (A) component and (B) component The amount is preferably 0.1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, and particularly preferably 5 to 800 parts by mass, per 1 part by mass. If the amount of the component (C) is too small, the expected coating properties and cured product properties may not be obtained by the blending of the component (C). If the amount is too large, the antifouling properties expected of the component (A) are obtained. It may not be possible.
Furthermore, the blending amount in the case of blending the component (D) is preferably 0.1 to 10 parts by mass when the total amount of the components (A), (B) and (C) component is 100 parts by mass, Particularly preferably, it is 0.5 to 5 parts by mass. If the amount of the component (D) is too small, curing defects may occur and expected cured product properties may not be obtained. If the amount is too large, defects may occur on the surface of the cured material or turbidity may occur on the cured material. , And may become strong.
なお、上記（Ｃ）成分に（Ｄ）成分が配合されたアクリル組成物及びハードコート剤は各社から様々なものが市販されている。本発明の含フッ素活性エネルギー線硬化性組成物は、このような市販品に（Ａ）成分、又は（Ａ）成分と（Ｂ）成分を添加したものであってもよい。市販品のハードコート剤として、例えば、荒川化学工業（株）「ビームセット」、大橋化学工業（株）「ユービック」、オリジン電気（株）「ＵＶコート」、カシュー（株）「カシューＵＶ」、ＪＳＲ（株）「デソライト」、大日精化工業（株）「セイカビーム」、日本合成化学（株）「紫光」、藤倉化成（株）「フジハード」、三菱レイヨン（株）「ダイヤビーム」、武蔵塗料（株）「ウルトラバイン」、ＤＩＣ（株）「ユニディック」等が挙げられる。またこれらの市販の組成物を使用した場合も、必要に応じて（Ｃ）成分、（Ｄ）成分を追加してもよい。
Various acrylic compositions and hard coat agents in which the component (D) is blended with the component (C) are commercially available from various companies. The fluorine-containing active energy ray curable composition of the present invention may be one obtained by adding the component (A) or the components (A) and (B) to such a commercial product. Commercially available hard coating agents include, for example, Arakawa Chemical Industries, Ltd. “Beam Set”, Ohashi Chemical Industries, Ltd. “Eubik”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd. “Cashew UV”, JSR Co., Ltd. "Desorite", Dainichi Seika Kogyo Co., Ltd. "Seika Beam", Nippon Gohsei Kagaku Co., Ltd. "Shikomitsu", Fujikura Kasei Co., Ltd. "Fujihard", Mitsubishi Rayon Co., Ltd. "Dia Beam", Musashi Paint Examples thereof include "Ultra Bine", DIC Corporation "Unidic" and the like. Moreover, also when using these commercially available compositions, you may add (C) component and (D) component as needed.
［その他の添加剤］
本発明の含フッ素活性エネルギー線硬化性組成物には、更に、目的に応じて、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラー等を配合することもできる。また、上記のように市販品のハードコート剤を用いる場合であっても、目的に応じて、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラー等を配合することができる。 [Other additives]
The fluorine-containing active energy ray-curable composition of the present invention further comprises, according to the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a heat resistant stabilizer, oxidation Inhibitors, surfactants, colorants, fillers and the like can also be blended. In addition, even when using a commercially available hard coating agent as described above, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, and heat stability Agents, antioxidants, surfactants, colorants, fillers and the like can be blended.
本発明の含フッ素活性エネルギー線硬化性組成物には、更に、目的に応じて、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラー等を配合することもできる。また、上記のように市販品のハードコート剤を用いる場合であっても、目的に応じて、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラー等を配合することができる。 [Other additives]
The fluorine-containing active energy ray-curable composition of the present invention further comprises, according to the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a heat resistant stabilizer, oxidation Inhibitors, surfactants, colorants, fillers and the like can also be blended. In addition, even when using a commercially available hard coating agent as described above, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, and heat stability Agents, antioxidants, surfactants, colorants, fillers and the like can be blended.
また、被膜強度、耐擦傷性、透明性などの各種特性向上、屈折率の調整等の特性向上のため、反応性・非反応性中空・中実シリカ微粒子などの各種無機微粒子を配合してもよい。
In addition, various inorganic fine particles such as reactive non-reactive hollow and solid silica fine particles may be blended to improve various properties such as film strength, scratch resistance and transparency, and to improve characteristics such as adjustment of refractive index. Good.
有機溶剤としては、１－プロパノール、２－プロパノール、イソプロピルアルコール、ｎ－ブタノール、イソブタノール、ｔｅｒｔ－ブタノール、ジアセトンアルコールなどのアルコール類；メチルプロピルケトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノンなどのケトン類；ジプロピルエーテル、ジブチルエーテル、アニソール、ジオキサン、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテートなどのエーテル類；酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸シクロヘキシルなどのエステル類、ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等のフッ素変性芳香族炭化水素系溶剤、メチルパーフルオロブチルエーテル等のフッ素変性エーテル系溶剤などを挙げることができる。上記有機溶剤は、１種を単独で用いてもよいし、２種以上を混合して用いてもよい。
有機溶剤の使用量は特に制限されるものではないが、（Ａ）～（Ｃ）成分の合計１００質量部に対し、５０～１０，０００質量部が好ましく、特に８０～１，０００質量部が好ましい。 As the organic solvent, alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, etc .; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK) And ketones such as cyclohexanone; dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), ethers such as propylene glycol monomethyl ether acetate; ethyl acetate, Esters such as propyl acetate, butyl acetate and cyclohexyl acetate, m-xylene hexafluoride, benzoto Fluorine-modified aromatic hydrocarbon solvents such as fluoride, and the like fluorine-modified ether solvents such as methyl perfluorobutyl ether. The organic solvents may be used alone or in combination of two or more.
Although the amount of the organic solvent used is not particularly limited, it is preferably 50 to 10,000 parts by mass, particularly 80 to 1,000 parts by mass, with respect to 100 parts by mass in total of the components (A) to (C). preferable.
有機溶剤の使用量は特に制限されるものではないが、（Ａ）～（Ｃ）成分の合計１００質量部に対し、５０～１０，０００質量部が好ましく、特に８０～１，０００質量部が好ましい。 As the organic solvent, alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, etc .; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK) And ketones such as cyclohexanone; dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), ethers such as propylene glycol monomethyl ether acetate; ethyl acetate, Esters such as propyl acetate, butyl acetate and cyclohexyl acetate, m-xylene hexafluoride, benzoto Fluorine-modified aromatic hydrocarbon solvents such as fluoride, and the like fluorine-modified ether solvents such as methyl perfluorobutyl ether. The organic solvents may be used alone or in combination of two or more.
Although the amount of the organic solvent used is not particularly limited, it is preferably 50 to 10,000 parts by mass, particularly 80 to 1,000 parts by mass, with respect to 100 parts by mass in total of the components (A) to (C). preferable.
またその他に、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラーとして、公知のものを本発明の目的を損なわない範囲で特に制限されず使用することができる。
In addition, known polymerization inhibitors, antistatic agents, antifoaming agents, viscosity regulators, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers according to the present invention may be used. It can be used without particular limitation as long as the purpose is not impaired.
本発明の含フッ素活性エネルギー線硬化性組成物の硬化方法は特に限定されず、（Ａ）成分単独、（Ａ）成分と（Ｂ）成分、（Ａ）成分と（Ｃ）成分、又は（Ａ）成分と（Ｂ）成分と（Ｃ）成分を含む組成物を、適宜溶剤で希釈、塗布したものを電子線等の活性エネルギー線によって硬化させることもできるが、更に（Ｄ）成分の光重合開始剤を含有する場合は、紫外線によって硬化させることができる。紫外線による硬化の場合、紫外線照射を空気中で行うこともできるが、酸素による硬化阻害を防止するため酸素濃度を５，０００ｐｐｍ以下に抑えることが好ましく、窒素、二酸化炭素、アルゴン等の不活性ガス雰囲気下で硬化させることが特に好ましい。
The curing method of the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, and component (A) alone, component (A) and component (B), component (A) and component (C), or (A) The composition containing the component (B) and the component (C) may be suitably diluted with a solvent, and the composition applied may be cured by active energy rays such as an electron beam, but further photopolymerization of the component (D) When it contains an initiator, it can be cured by ultraviolet light. In the case of curing by UV light, UV irradiation can be carried out in air, but in order to prevent the inhibition of curing by oxygen, it is preferable to suppress the oxygen concentration to 5,000 ppm or less, and inert gases such as nitrogen, carbon dioxide, argon etc. Curing under an atmosphere is particularly preferred.
またフィルム等の基材のコーティング、各種物品の塗料等として用いる場合、目的とする任意の特性に合わせて（Ｃ）成分やその他の添加剤を自由に配合することができる。
Moreover, when using as coating of base materials, such as a film, and a coating material of various articles | goods, (C) component and other additives can be mix | blended freely according to the arbitrary characteristics made into the objective.
