WO2016175315A1 - 含フッ素化合物、光硬化性組成物、コーティング液、ハードコート層形成用組成物および物品 - Google Patents
含フッ素化合物、光硬化性組成物、コーティング液、ハードコート層形成用組成物および物品 Download PDFInfo
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- WO2016175315A1 WO2016175315A1 PCT/JP2016/063462 JP2016063462W WO2016175315A1 WO 2016175315 A1 WO2016175315 A1 WO 2016175315A1 JP 2016063462 W JP2016063462 W JP 2016063462W WO 2016175315 A1 WO2016175315 A1 WO 2016175315A1
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
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- 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
- C08F290/067—Polyurethanes; Polyureas
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention is formed from a fluorine-containing compound, a photocurable composition and a coating liquid containing the fluorine-containing compound, a hard coat layer forming composition comprising the photocurable composition or the coating liquid, and the composition.
- the present invention relates to an article having a hard coat layer.
- Optical articles, displays, optical recording media and the like usually have a hard coat layer on the surface for preventing scratches and the like.
- the article has a characteristic that dirt (fingerprint, sebum, sweat, cosmetics, food, oil-based ink, etc.) is difficult to adhere to the surface and can be easily removed even if the dirt adheres to the surface, that is, antifouling property. It is desirable. For example, if dirt adheres to the surface of the spectacle lens, good visibility is hindered and the appearance is deteriorated. If dirt adheres to the surface of the optical recording medium, there may be a problem in signal recording and reproduction. When dirt adheres to the surface of the display, the visibility is lowered, and the operability is adversely affected in a display with a touch panel.
- a substance capable of imparting antifouling properties to the hard coat layer is obtained by reacting triisocyanate, a perfluoropolyether having one active hydrogen, and a monomer having an active hydrogen and a polymerizable carbon-carbon double bond.
- a fluorine-containing compound has been proposed (Patent Document 1).
- the hard coat layer formed from the composition containing the fluorine-containing compound described in Patent Document 1 is liable to deteriorate the antifouling property due to rubbing.
- the property that the antifouling property is hardly lowered by rubbing is also referred to as “antifouling rubbing resistance”.
- the present invention is a fluorine-containing compound capable of imparting antifouling properties (oil-based ink repellency, fingerprint stain removability) and antifouling scuff resistance superior to an object (such as a hard coat layer); antifouling properties and antifouling properties Photocurable composition and coating liquid capable of forming an object excellent in abrasion resistance; composition for forming a hardcoat layer capable of forming a hardcoat layer excellent in antifouling property and antifouling abrasion resistance; and antifouling property
- Another object of the present invention is to provide an article having a hard coat layer excellent in antifouling and abrasion resistance.
- the present invention provides a fluorine-containing compound having the following configurations [1] to [13], a method for producing the fluorine-containing compound, a photocurable composition, a coating liquid, a composition for forming a hard coat layer, and an article.
- a compound (a1) having a poly (oxyperfluoroalkylene) chain and one active hydrogen-containing group, a compound (a2) having a poly (oxyperfluoroalkylene) chain and two active hydrogen-containing groups, and a polymerizable carbon A reaction product of the compound (b) having a carbon double bond and an active hydrogen-containing group and the polyisocyanate (c), the part derived from the compound (a1) and the compound (a2) A fluorine-containing compound, wherein a ratio of a part derived from the compound (a1) to a total (100% by mass) with the part is 60 to 99.9% by mass.
- the compound (a1) has a number average molecular weight of 1,000 to 6,000
- the compound (a2) has a number average molecular weight of 1,000 to 6,000. Fluorine compound.
- the compound (a1) is a compound represented by the following formula (1): The fluorine-containing compound of [1] or [2], wherein the compound (a2) is a compound represented by the following formula (2).
- D 1 is D 11 —R f1 —O—CH 2 — or D 12 —O—
- D 11 is CF 3 — or CF 3 —O—
- R f1 is a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom.
- E 21 and E 22 are each independently a monovalent organic group having one hydroxy group
- m2 is an integer from 1 to 6
- n2 is an integer of 2 to 200
- (C m2 F 2m2 O) n2 may be composed of two or more types of C m2 F 2m2 O different in m2.
- (C m1 F 2m1 O) n1 and (C m2 F 2m2 O) n2 are both ⁇ (CF 2 O) n11 (CF 2 CF 2 O) n12 ⁇ (where n11 is 1 And n12 is an integer of 1 or more, n11 + n12 is an integer of 2 to 200, and the bonding order of n11 CF 2 O and n12 CF 2 CF 2 O is not limited.)
- the D 11 —R f1 —O—CH 2 — is R F2 —O—CHFCF 2 —O—CH 2 — (wherein R F2 has a carbon number of 1 to 6 and is terminated with CF 3 .
- the compound (a1), the compound E 21 or E 22 of (a2) is a compound obtained by converting into D 1, [3] one of the fluorine-containing compound to [5].
- the ratio of the compound (a1) having a poly (oxyperfluoroalkylene) chain and one active hydrogen-containing group to the compound (a1) (100% by mass) is 0.1 to 40% by mass.
- the ratio of the amount of the compound (a2) having a poly (oxyperfluoroalkylene) chain and two active hydrogen-containing groups to the total (100% by mass) of the compound (a1) and the compound (a2) is 10 to 50.
- the compound (b) having a polymerizable carbon-carbon double bond and an active hydrogen-containing group in an amount of mass% is reacted with the polyisocyanate (c) in such a ratio that the isocyanate group of the polyisocyanate (c) does not remain.
- a method for producing a fluorine-containing compound comprising: [8] A reaction intermediate having an isocyanate group is produced by reacting the mixture of the compound (a1) and the compound (a2) with the polyisocyanate (c), and then the compound (b) is added to the reaction intermediate. The production method of [7], which is reacted. [9] The compound (a1) is a compound obtained by converting one of the active hydrogen-containing groups of the compound (a2) to a group other than the active hydrogen-containing group, and the compound (a1) and the compound (a2) ) Is a mixture of the produced compound (a1) and the unconverted compound (a2) obtained in the conversion, [8].
- a light comprising the fluorine-containing compound according to any one of the above [1] to [6], a photopolymerizable compound (excluding the fluorine-containing compound), and a photopolymerization initiator.
- Curable composition [11] A coating liquid comprising the photocurable composition of [10] and a solvent.
- An article comprising a base material and a hard coat layer formed from the hard coat layer forming composition of [12].
- the fluorine-containing compound of the present invention can impart excellent antifouling properties and antifouling scuff resistance to an object.
- the photocurable composition and coating liquid of the present invention can form an object having excellent antifouling properties and antifouling scuff resistance.
- the composition for forming a hard coat layer of the present invention can form a hard coat layer excellent in antifouling properties and antifouling scuff resistance.
- the article of the present invention has a hard coat layer having excellent antifouling properties and antifouling rub resistance.
- a compound represented by the formula (1) is referred to as a compound (1).
- a photocurable composition, a coating liquid, and a composition for forming a hard coat layer may be collectively referred to as “curable composition”.
- curable composition when they contain a solvent, the composition of components other than a solvent is said.
- Poly (oxyperfluoroalkylene) chain means a molecular chain in which two or more oxyperfluoroalkylene units are linked.
- the “oxyperfluoroalkylene unit” means a unit having an oxygen atom at one end of the perfluoroalkylene group, and the chemical formula thereof is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
- the “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
- “Fluoroalkylene group” means a group in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms, and “perfluoroalkylene group” means that all of the hydrogen atoms in the alkylene group are substituted with fluorine atoms. Means the group formed.
- the “perfluoroalkyl group” means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.
- the “(meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
- “(Meth) acrylate” is a general term for acrylate and methacrylate.
- Object means an object to which antifouling property is imparted. Examples of the object include a hard coat layer, a liquid repellent layer, a release layer, and a molded product.
- fluorine-containing compound (X) includes a compound (a1) having a poly (oxyperfluoroalkylene) chain and one active hydrogen-containing group, and a poly (oxyperfluoroalkylene).
- the ratio of the part derived from the compound (a1) to the total (100% by mass) of the part derived from the compound (a1) and the part derived from the compound (a2) is 60 to 99.9% by mass.
- the fluorine-containing compound (X) is a reaction product and the compound (a2) and the polyisocyanate (c) are polyfunctional compounds
- the fluorine-containing compound (X) is usually not a single compound, It is a mixture of compounds in which the number of parts derived from the respective reactive compounds is different.
- the compound (a1), the compound (a2), the compound (b), and the polyisocyanate (c) are reacted to obtain the fluorine-containing compound (X), the polyisocyanate (c) and the compound (a1) that reacts with the polyisocyanate (c), It is considered that the following fluorine-containing compounds (X1) to (X4) are generated by the combination with the compound (a2) and the compound (b).
- (X1) A fluorine-containing compound obtained by reacting compound (a1) and compound (b) with polyisocyanate (c).
- (X2) A fluorine-containing compound obtained by reacting only the compound (a1) with the polyisocyanate (c).
- (X3) A fluorine-containing compound obtained by reacting only the compound (b) with the polyisocyanate (c).
