WO2020170698A1 - 含フッ素硬化性組成物及び物品 - Google Patents
含フッ素硬化性組成物及び物品 Download PDFInfo
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- WO2020170698A1 WO2020170698A1 PCT/JP2020/002114 JP2020002114W WO2020170698A1 WO 2020170698 A1 WO2020170698 A1 WO 2020170698A1 JP 2020002114 W JP2020002114 W JP 2020002114W WO 2020170698 A1 WO2020170698 A1 WO 2020170698A1
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- Prior art keywords
- fluorine
- och
- meth
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 167
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 160
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
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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
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- 210000002374 sebum Anatomy 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/18—Esters containing halogen
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
-
- 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
-
- 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
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
Definitions
- the present invention relates to a fluorine-containing curable composition having excellent antifouling properties and slipperiness, and an article having a cured coating film of the composition on its surface.
- hard coat treatment has been widely used as a means for protecting the surface of resin moldings and the like.
- This forms a hard cured resin layer (hard coat layer) on the surface of the molded body to make it hard to scratch.
- a curable composition using active energy rays such as a thermosetting resin or an ultraviolet ray or electron beam curable resin is often used.
- hardened resin layer (hard coat layer). Staining is required. This imparts properties such as water repellency and oil repellency to the surface of the hard coat layer, so that the hard coat layer is hardly soiled or can be easily removed even if soiled.
- Patent Document 1 discloses the production of a hard coat layer having an antifouling property by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition. ing.
- antifouling represented by water repellency can be achieved in hard coats, especially on the surface of large displays, and on the surface treatment of displays and housings of portable information devices such as smartphones and tablets.
- Higher performance is required for wear resistance represented by performance and slipperiness.
- One means to meet these demands is to arrange components having higher fluorine modification on the surface.
- the fluorine content is increased with a single structure fluorine-containing acrylic compound, the solubility of the hard coating agent that is not fluorinated in other components will decrease, and the coating surface will be coated with non-uniform parts such as defects. Defects occur.
- the present invention has been made in view of the above circumstances, has a stable solubility, a high antifouling property after curing, and a fluorine-containing curable composition having high slipperiness, and a cured coating film of the composition.
- the purpose of the present invention is to provide an article.
- JP 2010-53114 A Patent Document 2
- JP 2010 138112 Patent Document 3
- JP 2010-285501 A Patent Document 4
- a method of increasing the content of the fluorine component in the compound can be considered.
- the solubility of the fluorine-containing acrylic compound having a single structure is improved in the non-fluorinated component, the concentration of the fluorine component on the coating surface is less likely to occur, resulting in the development of antifouling performance. It may be difficult to do.
- the present inventor has found that it is a linear polymer having a fluoropolyether as a main chain and has one or two (meth)acryl groups at the end and The average value of the number of (meth)acrylic groups contained in is not more than 2, and the component (A) consisting of a compound having a fluorine content of 48% by mass or more and less than 62% by mass, having a fluoropolyether in the main chain
- the chain polymer has two or more (meth)acryl groups at each end in one molecule, has an average of 4 to 10 (meth)acryl groups in one molecule, and has a fluorine content of 25.
- Component (B) comprising a compound in an amount of at least 45% by mass and less than 45% by mass, and a non-fluorinated acrylic compound that does not include a fluoropolyether structure and has an average of two or more (meth)acrylic groups in one molecule. It was found that a fluorine-containing curable composition containing each of the components (C) in a predetermined mixing ratio can form a cured film having excellent antifouling property/water repellency and a low dynamic friction coefficient, and thus forming the present invention. I arrived.
- the present invention provides the following fluorine-containing curable composition, and an article having a cured coating film of the composition on its surface.
- Has 2 or more (meth)acryl groups at each molecular chain end has 4 to 10 (meth)acryl groups on average in one molecule, and has a fluorine content of 25% by mass or more and 45% by mass or more.
- the total amount of the component (A) and the component (B) compounded is 0.05 to 50 parts by mass with respect to 100 parts by mass of the component (C), and the component relative to 100 parts by mass of the component (B).
- the fluorine-containing curable composition according to [1] which further comprises a photopolymerization initiator (D).
- D photopolymerization initiator
- Rf 1 is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom
- Rf 2 is the following two kinds of repeating units —CF 2 O— -CF 2 CF 2 O- Is a divalent perfluoropolyether group having a molecular weight of 600 to 20,000 randomly arranged.
- Z 1 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one hetero atom selected from oxygen atom, nitrogen atom and silicon atom, —C( ⁇ O)— and — It is a linking group selected from C( ⁇ O)O—, and the divalent hydrocarbon group may have a cyclic structure on the way, and some of hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. May be.
- X 1 is independently a monovalent organic group having a (meth)acryl group which may contain an oxygen atom and/or a nitrogen atom, and X 2 is a hydroxyl group or X 1 .
- Z 2 s are each independently a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain an oxygen atom and/or a nitrogen atom, and may have a cyclic structure on the way.
- R 1 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.
- R 2 is independently a monovalent organic group having a hydrogen atom, or a (meth)acryl group which may contain an oxygen atom and/or a nitrogen atom, provided that R 2 is at each terminal in one molecule. It has two or more and an average of 4 to 10 monovalent organic groups in one molecule.
- Z 3 is a linking group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms, which may independently contain at least one hetero atom selected from oxygen atom, nitrogen atom and silicon atom, and has an intermediate cyclic structure. May be included, and a part of hydrogen atoms bonded to carbon atoms may be replaced with fluorine atoms.
- X 1 in the general formula (1) or (2) is represented by any of the following [3] to [5]. ..
- Q 1 in the general formula (3) is represented by the following formula, wherein the fluorine-containing curable composition according to any one of [4] to [8]. (In the formula, a1 is 2 or 3.) [10]
- the fluorine-containing acrylic compound represented by the general formula (3) is any one of [4] to [9] which is a fluorine-containing acrylic compound represented by the following general formula (4) or (5).
- Rf′ is —CF 2 O(CF 2 O) m (CF 2 CF 2 O) n CF 2 —, and m is 1 to 200.
- N is an integer of 1 to 170
- m+n is an integer of 6 to 201
- the arrangement of —(CF 2 O)— and —(CF 2 CF 2 O)— is random
- R 3 is a hydrogen atom.
- the non-fluorinated acrylic compound as the component (C) is a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or this polyfunctional acrylic compound and an aliphatic polyisocyanate.
- the fluorinated curable composition of the present invention has a stable solubility and can provide a cured film having high antifouling property, stain wiping property and slipperiness.
- the fluorine-containing curable composition of the present invention is a linear polymer having a fluoropolyether as a main chain, and has one or two (meth)acrylic groups at one end or both ends of the molecular chain, Component (A) comprising a compound having an average number of (meth)acrylic groups contained in one molecule of 2 or less and a fluorine content of 48% by mass or more and less than 62% by mass, a fluoropolyether main chain
- each molecule chain end that is, both ends of the molecule chain
- the average number of molecules in the molecule is 4-10.
- Component (B) consisting of a compound having a (meth)acrylic group and having a fluorine content of 25% by mass or more and less than 45% by mass, and containing no fluoropolyether structure, an average of 2 or more in one molecule. It is composed of a component (C) composed of a non-fluorinated acrylic compound having a (meth)acrylic group, and the above components (A), (B) and (C) are essential components.
- the “acrylic compound” is a general term for compounds having an acrylic group or a methacrylic group, and the “(meth)acrylic group” indicates one or both of an acrylic group and a methacrylic group, and “( “Meth)acrylic acid” means one or both of acrylic acid and methacrylic acid, and “(meth)acrylate” means one or both of acrylate and methacrylate.
- “acrylates” is a general term for compounds having acrylate and methacrylate.
- each of the components (A), (B), and (C) does not have to be a single compound.
- the components (A), (B), and The sum of the compounding amounts of the mixture of a plurality of compounds that meet the respective conditions of (C) may be considered as the respective component amounts.
- the component (A) which is the first essential component in the fluorine-containing curable composition of the present invention, is a linear polymer having a fluoropolyether as a main chain, and one or both ends of the molecular chain or It has two (meth)acrylic groups and the average value of the number of (meth)acrylic groups contained in one molecule is 2 or less (1 to 2) (that is, the molecular chain of the linear polymer. It has one (meth)acrylic group at each end, or has one or two (meth)acrylic groups at one end of the molecular chain), and the fluorine content is 48% by mass or more and 62% by mass or more. Consists of less than% compound.