また、本発明の含フッ素活性エネルギー線硬化性組成物の一般的な使用形態としては、本発明の含フッ素活性エネルギー線硬化性組成物層が硬化後に密着又は接着するものであればいかなる基材上に塗布することもできるが、特に樹脂基材、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリプロピレン、セロファン、ジアセチルセルロース、トリアセチルセルロース、アセチルセルロースブチレート、セルロースアセテートプロピオネート、シクロオレフィンポリマー、シクロオレフィンコポリマー、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン－酢酸ビニル共重合体、ポリスチレン、ポリカーボネート、ポリメチルペンテン、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド、フッ素樹脂、ナイロン、アクリル樹脂等の樹脂を挙げることができる。これらは、フィルム、板状、及び成形部材等任意の形態をとるものに対してその表面に使用できる。
Moreover, as a general usage form of the fluorine-containing active energy ray curable composition of the present invention, any substrate can be used as long as the fluorine-containing active energy ray curable composition layer of the present invention adheres or adheres after curing. It can also be applied on top, but in particular resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate , Cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone , Mention may be made of polyether ether ketone, polyether sulfone, polyether imide, polyimide, fluorocarbon resin, nylon, a resin such as an acrylic resin. These can be used on the surface of films, plates, and molded members such as molded members.
またフィルム基材に塗工した場合、含フッ素活性エネルギー線硬化性組成物層を塗布・形成したのと反対の面に粘着剤を塗布した構造をとっていてもよく、更に粘着剤を保護するための離型フィルムを配置してもよい。
When applied to a film substrate, it may have a structure in which an adhesive is applied to the surface opposite to that on which the fluorine-containing active energy ray curable composition layer is applied and formed, and further protects the adhesive A mold release film may be disposed.
また、前記フィルム基材は、上記で挙げた樹脂フィルムのみからなる基材であってもよいが、本発明の含フッ素活性エネルギー線硬化性組成物との密着性を向上させるために、前記樹脂フィルムにプライマー層を設けたフィルム基材であってもよい。前記プライマー層としては、例えば、ポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂等からなるものが挙げられる。
The film substrate may be a substrate consisting only of the resin film mentioned above, but in order to improve the adhesion with the fluorine-containing active energy ray curable composition of the present invention, the resin It may be a film substrate provided with a primer layer on the film. Examples of the primer layer include those made of polyester resins, urethane resins, acrylic resins and the like.
また本発明の含フッ素活性エネルギー線硬化性組成物は、硬化・未硬化の本発明に該当しない硬化性組成物層上に塗工硬化してもよい。例えば、硬度、耐久性、帯電防止性、カールなどの変形防止性がより高い硬化物層の上に本発明の含フッ素活性エネルギー線硬化性組成物を重ね塗りすることができる。
In addition, the fluorine-containing active energy ray curable composition of the present invention may be coated and cured on a curable / uncured curable composition layer that does not fall under the present invention. For example, the fluorine-containing active energy ray curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic properties, and deformation prevention properties such as curl.
また、本発明の含フッ素活性エネルギー線硬化性組成物との密着性を向上させる目的で、樹脂フィルム表面を、サンドブラスト法、溶剤処理法等による表面の凹凸化処理、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理、酸化処理等により処理を施すこともできる。
Further, for the purpose of improving the adhesion to the fluorine-containing active energy ray curable composition of the present invention, the surface of the resin film is subjected to surface roughening treatment by corona blasting, solvent treatment, etc., corona discharge treatment, chromic acid treatment The treatment can also be performed by flame treatment, hot air treatment, ozone / ultraviolet radiation treatment, oxidation treatment or the like.
本発明の含フッ素活性エネルギー線硬化性組成物を上記基材や物品に塗布する方法としては、特に制限はされないが、例えば、ロールコート、グラビアコート、フローコート、カーテンコート、ディップコート、スプレーコート、スピンコート、バーコート、スクリーン印刷等の公知の塗工方法を用いることができる。
塗工後、塗膜に活性エネルギー線を照射してこれを硬化させる。ここで、活性エネルギー線としては、電子線、紫外線等任意のものを用いることができるが、特に紫外線が好ましい。紫外線源としては、水銀ランプ、メタルハライドランプ、ＬＥＤランプが好適である。紫外線照射量としては、少なすぎると未硬化成分が残存し、多すぎると塗膜及び基材が劣化する可能性があるため、１０～１０，０００ｍＪ／ｃｍ2、特に１００～４，０００ｍＪ／ｃｍ2の範囲にあることが望ましい。
また酸素による硬化阻害を防止するために、紫外線照射時に照射雰囲気を窒素、二酸化炭素、アルゴン等の酸素分子を含まない不活性ガスで置換したり、塗膜表面を離型性を持つ紫外線透過性のある保護層で覆い、その上から紫外線を照射したり、基材が紫外線透過性を有する場合は塗膜表面を離型性のある保護層で覆った上で基材の塗工面とは反対側から紫外線を照射してもよい。また塗膜のレベリングあるいは塗膜中の（メタ）アクリル基の重合を効果的に行うため、紫外線照射前及び照射中に塗膜及び基材を赤外線や熱風乾燥炉等任意の手法で加熱してもよい。 The method for applying the fluorine-containing active energy ray-curable composition of the present invention to the above-mentioned substrate or article is not particularly limited. For example, roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating Known coating methods such as spin coating, bar coating and screen printing can be used.
After coating, the coating film is irradiated with active energy rays to cure it. Here, as the active energy ray, an electron beam, an ultraviolet ray, or the like can be used, but the ultraviolet ray is particularly preferable. As the ultraviolet light source, a mercury lamp, a metal halide lamp, and an LED lamp are preferable. If the amount of UV irradiation is too small, the uncured component will remain, and if too much, the coating film and the substrate may deteriorate, so 10 to 10,000 mJ / cm 2 , especially 100 to 4,000 mJ / cm. It is desirable to be in the range of 2 .
In addition, in order to prevent the inhibition of curing by oxygen, at the time of ultraviolet irradiation, the irradiation atmosphere is replaced with an inert gas containing no oxygen molecule such as nitrogen, carbon dioxide, argon, etc. Covered with a protective layer, and irradiated with ultraviolet light from above, or if the substrate is transparent to ultraviolet light, the coated surface is covered with a protective layer having releasability, and it is opposite to the coated surface of the substrate You may irradiate an ultraviolet-ray from the side. Also, in order to effectively perform coating leveling or (meth) acrylic group polymerization in the coating, the coating and substrate are heated by an arbitrary method such as infrared rays or a hot air drying furnace before and during ultraviolet irradiation. It is also good.
塗工後、塗膜に活性エネルギー線を照射してこれを硬化させる。ここで、活性エネルギー線としては、電子線、紫外線等任意のものを用いることができるが、特に紫外線が好ましい。紫外線源としては、水銀ランプ、メタルハライドランプ、ＬＥＤランプが好適である。紫外線照射量としては、少なすぎると未硬化成分が残存し、多すぎると塗膜及び基材が劣化する可能性があるため、１０～１０，０００ｍＪ／ｃｍ2、特に１００～４，０００ｍＪ／ｃｍ2の範囲にあることが望ましい。
また酸素による硬化阻害を防止するために、紫外線照射時に照射雰囲気を窒素、二酸化炭素、アルゴン等の酸素分子を含まない不活性ガスで置換したり、塗膜表面を離型性を持つ紫外線透過性のある保護層で覆い、その上から紫外線を照射したり、基材が紫外線透過性を有する場合は塗膜表面を離型性のある保護層で覆った上で基材の塗工面とは反対側から紫外線を照射してもよい。また塗膜のレベリングあるいは塗膜中の（メタ）アクリル基の重合を効果的に行うため、紫外線照射前及び照射中に塗膜及び基材を赤外線や熱風乾燥炉等任意の手法で加熱してもよい。 The method for applying the fluorine-containing active energy ray-curable composition of the present invention to the above-mentioned substrate or article is not particularly limited. For example, roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating Known coating methods such as spin coating, bar coating and screen printing can be used.
After coating, the coating film is irradiated with active energy rays to cure it. Here, as the active energy ray, an electron beam, an ultraviolet ray, or the like can be used, but the ultraviolet ray is particularly preferable. As the ultraviolet light source, a mercury lamp, a metal halide lamp, and an LED lamp are preferable. If the amount of UV irradiation is too small, the uncured component will remain, and if too much, the coating film and the substrate may deteriorate, so 10 to 10,000 mJ / cm 2 , especially 100 to 4,000 mJ / cm. It is desirable to be in the range of 2 .
In addition, in order to prevent the inhibition of curing by oxygen, at the time of ultraviolet irradiation, the irradiation atmosphere is replaced with an inert gas containing no oxygen molecule such as nitrogen, carbon dioxide, argon, etc. Covered with a protective layer, and irradiated with ultraviolet light from above, or if the substrate is transparent to ultraviolet light, the coated surface is covered with a protective layer having releasability, and it is opposite to the coated surface of the substrate You may irradiate an ultraviolet-ray from the side. Also, in order to effectively perform coating leveling or (meth) acrylic group polymerization in the coating, the coating and substrate are heated by an arbitrary method such as infrared rays or a hot air drying furnace before and during ultraviolet irradiation. It is also good.
このようにして得られる含フッ素活性エネルギー線硬化性組成物の硬化物層の厚みとしては特に制限されないが、０．０１～５，０００μｍ、特に０．０５～２００μｍであることが好ましい。
The thickness of the cured product layer of the fluorine-containing active energy ray-curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 μm, particularly preferably 0.05 to 200 μm.