- (X4) The compound (a2) is linked between two or more polyisocyanates (c), and the isocyanate groups that do not contribute to crosslinking of each polyisocyanate (c) are bonded to the compounds (a1) and (b). A cross-linking type fluorine-containing compound in which either one or both are reacted.
- the fluorine-containing compound (X1) there are (the number of isocyanate groups in the polyisocyanate (c) minus 1) types of fluorine-containing compounds (X1).
- the fluorine-containing compound obtained by reacting two compounds (a1) and one compound (b) with the polyisocyanate (c) and the polyisocyanate (c ) Include two types of fluorine-containing compounds obtained by reacting one compound (a1) and two compounds (b).
- fluorine-containing compound (X4) depending on the total number of compounds (a2) and polyisocyanate (c), and the combination of compound (a1) and compound (b) that reacts with each polyisocyanate (c) There are countless types.
- the active hydrogen-containing group is a hydroxy group and the polyisocyanate (c) is a triisocyanate, as shown in the following formula, the compound (a1) having one end of a trifluoromethyl group and the compound (a2)
- the compound (b) and the polyisocyanate (c) react with each other, a mixture of fluorine-containing compounds (X1) to (X4) in which each compound is bonded by a urethane bond can be produced.
- Ra1 is a residue obtained by removing the terminal trifluoromethyl group and hydroxy group from the compound (a1)
- Ra2 is a residue obtained by removing both terminal hydroxy groups from the compound (a2)
- Rb is represented by
- Rc is a residue obtained by removing an isocyanate group from polyisocyanate (c).
- the fluorine-containing compound (X4) is an example of many types.
- a poly (oxyperfluoroalkylene) chain is a molecular chain in which two or more oxyperfluoroalkylene units are linked, and one end of the poly (oxyperfluoroalkylene) chain is a carbon atom and the other end is an oxygen atom.
- the chemical formula is represented by describing the carbon terminal side on the left side and the oxygen terminal side on the right side.
- Compound (a1) and compound (a2) have a poly (oxyperfluoroalkylene) chain.
- the poly (oxyperfluoroalkylene) chain in each compound may be the same or different.
- the compound (a1) and the compound (a2) having the same poly (oxyperfluoroalkylene) chain are produced by producing the compound (a1) and the compound (a2) from a raw material compound having a poly (oxyperfluoroalkylene) chain.
- a raw material compound having a poly (oxyperfluoroalkylene) chain are used to produce the fluorine-containing compound (X).
- the compound having the same poly (oxyperfluoroalkylene) chain ( a1) and compound (a2) are used.
- the poly (oxyperfluoroalkylene) chain imparts antifouling properties to the object.
- the poly (oxyperfluoroalkylene) chain is preferably a chain represented by the following formula from the viewpoint of sufficiently imparting antifouling properties to the object.
- m1 and m2 are integers of 1 to 6
- n1 and n2 are integers of 2 to 200
- (C m1 F 2m1 O) n1 is two or more kinds of C m1 F 2m1 O different in m1.
- (C m2 F 2m2 O) n2 may be made of C m2 F 2m2 O of two or more different m @ 2.
- n1 is preferably an integer of 1 to 3, particularly preferably 1 or 2, from the viewpoint of sufficiently imparting antifouling properties to an object.
- C m1 F 2m1 may be linear or branched. From the viewpoint of sufficiently imparting antifouling properties to the object, a straight chain is preferable.
- N1 is preferably an integer of 3 or more, more preferably an integer of 4 or more, and particularly preferably an integer of 5 or more from the viewpoint of sufficiently imparting antifouling properties to an object. If the number average molecular weight of the compound (a1) or the compound (a2) is too large, the number of polymerizable carbon-carbon double bonds present per unit molecular weight of the fluorine-containing compound (X) decreases, and the antifouling of the target object N1 is preferably an integer of 100 or less, and an integer of 80 or less is preferable from the viewpoint that the rubbing resistance of the composition is reduced and that the fluorine-containing compound (X) in the curable composition is excellent in compatibility with other components. More preferably, an integer of 60 or less is particularly preferable.
- each C m1 F 2m1 O is not limited.
- CF 2 O and CF 2 CF 2 O may be randomly or alternately arranged, and a block composed of a plurality of CF 2 O and a plurality of CF 2 CF A block composed of 2 O may be connected.
- (C m1 F 2m1 O) n1 is ⁇ (CF 2 O) n11 (CF 2 CF 2 O) n12 ⁇ (provided that n11 is 1 or more) from the viewpoint of sufficiently imparting antifouling properties to an object.
- N12 is an integer of 1 or more
- n11 + n12 is an integer of 2 to 200
- the bonding order of n11 CF 2 O and n12 CF 2 CF 2 O is not limited.
- ⁇ (CF 2 O) n11 (CF 2 CF 2 O) n12 ⁇ is excellent in mobility, and therefore the lubricity of the object is excellent.
- (CF 2 O) n11 is superior in mobility because it is a group having 1 carbon atom and having an oxygen atom.
- ⁇ (CF 2 O) n11 (CF 2 CF 2 O) n12 ⁇ represents ⁇ (CF 2 O) n11 (CF 2 CF 2 ) from the viewpoint of ease of production of the compound (a1) and the compound (a2).
- the terminal of O) n12 ⁇ on the side to be bonded to —CH 2 — of D 11 described later is preferably CF 2 O.
- -CH 2 - the ends of the side to be bonded to is CF 2 O ⁇ (CF 2 O ) n11 (CF 2 CF 2 O) n12 ⁇ , hereinafter, CF 2 O ⁇ (CF 2 O) n11-1 (CF It represents a 2 CF 2 O) n12 ⁇ .
- n11-1 (CF 2 CF 2 O) n12 ⁇ , as described above, (n11-1) (CF 2 O) and n12 (CF 2
- the order of bonding of CF 2 O) is not limited.
- N11 is preferably an integer of 2 or more, and particularly preferably an integer of 3 or more, from the viewpoint of sufficiently imparting antifouling properties to an object. If the number average molecular weight of the compound (a1) is too large, the number of polymerizable carbon-carbon double bonds present per unit molecular weight of the fluorine-containing compound (X) is reduced, and the antifouling resistance and abrasion resistance of the object is reduced. From the viewpoint of lowering and excellent compatibility between the fluorine-containing compound (X) and other components in the curable composition, n11 is preferably an integer of 50 or less, more preferably an integer of 40 or less, and 30 or less. The integer of is particularly preferable.
- N12 is particularly preferably an integer of 2 or more from the viewpoint of sufficiently imparting antifouling properties to the object. If the number average molecular weight of the compound (a1) or the compound (a2) is too large, the number of polymerizable carbon-carbon double bonds present per unit molecular weight of the fluorine-containing compound (X) decreases, and the antifouling of the target object N12 is preferably an integer of 50 or less, and an integer of 40 or less is preferable from the viewpoint that the rub resistance of the adhesive property is reduced and that the fluorine-containing compound (X) in the curable composition is excellent in compatibility with other components. More preferably, an integer of 30 or less is particularly preferable.
- the ratio of n11 and n12 is preferably 1 to 3 times n11 from the viewpoint of sufficiently imparting lubricity to the object.
- the compound (a1) and the compound (a2) can be produced as a mixture of a plurality of types of compounds having different numbers of n1 in (C m1 F 2m1 O) n1 .
- the average value of n1 as a mixture is preferably 2 to 100, particularly preferably 4 to 80.
- the compound (a1) and the compound (a2) can be produced as a mixture of a plurality of types of compounds having different numbers of n11 and n12 in ⁇ (CF 2 O) n11 (CF 2 CF 2 O) n12 ⁇ .
- the average value of n11 as a mixture is preferably 1 to 50
- the average value of n12 is preferably 1 to 50.
- the active hydrogen-containing group in the compound (a1) and the compound (a2) reacts with the isocyanate group of the polyisocyanate (c), and the structure of the compound (a1) and the compound (a2) is changed to the structure of the fluorine-containing compound (X).
- the active hydrogen-containing group include a hydroxy group, a carboxy group, and an amino group. From the viewpoint of availability of raw materials, a hydroxy group is particularly preferable.
- the compound (a1) is a compound having the poly (oxyperfluoroalkylene) chain and one active hydrogen-containing group.
- the compound (a1) preferably has one perfluoroalkyl group from the viewpoint of sufficiently imparting antifouling properties to an object (such as a hard coat layer).
- the compound (1) represented by the following formula (1) is preferable from the viewpoint of sufficiently imparting antifouling properties to the object.
- D 1 is D 11 —R f1 —O—CH 2 — or D 12 —O—
- D 11 is CF 3 — or CF 3 —O—
- R f1 is a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom.
- the compound (1) can sufficiently impart antifouling properties to the object.
- the number of hydrogen atoms in R f1 is preferably 1 or more from the viewpoint of sufficiently imparting lubricity to the object.
- the number of hydrogen atoms in R f1 is (the number of carbon atoms in R f1 ) ⁇ 2 or less, and is preferably (the number of carbon atoms in R f1 ) or less from the viewpoint of sufficiently imparting antifouling properties to an object. From the viewpoint of sufficiently imparting antifouling properties to the object, it is preferable that R f1 does not contain a hydrogen atom.