- the fluorine content of the compound of the component (A) is 48% by mass or more and less than 62% by mass, preferably 55% by mass or more and 61.5% by mass or less, and more preferably 57% by mass or more and 61% by mass. % Or less. If the fluorine content is less than 48% by mass, the improvement of antifouling performance is insufficient as compared with the case where the component (A) is not used, and if it is 62% by mass or more, the solubility in the component (C) is insufficient. However, it is difficult to obtain a coated surface with a cured coating that is smooth.
- the fluorine content is the mass% value of fluorine atom in the molecule with respect to the number average molecular weight calculated from the molecular formula of the compound obtained from 19 F-NMR and 1 H-NMR (hereinafter the same).
- Examples of such a compound include a fluorine-containing acrylic compound represented by the following general formula (1) or (2).
- Rf 1 is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom, and specifically, , Fluorine atom, trifluoromethyl group, pentafluoroethyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, and CF 3 OCF 2 CF 2 — CF 3 OCF 2 CF 2 CF 2- CF 3 CF 2 OCF 2 CF 2- (CF 3 ) 2 CFOCF 2 CF 2- CF 3 OCF 2 CF 2 CF 2 CF 2- CF 3 CF 2 OCF 2 CF 2 CF 2- CF 3 CF 2 OCF 2 CF 2- (CF 3 ) 2 CFCF 2 OCF 2 CF 2- CF 3 CF 2 CF 2 OCF 2 CF 2- (CF 3 ) 2 CFCF 2 OCF
- Rf 2 is the following two types of repeating units —CF 2 O— -CF 2 CF 2 O- Is a divalent perfluoropolyether group having a molecular weight of 600 to 20,000, preferably 1,200 to 10,000, which is randomly arranged, and can be represented, for example, as follows. -(CF 2 O) m (CF 2 CF 2 O) n-
- m is an integer of 1 to 200, preferably 6 to 50
- n is an integer of 1 to 170, preferably 6 to 50
- m+n is an integer of 6 to 201, preferably 12 to 100. If the values of m, n, and m+n, which are integers, are too small, the effect of imparting antifouling property to the cured composition becomes small, and if it is more than this, the compatibility with the non-fluorinated component becomes poor, It may cause turbidity of coating liquid or coating failure.
- the values of m and n may have a distribution, and in the case of having a distribution, the value of m+n obtained from 19 F-NMR and the like preferably satisfies the above range in number average.
- Z 1 is independently a divalent hydrocarbon having 1 to 20 carbon atoms and optionally containing at least one hetero atom selected from oxygen atom, nitrogen atom and silicon atom.
- Group, a linking group selected from —C( ⁇ O)— and —C( ⁇ O)O—, and the divalent hydrocarbon group may have a cyclic structure in the middle, and hydrogen bonded to a carbon atom. A part of the atoms may be replaced by a fluorine atom.
- Examples of a suitable structure for Z 1 include the structure groups shown below.
- X 1 is independently a monovalent organic group having preferably 1 or 2 (meth)acryl groups optionally containing an oxygen atom and/or a nitrogen atom. However, it has one or two monovalent organic groups in one molecule. Further, in the above formula (2), X 2 is a hydroxyl group or X 1 .
- component (A) include compounds represented by the following structural groups.
- examples of the isocyanate compound containing a (meth)acrylic group represented by the formula (9) include the compounds shown below. CH 2 ⁇ CHC( ⁇ O)OCH 2 CH 2 —N ⁇ C ⁇ O CH 2 ⁇ C(CH 3 )C( ⁇ O)OCH 2 CH 2 —N ⁇ C ⁇ O
- These (meth)acrylic acid halides or isocyanate compounds containing a (meth)acrylic group may be charged in an amount of equimolar or more with respect to the total amount of the hydroxyl groups of the fluorine-containing alcohol compound to cause a reaction, and all the hydroxyl groups may be reacted.
- 1 mol or more of (meth)acryl group may be introduced on average with respect to 1 mol of the fluorine-containing alcohol compound.
- An acrylic acid halide or an isocyanate compound containing a (meth)acrylic group may not be allowed to remain.
- the amount of the fluorinated alcohol compound in the reaction system is x mol and the total amount of the hydroxyl groups of the fluorinated alcohol compound is y mol
- a (meth)acrylic acid halide or a (meth)acrylic group-containing isocyanate is used.
- the amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less.
- the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may decrease.
- the amount is too large, it becomes difficult to remove the unreacted (meth)acrylic acid halide or the residual isocyanate compound containing a (meth)acrylic group.
- reaction may be carried out by diluting with a suitable solvent, if necessary.
- a suitable solvent a solvent which does not react with a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of a (meth)acrylic acid halide, or an isocyanate group of an isocyanate compound containing a (meth)acrylic group can be used without particular limitation.
- hydrocarbon solvents such as toluene, xylene and isooctane, tetrahydrofuran (THF), ether solvents such as diisopropyl ether and dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
- Examples thereof include a ketone-based solvent, m-xylene hexafluoride (also known as hexafluorometa-xylene), a fluorinated aromatic hydrocarbon solvent such as benzotrifluoride, and a fluorinated ether solvent such as methyl perfluorobutyl ether.
- This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a diluted solution as it is depending on the intended use.
- the amount of the solvent used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If the amount of solvent used is too large, there is a danger that the reaction rate will decrease significantly.
- the polymerization inhibitor is not particularly limited, but those generally used as polymerization inhibitors for acrylic compounds can be used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
- the amount of the polymerization inhibitor used may be determined based on 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.
- a (meth)acrylic acid halide When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride and methacrylic acid chloride to generate an ester.
- the ester-forming reaction is carried out by adding the (meth)acrylic acid halide dropwise while stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor.
- the acid acceptor triethylamine, pyridine, urea or the like can be used.
- the amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. When the amount is too small, a large amount of untrapped acid remains, and when the amount is too large, it becomes difficult to remove the excess acid acceptor.
- the (meth)acrylic acid halide is added dropwise over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35°C. Then, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, and the like are removed by a method such as distillation, adsorption, filtration, and washing to obtain the above formula (1) or (2).
- a fluorine-containing acrylic compound represented by can be obtained.
- alcohol compounds such as methanol and ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide.
- the generated acrylic acid ester can be removed by the same method as that for removing the unreacted (meth)acrylic acid halide, but can be used as it is.
- a suitable catalyst may be added to increase the reaction rate.
- the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate and other alkyl tin ester compounds, tetraisopropoxytitanium, tetra Titanic acid esters or titanium chelate compounds such as n-butoxy titanium, tetrakis(2-ethylhexoxy) titanium, dipropoxybis(acetylacetona) titanium, titanium isopropoxyoctylene glycol, zirconium tetraacetylacetonate, zirconium tributoxy monoacetyl.
- Examples thereof include acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, and zirconium chelate compound. These are not limited to one type thereof, and can be used as a mixture of two or more types.
- the reaction rate can be increased by adding 0.01 to 2% by mass, preferably 0.05 to 1% by mass, relative to the total mass of the reactants.
- 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, the (meth)acrylic group may be polymerized as a side reaction.
- the unreacted isocyanate compound and the reaction solvent are removed by a method such as distillation, adsorption, filtration and washing to obtain a fluorine-containing acrylic compound represented by the above formula (1) or (2). be able to.
- an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with an unreacted isocyanate compound.
- the generated urethane acrylates can be removed by the same method as the unreacted isocyanate compound, but can be used as it is.
- Component (B) which is the second essential component in the fluorine-containing curable composition of the present invention, is the end of each molecular chain (that is, both molecular chain ends) in one molecule of a linear polymer having fluoropolyether as the main chain.
- Each has 2 or more (preferably 2 to 4) (meth)acryl groups at each end, and has 4 to 10 (preferably 4 to 8) (meth)acryl groups in one molecule on average.
- the fluorine content is 25% by mass or more and less than 45% by mass.
- the fluorine content of the compound of the component (B) is 25% by mass or more and less than 45% by mass, preferably 28% by mass or more and 43% by mass or less, and more preferably 33% by mass or more and 42% by mass or less. Is. If the fluorine content is less than 25% by mass, the solubility for the component (A) will decrease, and if it is 45% by mass or more, the solubility for the component (C) will decrease, so the composition as a whole will be applied smoothly. Becomes difficult.
- Rf 2 is the formula (1) is the same as Rf 2 in the (2).
- R 1 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms.
- the monovalent hydrocarbon group specifically, methyl is used.