また、このようにして得られる本発明の含フッ素活性エネルギー線硬化性組成物の硬化物層は、イオン交換水の２μＬの液滴が接液から１秒後に液面と固体面とのなす角により測定した静的水接触角が１００°以上、特に１０５°以上、オレイン酸の４μＬの液滴が接液から１秒後に液面と固体面とのなす角により測定した静的オレイン酸接触角が６０°以上、特に６５°以上である撥水撥油性表面となり得ることが好ましい。なお、上記接触角とするためには、本発明の含フッ素活性エネルギー線硬化性組成物の硬化物層が、該硬化物層の全表面積に対して平均して厚さ１０ｎｍ以上の層をなせる量であることが好ましい。また、硬化物層表面には未反応の（メタ）アクリル基が残存していないほど好ましく、このため窒素、二酸化炭素等の不活性ガス雰囲気下で硬化させた硬化物層であることが望ましい。
In addition, the cured product layer of the fluorine-containing active energy ray-curable composition of the present invention thus obtained has an angle formed between the liquid surface and the solid surface after 2 seconds of 2 μL droplets of ion exchanged water coming into contact with the liquid. Static water contact angle measured by 100 ° C or more, in particular 105 ° or more, Static oleic acid contact angle measured by the angle between the liquid surface and the solid surface after 4 seconds of liquid drop of oleic acid It is preferable that it can be a water and oil repellent surface having an angle of 60 ° or more, particularly 65 ° or more. In order to obtain the above contact angle, the cured product layer of the fluorine-containing active energy ray curable composition of the present invention is a layer having a thickness of 10 nm or more on average with respect to the total surface area of the cured product layer. Preferably, the amount is Further, it is preferable that no unreacted (meth) acrylic group remain on the surface of the cured product layer, and therefore, it is desirable that the cured product layer be cured under an inert gas atmosphere such as nitrogen or carbon dioxide.
以上のように、本発明の含フッ素活性エネルギー線硬化性組成物は、紫外線等の活性エネルギー線によって硬化可能であり、物品の表面に、撥水撥油性、防汚性、すべり性、耐摩耗性に優れた硬化樹脂層を形成することができる。
As described above, the fluorine-containing active energy ray curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and the water and oil repellency, stain resistance, slipperiness, and abrasion resistance on the surface of an article It is possible to form a cured resin layer having excellent properties.
更に、本発明では、上述した本発明の含フッ素活性エネルギー線硬化性組成物を表面に塗布し硬化させた硬化被膜を有する物品を提供する。上述したように、本発明の含フッ素活性エネルギー線硬化性組成物を用いれば、基材（物品）の表面に優れた表面特性を有する硬化被膜（硬化樹脂層）を形成することが可能になる。特に、アクリルハードコートの表面に撥水性、撥油性、防汚性を付与するのに有用である。これによって、指紋、皮脂、汗などの人脂、化粧品等による汚れ、機械油などが付着し難くなり、かつ拭き取り性にも優れたハードコート表面を基材に与えることができる。このため、本発明の含フッ素活性エネルギー線硬化性組成物は、人が触れて人脂、化粧品等により汚される可能性のある基材（物品）、また作業者の人脂や機械油などで汚染される可能性のある機械内部に用いられる工程材料フィルム等の表面に対する防汚塗装膜もしくは保護膜を提供することができる。
Furthermore, the present invention provides an article having a cured film obtained by applying the above-mentioned fluorine-containing active energy ray curable composition of the present invention to the surface and curing the composition. As described above, when the fluorine-containing active energy ray curable composition of the present invention is used, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of a substrate (article). . In particular, it is useful for imparting water repellency, oil repellency and stain resistance to the surface of an acrylic hard coat. As a result, fingerprints, sebum, sweat and other human fats, stains due to cosmetics and the like, mechanical oil and the like are less likely to adhere, and a hard coat surface excellent in wiping properties can be provided to the substrate. For this reason, the fluorine-containing active energy ray-curable composition of the present invention is a substrate (article) which may be contaminated with human fat, cosmetics, etc. by human contact, with human fat, mechanical oil, etc. of workers. An antifouling coating film or a protective film can be provided on the surface of a process material film or the like used inside a machine that may be contaminated.
本発明の含フッ素活性エネルギー線硬化性組成物を用いて形成される硬化被膜（硬化樹脂層）は、タブレット型コンピュータ、ノートＰＣ、携帯電話・スマートフォン等の携帯（通信）情報端末、デジタルメディアプレイヤー、電子ブックリーダーなど各種機器の筐体、時計型・眼鏡型ウェアラブルコンピュータ；液晶ディスプレイ、プラズマディスプレイ、有機ＥＬ（エレクトロルミネッセンス）ディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、フィールドエミッションプロジェクションディスプレイ、ＣＲＴ、トナー系ディスプレイなどの各種フラットパネルディスプレイ及びＴＶの画面などの表示操作機器表面及びこれらの内部に使用される各種光学フィルム類、自動車の外装、ピアノや家具の光沢表面、大理石等の建築用石材表面、トイレ、風呂、洗面所等の水周りの装飾建材、美術品展示用保護ガラス、ショーウインドー、ショーケース、フォトフレーム用カバー、腕時計、自動車窓用ガラス、列車、航空機等の窓ガラス、自動車ヘッドライト、テールランプなどの透明なガラス製又は透明なプラスチック製（アクリル、ポリカーボネートなど）部材、各種ミラー部材等の塗装膜及び表面保護膜として有用である。
The cured film (cured resin layer) formed by using the fluorine-containing active energy ray curable composition of the present invention is a tablet computer, a notebook PC, a portable (communication) information terminal such as a mobile phone or a smartphone, a digital media player , Housings for various devices such as e-book readers, watch-type and glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, Various flat panel displays such as CRT and toner type display, display operation equipment surface such as TV screen, various optical films used in these, exterior of car, glossy surface of piano or furniture, marble etc Architectural stone surface, decoration building materials around water such as toilet, bath, washroom, etc., protective glass for art display, show window, showcase, cover for photo frame, watch, glass for automobile window, window glass for train, aircraft etc. It is useful as a coating film and surface protective film of transparent glass or transparent plastic (acrylic, polycarbonate etc.) members such as automobile headlights and tail lamps, various mirror members and the like.
中でも特に、タッチパネルディスプレイなど人の指あるいは手のひらで画面上の操作を行う表示入力装置を有する各種機器、例えば、タブレット型コンピュータ、ノートＰＣ、スマートフォン、携帯電話、その他携帯（通信）情報端末、スマートウォッチ、デジタルメディアプレイヤー、電子ブックリーダー、デジタルフォトフレーム、ゲーム機、デジタルカメラ、デジタルビデオカメラ、ＧＰＳ表示記録機器、自動車用等のナビゲーション装置、自動車用等の制御パネル、自動現金引出し預け入れ装置、現金自動支払機、自動販売機、デジタルサイネージ（電子看板）、セキュリティーシステム端末、ＰＯＳ端末、リモートコントローラなど各種コントローラ、車載装置用パネルスイッチなどの表示入力装置などの表面保護膜として有用である。
Above all, various devices having a display input device that performs operations on the screen with a human finger or palm such as a touch panel display, for example, tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, smart watches , Digital media player, e-book reader, digital photo frame, game machine, digital camera, digital video camera, GPS display recording device, navigation device for cars etc., control panel for cars etc, automatic cash withdrawal depositor, cash automatic Useful as surface protection films for various controllers such as payment machines, vending machines, digital signage (electronic signs), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices A.
更に本発明の含フッ素活性エネルギー線硬化性組成物により形成される硬化被膜は、光磁気ディスク、光ディスク等の光記録媒体；メガネレンズ、プリズム、レンズシート、ペリクル膜、偏光板、光学フィルター、レンチキュラーレンズ、フレネルレンズ、反射防止膜、各種カメラ用レンズ、各種レンズ用保護フィルター、光ファイバーや光カプラーなどの光学部品・光デバイスの表面保護被膜としても有用である。
Furthermore, the cured film formed of the fluorine-containing active energy ray curable composition of the present invention is an optical recording medium such as a magneto-optical disc or an optical disc; spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticulars It is also useful as a surface protective film of optical components and optical devices such as lenses, Fresnel lenses, antireflective films, lenses for various cameras, protective filters for various lenses, optical fibers and optical couplers.
以上のような、本発明の含フッ素活性エネルギー線硬化性組成物は、目的とする物品の表面に本発明に係る含フッ素化合物（Ａ）のパーフルオロポリエーテル構造を配置させることにより、撥水性、撥油性、すべり性、防汚性、指紋の目立ちにくさ、指紋拭き取り性、耐摩耗性、低屈折率特性、耐溶剤性、耐薬品性等の優れた性質を与えることをその本質としている。
As described above, the fluorine-containing active energy ray curable composition of the present invention is water repellent by arranging the perfluoropolyether structure of the fluorine-containing compound (A) according to the present invention on the surface of an article to be aimed Essential to impart excellent properties such as oil repellency, slipperiness, stain resistance, fingerprint inconspicuousness, fingerprint wiping resistance, abrasion resistance, low refractive index characteristics, solvent resistance, chemical resistance, etc. .