- R f1 When R f1 has a hydrogen atom, the mobility of the above (C m1 F 2m1 O) n1 is further improved, lubricity can be sufficiently imparted to the object, and the fluorine-containing compound (X) in the curable composition Excellent compatibility with other components. On the other hand, when R f1 does not have a hydrogen atom, sufficient lubricity cannot be imparted to the object, and the compatibility between the fluorinated compound (X) and other components in the curable composition is insufficient. The storage stability of the composition is insufficient.
- R f1 is a group represented by the following formula (g1-1), a group represented by the following formula (g1-2), or a group represented by the following formula (g1- The group represented by 3) is preferred.
- R F is a group bonded to D 11 .
- R F is a single bond, a perfluoroalkylene group having 1 to 15 carbon atoms, or a perfluoroalkylene group having 2 to 15 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, and z is 1 to 4 Is an integer.
- R F is a perfluoroalkylene group having 1 to 9 carbon atoms or a perfluoroalkylene group having 2 to 13 carbon atoms having an etheric oxygen atom between carbon-carbon atoms from the viewpoint of sufficiently imparting antifouling properties to an object. Is preferred.
- the perfluoroalkylene group may be linear or branched.
- z is preferably an integer of 1 to 3. When z is 3 or more, C z H 2z may be linear or branched, and is preferably linear.
- R f1 is preferably a group represented by the formula (g1-1) from the viewpoint of ease of production of the compound (1).
- Examples of the D 11 —R f1 —O—CH 2 — group include The group represented by the formula (g2) is preferable.
- R F2 is a C 1-6 perfluoroalkyl group having a terminal CF 3 .
- Specific examples of the group represented by the formula (g2) include the following groups. CF 3 O—CHFCF 2 —O—CH 2 —, CF 3 CF 2 —O—CHFCF 2 —O—CH 2 —, CF 3 CF 2 CF 2 —O—CHFCF 2 —O—CH 2 —, CF 3 CF 2 CF 2 —O—CHFCF 2 —O—CH 2 —, CF 3 CF 2 CF 2 CF 2 CF 2 —O—CHFCF 2 —O—CH 2 —.
- the perfluoroalkyl group for D 12 may be linear or branched.
- D 12 a perfluoroalkyl group having 1 to 3 carbon atoms is preferable, and CF 3 — or CF 3 CF 2 — is particularly preferable from the viewpoint of sufficiently imparting antifouling property to an object.
- E 1 includes —R 1 —OH (where R 1 is a divalent organic group which may have a fluorine atom).
- R 1 is preferably an alkylene group having 10 or less carbon atoms, or a fluoroalkylene group having 10 or less carbon atoms in which the —OH side terminal is a methylene group.
- E 1 is preferably —CF 2 CH 2 —OH, —CF 2 CF 2 CH 2 —OH, or —CF 2 CF 2 CF 2 CH 2 —OH.
- the compound (1) include the following. CF 3 CF 2 —O— (CF 2 CF 2 CF 2 O) n1 —CF 2 CF 2 CH 2 —OH (11) CF 3 —CF 2 CF 2 —O—CHFCF 2 —O—CH 2 —CF 2 O ⁇ (CF 2 O) n11-1 (CF 2 CF 2 O) n12 ⁇ —CF 2 CH 2 —OH.
- the number average molecular weight of the compound (a1) is preferably 1,000 to 6,000, more preferably 1,000 to 5,000, and particularly preferably 1,200 to 4,000. When the number average molecular weight of the compound (a1) is within this range, the object can be sufficiently imparted with antifouling properties, and the compound (a1) is excellent in compatibility with other components in the curable composition.
- the number average molecular weight of the compound (a1) is compared with the outflow time of polymethyl methacrylate by gel permeation chromatography (GPC), or the terminal functional group of the internal standard substance and the compound (a1) by a nuclear magnetic resonance apparatus (NMR). It is obtained by comparing the integration ratio of. When it is difficult to separate the compound (a1), the compound (a2), and the compound (e1) in the production methods of the compound (a1) and the compound (a2) described later, the compound (a1), the compound (a2) ) And the compound (e1).
- Compound (a2) is a compound having the poly (oxyperfluoroalkylene) chain and two active hydrogen-containing groups.
- the poly (oxyperfluoroalkylene) chain imparts antifouling properties to an object (such as a hard coat layer).
- Compound (a2) may have the same poly (oxyperfluoroalkylene) chain as the poly (oxyperfluoroalkylene) chain of compound (a1) from the viewpoint of ease of production of compound (a1) and compound (a2). preferable.
- the compound (2) represented by the following formula (2) is preferable from the viewpoint of sufficiently imparting antifouling property to the object.
- E 21 and E 22 are each independently a monovalent organic group having one hydroxy group
- m2 is an integer from 1 to 6
- n2 is an integer of 2 to 200
- (C m2 F 2m2 O) n2 may be composed of two or more types of C m2 F 2m2 O different in m2.
- E 21 includes HO—R 21 — (wherein R 21 is a divalent organic group).
- R 21 is preferably an alkylene group having 10 or less carbon atoms.
- E 21 is preferably HO—CH 2 —.
- E 22 includes —R 22 —OH (wherein R 22 is a divalent organic group which may have a fluorine atom).
- R 22 is preferably an alkylene group having 10 or less carbon atoms, or a fluoroalkylene group having 10 or less carbon atoms in which the —OH side terminal is a methylene group.
- E 22 is preferably —CF 2 CH 2 —OH, —CF 2 CF 2 CH 2 —OH, or —CF 2 CF 2 CF 2 CH 2 —OH.
- the compound (2) include the following. HO—CH 2 —CF 2 CF 2 O (CF 2 CF 2 CF 2 O) n2-1 —CF 2 CF 2 CH 2 —OH (21) HO—CH 2 —CF 2 O ⁇ (CF 2 O) n21-1 (CF 2 CF 2 O) n22 ⁇ —CF 2 CH 2 —OH (23) HO—CH 2 —CF 2 CF 2 CF 2 O [(CF 2 CF 2 O—CF 2 CF 2 CF 2 CF 2 O) n23 —CF 2 CF 2 O] —CF 2 CF 2 CF 2 CH 2 —OH (24) HO—CH 2 —CF 2 O (CF 2 CF 2 O) n2-1 —CF 2 CH 2 OH (25) However, n23 ⁇ 2 + 2 is an integer of 4 to 200.
- the number average molecular weight of the compound (a2) is preferably 1,000 to 6,000, more preferably 1,000 to 5,000, and particularly preferably 1,200 to 4,000. If the number average molecular weight of the compound (a2) is within this range, the antifouling property can be sufficiently imparted to the object, and the compound (a2) is excellent in compatibility with other components in the curable composition.
- the number average molecular weight of the compound (a2) is determined by the same method as that for the compound (a1).
- Compound (a1) and compound (a2) may be produced separately or simultaneously from one starting material. Moreover, you may manufacture a compound (a1) from a compound (a2).
- a method for producing the compound (a1) and the compound (a2) when the active hydrogen-containing group is a hydroxy group, for example, the following method (1) or method (2) may be mentioned.
- a commercially available compound can be used as the compound having a poly (oxyperfluoroalkylene) chain and two carboxy groups.
- a commercially available compound can be used as the compound having a poly (oxyperfluoroalkylene) chain and two hydroxy groups. Examples of commercially available compounds include “FLUOROLINK D” (trade name), “Fomblin Z-Dol” (trade name), and the like.
- a compound (a2) can be used as a compound which has two hydroxy groups in the said method (2).
- a mixture of the compound (a1) and the compound (a2) can be obtained by leaving a part of the raw material compound (a2) as an unreacted substance.
- the content rate of both compounds in a mixture can be adjusted by changing the conversion ratio of the compound (a2) to the compound (a1).
- Method (1) A specific example of the method (1) will be described below.
- the compound (53-1) is contacted with fluorine gas to obtain a mixture (x) composed of the compound (43-1), the unreacted compound (53-1) and the compound (33-1).
- CF 3 —O — ⁇ (CF 2 O) p (CF 2 CF 2 O) q ⁇ —CF 2 C ( ⁇ O) OH (43-1) HO—C ( ⁇ O) —CF 2 O ⁇ (CF 2 O) p (CF 2 CF 2 O) q ⁇ —CF 2 C ( ⁇ O) —OH (53-1) CF 3 —O — ⁇ (CF 2 O) p (CF 2 CF 2 O) q ⁇ —CF 3 (33-1)
- p is an integer of 1 or more
- q is an integer of 0 or more
- p + q + 1 is an integer of 3 to 200
- the bonding order of p CF 2 O and q CF 2 CF 2 O is not limited. .
- the mixture (x) is treated with a reducing agent (such as sodium bis (2-methoxyethoxy) aluminum hydride) to give the compound (13-1), the compound (23-1) and the unreacted compound (33-1).
- a reducing agent such as sodium bis (2-methoxyethoxy) aluminum hydride
- a compound (e1) having a poly (oxyperfluoroalkylene) chain and two perfluoroalkyl groups and having no active hydrogen-containing group can be by-produced.