- R 1 is preferably a hydrogen atom or a methyl group.
- R 2 is independently a hydrogen atom, or a monovalent organic group having a (meth)acryl group which may contain an oxygen atom and/or a nitrogen atom.
- a group having at least one, preferably one or two (meth)acryl groups at the terminal is preferable.
- the structure may have an amide bond, an ether bond, an ester bond, or the like.
- a is independently an integer of 2 to 5, preferably an integer of 2 to 4, and more preferably 2 or 3.
- solubility in component (C) may be reduced, and when a is greater than 5, solubility in component (A) may be reduced.
- Q 1 is independently a (a+1)-valent linking group containing at least (a+1) silicon atoms and may have a cyclic structure.
- Preferred examples of Q 1 include a siloxane structure having at least (a+1) silicon atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof (a+1). Examples include valent linking groups.
- the (a+1) bonds have (a+1) silicon atoms.
- the following structures are specifically shown as particularly preferable structures. However, in the following structure, a is the same as a in the above formula (3). Further, b is an integer of 1 to 5, and preferably an integer of 1 to 3.
- the arrangement of the units is random, and the bonds of (a+1) units and the like bond to any groups of Z 3 and a CH 2 groups enclosed by [].
- T′ is a (a+1)-valent linking group, and examples thereof include the following.
- Z 2 is independently a divalent hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 40 carbon atoms, which may contain an oxygen atom and/or a nitrogen atom. It may include a ring structure.
- particularly preferable structures include the following two structures, and among them, those in which d is an integer of 0 to 10 and e is an integer of 0 to 10 are preferable. —CH 2 [OC 2 H 4 ] d OC 2 H 4 — -CH 2 [OC 3 H 6 ] e OCH 2 CH(CH 3 )-
- Z 2 may also have the following structure.
- Z 3 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one hetero atom selected from oxygen atom, nitrogen atom and silicon atom. It is a group and may include a cyclic structure on the way, and a part of hydrogen atoms bonded to carbon atoms may be replaced by fluorine atoms. Examples of a suitable structure for Z 3 include the structures shown below. -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 OCH 2 CH 2 CH 2- -CH 2 OCH 2 CH 2 CH 2-
- fluorine-containing acrylic compound represented by the above formula (3) more preferable structures include those represented by the following general formulas (4) and (5).
- Z 3 , Q 1 and a are as described above, Rf′ is —CF 2 O(CF 2 O) m (CF 2 CF 2 O) n CF 2 —, and m, n, m+n Is the same as above, the arrangement of —(CF 2 O)— and —(CF 2 CF 2 O)— is random, R 3 is a hydrogen atom or a methyl group, and d1 and e1 are 0 to 10
- the fluorine content is 25% by mass or more and less than 45% by mass.
- component (B) examples include those shown below.
- e2 is an integer of 1 to 10, for example, 4.
- fluorine-containing acrylic compound represented by the formula (3) of the above component (B) can be synthesized by the methods disclosed in JP 2010-285501 A and JP 2015-199910 A, for example.
- the fluorine-containing acrylic compound represented by the above formula (3) is first prepared by the following general formula (10).
- Rf 2 , Z 3 , Q 1 and a are the same as above, and all a Hs enclosed by [] are bonded to a silicon atom in the Q 1 structure.
- a fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (11) CH 2 CR 1 -Z 2 -OH (11)
- R 1 and Z 2 are the same as above.
- a fluorine-containing alcohol compound as an intermediate can be obtained by hydrosilylating a terminal unsaturated group-containing alcohol represented by (a compound having an alkenyl group and a hydroxyl group at the molecular end).
- Examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (10) include the compounds shown below. (In the formula, Rf′ is the same as above.)
- Examples of the terminal unsaturated group-containing alcohol represented by the above formula (11) include those shown below.
- CH 2 CH-CH 2 -OCH 2 CH 2 -OH CH 2 ⁇ CH—CH 2 —OCH 2 CH(CH 3 )—OH CH 2 ⁇ CH—CH 2 —(OC 3 H 6 ) 2 —OCH 2 CH(CH 3 )—OH CH 2 ⁇ CH—CH 2 —(OC 3 H 6 ) 4 —OCH 2 CH(CH 3 )—OH CH 2 ⁇ CH—CH 2 —(OC 3 H 6 ) 9 —OCH 2 CH(CH 3 )—OH
- a fluoropolyether compound having a polyfunctional Si—H group represented by the formula (10) is mixed with a terminal unsaturated group-containing alcohol represented by the formula (11), and platinum is added. It is desirable to carry out the reaction in the presence of a group metal-based addition reaction catalyst at a reaction temperature of 50 to 150° C., preferably 60 to 120° C., for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without proceeding sufficiently, and if it is too high, the reaction heat cannot be controlled due to the temperature rise due to the reaction heat of hydrosilylation, and bumping or decomposition of raw materials may occur. There is.
- the reaction ratio between the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (10) and the terminal unsaturated group-containing alcohol represented by the formula (11) is represented by the formula (10).
- the amount of the terminal unsaturated group-containing alcohol represented by the formula (11) is less than this, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility, and if it is more than this, the reaction solution becomes homogeneous.
- the conditions such as heating, depressurization and extraction are used to remove excess unreacted alcohol. It becomes necessary to be stricter as the number increases.
- a compound containing a platinum group metal such as platinum, rhodium or palladium
- a compound containing platinum is preferable, and hexachloroplatinum(IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, Alternatively, platinum supported on activated carbon can be used.
- the addition reaction catalyst is added in such an amount that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (10).
- the amount is preferably 0.2 to 1,000 mass ppm.
- the above-mentioned addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent if necessary.
- a solvent e.g., benzyl alcohol, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, but the boiling point is not lower than the intended reaction temperature and does not inhibit the reaction, and it may be formed after the reaction. It is preferable that the fluoroalcohol compound is soluble at the above reaction temperature.
- a solvent examples include partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. Is preferable, and m-xylene hexafluoride is particularly preferable.
- a solvent when used, its amount is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (10). It is more preferably 50 to 500 parts by mass. If it is less than this range, the effect of dilution with a solvent becomes weak, and if it is more than that, the degree of dilution becomes too high and the reaction rate may decrease.
- Examples of the fluorine-containing alcohol compound thus obtained include the compounds shown below. (In the formula, Rf′ and e are the same as above.)
- a fluorine-containing acrylic compound can be obtained.
- a method of introducing a (meth)acrylic group into a fluorine-containing alcohol compound one is a method of reacting with a (meth)acrylic acid halide represented by the following formula (12) to form an ester, and the other is the following formula: Examples thereof include a method of reacting with a (meth)acrylic group-containing isocyanate compound represented by (13), and the fluorine-containing acrylic compound intended by the present invention can be obtained by these methods.
- examples of the isocyanate compound containing a (meth)acrylic group represented by the formula (13) include the compounds shown below. CH 2 ⁇ CHC( ⁇ O)OCH 2 CH 2 —N ⁇ C ⁇ O CH 2 ⁇ C(CH 3 )C( ⁇ O)OCH 2 CH 2 —N ⁇ C ⁇ O
- These (meth)acrylic acid halides or isocyanate compounds containing a (meth)acrylic group may be charged in an amount of equimolar or more with respect to the total amount of the hydroxyl groups of the fluorine-containing alcohol compound to cause a reaction, and all the hydroxyl groups may be reacted. It is sufficient to introduce an average of 1 mol or more of (meth)acrylic group with respect to 1 mol of the fluorine-containing alcohol compound, and by making the hydroxyl group excessive, unreacted (meth)acrylic acid halide or (meth) The acrylic compound-containing isocyanate compound may not be allowed to remain.
- the amount of the fluorinated alcohol compound in the reaction system is x mol and the total amount of the hydroxyl groups of the fluorinated alcohol compound is y mol
- a (meth)acrylic acid halide or a (meth)acrylic group-containing isocyanate is used.
- the amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less.
- the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may decrease.
- the amount is too large, it becomes difficult to remove the unreacted (meth)acrylic acid halide or the residual isocyanate compound containing a (meth)acrylic group.
- reaction may be carried out by diluting with a suitable solvent, if necessary.
- a suitable solvent a solvent which does not react with a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of a (meth)acrylic acid halide, or an isocyanate group of an isocyanate compound containing a (meth)acrylic group can be used without particular limitation.
- hydrocarbon solvents such as toluene, xylene and isooctane
- ether solvents such as THF, diisopropyl ether and dibutyl ether
- ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone.
- Fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether.
- This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a diluted solution as it is depending on the intended use.
- the amount of the solvent used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If the amount of solvent used is too large, there is a danger that the reaction rate will decrease significantly.
- the polymerization inhibitor is not particularly limited, but those generally used as polymerization inhibitors for acrylic compounds can be used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
- the amount of the polymerization inhibitor used may be determined based on 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.
- a (meth)acrylic acid halide When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride and methacrylic acid chloride to generate an ester.
- the ester-forming reaction is carried out by adding the (meth)acrylic acid halide dropwise while stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor.
- the acid acceptor triethylamine, pyridine, urea or the like can be used.
- the amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. When the amount is too small, a large amount of untrapped acid remains, and when the amount is too large, it becomes difficult to remove the excess acid acceptor.
- the (meth)acrylic acid halide is added dropwise over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35°C. Then, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, and the like are removed by a method such as distillation, adsorption, filtration, and washing, whereby the compound is represented by the above formula (3).
- a fluorinated acrylic compound can be obtained.
- alcohol compounds such as methanol and ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide.
- the generated (meth)acrylic acid ester can be removed by a method similar to the method for removing unreacted (meth)acrylic acid halide, but it can be used as it is.
- an appropriate catalyst may be added to increase the reaction rate.
- the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate, etc., alkyl tin ester compounds, tetraisopropoxytitanium, tetra Titanic acid esters or titanium chelate compounds such as n-butoxy titanium, tetrakis(2-ethylhexoxy) titanium, dipropoxybis(acetylacetona) titanium, titanium isopropoxyoctylene glycol, zirconium tetraacetylacetonate, zirconium tributoxy monoacetyl.
- Examples thereof include acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, and zirconium chelate compound. These are not limited to one kind and can be used as a mixture of two kinds or more, but it is particularly preferable to use a titanium compound or a tin compound which has a low influence on the environment.
- the reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.
- 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, the (meth)acrylic group may be polymerized as a side reaction.
- the fluorine-containing acrylic compound represented by the above formula (3) can be obtained by removing the unreacted isocyanate compound, the reaction solvent and the like by a method such as distillation, adsorption, filtration and washing.
- an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with an unreacted isocyanate compound.
- the generated urethane acrylates can be removed by the same method as the unreacted isocyanate compound, but can be used as it is.
- Component (C) which is the third essential component in the fluorine-containing curable composition of the present invention, does not contain a fluoropolyether structure and is a non-polymer having an average of two or more (meth)acrylic groups in one molecule. It is a fluorinated acrylic compound.
- the component (C) also includes urethane acrylates having a urethane bond in the molecule, and compounds in which two or more (meth)acrylic groups are introduced into the side chains or terminals of various polymers by an arbitrary method.
- the non-fluorinated acrylic compound (C) may be one having two or more (meth)acrylic groups in one molecule, and examples thereof include 1,6-hexanediol di(meth)acrylate and neopentyl.
- urethane acrylates those obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyisocyanate and a polyester of a terminal diol with a (meth)acrylate having a hydroxyl group, and an excess of a polyol. It is also possible to use a polyisocyanate obtained by reacting with the diisocyanate of (1) and a (meth)acrylate having a hydroxyl group.
- the component (C) may be used alone, or may be used in combination with a plurality of corresponding compounds in order to improve coatability and properties of the coating after curing.
- a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and having no urethane bond, or this polyfunctional acrylic compound is reacted with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group. It is preferable to use a mixture of at least two kinds of acrylic compounds containing the polyfunctional urethane acrylates having three or more (meth)acrylic groups in one molecule obtained in this way.
- the polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and having no urethane bond trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and Examples thereof include compounds obtained by modifying these with ethylene oxide or propylene oxide.
- Hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate are used as polyfunctional urethane acrylates having three or more (meth)acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group.
- trimers and bifunctional or trifunctional isocyanates obtained by reacting these bifunctional or trifunctional isocyanates with an aliphatic diol, an aliphatic polyol, or a polyacrylate having a hydroxyl group in a side chain, Trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate and those obtained by reacting these ethylene oxide and propylene oxide modified products, aliphatic polyols and polyacrylates having a hydroxyl group in the side chain and 2-isocyanatoethyl (meth)acrylate, 1, It can be shown by reacting an acrylic compound having an isocyanate group such as 1-(
- the component (C) may include not only a liquid component, but also a material in which the surface of a fine particle-shaped high molecular weight material or the surface of inorganic filler particles is modified with a (meth)acrylic group.
- the composition ratio of each component is such that the total amount of the components (A) and (B) is 0.05 to 50 parts by mass with respect to 100 parts by mass of the component (C). Parts, particularly preferably 0.1 to 10 parts by mass, and the compounding amount of the component (A) with respect to 100 parts by mass of the component (B) is 1 to 100 parts by mass, particularly preferably 3 to 50 parts by mass. Is desirable. If the total amount of the components (A) and (B) is larger than that of the component (C), the performance as a hard coat film deteriorates, and if it is too small, sufficient antifouling performance cannot be exhibited.
- the solubility in the component (C) may be too poor and coating failure may occur. If the amount is too small, the component (B) alone may be used. No difference is seen for use in.
- the fluorine-containing curable composition of the present invention requires the above-mentioned three components (A), (B), and (C) as essential components, and a mixture containing only these components is cured by heat, electron beam, or the like.
- components other than these three components depending on workability and need.
- a curable composition having improved curability when ultraviolet rays are used as active energy rays can be obtained.
- the photopolymerization initiator of the component (D) is not particularly limited as long as it can cure an acrylic compound by ultraviolet irradiation, but, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- is preferable.
- the content of the component (D) can be appropriately determined depending on the curing conditions and the desired physical properties of the composition. For example, 0.1 to 15 parts by mass relative to 100 parts by mass of the component (C), It is particularly desirable that the amount be 1 to 10 parts by mass. If the amount added is less than this, the curability may decrease, and if it exceeds this amount, the physical properties after curing may be significantly affected.
- the components (A), (B), (C), and (D) can be used as one kind of compound or a mixture of a plurality of compounds having the structures corresponding to the definitions of each compound.
- the total mass of each compound group may be considered as each mass in order to consider the blending amount.
- the fluorine-containing curable composition of the present invention further comprises, according to the purpose, an active energy ray-reactive compound other than a (meth)acrylic group, such as a monofunctional acrylic compound as a reactive diluent, a thiol compound or a maleimide compound.
- an active energy ray-reactive compound other than a (meth)acrylic group such as a monofunctional acrylic compound as a reactive diluent, a thiol compound or a maleimide compound.
- organic solvent examples include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol and diacetone alcohol; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- Ketones such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, butyl acetate, cyclohexyl acetate, etc.
- aromatics such as toluene, xylene, triethylbenzene, and alkylbenzenes.
- the above solvents may be used alone or in combination of two or more.
- the amount of the solvent used is not particularly limited, but is preferably 20 to 10,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the components (A) to (C) in total. ..
- the polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, heat resistance stabilizer, antioxidant, surfactant, colorant, and filler are not particularly limited, and known ones may be used. It can be used within a range that does not impair the object of the present invention.
- the fluorine-containing curable composition of the present invention may be one obtained by adding the component (A) and the component (B) to such a commercially available hard coat agent.
- Examples of commercially available hard coat agents include Arakawa Chemical Co., Ltd. “Beamset”, Ohashi Chemical Co., Ltd. “Ubic”, Origin Electric Co., Ltd. “UV coat”, Cashew Co., Ltd. “Cashew UV”, JSR Corporation “Desolite”, Dainichiseika Kogyo Co., Ltd. "Seika Beam”, Nippon Synthetic Chemical Co., Ltd. “Shikou”, Fujikura Kasei Co., Ltd. "Fujihard”, Mitsubishi Rayon Co., Ltd. "Diabeam”, Musashi Paint “Ultra Vine” etc. are mentioned.
- an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, a light resistance stabilizer, a heat stability Agents, antioxidants, surfactants, colorants, fillers and the like can be added and blended.
- the method for blending the fluorine-containing curable composition of the present invention may be any method depending on the application and is not particularly limited, but the component (A) and the component (B) may be mixed before mixing with other components. It is desirable that the components are well mixed, for example, the component (A) and the component (B) are mixed at a required ratio and, if necessary, diluted with a solvent and then mixed with the component (C) and other components, or A method in which the component (A) diluted with a solvent and the component (B) diluted with a solvent are mixed and then mixed with the component (C) and other components are suitable.