このような本発明の含フッ素活性エネルギー線硬化性組成物を使用する際は、配合物の組み合わせ、組成比、どのような特性を重視するかに応じて、適切な使用方法をそれぞれの用途に応じた公知の技術を元に選定すればよい。このような公知の技術は、フッ素を含む組成物に対するものだけでなく既存の活性エネルギー線硬化性組成物に用いられている手法を含めて検討の範囲に含めることができる。
When using such a fluorine-containing active energy ray-curable composition of the present invention, an appropriate method of use may be applied to each application depending on the combination of the composition, the composition ratio, and what property is to be emphasized. The selection may be made based on known techniques according to the requirements. Such known techniques can be included in the scope of the study, not only for compositions containing fluorine but also for methods used in existing active energy ray curable compositions.
例えば、本発明の含フッ素活性エネルギー線硬化性組成物を配合調製するにあたり、本発明に係る含フッ素化合物（Ａ）に加えて、前記した本硬化性組成物における各種配合物を組み合わせる際に、低屈折率特性やこれを利用した低反射特性を重視する場合には、反応性中空シリカや反応性基を有しない中空シリカ、多官能アクリル化合物を使用すること、また被膜強度や耐擦傷性を向上させる場合には、多官能アクリル化合物を好適な量に配合すること、あるいは硬度と屈曲性のバランスをとるためには、６官能以上の多官能アクリル化合物と３官能以下のアクリル化合物の組み合わせを行うこと等は、公知のアクリル硬化性組成物配合の知見から容易に類推できる。
For example, when the fluorine-containing active energy ray curable composition of the present invention is compounded and prepared, in addition to the fluorine-containing compound (A) according to the present invention, when combining various compounds in the above-mentioned main curable composition When importance is attached to low refractive index characteristics and low reflection characteristics utilizing this, it is necessary to use reactive hollow silica, hollow silica having no reactive group, polyfunctional acrylic compound, film strength and scratch resistance. In the case of improving, in order to mix the polyfunctional acrylic compound in a suitable amount, or to balance the hardness and the flexibility, the combination of the polyfunctional acrylic compound having 6 or more functions and the acrylic compound having 3 or less functional is used. What to do can be easily inferred from the knowledge of the known acrylic curable composition formulation.
また、本発明の含フッ素活性エネルギー線硬化性組成物を塗布することで物品を得る場合、例えば、フィルム基材への塗工を行う際、干渉縞を防ぐために適切な塗工膜厚となるように調整を行うこと、フィルム基材の厚さを調整してカールを抑制しやすくしたり、基材フィルムの弾性率を調整することで含フッ素活性エネルギー線硬化性組成物の塗膜硬化後の変形や塗膜の割れを抑制すること等は、それぞれの特性に応じた既存の条件の組み合わせを元にスクリーニング作業を行って選定させるものであり、既存技術の組み合わせにより容易に達成可能である。
When an article is obtained by applying the fluorine-containing active energy ray-curable composition of the present invention, for example, when coating on a film substrate, an appropriate coating film thickness is obtained to prevent interference fringes. Adjusting the thickness of the film substrate to make it easy to suppress curling, or adjusting the elastic modulus of the substrate film to cure the coating of the fluorine-containing active energy ray curable composition Of suppressing the deformation of the coating film and cracking of the coating film, etc. is to perform screening work based on the combination of the existing conditions according to the respective characteristics, and can be easily achieved by the combination of the existing techniques .
以下に、合成例、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
EXAMPLES The present invention will be specifically described below by showing Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［合成例１］含フッ素アクリル化合物（Ａ－１）の合成
乾燥空気雰囲気下で、下記式
Ｒｆ1：－ＣＦ2Ｏ（ＣＦ2Ｏ）p1（ＣＦ2ＣＦ2Ｏ）q1ＣＦ2－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）
で示される含フッ素アルコール化合物（Ｅ－１）５０．０ｇ（水酸基量０．０５６モル）に、メチルエチルケトン５０．０ｇ、及びアクリロイルオキシエチルイソシアネート１．３４ｇ（０．００９５０モル）を混合し、５０℃に加熱して１時間攪拌した。そこにジオクチル錫ジラウレート０．０５ｇを添加し、５０℃下８時間攪拌した。1Ｈ－ＮＭＲの結果から、未反応のアクリロイルオキシエチルイソシアネートの４．２ｐｐｍのメチレンピークが、ウレタン結合形成後の４．１ｐｐｍのメチレンピークへ全て変化したことを確認し、またＩＲスペクトルから２，２６０ｃｍ-1のイソシアネート基のピークの消失を確認した。加熱終了後、得られた反応液に活性炭処理を行い、得られた淡黄色液体をエバボレーターで８０℃／１３３Ｐａで２時間処理し、下記式で示されるアクリル基／水酸基量＝０．２０の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－１）４７．２ｇを得た。
Ｒｆ1：－ＣＦ2Ｏ（ＣＦ2Ｏ）p1（ＣＦ2ＣＦ2Ｏ）q1ＣＦ2－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Synthesis Example 1 Synthesis of Fluorine-Containing Acrylic Compound (A-1) Under a dry air atmosphere, the following formula
Rf 1 : -CF 2 O (CF 2 O) p 1 (CF 2 CF 2 O) q 1 CF 2-
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
Mixed with 50.0 g of the fluorine-containing alcohol compound (E-1) (hydroxyl group content: 0.056 mol), 1.40 g (0.00950 mol) of acryloyloxyethyl isocyanate, and 50.degree. C. And stirred for 1 hour. Thereto, 0.05 g of dioctyl tin dilaurate was added, and the mixture was stirred at 50 ° C. for 8 hours. From the results of 1 H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted acryloyloxyethyl isocyanate had completely changed to the 4.1 ppm methylene peak after urethane bond formation, and also from IR spectrum 2, The disappearance of the peak of the isocyanate group at 260 cm -1 was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, the obtained pale yellow liquid is treated with an evaporator at 80 ° C./133 Pa for 2 hours, and the lightness of acrylic group / hydroxyl group represented by the following formula is 0.20 47.2 g of a fluorine-containing acrylic compound (A-1) which is a yellow highly viscous substance was obtained.
Rf 1 : -CF 2 O (CF 2 O) p 1 (CF 2 CF 2 O) q 1 CF 2-
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
乾燥空気雰囲気下で、下記式
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５）
で示される含フッ素アルコール化合物（Ｅ－１）５０．０ｇ（水酸基量０．０５６モル）に、メチルエチルケトン５０．０ｇ、及びアクリロイルオキシエチルイソシアネート１．３４ｇ（０．００９５０モル）を混合し、５０℃に加熱して１時間攪拌した。そこにジオクチル錫ジラウレート０．０５ｇを添加し、５０℃下８時間攪拌した。1Ｈ－ＮＭＲの結果から、未反応のアクリロイルオキシエチルイソシアネートの４．２ｐｐｍのメチレンピークが、ウレタン結合形成後の４．１ｐｐｍのメチレンピークへ全て変化したことを確認し、またＩＲスペクトルから２，２６０ｃｍ-1のイソシアネート基のピークの消失を確認した。加熱終了後、得られた反応液に活性炭処理を行い、得られた淡黄色液体をエバボレーターで８０℃／１３３Ｐａで２時間処理し、下記式で示されるアクリル基／水酸基量＝０．２０の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－１）４７．２ｇを得た。
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Synthesis Example 1 Synthesis of Fluorine-Containing Acrylic Compound (A-1) Under a dry air atmosphere, the following formula
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
Mixed with 50.0 g of the fluorine-containing alcohol compound (E-1) (hydroxyl group content: 0.056 mol), 1.40 g (0.00950 mol) of acryloyloxyethyl isocyanate, and 50.degree. C. And stirred for 1 hour. Thereto, 0.05 g of dioctyl tin dilaurate was added, and the mixture was stirred at 50 ° C. for 8 hours. From the results of 1 H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted acryloyloxyethyl isocyanate had completely changed to the 4.1 ppm methylene peak after urethane bond formation, and also from IR spectrum 2, The disappearance of the peak of the isocyanate group at 260 cm -1 was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, the obtained pale yellow liquid is treated with an evaporator at 80 ° C./133 Pa for 2 hours, and the lightness of acrylic group / hydroxyl group represented by the following formula is 0.20 47.2 g of a fluorine-containing acrylic compound (A-1) which is a yellow highly viscous substance was obtained.
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
［合成例２］含フッ素アクリル化合物（Ａ－２）の合成
合成例１のアクリロイルオキシエチルイソシアネートの使用量を２．６４ｇ（０．０１８７モル）とした以外は同様の操作を行い、アクリル基／水酸基量＝０．５の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－２）４８．０ｇを得た。 Synthesis Example 2 Synthesis of Fluorine-Containing Acrylic Compound (A-2) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was 2.64 g (0.0187 mol). 48.0 g of a fluorine-containing acrylic compound (A-2) which is a pale yellow highly viscous substance having a hydroxyl group content of 0.5 was obtained.