- the compound (e1) may be mixed into a mixture containing the compound (a1) and the compound (a2) obtained by the method (1) or the method (2), and the mixture containing the compound (a1) and the compound (a2) It may be mixed in the fluorinated compound (X) produced by using the curable composition prepared using the fluorinated compound (X), or may be formed from a hard coat layer forming composition. You may mix in a coating layer. However, since the compound (e1) has low compatibility with other components, the curable composition becomes cloudy when the compound (e1) remains in the curable composition. When the mixture obtained by the method (1) or the method (2) contains the compound (e1), the compound (e1) may be removed by purification.
- the compound (e1) include the following. CF 3 CF 2 —O— (CF 2 CF 2 CF 2 O) n3 —CF 2 CF 3 (31) CF 3 -CF 2 CF 2 -O- CHFCF 2 -O-CH 2 -CF 2 O ⁇ (CF 2 O) n31-1 (CF 2 CF 2 O) n32 ⁇ -CF 2 CH 2 -O-CF 2 CHF —O—CF 2 CF 2 —CF 3 (32) CF 3 -O - ⁇ (CF 2 O) n31 (CF 2 CF 2 O) n32 ⁇ -CF 3 ⁇ (33) CF 3 —O— (CF 2 CF 2 O) n3 —CF 3 (35)
- n3 is an integer of 2 to 200
- n31 is an integer of 1 or more
- n32 is an integer of 0 or more
- n31 + n32 is an integer of 2 to 200
- n31 CF 2 O The order of bonding n
- the compound (b) is a compound having a polymerizable carbon-carbon double bond and an active hydrogen-containing group.
- the polymerizable carbon-carbon double bond reacts with a photopolymerizable compound described later contained in the curable composition by light irradiation, and imparts abrasion resistance to the target object (hard coat layer or the like).
- the group having a polymerizable carbon-carbon double bond include a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group, and a maleimide group.
- a (meth) acryloyl group is preferable and an acryloyl group is particularly preferable from the viewpoint of sufficiently imparting abrasion resistance to the object.
- the number of polymerizable carbon-carbon double bonds is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 per molecule of the compound (b).
- the number of active hydrogen-containing groups is preferably 1 per molecule of the compound (b).
- the active hydrogen-containing group is preferably a hydroxy group.
- Examples of the compound (b) include hydroxyalkyl (meth) acrylate and polyoxyalkylene glycol mono (meth) acrylate.
- a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 10 carbon atoms is preferable, and a hydroxyalkyl acrylate having a linear hydroxyalkyl group having a hydroxy group at the terminal is particularly preferable.
- R is a hydrogen atom or a methyl group
- i is an integer of 2 to 10
- k is an integer of 2 to 20.
- the polyisocyanate (c) is a compound having two or more isocyanate groups.
- the isocyanate group reacts with the active hydrogen-containing group of the compound (a1), the active hydrogen-containing group of the compound (a2) and the active hydrogen-containing group of the compound (b), and the structure of the polyisocyanate (c) is changed to a fluorine-containing compound ( X) for incorporation as part of the structure.
- the number of isocyanate groups is preferably 2 to 4, particularly preferably 3.
- polyisocyanate (c) examples include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and modified diisocyanates. And triisocyanate.
- diisocyanate non-yellowing diisocyanate (that is, a diisocyanate having no isocyanate group directly bonded to an aromatic nucleus) is preferable, and alkylene diisocyanate and alicyclic diisocyanate are preferable.
- modified diisocyanate examples include an isocyanurate-modified product, a burette-modified product, and a polyhydric alcohol-modified product modified with a trivalent or tetravalent alcohol.
- trivalent or tetravalent alcohol examples include glycerin, trimethylolpropane, pentaerythritol and the like.
- triisocyanate examples include the following. Isocyanurate-modified alkylene diisocyanate represented by the following formula (6-1) (cyclic trimer of alkylene diisocyanate), Isocyanurate-modified tolylene diisocyanate represented by the following formula (6-2) (a cyclic trimer of tolylene diisocyanate), Isocyanurate-modified isophorone diisocyanate (cyclic trimer of isophorone diisocyanate) represented by the following formula (6-3): A burette-modified alkylene diisocyanate represented by the following formula (6-4): Glycerol-modified alkylene diisocyanate represented by the following formula (6-5): However, s, t and u are each independently an integer of 2 to 10.
- the fluorine-containing compound (X) is prepared by simultaneously adding a compound having an active hydrogen-containing group (compound (a1), compound (a2) and compound (b)) to polyisocyanate (c) It is produced by reacting the compound (a1), the compound (a2), and the compound (b) sequentially with the isocyanate (c).
- the equivalent ratio of the total equivalent of the compound having an active hydrogen-containing group to the polyisocyanate (c) is theoretically 1: 1, but unreacted isocyanate groups do not remain in the fluorine-containing compound (X).
- a compound having an active hydrogen-containing group in an excess of 1.01 to 1.5 times equivalent.
- a by-product is also usually produced
- a compound having an unreacted active hydrogen-containing group may remain.
- the compound (a1) and the compound (a2) also remain in the finally obtained curable composition. Since the compound (a1) and the compound (a2) have low compatibility with other components, when the compound (a1) and the compound (a2) remain in the curable composition, the curable composition becomes cloudy.
- the compound (a1) and the compound (a2) are reacted with an excess equivalent amount of the polyisocyanate (c), and the compound (a1) and the compound ( After reacting all the active hydrogen groups in a2) with an isocyanate group, it is preferable to react an equivalent amount or more of the compound (b) with respect to the remaining isocyanate group.
- the total ratio of the compound (a1) and the compound (a2) and the mass ratio of the compound (b) depends on characteristics (antifouling property, abrasion resistance, etc.) required for the object (hard coat layer, etc.) What is necessary is just to set suitably. From the point of balance between antifouling properties and abrasion resistance imparted to the object, the ratio of the compound (b) to the total (100% by mass) of the compound (a1), the compound (a2) and the compound (b) Is preferably 10 to 50% by mass, particularly preferably 20 to 40% by mass.
- the proportion of the portion derived from the compound (a1) is 60 to 99 .9% by mass. Therefore, the ratio of the portion derived from the compound (a2) is 0.1 to 40% by mass. If the ratio of the part derived from the compound (a1) is not less than the lower limit of the above range, the object can be imparted with antifouling properties. In addition, the compatibility between the fluorine-containing compound (X) and other components is also excellent. If the ratio of the part derived from the compound (a1) is not more than the upper limit of the above range, the object can be imparted with antifouling rub resistance.
- the compound (a1), the compound (a2), and the compound (a2) are combined so that the ratio of the part derived from the compound (a1) and the part derived from the compound (a2) is the above ratio.
- the proportion of the compound (a1) in the total (100% by mass) is preferably 60 to 99.9% by mass, more preferably 70 to 99% by mass, and particularly preferably 80 to 95% by mass.
- the ratio of the compound (a2) in the total (100% by mass) of the compound (a1) and the compound (a2) is 0.1 to 40% by mass, preferably 1 to 30% by mass, and 5 to 20% by mass. Is particularly preferred.
- the ratio of the compound (a2) is at least the lower limit of the above range, antifouling rub resistance can be imparted to the object. If the ratio of the compound (a2) is not more than the upper limit of the above range, the antifouling property can be imparted to the object.
- the compatibility between the fluorine-containing compound (X) and other components is also excellent.
- urethanization catalyst examples include cobalt naphthenate, zinc naphthenate, zinc 2-ethylhexanoate, dibutyltin dilaurate, tin 2-ethylhexanoate, triethylamine, 1,4-diabicyclo [2.2.2] octane, and the like. It is done.
- an additive necessary for production hereinafter, also referred to as “manufacturing additive” may be used.
- the manufacturing additive include a polymerization inhibitor.
- the reaction between the compound having an active hydrogen-containing group and the polyisocyanate (c) is preferably performed in an organic solvent.
- the organic solvent may be a fluorinated organic solvent, a non-fluorinated solvent, or a combination of both solvents.
- fluorine-based organic solvent fluoroalkanes, chlorofluoroalkanes, fluoroaromatic compounds, and fluoroalkyl ethers are preferable, and chlorofluoroalkanes and fluoroalkyl ethers are preferable because each raw material and the fluorine-containing compound (X) are easily dissolved.
- the non-fluorinated solvent glycol ether organic solvents and ketone organic solvents are preferable.
- the number average molecular weight of the fluorine-containing compound (X) is preferably 1,200 to 8,000, more preferably 1,200 to 7,000, and particularly preferably 1,200 to 5,000. If the number average molecular weight is within this range, the object (hard coat layer, etc.) can be sufficiently imparted with antifouling and antifouling rub resistance, and in the curable composition, the fluorine-containing compound and other components Excellent compatibility.
- the number average molecular weight of the fluorine-containing compound is a number average molecular weight in terms of polymethyl methacrylate determined by gel permeation chromatography (GPC).
- the ratio of the portion derived from the compound (a1) out of the total of the portion derived from the compound (a1) and the portion derived from the compound (a2) is Since the content is 60% by mass or more, the surface energy of the surface of the target object (hard coat layer, etc.) is lowered by the structure of the portion derived from the compound (a1) (particularly the terminal CF 3- ). As a result, antifouling properties can be imparted to the object.