- the method for curing the fluorine-containing curable composition of the present invention is not particularly limited, and the composition containing the components (A), (B) and (C) is appropriately diluted with a solvent and applied, and heat, electron beam, etc. Although it can be cured by the active energy ray of 1., when it further contains the component (D) photopolymerization initiator, it can be cured by ultraviolet rays. In the case of curing with ultraviolet rays, irradiation with ultraviolet rays can be performed in the air, but it is preferable to keep the oxygen concentration to 5,000 ppm or less in order to prevent inhibition of curing by oxygen, and an inert gas such as nitrogen, carbon dioxide or argon. It is particularly preferable to cure under an atmosphere.
- the fluorine-containing curable composition of the present invention may be applied on any substrate as long as the fluorine-containing curable composition layer of the present invention adheres or adheres after curing.
- resin base materials such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cyclo Olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, Resins such as nylon and acrylic
- a film substrate When applied to a film substrate, it may have a structure in which a pressure-sensitive adhesive is applied on the side opposite to the side on which the fluorine-containing curable composition layer is applied/formed, and a layer for protecting the pressure-sensitive adhesive is further provided.
- a mold film may be arranged.
- the film substrate may be a substrate consisting only of the resin film listed above, but in order to improve the adhesion with the fluorine-containing curable composition of the present invention, a primer on the resin film It may be a film substrate provided with a layer.
- the primer layer include those made of polyester resin, urethane resin, acrylic resin and the like.
- the fluorine-containing curable composition of the present invention may be applied and cured on a cured or uncured curable composition layer which does not correspond to the present invention.
- the fluorine-containing curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic property, and curl prevention property.
- the surface of the resin substrate is subjected to sandblasting, surface roughening treatment by a solvent treatment method, corona discharge treatment, chromic acid treatment, flame.
- the treatment can also be performed by treatment, hot air treatment, ozone/ultraviolet irradiation treatment, oxidation treatment, or the like.
- the method for applying the fluorine-containing curable composition of the present invention to the above-mentioned substrate or article is not particularly limited, but for example, roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating.
- Known coating methods such as bar coating, bar coating, and screen printing can be used.
- the coating film is irradiated with active energy rays to cure it.
- active energy ray any ray such as an electron beam or ultraviolet ray can be used, but ultraviolet ray is particularly preferable.
- the ultraviolet ray source a mercury lamp, a metal halide lamp, and an LED lamp are suitable. If the amount of UV irradiation is too small, the uncured component remains, and if it is too large, the coating film and the base material may deteriorate, so 10 to 10,000 mJ/cm 2 , particularly 100 to 4,000 mJ/cm 2. It is desirable to be in the range of 2 .
- the irradiation atmosphere during ultraviolet irradiation is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon, and the surface of the coating film is UV transparent with releasability.
- an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon
- the surface of the coating film is UV transparent with releasability.
- the coating surface is covered with a protective layer that has releasability and is the opposite of the coated surface of the base material. Ultraviolet rays may be irradiated from the side.
- the coating film and the base material may be heated by an arbitrary method such as infrared rays or a hot air drying oven before and during the irradiation with ultraviolet rays. Good.
- the thickness of the cured product layer of the fluorine-containing 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 curable composition of the present invention was measured by the angle between the liquid surface and the solid surface 1 second after the contact of 2 ⁇ L of the ion-exchanged water with the liquid.
- the static water contact angle is 114° or more, particularly 115° or more, and the static oleic acid contact angle measured by the angle formed by the liquid surface and the solid surface 1 second after the contact of 4 ⁇ L of oleic acid is 73°.
- a water- and oil-repellent surface having an angle of 74° or more can be obtained.
- the cured product layer of the fluorine-containing curable composition of the present invention can be a water- and oil-repellent surface having a low dynamic friction coefficient such that the cured film has a dynamic friction coefficient of 0.10 or less, particularly 0.09 or less. ..
- the cured product layer of the fluorine-containing curable composition of the present invention has a thickness of 10 nm or more on average with respect to the total surface area of the cured product layer.
- the amount is preferably such that Further, it is preferable that the unreacted (meth)acrylic group does not remain on the surface of the cured product layer. Therefore, it is desirable that the cured product layer is cured in an atmosphere of an inert gas such as nitrogen or carbon dioxide.
- the fluorine-containing curable composition of the present invention is curable by active energy rays such as ultraviolet rays, and has excellent water and oil repellency, antifouling property, slipperiness, and abrasion resistance on the surface of an article.
- a cured resin layer can be formed.
- the present invention provides an article having a cured coating obtained by applying the above-mentioned fluorine-containing curable composition of the present invention to the surface and curing the composition.
- a cured coating obtained by applying the above-mentioned fluorine-containing curable composition of the present invention to the surface and curing the composition.
- the fluorine-containing curable composition of the present invention it becomes possible to form a cured coating (cured resin layer) having excellent surface characteristics on the surface of a substrate (article).
- it is useful for imparting water repellency, oil repellency, and antifouling property to the surface of the acrylic hard coat.
- the fluorine-containing curable composition of the present invention is contaminated with a base material (article) that may be touched by humans and contaminated with human fat, cosmetics, etc., and also with human fat and machine oil of workers. It is possible to provide an antifouling coating film or a protective film for the surface of a process material film or the like used inside a machine that has a possibility.
- a cured film (cured resin layer) formed by using the fluorine-containing curable composition of the present invention is a tablet computer, a notebook PC, a portable (communication) information terminal such as a mobile phone/smartphone, a digital media player, an electronic book.
- Cases of various devices such as readers, watch-type/spectacle-type wearable computers, head-mounted displays, liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays , CRTs, toner-based displays, various flat panel displays such as quantum dot (QD) displays, and display operation equipment surfaces such as TV screens, and various optical films used inside these, exteriors of automobiles, pianos and furniture Glossy surface, architectural stone surface such as marble, decorative building material around water such as toilet, bath, washroom, protective glass for art exhibition, show window, showcase, photo frame cover, wrist watch, cosmetic container exterior, decoration Exterior of product containers, window glass for automobiles, window glass for trains, aircrafts, etc., transparent glass such as automobile headlights, tail lamps, etc. or transparent plastic (acrylic, polycarbonate etc.) members, car sensors such as millimeter wave radar It is useful as a coating film and a surface protection film for cover members, various mirror members, and the like.
- various devices having a display input device such as a touch panel display for performing on-screen operations with a human finger or a palm, for example, tablet computer, notebook PC, smartphone, mobile phone, other portable (communication) information terminal, smart watch.
- controllers such as a payment machine, a vending machine, a digital signage (electronic signboard), a security system terminal, a POS terminal, a remote controller, and a panel switch for an in-vehicle device.
- the cured film formed from the fluorine-containing curable composition of the present invention is an optical recording medium such as a magneto-optical disc or an optical disc; spectacle lens, prism, lens sheet, pellicle film, polarizing plate, optical filter, lenticular lens, Fresnel. It is also useful as a surface protective film for lenses, antireflection films, lenses for various cameras, protective filters for various lenses, optical parts and optical devices such as optical fibers and optical couplers.
- the fluorine-containing curable composition of the present invention can be repelled by disposing the fluoropolyether structure in the compound of the components (A) and (B) according to the present invention on the surface of the target article.
- it imparts excellent properties such as water resistance, oil repellency, slipperiness, antifouling property, fingerprint inconspicuousness, fingerprint wiping property, abrasion resistance, low refractive index characteristics, solvent resistance, chemical resistance, etc.
- fluorine-containing curable composition of the present invention when compounded and prepared, in addition to the components (A) and (B) according to the present invention, various formulations in the above-mentioned fluorine-containing curable composition are combined.
- non-fluorine-based polyfunctional acrylic compounds in a suitable amount, or the hardness.
- a combination of a non-fluorine-based polyfunctional acrylic compound having a functionality of 6 or more and an acrylic compound having a functionality of 3 or less is used as the component (C). It can be easily inferred from the formulation knowledge. Further, when an article is obtained by applying the fluorine-containing curable composition of the present invention, for example, when applying to a film substrate, adjustment is performed so as to have an appropriate applied film thickness in order to prevent interference fringes.
- Rf′ —CF 2 O(CF 2 CF 2 O) 20.9 (CF 2 O) 21.2 CF 2 —
- the compound (V) obtained above Si—H group amount of 0.0657 mol
- 7.05 g (0.0690 mol) of 2-allyloxyethanol, m-xylene hexa 50.0 g of fluoride and 0.0442 g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (containing 1.1 ⁇ 10 ⁇ 7 mol of Pt as a simple substance) were mixed and stirred at 100° C. for 4 hours.