合成例１のアクリロイルオキシエチルイソシアネートの使用量を２．６４ｇ（０．０１８７モル）とした以外は同様の操作を行い、アクリル基／水酸基量＝０．５の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－２）４８．０ｇを得た。 Synthesis Example 2 Synthesis of Fluorine-Containing Acrylic Compound (A-2) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was 2.64 g (0.0187 mol). 48.0 g of a fluorine-containing acrylic compound (A-2) which is a pale yellow highly viscous substance having a hydroxyl group content of 0.5 was obtained.
［合成例３］含フッ素アクリル化合物（Ａ－３）の合成
合成例１のアクリロイルオキシエチルイソシアネートの使用量を７．５０ｇ（０．０５３２モル）とした以外は同様の操作を行い、アクリル基／水酸基量＝１９の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－３）５２．８ｇを得た。 Synthesis Example 3 Synthesis of Fluorine-Containing Acrylic Compound (A-3) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was changed to 7.50 g (0.0532 mol). 52.8 g of a fluorine-containing acrylic compound (A-3), which is a pale yellow highly viscous substance having a hydroxyl content of 19 was obtained.
合成例１のアクリロイルオキシエチルイソシアネートの使用量を７．５０ｇ（０．０５３２モル）とした以外は同様の操作を行い、アクリル基／水酸基量＝１９の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－３）５２．８ｇを得た。 Synthesis Example 3 Synthesis of Fluorine-Containing Acrylic Compound (A-3) The same procedure as in Synthesis Example 1 was repeated except that the amount of acryloyloxyethyl isocyanate used was changed to 7.50 g (0.0532 mol). 52.8 g of a fluorine-containing acrylic compound (A-3), which is a pale yellow highly viscous substance having a hydroxyl content of 19 was obtained.
［合成例４］含フッ素アクリル化合物（Ａ－４）の合成
乾燥空気雰囲気下で、下記式
Ｒｆ2：－ＣＦ2Ｏ（ＣＦ2Ｏ）p2（ＣＦ2ＣＦ2Ｏ）q2ＣＦ2－
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５）
で示される含フッ素アルコール化合物（Ｅ－２）５０．０ｇ（水酸基量０．０９８モル）に、メチルエチルケトン５０．０ｇ、及びアクリロイルオキシエチルイソシアネート４．６１ｇ（０．０３２７モル）を混合し、５０℃に加熱して１時間攪拌した。そこにジオクチル錫ジラウレート０．１０ｇを添加し、５０℃下８時間攪拌した。1Ｈ－ＮＭＲの結果から、未反応のアクリロイルオキシエチルイソシアネートの４．２ｐｐｍのメチレンピークが、ウレタン結合形成後の４．１ｐｐｍのメチレンピークへ全て変化したことを確認し、またＩＲスペクトルから２，２６０ｃｍ-1のイソシアネート基のピークの消失を確認した。加熱終了後、得られた反応液に活性炭処理を行い、得られた淡黄色液体をエバボレーターで６０℃／１３３Ｐａで２時間処理し、下記式で示されるアクリル基／水酸基量＝０．５の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－４）５０．８ｇを得た。
Ｒｆ2：－ＣＦ2Ｏ（ＣＦ2Ｏ）p2（ＣＦ2ＣＦ2Ｏ）q2ＣＦ2－
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） Synthesis Example 4 Synthesis of Fluorine-Containing Acrylic Compound (A-4) In a dry air atmosphere, the following formula
Rf 2 : -CF 2 O (CF 2 O) p 2 (CF 2 CF 2 O) q 2 CF 2-
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
Mixed with 50.0 g of the fluorine-containing alcohol compound (E-2) (hydroxyl content: 0.098 mol), methyl ethyl ketone 50.0 g and acryloyloxyethyl isocyanate 4.61 g (0.0327 mol), and And stirred for 1 hour. Thereto, 0.10 g of dioctyl tin dilaurate was added, and stirred at 50 ° C. for 8 hours. From the results of 1 H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted acryloyloxyethyl isocyanate had completely changed to the 4.1 ppm methylene peak after urethane bond formation, and also from IR spectrum 2, The disappearance of the peak of the isocyanate group at 260 cm -1 was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, and the obtained pale yellow liquid is treated with an evaporator at 60 ° C./133 Pa for 2 hours, and the amount of acrylic group / hydroxyl group = 0.5 shown by the following formula 50.8 g of a fluorine-containing acrylic compound (A-4) which is a yellow highly viscous substance was obtained.
Rf 2 : -CF 2 O (CF 2 O) p 2 (CF 2 CF 2 O) q 2 CF 2-
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
乾燥空気雰囲気下で、下記式
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５）
で示される含フッ素アルコール化合物（Ｅ－２）５０．０ｇ（水酸基量０．０９８モル）に、メチルエチルケトン５０．０ｇ、及びアクリロイルオキシエチルイソシアネート４．６１ｇ（０．０３２７モル）を混合し、５０℃に加熱して１時間攪拌した。そこにジオクチル錫ジラウレート０．１０ｇを添加し、５０℃下８時間攪拌した。1Ｈ－ＮＭＲの結果から、未反応のアクリロイルオキシエチルイソシアネートの４．２ｐｐｍのメチレンピークが、ウレタン結合形成後の４．１ｐｐｍのメチレンピークへ全て変化したことを確認し、またＩＲスペクトルから２，２６０ｃｍ-1のイソシアネート基のピークの消失を確認した。加熱終了後、得られた反応液に活性炭処理を行い、得られた淡黄色液体をエバボレーターで６０℃／１３３Ｐａで２時間処理し、下記式で示されるアクリル基／水酸基量＝０．５の淡黄色高粘稠物質である含フッ素アクリル化合物（Ａ－４）５０．８ｇを得た。
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） Synthesis Example 4 Synthesis of Fluorine-Containing Acrylic Compound (A-4) In a dry air atmosphere, the following formula
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
Mixed with 50.0 g of the fluorine-containing alcohol compound (E-2) (hydroxyl content: 0.098 mol), methyl ethyl ketone 50.0 g and acryloyloxyethyl isocyanate 4.61 g (0.0327 mol), and And stirred for 1 hour. Thereto, 0.10 g of dioctyl tin dilaurate was added, and stirred at 50 ° C. for 8 hours. From the results of 1 H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted acryloyloxyethyl isocyanate had completely changed to the 4.1 ppm methylene peak after urethane bond formation, and also from IR spectrum 2, The disappearance of the peak of the isocyanate group at 260 cm -1 was confirmed. After completion of heating, the obtained reaction liquid is treated with activated carbon, and the obtained pale yellow liquid is treated with an evaporator at 60 ° C./133 Pa for 2 hours, and the amount of acrylic group / hydroxyl group = 0.5 shown by the following formula 50.8 g of a fluorine-containing acrylic compound (A-4) which is a yellow highly viscous substance was obtained.