- the ratio of the part derived from the compound (a2) in the total of the part derived from the compound (a1) and the part derived from the compound (a2) is 0.1% by mass or more, the compound (a2)
- the structure of the derived part is sufficiently introduced into the fluorine-containing compound. Therefore, the fluorine-containing compound (X) has a high molecular weight, and the fluorine-containing compound (X) is firmly fixed to a cured film (hard coat layer or the like) formed from a curable composition containing the fluorine-containing compound (X).
- a cured film hard coat layer or the like
- the ratio of a compound (a2) is 40 mass% or less among the sum total of a compound (a1) and a compound (a2), the molecular weight of a fluorine-containing compound (X) does not become large too much. As a result, the compatibility between the fluorine-containing compound (X) and other components is also excellent.
- the photocurable composition of the present invention contains a fluorine-containing compound (X), a photopolymerizable compound (excluding the fluorine-containing compound (X)), and a photopolymerization initiator.
- the photocurable composition of this invention may further contain the additive for photocurable compositions as needed.
- a photopolymerizable compound is a monomer that initiates a polymerization reaction when irradiated with light in the presence of a photopolymerization initiator described later.
- Examples of the photopolymerizable compound include a polyfunctional monomer and a monofunctional monomer. From the viewpoint of imparting abrasion resistance to an object (such as a hard coat layer), those containing a polyfunctional monomer as an essential component are preferable.
- a photopolymerizable compound may be used individually by 1 type, and may use 2 or more types together.
- Examples of the polyfunctional monomer include compounds having two or more (meth) acryloyl groups in one molecule.
- the number of (meth) acryloyl groups is preferably 3 and particularly preferably 3 to 30 per molecule of the polyfunctional monomer.
- a polyfunctional monomer a monomer having three or more (meth) acryloyl groups and a molecular weight of 120 or less per (meth) acryloyl group from the viewpoint of imparting sufficient abrasion resistance to the object.
- a monomer having three or more of a urethane bond and a (meth) acryloyl group is a monomer having three or more of a urethane bond and a (meth) acryloyl group.
- Polyfunctional monomers include poly (meth) acrylates of polyols (trimethylolpropane, glycerol, pentaerythritol, their multimers, etc.), tris (2-acryloyloxyethyl) isocyanurate, polyols, polyisocyanates and hydroxyalkyl (A reaction product with a (meth) acrylate, a reaction product with a monofunctional monomer having a hydroxy group and a polyisocyanate, and the like can be mentioned.
- Photopolymerization initiator examples include known photopolymerization initiators such as aryl ketone photopolymerization initiators (acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, Benzoylbenzoates, ⁇ -acyloxime esters, etc.), sulfur-containing photopolymerization initiators (sulfides, thioxanthones, etc.), acylphosphine oxides (acyl diarylphosphine oxide, etc.), and other photopolymerization initiators.
- a photoinitiator may be used individually by 1 type and may use 2 or more types together.
- the photopolymerization initiator may be used in combination with a photosensitizer such as amines.
- Additives for photocurable compositions include colloidal silica, photosensitizers, UV absorbers, light stabilizers, thermosetting stabilizers, antioxidants, leveling agents, antifoaming agents, thickeners, antisettling agents Pigments, dyes, dispersants, antistatic agents, surfactants (antifogging agents, leveling agents, etc.), metal oxide particles, various resins (epoxy resins, unsaturated polyester resins, polyurethane resins, etc.) and the like.
- composition of photocurable composition The content of the fluorine-containing compound (solvent) is preferably 0.01 to 5% by mass, and 0.02 to 4% by mass in the photocurable composition (excluding the solvent) (100% by mass). More preferred is 0.05 to 3% by mass. If the content of the fluorine-containing compound (X) is within the above range, the storage stability of the photocurable composition, the appearance of the object (hard coat layer, etc.), abrasion resistance, antifouling property and antifouling property Excellent rub resistance.
- the content of the photopolymerizable compound is preferably 20 to 99.99% by mass, more preferably 50 to 99.99% by mass in the photocurable composition (excluding the solvent) (100% by mass). 60 to 99.99% by mass is more preferable, and 80 to 99.99% by mass is particularly preferable.
- the content of the photopolymerizable compound is within the above range, the storage stability of the photocurable composition, the appearance of the object, the abrasion resistance, the antifouling property and the antifouling property are excellent.
- the content of the photopolymerization initiator is preferably 1 to 15% by mass, more preferably 3 to 15% by mass, of the photocurable composition (excluding the solvent) (100% by mass), more preferably 3 to 10% by mass. Mass% is particularly preferred. If content of a photoinitiator is in the said range, it is excellent in compatibility with a photopolymerizable compound. Moreover, it is excellent in the sclerosis
- the content of the additive for photocurable composition is 0.5% of the photocurable composition (excluding the solvent) (100% by mass). -20% by mass is preferable, 1-15% by mass is more preferable, and 1-10% by mass is particularly preferable.
- the photocurable composition of the present invention comprises by-products (compound (e1), etc.) produced during the production of the fluorine-containing compound (X), unreacted raw materials (compound (a1), compound (a2), compound (B), polyisocyanate (c), etc.) and impurities such as production additives (polymerization inhibitors etc.) used in the production of the fluorine-containing compound (X) may be contained.
- impurities such as production additives (polymerization inhibitors etc.) used in the production of the fluorine-containing compound (X) may be contained.
- the impurities the compound (a1), the compound (a2), and the compound (e1) have low compatibility with other components, so that the curable composition contains the compound (a1), the compound (a2), and the compound (e1). When remains, the curable composition becomes cloudy.
- the total content of the compound (a1), the compound (a2) and the compound (e1) is preferably 10% by mass or less, particularly preferably 5% by mass or less, with respect to the fluorine-containing compound (X) (100% by mass).
- the impurities polyisocyanate (c) has high reactivity with other components, and therefore, when polyisocyanate (c) remains in the curable composition, the storage stability of the curable composition decreases. Therefore, the content of the polyisocyanate (c) is preferably 4% by mass or less, particularly preferably 1% by mass or less, with respect to the fluorine-containing compound (X) (100% by mass). Impurities are identified and quantified by 1 H-NMR and 19 F-NMR or gas chromatography.
- the coating liquid of the present invention contains the photocurable composition of the present invention and a solvent.
- the coating liquid of the present invention is prepared for easy application of the photocurable composition of the present invention to a substrate.
- solvent an organic solvent is preferable.
- organic solvent an organic solvent having a boiling point suitable for the coating method is preferable.
- the organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or a combination of both solvents.
- fluorine-based organic solvent examples include fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, and fluoroalcohols.
- fluorine-based organic solvent a fluoroalkane, a fluoroaromatic compound, a fluoroalcohol, and a fluoroalkyl ether are preferable, and a fluoroalcohol or a fluoroalkyl ether is particularly preferable because the fluorine-containing compound (X) is easily dissolved.
- non-fluorine-based organic solvent a compound consisting of only hydrogen atoms and carbon atoms, a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ethers. And organic ether solvents, glycol ether organic solvents, and ester organic solvents.
- a glycol ether organic solvent and a ketone organic solvent are particularly preferable because the fluorine-containing compound (X) is easily dissolved.
- the solvent is selected from the group consisting of fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalcohols, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms.
- At least one organic solvent is preferable, and a fluorine-based organic solvent selected from fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, and fluoroalcohols is particularly preferable.
- the solvent from the viewpoint of enhancing the solubility of the fluorine-containing compound (X), a group consisting of a fluoroalkane, a fluoroaromatic compound, a fluoroalkyl ether, a fluoroalcohol, and a compound consisting of only a hydrogen atom, a carbon atom and an oxygen atom It is preferable to include at least one organic solvent selected from the group consisting of 90% by mass or more of the total solvent.
- the content of the solvent is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass in the coating liquid (100% by mass).
- composition for forming a hard coat layer of the present invention comprises the photocurable composition of the present invention or the coating liquid of the present invention. Since the photocurable composition and the coating liquid of the present invention do not require heating when the coating film formed from them is cured, a hard coat layer is formed on a substrate made of a resin having lower heat resistance than glass or the like. It is used suitably when forming.
- the article of the present invention has a base material and a hard coat layer formed from the composition for forming a hard coat layer of the present invention.
- the hard coat layer may be directly formed on at least one surface of the substrate, or may be formed on at least one surface of the substrate via a primer layer described later.
- the thickness of the hard coat layer is preferably from 0.5 to 20 ⁇ m, particularly preferably from 1 to 15 ⁇ m, from the viewpoints of wear resistance and antifouling properties.
- the base material is a main body part of various articles (optical lenses, displays, optical recording media, etc.) that require wear resistance and antifouling property, or a member constituting the surface of the article.
- the material for the surface of the substrate include metals, resins, glass, ceramics, stones, and composite materials thereof.
- As a material for the surface of the substrate in the optical lens, display, or optical recording medium glass or a transparent resin substrate is preferable.
- the article of the present invention may further have a primer layer between the substrate and the hard coat layer from the viewpoint of improving the adhesion between the substrate and the hard coat layer.
- the primer layer include known ones.
- the primer layer is formed, for example, by applying a primer layer forming composition containing a solvent to the surface of the substrate and evaporating and removing the solvent.
- the article of the present invention is suitable as a member constituting a touch panel.