- Rf′′ —CF 2 O(CF 2 CF 2 O) 9.8 (CF 2 O) 9.1 CF 2 —
- 15.1 g (0.149 mol) of 2-allyloxyethanol and m-xylene hexa were added to 50.0 g of the compound (VII) obtained above (0.121 mol of Si—H group).
- 100.0 g of fluoride and 0.0884 g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (containing 2.2 ⁇ 10 ⁇ 7 mol as a Pt simple substance) were mixed and stirred at 100° C. for 4 hours.
- compositions of Comparative Examples 1 to 3 in which the component (B) was not blended and only the components (A) and (C) were blended the dissolved state of the composition was poor and precipitates were formed.
- the compositions of Examples 1 to 11 of the present invention in which the components (A), (B) and (C) are blended can produce a transparent and uniform coating liquid, and the composition of the present invention can be prepared.
- the compositions of Examples 1 to 11 had higher liquid repellency than the compositions of Comparative Examples 4, 5 and 7 in which the component (A) was not blended and only the components (B) and (C) were blended. A slippery surface can be formed.
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Abstract
Description
なお、本発明に関連する従来技術として、上述した文献と共に下記文献が挙げられる。
[1]
フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下であり、フッ素含有率が48質量%以上62質量%未満の化合物からなる成分(A)、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端にそれぞれ2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる成分(B)、及びフルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)を必須成分とし、成分(C)100質量部に対して、成分(A)と成分(B)の配合量の合計が0.05~50質量部であり、かつ成分(B)100質量部に対する成分(A)の配合量が1~100質量部である含フッ素硬化性組成物。
[2]
更に、光重合開始剤(D)を含有する[1]に記載の含フッ素硬化性組成物。
[3]
成分(A)が、下記一般式(1)又は(2)のいずれかで表される含フッ素アクリル化合物である[1]又は[2]に記載の含フッ素硬化性組成物。
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1はフッ素原子、又は酸素原子を含んでいてもよい炭素数1~8の1価の含フッ素アルキル基であり、Rf2は下記の2種類の繰り返し単位
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Z1は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基、-C(=O)-及び-C(=O)O-から選ばれる連結基であり、該2価の炭化水素基は途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。X1は独立に酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、X2は水酸基又はX1である。)
[4]
成分(B)が、下記一般式(3)で表される含フッ素アクリル化合物である[1]~[3]のいずれかに記載の含フッ素硬化性組成物。
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Q1は独立に少なくとも(a+1)個のケイ素原子を含む(a+1)価の連結基であり、環状構造をなしていてもよい。aは2~5の整数である。Z2はそれぞれ独立に酸素原子及び/又は窒素原子を含んでいてもよい炭素数1~100の2価の炭化水素基であり、途中環状構造を含んでいてもよい。R1は独立に水素原子又は炭素数1~8の1価の炭化水素基である。R2は独立に水素原子、又は酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、但し、R2は1分子中のそれぞれの末端に2個以上、かつ1分子中に平均して4~10個の前記1価の有機基を有する。Z3は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基からなる連結基であり、途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。)
[5]
成分(A)において、一般式(1)又は(2)中のZ1が、下記のいずれかの構造である[3]又は[4]に記載の含フッ素硬化性組成物。
-C(=O)-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2-
[6]
成分(A)において、一般式(1)又は(2)中のX1が、下記のいずれかで示されるものである[3]~[5]のいずれかに記載の含フッ素硬化性組成物。
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH2
-C[OC(=O)CH=CH2]2
-C[OC(=O)C(CH3)=CH2]2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2]2
-CH2[CH2OC(=O)C(CH3)=CH2]2
-C[CH2OC(=O)CH=CH2]
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2
[7]
成分(A)において、一般式(1)又は(2)で表される含フッ素アクリル化合物が、下記のいずれかで示されるものである[3]~[6]のいずれかに記載の含フッ素硬化性組成物。
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は上記と同じである。)
[8]
成分(B)において、一般式(3)中のZ3が、下記式のいずれかで表されるものである[4]~[7]のいずれかに記載の含フッ素硬化性組成物。
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[9]
成分(B)において、一般式(3)中のQ1が、下記式で表されるものである[4]~[8]のいずれかに記載の含フッ素硬化性組成物。
[10]
成分(B)において、一般式(3)で表される含フッ素アクリル化合物が、下記一般式(4)又は(5)で表される含フッ素アクリル化合物である[4]~[9]のいずれかに記載の含フッ素硬化性組成物。
[11]
成分(C)の非フッ素化アクリル化合物が、1分子中に2個以上の(メタ)アクリル基を有しウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類、又は前記多官能アクリル化合物とウレタンアクリレート類とを含む2種類以上のアクリル化合物の混合物である[1]~[10]のいずれかに記載の含フッ素硬化性組成物。
[12]
[1]~[11]のいずれかに記載の含フッ素硬化性組成物の硬化被膜を表面に有する物品。
本発明の含フッ素硬化性組成物における第一の必須成分である成分(A)は、フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下(1~2個)であり(即ち、該直鎖ポリマーの分子鎖両末端にそれぞれ1個ずつの(メタ)アクリル基を有するか、あるいは、分子鎖の片末端に1個又は2個の(メタ)アクリル基を有する)、フッ素含有率が48質量%以上62質量%未満の化合物からなる。
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
CF3OCF2CF2-
CF3OCF2CF2CF2-
CF3CF2OCF2CF2-
(CF3)2CFOCF2CF2-
CF3OCF2CF2CF2CF2-
CF3CF2OCF2CF2CF2-
CF3CF2CF2OCF2CF2-
(CF3)2CFCF2OCF2CF2-
CF3CF2CF2CF2OCF2CF2-
CF3CF2CF2OCF2CF2CF2-
が挙げられ、これらの中でも特にCF3-、CF3CF2-が好ましい。
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000、好ましくは1,200~10,000の2価のパーフルオロポリエーテル基であり、例えば以下のように表すことができる。
-(CF2O)m(CF2CF2O)n-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2-
-CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2-
が好ましい。
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH2
-C[OC(=O)CH=CH2]2
-C[OC(=O)C(CH3)=CH2]2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2]2
-CH2[CH2OC(=O)C(CH3)=CH2]2
-C[CH2OC(=O)CH=CH2]
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH2
である。
HO-
CH2=C(CH3)C(=O)O-
CH2=CHC(=O)O-
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は前記の通りであるが、成分(A)に該当する化合物としてのフッ素含有率の平均値が55質量%以上62質量%未満のものが特に好ましい。)
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1、Rf2、Z1、X1、X2は上記と同じである。)
で表される含フッ素アクリル化合物の好適な合成方法としては、例えば、下記一般式(6)又は(7)
Rf1-O-Rf2-CF2-CH2-OH (6)
HO-CH2-CF2O-Rf2-CF2-CH2-OH (7)
(式中、Rf1、Rf2は上記と同じである。)
で表される含フッ素アルコール化合物に、一つは下記一般式(8)
CH2=CR3C(=O)X (8)
(式中、R3は上記と同じであり、Xはフッ素原子、塩素原子、臭素原子等のハロゲン原子である。)
で表される(メタ)アクリル酸ハライドを反応させて、エステルを形成する方法、もう一つは下記一般式(9)
CH2=CR3C(=O)OCH2CH2-N=C=O (9)
(式中、R3は上記と同じである。)
で表される(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方法が挙げられ、これらの方法により、上記式(1)又は(2)で表される含フッ素アクリル化合物を得ることができる。