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
［合成例５］含フッ素アクリル化合物（Ｂ－１）の合成
合成例１のアクリロイルオキシエチルイソシアネートの使用量を８．５９ｇ（０．０６０９モル）とした以外は同様の操作を行い、13Ｃ－ＮＭＲスペクトルで６２ｐｐｍの水酸基に隣接した炭素原子の由来のピークの消失を確認し、下記式で示される水酸基の残存しない淡黄色高粘稠物質である含フッ素アクリル化合物（Ｂ－１）５３．０ｇを得た。
Ｒｆ1：－ＣＦ2Ｏ（ＣＦ2Ｏ）p1（ＣＦ2ＣＦ2Ｏ）q1ＣＦ2－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Except that the amount of acryloyloxyethyl isocyanate Synthesis Example 1 [Synthesis Example 5] The fluorine-containing acrylic compound (B-1) was 8.59 g (0.0609 mol) by the same operation, 13 C- The disappearance of the peak derived from the carbon atom adjacent to the 62 ppm hydroxyl group was confirmed in the NMR spectrum, and 53.0 g of a fluorine-containing acrylic compound (B-1) which is a pale yellow highly viscous substance having no remaining hydroxyl group represented by the following formula I got
Rf 1 : -CF 2 O (CF 2 O) p 1 (CF 2 CF 2 O) q 1 CF 2-
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
合成例１のアクリロイルオキシエチルイソシアネートの使用量を８．５９ｇ（０．０６０９モル）とした以外は同様の操作を行い、13Ｃ－ＮＭＲスペクトルで６２ｐｐｍの水酸基に隣接した炭素原子の由来のピークの消失を確認し、下記式で示される水酸基の残存しない淡黄色高粘稠物質である含フッ素アクリル化合物（Ｂ－１）５３．０ｇを得た。
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Except that the amount of acryloyloxyethyl isocyanate Synthesis Example 1 [Synthesis Example 5] The fluorine-containing acrylic compound (B-1) was 8.59 g (0.0609 mol) by the same operation, 13 C- The disappearance of the peak derived from the carbon atom adjacent to the 62 ppm hydroxyl group was confirmed in the NMR spectrum, and 53.0 g of a fluorine-containing acrylic compound (B-1) which is a pale yellow highly viscous substance having no remaining hydroxyl group represented by the following formula I got
(Q1 / p1 = 0.9, p1 + q1 ≒ 45)
［合成例６］含フッ素アクリル化合物（Ｂ－２）の合成
合成例４のアクリロイルオキシエチルイソシアネートの使用量を１５．１ｇ（０．１０７モル）とした以外は同様の操作を行い、13Ｃ－ＮＭＲスペクトルで６２ｐｐｍの水酸基に隣接した炭素原子の由来のピークの消失を確認し、下記式で示される水酸基の残存しない淡黄色高粘稠物質である含フッ素アクリル化合物（Ｂ－２）５８．９ｇを得た。
Ｒｆ2：－ＣＦ2Ｏ（ＣＦ2Ｏ）p2（ＣＦ2ＣＦ2Ｏ）q2ＣＦ2－
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） Synthesis Example 6 Synthesis of Fluorine-Containing Acrylic Compound (B-2) The same procedure as in Synthesis Example 4 was repeated except that the amount of acryloyloxyethyl isocyanate used was 15.1 g (0.107 mol), 13 C— The disappearance of the peak derived from the carbon atom adjacent to the 62 ppm hydroxyl group was confirmed in the NMR spectrum, and 58.9 g of a fluorine-containing acrylic compound (B-2) which is a pale yellow highly viscous substance having no remaining hydroxyl group represented by the following formula I got
Rf 2 : -CF 2 O (CF 2 O) p 2 (CF 2 CF 2 O) q 2 CF 2-
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
合成例４のアクリロイルオキシエチルイソシアネートの使用量を１５．１ｇ（０．１０７モル）とした以外は同様の操作を行い、13Ｃ－ＮＭＲスペクトルで６２ｐｐｍの水酸基に隣接した炭素原子の由来のピークの消失を確認し、下記式で示される水酸基の残存しない淡黄色高粘稠物質である含フッ素アクリル化合物（Ｂ－２）５８．９ｇを得た。
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） Synthesis Example 6 Synthesis of Fluorine-Containing Acrylic Compound (B-2) The same procedure as in Synthesis Example 4 was repeated except that the amount of acryloyloxyethyl isocyanate used was 15.1 g (0.107 mol), 13 C— The disappearance of the peak derived from the carbon atom adjacent to the 62 ppm hydroxyl group was confirmed in the NMR spectrum, and 58.9 g of a fluorine-containing acrylic compound (B-2) which is a pale yellow highly viscous substance having no remaining hydroxyl group represented by the following formula I got
(Q2 / p2 = 1.2, p2 + q2 ≒ 18.5)
［実施例１～７、比較例１～５］
含フッ素活性エネルギー線硬化性組成物の調製
下記表１、２に示す配合割合で、上記合成例で得られた化合物（Ａ－１）～（Ａ－４）、（Ｂ－１）、（Ｂ－２）、及び下記に示すアクリル化合物（Ｃ－１）～（Ｃ－４）、光重合開始剤（Ｄ－１）、（Ｄ－２）、有機溶剤（Ｓ－１）～（Ｓ－４）を混合して、含フッ素及び非フッ素の活性エネルギー線硬化性組成物を調製した。なお、各組成物の（Ａ）成分と（Ｂ）成分に含まれるアクリル基合計モル量の理論値をＮA、水酸基モル量の理論値をＮHとして各組成物におけるＮA／ＮHの値を下記表１、２に示した。 [Examples 1 to 7, Comparative Examples 1 to 5]
Preparation of Fluorine-Containing Active Energy Ray-Curable Composition The compounds (A-1) to (A-4), (B-1), and (B) obtained in the above-mentioned synthesis example were compounded at the mixing ratios shown in Tables 1 and 2 below -2), and acrylic compounds (C-1) to (C-4) shown below, photopolymerization initiators (D-1) and (D-2), organic solvents (S-1) to (S-4) Were mixed to prepare fluorine-containing and non-fluorine-containing active energy ray curable compositions. Incidentally, in the composition (A) component and (B) the theoretical value of the acryl group total molar amount present in component N A, the theoretical values of the hydroxyl groups the molar amount of N A / N H in each composition as a N H The values are shown in Tables 1 and 2 below.
含フッ素活性エネルギー線硬化性組成物の調製
下記表１、２に示す配合割合で、上記合成例で得られた化合物（Ａ－１）～（Ａ－４）、（Ｂ－１）、（Ｂ－２）、及び下記に示すアクリル化合物（Ｃ－１）～（Ｃ－４）、光重合開始剤（Ｄ－１）、（Ｄ－２）、有機溶剤（Ｓ－１）～（Ｓ－４）を混合して、含フッ素及び非フッ素の活性エネルギー線硬化性組成物を調製した。なお、各組成物の（Ａ）成分と（Ｂ）成分に含まれるアクリル基合計モル量の理論値をＮA、水酸基モル量の理論値をＮHとして各組成物におけるＮA／ＮHの値を下記表１、２に示した。 [Examples 1 to 7, Comparative Examples 1 to 5]
Preparation of Fluorine-Containing Active Energy Ray-Curable Composition The compounds (A-1) to (A-4), (B-1), and (B) obtained in the above-mentioned synthesis example were compounded at the mixing ratios shown in Tables 1 and 2 below -2), and acrylic compounds (C-1) to (C-4) shown below, photopolymerization initiators (D-1) and (D-2), organic solvents (S-1) to (S-4) Were mixed to prepare fluorine-containing and non-fluorine-containing active energy ray curable compositions. Incidentally, in the composition (A) component and (B) the theoretical value of the acryl group total molar amount present in component N A, the theoretical values of the hydroxyl groups the molar amount of N A / N H in each composition as a N H The values are shown in Tables 1 and 2 below.
（Ｃ－１）：ペンタエリスリトールトリアクリレート（分子中のアクリル基数：３個、水酸基数：１個）
（Ｃ－２）：ジペンタエリスリトールペンタアクリレート（分子中のアクリル基数：５個、水酸基数：１個）／ジペンタエリスリトールヘキサアクリレート（分子中のアクリル基数：６個、水酸基数：０個）の混合物
（Ｃ－３）：新中村化学株式会社製 多官能ウレタンアクリレート「Ｕ－６ＬＰＡ」（分子中のアクリル基数：６個以上）
（Ｃ－４）：根上工業株式会社製 多官能ウレタンアクリレート「ＵＮ－３３２０ＨＳ」（分子中のアクリル基数：６個以上）
（Ｄ－１）：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン
（Ｄ－２）：２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン
（Ｓ－１）：メチルエチルケトン
（Ｓ－２）：酢酸エチル
（Ｓ－３）：プロピレングリコールモノメチルエーテル
（Ｓ－４）：２－プロパノール (C-1): pentaerythritol triacrylate (number of acrylic groups in molecule: 3 and number of hydroxyl groups: 1)
(C-2): dipentaerythritol pentaacrylate (number of acrylic groups in molecule: 5, hydroxyl number: 1) / dipentaerythritol hexaacrylate (number of acrylic groups in molecule: 6, hydroxyl number: 0) Mixture (C-3): Shin-Nakamura Chemical Co., Ltd. Multifunctional urethane acrylate "U-6 LPA" (number of acrylic groups in molecule: 6 or more)
(C-4): Negami Industrial Co., Ltd. Multifunctional Urethane Acrylate “UN-3320HS” (Number of Acrylic Groups in Molecule: 6 or More)
(D-1): 1-hydroxy-cyclohexyl-phenyl-ketone (D-2): 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-Methyl-propan-1-one (S-1): methyl ethyl ketone (S-2): ethyl acetate (S-3): propylene glycol monomethyl ether (S-4): 2-propanol
（Ｃ－２）：ジペンタエリスリトールペンタアクリレート（分子中のアクリル基数：５個、水酸基数：１個）／ジペンタエリスリトールヘキサアクリレート（分子中のアクリル基数：６個、水酸基数：０個）の混合物
（Ｃ－３）：新中村化学株式会社製 多官能ウレタンアクリレート「Ｕ－６ＬＰＡ」（分子中のアクリル基数：６個以上）
（Ｃ－４）：根上工業株式会社製 多官能ウレタンアクリレート「ＵＮ－３３２０ＨＳ」（分子中のアクリル基数：６個以上）
（Ｄ－１）：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン
（Ｄ－２）：２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン
（Ｓ－１）：メチルエチルケトン
（Ｓ－２）：酢酸エチル
（Ｓ－３）：プロピレングリコールモノメチルエーテル
（Ｓ－４）：２－プロパノール (C-1): pentaerythritol triacrylate (number of acrylic groups in molecule: 3 and number of hydroxyl groups: 1)
(C-2): dipentaerythritol pentaacrylate (number of acrylic groups in molecule: 5, hydroxyl number: 1) / dipentaerythritol hexaacrylate (number of acrylic groups in molecule: 6, hydroxyl number: 0) Mixture (C-3): Shin-Nakamura Chemical Co., Ltd. Multifunctional urethane acrylate "U-6 LPA" (number of acrylic groups in molecule: 6 or more)
(C-4): Negami Industrial Co., Ltd. Multifunctional Urethane Acrylate “UN-3320HS” (Number of Acrylic Groups in Molecule: 6 or More)
(D-1): 1-hydroxy-cyclohexyl-phenyl-ketone (D-2): 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-Methyl-propan-1-one (S-1): methyl ethyl ketone (S-2): ethyl acetate (S-3): propylene glycol monomethyl ether (S-4): 2-propanol
塗工と硬化膜の作製
実施例及び比較例の各活性エネルギー線硬化性組成物をポリカーボネート基板上にスピンコートで塗工した。コンベヤ式メタルハライドＵＶ照射装置（パナソニック電工株式会社製）を使用し、窒素雰囲気中で、積算照射量１，６００ｍＪ／ｃｍ2の紫外線を塗工面に照射して組成物を硬化させ、厚さ約５μｍ、実施例５については約３μｍの硬化膜を得た。 Preparation of Coating and Cured Film Each active energy ray-curable composition of Examples and Comparative Examples was spin-coated on a polycarbonate substrate. Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.), the coated surface is irradiated with ultraviolet light with an accumulated irradiation amount of 1,600 mJ / cm 2 in a nitrogen atmosphere to cure the composition, and the thickness is about 5 μm For Example 5, a cured film of about 3 μm was obtained.