- the touch panel is an input device of an input / display device (touch panel device) that combines a display device and a device that inputs contact position information by contact with a finger or the like.
- the touch panel includes a base material and input detection means.
- the input detection means is composed of, for example, a transparent conductive film, electrodes, wiring, IC, and the like.
- Example and comparative example which concern on this invention are described. However, the present invention is not limited to the examples. Examples 2, 3, 6, 8, and 9 are examples, and examples 1, 4, 5, 7, 10, and 11 are comparative examples.
- AC-2000 C 6 F 13 H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-2000), AE-3000: CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass (registered trademark) AE-3000, manufactured by Asahi Glass Co., Ltd.), AK-225: a mixture of CF 3 CF 2 CHCl 2 and CClF 2 CF 2 CHClF (Asahi Kulin (registered trademark) AK-225, manufactured by Asahi Glass Co., Ltd.), DBTDL: dibutyltin dilaurate, L: liter, Mn: Number average molecular weight.
- the fluorine-containing compound was diluted to 1.0% by mass with the above mixed solvent and passed through a 0.5 ⁇ m filter, and then the GPC of the fluorine-containing compound was measured using a GPC measuring apparatus. Mn of the fluorine-containing compound was determined by computer analysis of the GPC spectrum of the fluorine-containing compound using a calibration curve.
- ⁇ (possible): The oil-based ink is not repelled in a ball shape but is repelled in a linear shape, and the line width is 50% or more and less than 100% of the width of the pen tip of the felt pen.
- X (defect): The oil-based ink is not repelled in a ball shape or a linear shape, and a clean line can be drawn on the surface.
- the mixture was developed on silica gel column chromatography (developing solvent: AC-2000 and AE-3000) to fractionate the desired product. After fractionation, the compound (13-1-1), the compound (23-1-1) and the compound (33-1-1) are mixed so that the mass ratio shown in Table 1 is obtained. ) To (p1-6) were prepared. The Mn of the compound (13-1-1) is 1,540, the Mn of the compound (23-1-1) is 1,570, and the Mn of the compound (33-1-1) is 1,540. It was.
- the mixture was diluted with 144 g of AC-2000 and developed on silica gel column chromatography (developing solvent: AC-2000 and AE-3000) to obtain the target product. After fractionation, compound (12-1-1) and compound (23-1-2) are mixed so that the mass ratio shown in Table 2 is obtained to prepare mixtures (p2-1) to (p2-5) did.
- the Mn of the compound (12-1-1) was 1,830, and the Mn of the compound (23-1-2) was 1,570.
- Example 1 (Production of fluorine-containing compounds)
- a 50 mL two-necked flask equipped with a stirrer 1.0 g of triisocyanate (c-1) and 6.0 g of AK-225 were added, 7.5 mg of DBTDL and 2,6-di-tert-butyl. -0.3 mg of p-cresol was added.
- a solution obtained by dissolving 0.98 g of the mixture (p1-1) in 1.0 g of AK-225 was added dropwise over 1 hour with stirring at room temperature in a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours.
- composition for forming hard coat layer (Preparation of composition for forming hard coat layer)
- 1 mg of fluorine-containing compound, 94 mg of photopolymerizable compound (m-1), 94 mg of photopolymerizable compound (m-2), 11 mg of photopolymerization initiator (i-1), organic solvent 18 mg of (s-1) and 117 mg of organic solvent (s-2) were added and stirred for 1 hour at room temperature and in the light-shielded state to obtain a composition for forming a hard coat layer.
- the composition for forming a hard coat layer was applied to the surface of a polyethylene terephthalate substrate by bar coating to form a coating film, and dried on a hot plate at 50 ° C. for 1 minute to form a dry film on the surface of the substrate.
- a high pressure mercury lamp was used to irradiate ultraviolet rays (light quantity: 300 mJ / cm 2 , ultraviolet integrated energy amount of wavelength 365 nm) to form a hard coat layer having a thickness of 5 ⁇ m on the surface of the substrate.
- Table 3 shows the evaluation results of Mn of the fluorine-containing compound, the composition for forming the hard coat layer, and the hard coat layer.
- Examples 2 to 6 A fluorine-containing compound was produced in the same manner as in Example 1 except that the mixture (p1-1) was changed to the mixtures (p1-2) to (p1-6), and a hard coat layer forming composition was prepared. A coat layer was formed. Table 3 shows the evaluation results of Mn of the fluorine-containing compound, the composition for forming the hard coat layer, and the hard coat layer.
- Example 7 to 11 A fluorine-containing compound was produced in the same manner as in Example 1 except that the mixture (p1-1) was changed to the mixtures (p2-1) to (p2-5), and a hard coat layer forming composition was prepared. A coat layer was formed.
- Table 4 shows the evaluation results of Mn of the fluorine-containing compound, the composition for forming the hard coat layer, and the hard coat layer.
- the fluorine-containing compounds of Examples 2, 3, 6, 8, and 9 were obtained by reacting the compound (a1), the compound (a2), the compound (b), and the polyisocyanate (c). Since the ratio of the compound (a1) in the total of the (a1) and the compound (a2) is 99.9 to 60% by mass, the antifouling property and antifouling property of the hard coat layer are excellent. In the fluorine-containing compounds of Examples 1 and 7, the ratio of the compound (a1) is 100% by mass and the ratio of the compound (a2) is 0% by mass, so that the antifouling rub resistance is slightly inferior.