CH2=CHC(=O)X
CH2=C(CH3)C(=O)X
(式中、Xは上記と同じである。)
特にアクリル酸クロリド、メタクリル酸クロリドが好ましい。
CH2=CHC(=O)OCH2CH2-N=C=O
CH2=C(CH3)C(=O)OCH2CH2-N=C=O
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。溶剤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。
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。
本発明の含フッ素硬化性組成物における第二の必須成分である成分(B)は、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端(即ち、分子鎖両末端)にそれぞれ2個以上、好ましくは2~4個の(メタ)アクリル基を有し、1分子中に平均して4~10個、好ましくは4~8個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる。
CH2=CHC(=O)-
CH2=C(CH3)C(=O)-
CH2=CHC(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2OCH2CH2-NHC(=O)-
(CH2=CHC(=O)OCH2CH2)2C(CH3)-NHC(=O)-
CH2=CHC(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-
但し、下記の構造において、aは上記式(3)のaと同じである。また、bは1~5の整数であり、好ましくは1~3の整数である。各ユニットの並びはランダムであり、(a+1)個の各ユニット等の結合手は、Z3及び[ ]で括られたa個のCH2のいずれかの基と結合する。
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCcH2c-
(式中、dは0~29の整数、好ましくは0~10の整数であり、eは0~29の整数、好ましくは0~10の整数であり、fは0~14の整数、好ましくは0~7の整数であり、cは2~4の整数である。上記構造の合計として炭素数3~100、好ましくは炭素数3~30を満たせばよい。繰り返し単位の配列は、種類にかかわらずランダムである。また各繰り返し単位は単体でなく構造異性体の混合物でもよい。)
-CH2[OC2H4]dOC2H4-
-CH2[OC3H6]eOCH2CH(CH3)-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
が好ましい。
で表される多官能Si-H基を有するフルオロポリエーテル化合物と、下記一般式(11)
CH2=CR1-Z2-OH (11)
(式中、R1、Z2は上記と同じである。)
で表される末端不飽和基含有アルコール(分子末端にアルケニル基と水酸基を有する化合物)とをヒドロシリル化反応させることにより、中間体である含フッ素アルコール化合物を得ることができる。
CH2=CH-CH2-OCH2CH2-OH
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
付加反応触媒の配合量は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物に対し、含まれる金属量が0.1~5,000質量ppmとなる量であることが好ましく、より好ましくは0.2~1,000質量ppmとなる量である。
溶剤を使用する場合、その使用量は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物100質量部に対して、好ましくは5~2,000質量部であり、より好ましくは50~500質量部である。これより少なければ溶剤による希釈の効果が薄くなり、多ければ希釈度が高くなりすぎて反応速度の低下を招く場合がある。
CH2=CR3C(=O)OCH2CH2-N=C=O (13)
(式中、R3、Xは上記と同じである。)
CH2=CHC(=O)X
CH2=C(CH3)C(=O)X
(式中、Xは上記と同じである。)
特にアクリル酸クロリド、メタクリル酸クロリドが好ましい。
CH2=CHC(=O)OCH2CH2-N=C=O
CH2=C(CH3)C(=O)OCH2CH2-N=C=O
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。溶剤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。
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。
本発明の含フッ素硬化性組成物における第三の必須成分である成分(C)は、フルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物である。成分(C)は、分子内にウレタン結合を有するウレタンアクリレート類や、各種重合体の側鎖や末端に任意の方法で2個以上の(メタ)アクリル基を導入した化合物も含む。
特に1分子中に2個以上の(メタ)アクリル基を有し、ウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と、脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類からなるものとを含む少なくとも2種類のアクリル化合物の混合物を用いることが好ましい。
特に成分(D)として光重合開始剤を含有することで、活性エネルギー線として紫外線を用いた場合の硬化性を高めた硬化性組成物とすることができる。
成分(D)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、1種単独でも2種以上を併用してもよい。
溶剤の使用量は特に制限されるものではないが、成分(A)~(C)の合計100質量部に対し、20~10,000質量部が好ましく、特に100~1,000質量部が好ましい。
また、本発明の含フッ素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したりすることで含フッ素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、本発明と既存技術の組み合わせにより容易に達成可能である。
還流装置と攪拌装置を備えた300L四つ口フラスコに、平均構造が下記式(I)
HOCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OH (I)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0508mol)、下記式(II)
CH2=CHC(=O)OCH2CH2-N=C=O (II)
で表される化合物7.17g、ヘキサフルオロメタキシレン200gを仕込み、乾燥空気雰囲気下で攪拌しながら40℃まで加熱した。ついで、0.01gのジオクチル錫ジラウレートを投入し、6時間加熱攪拌を継続してから、加熱を停止した。反応液の19F-NMRにより、-OCF2CH2OHのCF2に由来するピーク(-81.1ppm、-83.15ppm)がすべて、-OCF2CH2OC(=O)-に由来する(-78.4ppm、-80.4ppm)に変化したのを確認した。得られた反応液に活性炭2gを投入し、室温で3時間攪拌したのちに、ろ過板でろ過を行った。得られたろ液を50℃で減圧留去し、目的とするフッ素含有率57.5質量%の下記(A-1)の平均構造を有する化合物97.8gを得た。
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-1)
合成例1において、上記式(I)の代わりに、平均構造として下記式(III)
HOCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OH
(III)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0345mol)を用い、上記式(II)の化合物の配合量を4.86gに変更した以外は合成例1と同様の手順で操作を行い、平均構造として下記のフッ素含有率59.2質量%の化合物(A-2)96.2gが得られた。
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-2)
還流装置と攪拌装置を備えた300L四つ口フラスコに、式(I)の化合物100g(OH基 0.0508mol)、トリエチルアミン7.20g、ヘキサフルオロメタキシレン150g、室温下、乾燥空気雰囲気下で攪拌しながら、アクリル酸クロライド6.38g(0.0704mol)とヘキサフルオロメタキシレン50gの混合液を30分かけて滴下した。6時間攪拌を継続してから停止し、ろ紙によるろ過を行った。得られたろ液はヘキサン1,000g中に投入し、発生した沈殿物を回収し、ヘキサフルオロメタキシレン100gで溶解させてから50℃で溶剤の減圧留去を行い、19F-NMRで目的とする下記の平均構造を有するフッ素含有率60.0質量%の化合物(A-3)90.5gが得られたことを確認した。
CH2=CHC(=O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(=O)CH=CH2 (A-3)
合成例1において、上記式(I)の代わりに、平均構造として下記式(IV)
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OH (IV)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0264mol)を用い、上記式(II)の化合物の配合量を4.11gに変更し、ジオクチル錫ジラウレートの代わりに、オルトチタン酸テトラキス(2-エチルヘキシル)0.2gを用いた以外は合成例1と同様の手順で操作を行い、平均構造として下記のフッ素含有率60.2質量%の化合物(A-4)97.5gが得られた。
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-4)
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた5,000mL三つ口フラスコに、下記式
CH2=CH-CH2-O-CH2-Rf’-CH2-O-CH2-CH=CH2
Rf’:-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
で表されるパーフルオロポリエーテル1,000g(0.245mol)と、m-キシレンヘキサフロライド1,400g、及びテトラメチルシクロテトラシロキサン722g(3.00mol)を投入し、攪拌しながら90℃まで加熱した。ここに白金/1,3-ジビニル-テトラメチルジシロキサン錯体のトルエン溶液0.884g(Pt単体として2.2×10-6molを含有)を投入し、内温を90℃以上に維持したまま4時間攪拌を継続した。1H-NMRで原料のアリル基が消失したのを確認した後、溶剤と過剰のテトラメチルシクロテトラシロキサンを減圧留去した。その後活性炭処理を行い、下記式で示される無色透明の液状化合物(V)993gを得た。
乾燥空気雰囲気下で、上記で得られた化合物(V)50.0g(Si-H基量0.0657mol)に対して、2-アリルオキシエタノール7.05g(0.0690mol)、m-キシレンヘキサフロライド50.0g、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液0.0442g(Pt単体として1.1×10-7molを含有)を混合し、100℃で4時間攪拌した。1H-NMR及びIRでSi-H基が消失したのを確認した後、溶剤と過剰の2-アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物(VI)54.9gを得た。