実施例及び比較例の各活性エネルギー線硬化性組成物をポリカーボネート基板上にスピンコートで塗工した。コンベヤ式メタルハライドＵＶ照射装置（パナソニック電工株式会社製）を使用し、窒素雰囲気中で、積算照射量１，６００ｍＪ／ｃｍ2の紫外線を塗工面に照射して組成物を硬化させ、厚さ約５μｍ、実施例５については約３μｍの硬化膜を得た。 Preparation of Coating and Cured Film Each active energy ray-curable composition of Examples and Comparative Examples was spin-coated on a polycarbonate substrate. Using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.), the coated surface is irradiated with ultraviolet light with an accumulated irradiation amount of 1,600 mJ / cm 2 in a nitrogen atmosphere to cure the composition, and the thickness is about 5 μm For Example 5, a cured film of about 3 μm was obtained.
硬化膜の評価
上記で得られた硬化膜について、下記に示す方法により水接触角とオレイン酸接触角の測定、耐摩耗性、耐指紋性及び耐マジック性の評価を行った。これらの結果を表３、４に示す。 Evaluation of Cured Film The cured film obtained above was subjected to measurement of water contact angle and oleic acid contact angle, evaluation of abrasion resistance, fingerprint resistance and magic resistance according to the following method. These results are shown in Tables 3 and 4.
上記で得られた硬化膜について、下記に示す方法により水接触角とオレイン酸接触角の測定、耐摩耗性、耐指紋性及び耐マジック性の評価を行った。これらの結果を表３、４に示す。 Evaluation of Cured Film The cured film obtained above was subjected to measurement of water contact angle and oleic acid contact angle, evaluation of abrasion resistance, fingerprint resistance and magic resistance according to the following method. These results are shown in Tables 3 and 4.
［水接触角測定］
接触角計（協和界面科学株式会社製 ＤｒｏｐＭａｓｔｅｒ）を用い、２μＬの液滴を硬化膜上に滴下して１秒後の接触角を測定した。Ｎ＝５の平均値を測定値とした。 [Water contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 2 μL droplets were dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measurement value.
接触角計（協和界面科学株式会社製 ＤｒｏｐＭａｓｔｅｒ）を用い、２μＬの液滴を硬化膜上に滴下して１秒後の接触角を測定した。Ｎ＝５の平均値を測定値とした。 [Water contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 2 μL droplets were dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measurement value.
［オレイン酸接触角測定］
接触角計（協和界面科学株式会社製 ＤｒｏｐＭａｓｔｅｒ）を用い、４μＬの液滴を硬化膜上に滴下して１秒後の接触角を測定した。Ｎ＝５の平均値を測定値とした。 [Oleic acid contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 4 μL droplets were dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measurement value.
接触角計（協和界面科学株式会社製 ＤｒｏｐＭａｓｔｅｒ）を用い、４μＬの液滴を硬化膜上に滴下して１秒後の接触角を測定した。Ｎ＝５の平均値を測定値とした。 [Oleic acid contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 4 μL droplets were dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measurement value.
［耐摩耗性］
以下の条件で往復摩耗試験を行い、２，０００回毎に水接触角を測定し、水接触角が１００°以下となった回数を記録した。
擦り材 ：不織布（旭化成株式会社製 ＢＥＭＣＯＴ Ｍ－３ＩＩ）
荷重 ：１ｋｇ
接触面積：３ｃｍ2
擦り速度：９０ｍｍ／ｓ
擦り距離：２０ｍｍ [Abrasion resistance]
A reciprocating wear test was conducted under the following conditions, the water contact angle was measured every 2,000 times, and the number of times the water contact angle became 100 ° or less was recorded.
Abrasive material: Non-woven fabric (BEMCOT M-3 II manufactured by Asahi Kasei Co., Ltd.)
Load: 1 kg
Contact area: 3 cm 2
Rubbing speed: 90 mm / s
Rubbing distance: 20 mm
以下の条件で往復摩耗試験を行い、２，０００回毎に水接触角を測定し、水接触角が１００°以下となった回数を記録した。
擦り材 ：不織布（旭化成株式会社製 ＢＥＭＣＯＴ Ｍ－３ＩＩ）
荷重 ：１ｋｇ
接触面積：３ｃｍ2
擦り速度：９０ｍｍ／ｓ
擦り距離：２０ｍｍ [Abrasion resistance]
A reciprocating wear test was conducted under the following conditions, the water contact angle was measured every 2,000 times, and the number of times the water contact angle became 100 ° or less was recorded.
Abrasive material: Non-woven fabric (BEMCOT M-3 II manufactured by Asahi Kasei Co., Ltd.)
Load: 1 kg
Contact area: 3 cm 2
Rubbing speed: 90 mm / s
Rubbing distance: 20 mm
［指紋の目立ちやすさの評価］
指紋を付けた際の目立ちやすさを以下の基準で目視評価した。
１：目立ちにくい
２：やや目立ちにくい
３：比較例１と同等 [Evaluation of the conspicuousness of the fingerprint]
The visibility of the fingerprint was visually evaluated according to the following criteria.
1: Less noticeable 2: Slightly less prominent 3: Equivalent to Comparative Example 1
指紋を付けた際の目立ちやすさを以下の基準で目視評価した。
１：目立ちにくい
２：やや目立ちにくい
３：比較例１と同等 [Evaluation of the conspicuousness of the fingerprint]
The visibility of the fingerprint was visually evaluated according to the following criteria.
1: Less noticeable 2: Slightly less prominent 3: Equivalent to Comparative Example 1
［指紋の拭き取りやすさの評価］
指紋をティッシュペーパーで拭き取る際の拭き取りやすさを以下の基準で目視評価した。
〇：容易に拭き取れる
×：拭き取れない [Evaluation of fingerprint wipeability]
Ease of wiping when fingerprints were wiped with a tissue paper was visually evaluated based on the following criteria.
○: Easy to wipe off ×: Can not wipe off
指紋をティッシュペーパーで拭き取る際の拭き取りやすさを以下の基準で目視評価した。
〇：容易に拭き取れる
×：拭き取れない [Evaluation of fingerprint wipeability]
Ease of wiping when fingerprints were wiped with a tissue paper was visually evaluated based on the following criteria.
○: Easy to wipe off ×: Can not wipe off
［マジックはじき性の評価］
硬化膜表面にマジックペン（ゼブラ株式会社製 ハイマッキー太字）で直線を描き、インクをはじくものを○、はじかないものを×とした。 [Evaluation of Magic Repellency]
A straight line was drawn on the surface of the cured film with a magic pen (Himackey bold, manufactured by Zebra Co., Ltd.), and those with ink repellence were marked with ○, and those without repellence with x.
硬化膜表面にマジックペン（ゼブラ株式会社製 ハイマッキー太字）で直線を描き、インクをはじくものを○、はじかないものを×とした。 [Evaluation of Magic Repellency]
A straight line was drawn on the surface of the cured film with a magic pen (Himackey bold, manufactured by Zebra Co., Ltd.), and those with ink repellence were marked with ○, and those without repellence with x.
［マジック拭き取り性の評価］
マジックはじき性の評価に用いた各サンプルについて、１０分後にティッシュペーパーで拭き取りを行い、跡を残さず拭き取れるものを○、跡が残るものを×とした。 [Evaluation of magic wiping performance]
About each sample used for evaluation of the magic repellence, it was wiped off with a tissue paper after 10 minutes, those which could be wiped off without leaving a mark were marked with ○, those with a mark being marked ×.
マジックはじき性の評価に用いた各サンプルについて、１０分後にティッシュペーパーで拭き取りを行い、跡を残さず拭き取れるものを○、跡が残るものを×とした。 [Evaluation of magic wiping performance]
About each sample used for evaluation of the magic repellence, it was wiped off with a tissue paper after 10 minutes, those which could be wiped off without leaving a mark were marked with ○, those with a mark being marked ×.