- the fluorine-containing compounds of Examples 4 and 10 have poor compatibility because the proportion of the compound (a1) is less than 60% by mass and the proportion of the compound (a2) is more than 40% by mass. Moreover, antifouling property is inferior. In the fluorine-containing compounds of Examples 5 and 11, since the proportion of the compound (a1) was 0% by mass and the proportion of the compound (a2) was 100% by mass, an insoluble matter was produced during the production of the fluorine-containing compound. .
- the fluorine-containing compound of the present invention can be suitably used for imparting excellent antifouling properties and antifouling rub resistance to an object (such as a hard coat layer).
- an object such as a hard coat layer
- it is used for mixing anti-fouling and anti-fouling rub resistance to molded products by mixing with resin materials, mold release agents, prevention of oil leakage from bearings, and processes for processing electronic parts, etc. It can be used for preventing adhesion of solutions, moisture-proofing processed products, and the like.
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Abstract
Description
また、該物品には、汚れ(指紋、皮脂、汗、化粧品、食品、油性インク等)が表面に付着しにくく、汚れが表面に付着しても容易に除去できる特性、すなわち防汚性を有することが望まれる。たとえば、メガネレンズの表面に汚れが付着すると、良好な視界を妨げ、見栄えを悪くする。光記録媒体の表面に汚れが付着すると、信号の記録および再生に障害が発生することがある。ディスプレイの表面に汚れが付着すると、視認性が低下し、タッチパネル付きディスプレイにおいては操作性に悪影響を及ぼす。
[2]前記化合物(a1)の数平均分子量が、1,000~6,000であり、前記化合物(a2)の数平均分子量が、1,000~6,000である、[1]の含フッ素化合物。
前記化合物(a2)が、下式(2)で表される化合物である、[1]または[2]の含フッ素化合物。
D1-(Cm1F2m1O)n1-E1 ・・・(1)
ただし、
D1は、D11-Rf1-O-CH2-またはD12-O-であり、
D11は、CF3-またはCF3-O-であり、
Rf1は、炭素数1~20のフルオロアルキレン基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のフルオロアルキレン基、炭素数1~20のアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のアルキレン基であり、
D12は、炭素数1~6のペルフルオロアルキル基であり、
m1は、1~6の整数であり、
n1は、2~200の整数であり、(Cm1F2m1O)n1は、m1の異なる2種以上のCm1F2m1Oからなるものであってもよく、
E1は、1つのヒドロキシ基を有する1価の有機基である。
E21-(Cm2F2m2O)n2-E22 ・・・(2)
ただし、
E21およびE22は、それぞれ独立に1つのヒドロキシ基を有する1価の有機基であり、
m2は、1~6の整数であり、
n2は、2~200の整数であり、(Cm2F2m2O)n2は、m2の異なる2種以上のCm2F2m2Oからなるものであってもよい。
[4]前記(Cm1F2m1O)n1および前記(Cm2F2m2O)n2が、いずれも、{(CF2O)n11(CF2CF2O)n12}(ただし、n11は、1以上の整数であり、n12は、1以上の整数であり、n11+n12は、2~200の整数であり、n11個のCF2Oおよびn12個のCF2CF2Oの結合順序は限定されない。)である、[3]の含フッ素化合物。
[5]前記D11-Rf1-O-CH2-が、RF2-O-CHFCF2-O-CH2-(ただし、RF2は、末端がCF3である、炭素数1~6のペルフルオロアルキル基である。)である、[3]または[4]の含フッ素化合物。
[6]前記化合物(a1)が、前記化合物(a2)のE21またはE22をD1に変換して得られた化合物である、[3]~[5]のいずれかの含フッ素化合物。
[8]前記化合物(a1)と前記化合物(a2)の混合物に前記ポリイソシアネート(c)を反応させてイソシアネート基を有する反応中間体を製造し、次いで該反応中間体に前記化合物(b)を反応させる、[7]の製造方法。
[9]前記化合物(a1)が前記化合物(a2)の活性水素含有基の1つを活性水素含有基以外の基に変換して得られた化合物であり、前記化合物(a1)と化合物(a2)の混合物が前記変換において得られた、生成した化合物(a1)と未変換の化合物(a2)との混合物である、[8]の製造方法。
[11]前記[10]の光硬化性組成物と、溶媒とを含むことを特徴とするコーティング液。
[12]前記[10]の光硬化性組成物または[11]のコーティング液からなる、ハードコート層形成用組成物。
[13]基材と、[12]のハードコート層形成用組成物から形成したハードコート層とを有することを特徴とする物品。
本発明の光硬化性組成物およびコーティング液は、防汚性および防汚性の擦れ耐性に優れる対象物を形成できる。
本発明のハードコート層形成用組成物は、防汚性および防汚性の擦れ耐性に優れるハードコート層を形成できる。
本発明の物品は、防汚性および防汚性の擦れ耐性に優れるハードコート層を有する。
本明細書において、光硬化性組成物、コーティング液およびハードコート層形成用組成物を総称して、「硬化性組成物」と記すこともある。ただし、それらが溶媒を含む場合は溶媒以外の成分の組成物をいう。
本明細書における下記の用語の意味は以下の通りである。
「ポリ(オキシペルフルオロアルキレン)鎖」とは、2つ以上のオキシペルフルオロアルキレン単位が連結した分子鎖を意味する。
「オキシペルフルオロアルキレン単位」とは、ペルフルオロアルキレン基の片末端に酸素原子を有する単位を意味し、その化学式は、酸素原子をペルフルオロアルキレン基の右側に記載して表すものとする。
「エーテル性酸素原子」とは、炭素-炭素原子間においてエーテル結合(-O-)を形成する酸素原子を意味する。
「フルオロアルキレン基」とは、アルキレン基の水素原子の一部またはすべてがフッ素原子に置換された基を意味し、「ペルフルオロアルキレン基」とは、アルキレン基の水素原子のすべてがフッ素原子に置換された基を意味する。
「ペルフルオロアルキル基」とは、アルキル基の水素原子のすべてがフッ素原子に置換された基を意味する。
「(メタ)アクリロイル基」とは、アクリロイル基およびメタクリロイル基の総称である。
「(メタ)アクリレート」とは、アクリレートおよびメタクリレートの総称である。
「対象物」とは、防汚性を付与されるものを意味する。対象物としては、たとえば、ハードコート層、撥液層、離型層、成形品等が挙げられる。
本発明の含フッ素化合物(以下、「含フッ素化合物(X)」とも記す。)は、ポリ(オキシペルフルオロアルキレン)鎖および1つの活性水素含有基を有する化合物(a1)と、ポリ(オキシペルフルオロアルキレン)鎖および2つの活性水素含有基を有する化合物(a2)と、重合性炭素-炭素二重結合および活性水素含有基を有する化合物(b)と、ポリイソシアネート(c)との反応生成物であり、化合物(a1)に由来する部分と化合物(a2)に由来する部分との合計(100質量%)に対する化合物(a1)に由来する部分の割合は60~99.9質量%である。
化合物(a1)、化合物(a2)、化合物(b)およびポリイソシアネート(c)を反応させて含フッ素化合物(X)を得る場合、ポリイソシアネート(c)と、これに反応する化合物(a1)、化合物(a2)および化合物(b)との組み合わせによって、以下の含フッ素化合物(X1)~(X4)が生成すると考えられる。
(X1)ポリイソシアネート(c)に化合物(a1)および化合物(b)が反応した含フッ素化合物。
(X2)ポリイソシアネート(c)に化合物(a1)のみが反応した含フッ素化合物。
(X3)ポリイソシアネート(c)に化合物(b)のみが反応した含フッ素化合物。
(X4)2つ以上のポリイソシアネート(c)の間を化合物(a2)が連結し、さらに各ポリイソシアネート(c)の、架橋に寄与しないイソシアナート基に化合物(a1)および化合物(b)のいずれか一方または両方が反応した架橋タイプの含フッ素化合物。
また、含フッ素化合物(X4)としては、全体の化合物(a2)およびポリイソシアネート(c)の数、および各ポリイソシアネート(c)に反応する化合物(a1)および化合物(b)の組み合わせに応じて、無数の種類が存在する。
ポリ(オキシペルフルオロアルキレン)鎖は、2つ以上のオキシペルフルオロアルキレン単位が連結した分子鎖であり、ポリ(オキシペルフルオロアルキレン)鎖の一端は炭素原子、他端は酸素原子である。本明細書ではその化学式を炭素末端側を左側に、酸素末端側を右側に記載して表す。
化合物(a1)および化合物(a2)はポリ(オキシペルフルオロアルキレン)鎖を有する。それぞれの化合物におけるポリ(オキシペルフルオロアルキレン)鎖は同一でも異なっていてもよい。通常は、ポリ(オキシペルフルオロアルキレン)鎖を有する原料化合物から化合物(a1)および化合物(a2)が製造されることより、ポリ(オキシペルフルオロアルキレン)鎖が同一の化合物(a1)と化合物(a2)とを使用して、含フッ素化合物(X)が製造される。また、化合物(a2)の活性水素含有基の1つを活性水素含有基以外の基に変換して得られた化合物(a1)を用いる場合もまたポリ(オキシペルフルオロアルキレン)鎖が同一の化合物(a1)と化合物(a2)とが使用される。
ポリ(オキシペルフルオロアルキレン)鎖としては、対象物に防汚性を充分に付与する点から、下式で表される鎖が好ましい。
化合物(a1)のポリ(オキシペルフルオロアルキレン)鎖:(Cm1F2m1O)n1
化合物(a2)のポリ(オキシペルフルオロアルキレン)鎖:(Cm2F2m2O)n2
ただし、m1、m2は、1~6の整数であり、n1、n2は、2~200の整数であり、(Cm1F2m1O)n1は、m1の異なる2種以上のCm1F2m1Oからなるものであってもよく、(Cm2F2m2O)n2は、m2の異なる2種以上のCm2F2m2Oからなるものであってもよい。
(Cm1F2m1O)n1、(Cm2F2m2O)n2は同じ意味を表すことより、以下、(Cm1F2m1O)n1を代表にしてポリ(オキシペルフルオロアルキレン)鎖を説明する。
m1が2以上の場合、Cm1F2m1は、直鎖状であってもよく、分岐状であってもよい。対象物に防汚性を充分に付与する点からは、直鎖状が好ましい。
{(CF2O)n11(CF2CF2O)n12}は運動性に優れ、そのため、対象物の潤滑性が優れる。特に(CF2O)n11は、炭素数が1で酸素原子を有する基であるため、運動性により優れる。