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物(VI)50.0g(水酸基量0.058mol)に対して、THF50.0gとアクリロイルオキシエチルイソシアネート9.00g(0.0638mol)を混合し、50℃に加熱した。そこにオルトチタン酸テトラキス(2-エチルヘキシル)0.15gを添加し、50℃下24時間攪拌した。加熱終了後、80℃/0.266kPaで減圧留去を行い、淡黄色のペースト状物質58.5gを得た。1H-NMR及びIRの結果から下記に示す、フッ素含有率41.0質量%の含フッ素アクリル化合物であることを確認した。
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた500mL三つ口フラスコに、下記式
CH2=CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH=CH2
Rf”:-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
で表されるパーフルオロポリエーテル100g(0.0501mol)と、m-キシレンヘキサフロライド100g、及びテトラメチルシクロテトラシロキサン121g(0.502mol)を投入し、攪拌しながら90℃まで加熱した。ここに白金/1,3-ジビニル-テトラメチルジシロキサン錯体のトルエン溶液0.442g(Pt単体として1.1×10-6molを含有)を投入し、内温を90℃以上に維持したまま4時間攪拌を継続した。1H-NMRで原料のアリル基が消失したのを確認した後、溶剤と過剰のテトラメチルシクロテトラシロキサンを減圧留去した。その後活性炭処理を行い、下記式で示される無色透明の液状化合物(VII)112gを得た。
乾燥空気雰囲気下で、上記で得られた化合物(VII)50.0g(Si-H基量0.121mol)に対して、2-アリルオキシエタノール15.1g(0.149mol)、m-キシレンヘキサフロライド100.0g、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液0.0884g(Pt単体として2.2×10-7molを含有)を混合し、100℃で4時間攪拌した。1H-NMR及びIRでSi-H基が消失したのを確認した後、溶剤と過剰の2-アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物(VIII)60.2gを得た。
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物(VIII)50.0g(水酸基量0.097mol)に対して、THF50.0gとアクリロイルオキシエチルイソシアネート17.7g(0.125mol)を混合し、50℃に加熱した。そこにジオクチル錫ジラウレート0.05gを添加し、50℃下24時間攪拌した。加熱終了後、80℃/0.266kPaで減圧留去を行い、淡黄色の高粘調液体63.5gを得た。1H-NMR及びIRの結果から下記に示す、フッ素含有率29.7質量%の含フッ素アクリル化合物であることを確認した。
本発明の含フッ素硬化性組成物の原料成分を下記に示す。
(A)含フッ素アクリル化合物
(A-1)合成例1で得られた含フッ素アクリル化合物
(A-2)合成例2で得られた含フッ素アクリル化合物
(A-3)合成例3で得られた含フッ素アクリル化合物
(A-4)合成例4で得られた含フッ素アクリル化合物
(B)含フッ素アクリル化合物
(B-1)合成例5で得られた含フッ素アクリル化合物
(B-2)合成例6で得られた含フッ素アクリル化合物
(C)非フッ素化アクリル化合物
(C-1)ペンタエリスリトールエトキシテトラアクリレート
[ダイセルオルネクス社製 EBECRYL 40]
(C-2)ペンタエリスリトールトリアクリレート
(C-3)ペンタエリスリトールトリアクリレートとヘキサメチレンジイソシアネートの反応物からなる多官能アクリレート[共栄社化学社製 UA-306H]
(D)光重合開始剤
(D-1)1-ヒドロキシシクロヘキシルフェニルケトン(商品名:IRGACURE 184、BASFジャパン社製)
(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(商品名:IRGACURE 127、BASFジャパン社製)
成分(A)及び(B)は全てメチルエチルケトンで20質量%に、成分(C)は酢酸ブチルで40質量%に希釈を行った。また(C-1)の希釈溶剤を酢酸ブチルから2-プロパノールに替えて40質量%に希釈したものを(C-4)として配合した。
成分(A)~(D)の各成分の溶剤成分を除いた配合比として下記表1となるように混合し、含フッ素硬化性組成物を得た。
各組成物の溶解状態(塗工液外観)を目視で観察した。なお、沈殿物が発生した組成物についてはこれ以降の評価を行わなかった。結果を表2に示す。
実施例及び比較例の各組成物をポリカーボネート基板上にワイヤーバーNo.7で塗工した(ウエット膜厚16.0μm)。塗工後100℃、1分間の乾燥を行った後、コンベヤ式メタルハライドUV照射装置(パナソニック電工製)を使用し、窒素雰囲気中で、積算照射量400mJ/cm2の紫外線を塗工面に照射して組成物を硬化させ、厚み5μmの硬化膜を得た。
1)水接触角測定
接触角計(協和界面科学社製 DropMaster)を用い、水2μLの液滴を硬化膜上に滴下して1秒後の水接触角を測定した。N=5の平均値を測定値とした。結果を表2に示す。
2)オレイン酸接触角測定
接触角計(協和界面科学社製 DropMaster)を用い、オレイン酸4μLの液滴を硬化膜上に滴下して1秒後のオレイン酸接触角を測定した。N=5の平均値を測定値とした。結果を表2に示す。
ベンコット(旭化成社製)に対する硬化膜の動摩擦係数を、表面性試験機14FW(新東科学社製)を用いて下記条件で測定した。結果を表2に示す。
接触面積:10mm×35mm
荷重:100g
硬化膜表面にマジックペン(ゼブラ社製 ハイマッキー太字)で直線を描き、そのハジキ具合を目視観察によって評価した。結果を表2に示す。
硬化膜表面にマジックペン(ゼブラ社製 ハイマッキー太字)で直線を描き、1分後にティッシュペーパーで軽く3回擦って、マジックの跡が残らなかったものを「拭き取れる」、跡が残ったものを「拭き取れない」で評価した。結果を表2に示す。
Claims (12)
- フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下であり、フッ素含有率が48質量%以上62質量%未満の化合物からなる成分(A)、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端にそれぞれ2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる成分(B)、及びフルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)を必須成分とし、成分(C)100質量部に対して、成分(A)と成分(B)の配合量の合計が0.05~50質量部であり、かつ成分(B)100質量部に対する成分(A)の配合量が1~100質量部である含フッ素硬化性組成物。
- 更に、光重合開始剤(D)を含有する請求項1に記載の含フッ素硬化性組成物。
- 成分(A)が、下記一般式(1)又は(2)のいずれかで表される含フッ素アクリル化合物である請求項1又は2に記載の含フッ素硬化性組成物。
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1はフッ素原子、又は酸素原子を含んでいてもよい炭素数1~8の1価の含フッ素アルキル基であり、Rf2は下記の2種類の繰り返し単位
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Z1は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基、-C(=O)-及び-C(=O)O-から選ばれる連結基であり、該2価の炭化水素基は途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。X1は独立に酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、X2は水酸基又はX1である。) - 成分(B)が、下記一般式(3)で表される含フッ素アクリル化合物である請求項1~3のいずれか1項に記載の含フッ素硬化性組成物。
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Q1は独立に少なくとも(a+1)個のケイ素原子を含む(a+1)価の連結基であり、環状構造をなしていてもよい。aは2~5の整数である。Z2はそれぞれ独立に酸素原子及び/又は窒素原子を含んでいてもよい炭素数1~100の2価の炭化水素基であり、途中環状構造を含んでいてもよい。R1は独立に水素原子又は炭素数1~8の1価の炭化水素基である。R2は独立に水素原子、又は酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、但し、R2は1分子中のそれぞれの末端に2個以上、かつ1分子中に平均して4~10個の前記1価の有機基を有する。Z3は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基からなる連結基であり、途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。) - 成分(A)において、一般式(1)又は(2)中のZ1が、下記のいずれかの構造である請求項3又は4に記載の含フッ素硬化性組成物。
-C(=O)-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2- - 成分(A)において、一般式(1)又は(2)中のX1が、下記のいずれかで示されるものである請求項3~5のいずれか1項に記載の含フッ素硬化性組成物。
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH2
-C[OC(=O)CH=CH2]2
-C[OC(=O)C(CH3)=CH2]2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2]2
-CH2[CH2OC(=O)C(CH3)=CH2]2
-C[CH2OC(=O)CH=CH2]
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2 - 成分(A)において、一般式(1)又は(2)で表される含フッ素アクリル化合物が、下記のいずれかで示されるものである請求項3~6のいずれか1項に記載の含フッ素硬化性組成物。
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は上記と同じである。) - 成分(B)において、一般式(3)中のZ3が、下記式のいずれかで表されるものである請求項4~7のいずれか1項に記載の含フッ素硬化性組成物。
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2- - 成分(B)において、一般式(3)で表される含フッ素アクリル化合物が、下記一般式(4)又は(5)で表される含フッ素アクリル化合物である請求項4~9のいずれか1項に記載の含フッ素硬化性組成物。
- 成分(C)の非フッ素化アクリル化合物が、1分子中に2個以上の(メタ)アクリル基を有しウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類、又は前記多官能アクリル化合物とウレタンアクリレート類とを含む2種類以上のアクリル化合物の混合物である請求項1~10のいずれか1項に記載の含フッ素硬化性組成物。
- 請求項1~11のいずれか1項に記載の含フッ素硬化性組成物の硬化被膜を表面に有する物品。
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KR20230160236A (ko) | 2021-03-25 | 2023-11-23 | 닛산 가가쿠 가부시키가이샤 | 2종의 퍼플루오로폴리에테르를 함유하는 경화성 조성물 |
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