上記の結果から明らかなように、含フッ素アクリル化合物（Ａ－１）～（Ａ－４）を配合してなる本発明の含フッ素活性エネルギー線硬化性組成物を用いた実施例１～７は、撥水性、撥油性、耐摩耗性、指紋の目立ちにくさ、指紋の拭き取りやすさ、マジックはじき性、マジック拭き取り性に優れるものである。また、含フッ素アクリル化合物（Ａ）を配合せず、含フッ素アクリル化合物（Ｂ－１）、（Ｂ－２）を配合してなる含フッ素活性エネルギー線硬化性組成物を用いた比較例１～４は、これらに相当する実施例よりも耐摩耗性に劣り、指紋が目立つものである。更に、含フッ素アクリル化合物（Ａ－１）～（Ａ－４）も含フッ素アクリル化合物（Ｂ－１）、（Ｂ－２）も配合しない非フッ素の活性エネルギー線硬化性組成物を用いた比較例５は、上記実施例よりも撥水性、撥油性、耐摩耗性、指紋の拭き取りやすさ、マジックはじき性、マジック拭き取り性に劣るものである。
As is clear from the above results, Examples 1 to 7 using the fluorine-containing active energy ray-curable composition of the present invention, which contains the fluorine-containing acrylic compounds (A-1) to (A-4), are Excellent in water repellency, oil repellency, abrasion resistance, fingerprint inconspicuousness, fingerprint wipeability, magic repellence, and magic wipeability. Further, Comparative Example 1 using a fluorine-containing active energy ray-curable composition obtained by mixing the fluorine-containing acrylic compounds (B-1) and (B-2) without containing the fluorine-containing acrylic compound (A) The sample No. 4 is inferior in abrasion resistance to the examples corresponding to these, and fingerprints stand out. Furthermore, comparison using a non-fluorine active energy ray-curable composition containing neither fluorine-containing acrylic compounds (A-1) to (A-4) nor fluorine-containing acrylic compounds (B-1) and (B-2) Example 5 is inferior to the said Example in water repellency, oil repellency, abrasion resistance, the ease of wiping off of a fingerprint, magic repellence, and magic wiping off.
Claims (11)
- ２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した水酸基と、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基とを、それぞれ両末端のシクロポリシロキサン構造のいずれか一方又は両方に有する含フッ素化合物（Ａ）を含有することを特徴とする含フッ素活性エネルギー線硬化性組成物。 A cyclopolysiloxane structure is bonded to both ends of a divalent perfluoropolyether group via a divalent linking group, and a hydroxy group bonded to the cyclopolysiloxane structure via a divalent linking group; It is characterized by containing a fluorine-containing compound (A) having a (meth) acrylic group bonded to a siloxane structure via a divalent linking group in any one or both of cyclopolysiloxane structures at both ends, respectively. Fluorine-containing active energy ray curable composition.
- 含フッ素化合物（Ａ）において、含フッ素化合物（Ａ）中に含まれる水酸基に対する（メタ）アクリル基のモル比［（メタ）アクリル基（モル）／水酸基（モル）］が、平均値として０．１以上２５以下である請求項１に記載の含フッ素活性エネルギー線硬化性組成物。 In the fluorine-containing compound (A), the molar ratio of (meth) acrylic group to hydroxyl group contained in the fluorine-containing compound (A) [(meth) acrylic group (mol) / hydroxyl group (mol)] is, as an average value, 0. The fluorine-containing active energy ray curable composition according to claim 1, which is 1 or more and 25 or less.
- 更に、２価のパーフルオロポリエーテル基の両末端に２価の連結基を介してシクロポリシロキサン構造が結合し、前記シクロポリシロキサン構造に２価の連結基を介して結合した（メタ）アクリル基を有し、かつ、水酸基を有さない構造を両末端に有する含フッ素化合物（Ｂ）を含むものである請求項１又は２に記載の含フッ素活性エネルギー線硬化性組成物。 Furthermore, a cyclopolysiloxane structure is bonded to both ends of the divalent perfluoropolyether group via a divalent linking group, and a (meth) acryl bonded to the cyclopolysiloxane structure via a divalent linking group The fluorine-containing active energy ray curable composition according to claim 1 or 2, comprising a fluorine-containing compound (B) having a group and a structure having no hydroxyl group at both ends.
- 組成物全体に含まれる平均値として、組成物中の含フッ素化合物（Ａ）に含まれる水酸基に対する含フッ素化合物（Ａ）に含まれる（メタ）アクリル基と含フッ素化合物（Ｂ）に含まれる（メタ）アクリル基の合計のモル比［（メタ）アクリル基の合計（モル）／水酸基（モル）］が、０．１以上２５以下である請求項３に記載の含フッ素活性エネルギー線硬化性組成物。 The (meth) acrylic group contained in the fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the fluorine-containing compound (A) with respect to the hydroxyl group contained in the fluorine-containing compound (A) in the composition 4. The fluorine-containing active energy ray-curable composition according to claim 3, wherein the molar ratio [total of (meth) acrylic groups (mol) / hydroxyl group (mol)] of the total of the (meth) acrylic groups is 0.1 or more and 25 or less. object.
- 含フッ素化合物（Ａ）が、下記一般式（１）
Ｘ1－Ｚ－Ｒｆ－Ｚ－Ｘ1 （１）
［式中、Ｒｆは下記式（２）～（５）
で表される基から選ばれる、分子量５００～３０，０００の２価のパーフルオロポリエーテル基であり、Ｘ1は互いに独立に、下記式（６）
で表される（メタ）アクリル基含有基であり、ａ及びｂはそれぞれ０～６の整数であり、但しａ＋ｂは２～１１である。各繰り返し単位はランダムに結合されていてもよい。〕
で表される基であり、分子中に存在するＸ1中のａ、ｂの合計はそれぞれ２以上である。Ｚは下記式
で表されるものである請求項１～４のいずれか１項に記載の含フッ素活性エネルギー線硬化性組成物。 The fluorine-containing compound (A) is represented by the following general formula (1)
X 1 -Z-Rf-Z-X 1 (1)
[Wherein, R f represents the following formulas (2) to (5)
In selected from the groups represented, a divalent perfluoropolyether group having a molecular weight of 500 ~ 30,000, X 1, independently of one another, the following formula (6)
And a and b each represent an integer of 0 to 6, provided that a + b is 2 to 11. Each repeating unit may be randomly combined. ]
And the sum of a and b in X 1 present in the molecule is 2 or more. Z is the following formula
The fluorine-containing active energy ray curable composition according to any one of claims 1 to 4, which is represented by - 更に、含フッ素化合物（Ａ）、（Ｂ）以外のアクリル化合物（Ｃ）を含む請求項１～５のいずれか１項に記載の含フッ素活性エネルギー線硬化性組成物。 The fluorine-containing active energy ray curable composition according to any one of claims 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compounds (A) and (B).
- アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基を有し、かつ分子中に水酸基を有さない非フッ素化多官能（メタ）アクリレートである請求項６に記載の含フッ素活性エネルギー線硬化性組成物。 The acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acryl groups in one molecule and having no hydroxyl group in the molecule. Fluorine-containing active energy ray curable composition.
- アクリル化合物（Ｃ）が、１分子中に３個以上の（メタ）アクリル基と１個以上の水酸基を有する非フッ素化多官能（メタ）アクリレートである請求項６に記載の含フッ素活性エネルギー線硬化性組成物。 The fluorine-containing active energy ray according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having three or more (meth) acrylic groups and one or more hydroxyl groups in one molecule. Curable composition.
- アクリル化合物（Ｃ）が、分子中にウレタン結合を有し、１分子中に６個以上の（メタ）アクリル基を有する非フッ素化多官能ウレタン（メタ）アクリレートである請求項６に記載の含フッ素活性エネルギー線硬化性組成物。 The acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in the molecule and having six or more (meth) acrylic groups in one molecule. Fluorine active energy ray curable composition.
- 更に、（Ｄ）光重合開始剤を含む請求項１～９のいずれか１項に記載の含フッ素活性エネルギー線硬化性組成物。 The fluorine-containing active energy ray curable composition according to any one of claims 1 to 9, further comprising (D) a photopolymerization initiator.
- 請求項１～１０のいずれか１項に記載の含フッ素活性エネルギー線硬化性組成物の硬化被膜を表面に有し、水接触角１０５°以上の撥水性表面を有する物品。 An article having a cured coating of the fluorine-containing active energy ray-curable composition according to any one of claims 1 to 10 on its surface, and having a water repellent surface having a water contact angle of 105 ° or more.
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| KR1020207023488A KR102624940B1 (en) | 2018-01-19 | 2018-12-14 | Fluorine-containing activated energy ray curable compositions and articles |
| JP2019565771A JP6954380B2 (en) | 2018-01-19 | 2018-12-14 | Fluorine-containing active energy ray-curable compositions and articles |
| CN201880086993.5A CN111615526B (en) | 2018-01-19 | 2018-12-14 | Fluorine-containing active energy ray-curable composition and article |
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| KR (1) | KR102624940B1 (en) |
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Also Published As
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| KR102624940B1 (en) | 2024-01-15 |
| CN111615526B (en) | 2024-02-27 |
| CN111615526A (en) | 2020-09-01 |
| TWI795507B (en) | 2023-03-11 |
| KR20200108059A (en) | 2020-09-16 |
| TW201936710A (en) | 2019-09-16 |
| JPWO2019142567A1 (en) | 2021-01-07 |
| JP6954380B2 (en) | 2021-10-27 |
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