化合物(a1)および化合物(a2)における活性水素含有基は、ポリイソシアネート(c)のイソシアナート基と反応し、化合物(a1)および化合物(a2)の構造を含フッ素化合物(X)の構造の一部として組み入れるためのものである。
活性水素含有基としては、ヒドロキシ基、カルボキシ基、アミノ基等が挙げられる。原料の入手容易性の点から、ヒドロキシ基が特に好ましい。
化合物(a1)は、前記ポリ(オキシペルフルオロアルキレン)鎖および1つの活性水素含有基を有する化合物である。化合物(a1)は、対象物(ハードコート層等)に防汚性を充分に付与する点から、1つのペルフルオロアルキル基を有することが好ましい。
D1-(Cm1F2m1O)n1-E1 ・・・(1)
ただし、
D1は、D11-Rf1-O-CH2-またはD12-O-であり、
D11は、CF3-またはCF3-O-であり、
Rf1は、炭素数1~20のフルオロアルキレン基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のフルオロアルキレン基、炭素数1~20のアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のアルキレン基であり、
D12は、炭素数1~6のペルフルオロアルキル基であり、
m1は、1~6の整数であり、
n1は、2~200の整数であり、(Cm1F2m1O)n1は、m1の異なる2種以上のCm1F2m1Oからなるものであってもよく、
E1は、1つのヒドロキシ基を有する1価の有機基である。
-RF-O-CHFCF2- ・・・(g1-1)
-RF-CHFCF2- ・・・(g1-2)
-RF-CzH2z- ・・・(g1-3)
ただし、RFは、単結合、炭素数1~15のペルフルオロアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~15のペルフルオロアルキレン基であり、zは、1~4の整数である。
zは、1~3の整数が好ましい。zが3以上の場合、CzH2zは、直鎖状であってもよく、分岐状であってもよく、直鎖状が好ましい。
RF2-O-CHFCF2-O-CH2- ・・・(g2)
ただし、RF2は、末端がCF3である、炭素数1~6のペルフルオロアルキル基である。
式(g2)で表される基は、HO-CH2-を有するポリ(オキシペルフルオロアルキレン)鎖含有化合物に、RF2-O-CF=CF2で表されるペルフルオロ(アルキルビニルエーテル)を付加させることにより形成できる。
式(g2)で表される基の具体例としては、以下の基が挙げられる。
CF3O-CHFCF2-O-CH2-、
CF3CF2-O-CHFCF2-O-CH2-、
CF3CF2CF2-O-CHFCF2-O-CH2-、
CF3CF2CF2CF2-O-CHFCF2-O-CH2-、
CF3CF2CF2CF2CF2CF2-O-CHFCF2-O-CH2-。
D12としては、対象物に防汚性を充分に付与する点から、炭素数1~3のペルフルオロアルキル基が好ましく、CF3-またはCF3CF2-が特に好ましい。
R1としては、炭素数10以下のアルキレン基、-OH側末端がメチレン基である炭素数10以下のフルオロアルキレン基が好ましい。
E1としては、-CF2CH2-OH、-CF2CF2CH2-OH、-CF2CF2CF2CH2-OHが好ましい。
CF3CF2-O-(CF2CF2CF2O)n1-CF2CF2CH2-OH ・・・(11)
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)n11-1(CF2CF2O)n12}-CF2CH2-OH ・・・(12)
CF3-O-{(CF2O)n11(CF2CF2O)n12}-CF2CH2-OH ・・・(13)
CF3-O-[(CF2CF2O-CF2CF2CF2CF2O)n13-CF2CF2O]-CF2CF2CF2CH2-OH ・・・(14)
CF3-O-(CF2CF2O)n1-CF2CH2-OH ・・・(15)
ただし、n13×2+1は、3~200の整数である。
化合物(a1)の数平均分子量は、1,000~6,000が好ましく、1,000~5,000がより好ましく、1,200~4,000が特に好ましい。化合物(a1)の数平均分子量が該範囲内であれば、対象物に防汚性を充分に付与できるとともに、化合物(a1)が硬化性組成物における他の成分との相溶性に優れる。
化合物(a1)の数平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)によってポリメチルメタクリレートの流出時間と比較すること、あるいは核磁気共鳴装置(NMR)によって内部標準物質と化合物(a1)の末端官能基の積分比を比較することにより求められる。
後述する化合物(a1)および化合物(a2)の製造方法において、化合物(a1)、化合物(a2)、化合物(e1)をそれぞれ分離することが困難な場合には、化合物(a1)、化合物(a2)および化合物(e1)の混合物の数平均分子量を求める。
化合物(a2)は、前記ポリ(オキシペルフルオロアルキレン)鎖および2つの活性水素含有基を有する化合物である。
ポリ(オキシペルフルオロアルキレン)鎖は、対象物(ハードコート層等)に防汚性を付与する。
化合物(a2)は、化合物(a1)および化合物(a2)の製造のしやすさの点から、化合物(a1)のポリ(オキシペルフルオロアルキレン)鎖と同じポリ(オキシペルフルオロアルキレン)鎖を有することが好ましい。
E21-(Cm2F2m2O)n2-E22 ・・・(2)
ただし、
E21およびE22は、それぞれ独立に1つのヒドロキシ基を有する1価の有機基であり、
m2は、1~6の整数であり、
n2は、2~200の整数であり、(Cm2F2m2O)n2は、m2の異なる2種以上のCm2F2m2Oからなるものであってもよい。
R21としては、炭素数10以下のアルキレン基が好ましい。
E21としては、HO-CH2-が好ましい。
R22としては、炭素数10以下のアルキレン基、-OH側末端がメチレン基である炭素数10以下のフルオロアルキレン基が好ましい。
E22としては、-CF2CH2-OH、-CF2CF2CH2-OH、-CF2CF2CF2CH2-OHが好ましい。
HO-CH2-CF2CF2O(CF2CF2CF2O)n2-1-CF2CF2CH2-OH ・・・(21)
HO-CH2-CF2O{(CF2O)n21-1(CF2CF2O)n22}-CF2CH2-OH ・・・(23)
HO-CH2-CF2CF2CF2O[(CF2CF2O-CF2CF2CF2CF2O)n23-CF2CF2O]-CF2CF2CF2CH2-OH ・・・(24)
HO-CH2-CF2O(CF2CF2O)n2-1-CF2CH2OH ・・・(25)
ただし、n23×2+2は、4~200の整数である。
化合物(a2)の数平均分子量は、1,000~6,000が好ましく、1,000~5,000がより好ましく、1,200~4,000が特に好ましい。化合物(a2)の数平均分子量が該範囲内であれば、対象物に防汚性を充分に付与できるとともに、化合物(a2)が硬化性組成物における他の成分との相溶性に優れる。
化合物(a2)の数平均分子量は、化合物(a1)と同様の方法で求められる。
化合物(a1)および化合物(a2)は、それぞれを別々に製造してもよく、1つの出発物質から同時に製造してもよい。また、化合物(a2)から化合物(a1)を製造してもよい。
化合物(a1)および化合物(a2)を製造する方法としては、活性水素含有基がヒドロキシ基である場合、たとえば、下記の方法(1)または方法(2)が挙げられる。
(1)ポリ(オキシペルフルオロアルキレン)鎖および2つのカルボキシ基を有する化合物にフッ素ガスを接触させて、カルボキシ基の一部をフッ素化した後、残りのカルボキシ基を還元する方法(特開2011-116947号公報参照)。ポリ(オキシペルフルオロアルキレン)鎖および2つのカルボキシ基を有する化合物としては市販の化合物を使用できる。
(2)ポリ(オキシペルフルオロアルキレン)鎖および2つのヒドロキシ基を有する化合物と、ペルフルオロ(アルキルビニルエーテル)とを反応させ、ヒドロキシ基の一部にペルフルオロ(アルキルビニルエーテル)を付加させる方法。ポリ(オキシペルフルオロアルキレン)鎖および2つのヒドロキシ基を有する化合物としては、市販の化合物を使用できる。市販の化合物としては、たとえば、「FLUOROLINK D」(商品名)、「Fomblin Z-Dol」(商品名)等が挙げられる。
また、上記方法(2)における2つのヒドロキシ基を有する化合物として化合物(a2)を用いることができる。その場合、原料である化合物(a2)の一部を未反応物として残存させることより、化合物(a1)と化合物(a2)の混合物を得ることができる。また、化合物(a2)の化合物(a1)への変換割合を変えることにより、混合物における両化合物の含有割合を調整することができる。
方法(1)の具体的な一例を以下に説明する。
化合物(53-1)をフッ素ガスと接触させて、化合物(43-1)、未反応の化合物(53-1)および化合物(33-1)からなる混合物(x)を得る。
CF3-O-{(CF2O)p(CF2CF2O)q}-CF2C(=O)OH ・・・(43-1)
HO-C(=O)-CF2O{(CF2O)p(CF2CF2O)q}-CF2C(=O)-OH ・・・(53-1)
CF3-O-{(CF2O)p(CF2CF2O)q}-CF3 ・・・(33-1)
ただし、pは1以上の整数であり、qは0以上の整数であり、p+q+1は3~200の整数であり、pのCF2Oおよびq個のCF2CF2Oの結合順序は限定されない。
CF3-O-{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(13-1)
HO-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(23-1)
CF3-O-{(CF2O)p(CF2CF2O)q}-CF3 ・・・(33-1)
方法(2)の具体的な一例を以下に説明する。
化合物(23-1)とペルフルオロ(n-プロピルビニルエーテル)(CF3CF2CF2-O-CF=CF2)とを反応させて、化合物(12-1)、未反応の化合物(23-1)および化合物(32-1)からなる混合物を得る。
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(12-1)
HO-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(23-1)
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-O-CF2CHF-O-CF2CF2-CF3 ・・・(32-1)
方法(1)および方法(2)においては、ポリ(オキシペルフルオロアルキレン)鎖および2つのペルフルオロアルキル基を有し、活性水素含有基を有しない化合物(e1)が副生され得る。
CF3CF2-O-(CF2CF2CF2O)n3-CF2CF3 ・・・(31)
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)n31-1(CF2CF2O)n32}-CF2CH2-O-CF2CHF-O-CF2CF2-CF3 ・・・(32)
CF3-O-{(CF2O)n31(CF2CF2O)n32}-CF3 ・・・(33)
CF3-O-(CF2CF2O)n3-CF3 ・・・(35)
ただし、n3は、2~200の整数であり、n31は、1以上の整数であり、n32は、0以上の整数であり、n31+n32は、2~200の整数であり、n31個のCF2Oおよびn32個のCF2CF2Oの結合順序は限定されない。
化合物(b)は、重合性炭素-炭素二重結合および活性水素含有基を有する化合物である。
重合性炭素-炭素二重結合を有する基としては、(メタ)アクリロイル基、ビニル基、アリル基、スチリル基、マレイミド基等が挙げられる。対象物に耐摩耗性を充分に付与する点から、(メタ)アクリロイル基が好ましく、アクリロイル基が特に好ましい。
重合性炭素-炭素二重結合の数は、化合物(b)の1分子あたり、1~8が好ましく、1~4がより好ましく、1が特に好ましい。
活性水素含有基の数は、化合物(b)の1分子あたり、1が好ましい。活性水素含有基としてはヒドロキシ基が好ましい。
HOCH2CH2OC(=O)C(R)=CH2、
H2NCH2CH2OC(=O)C(R)=CH2、
HO(CH2CH2O)i-C(=O)C(R)C=CH2、
CH3CH(OH)CH2OC(=O)C(R)C=CH2、
CH3CH2CH(OH)CH2OC(=O)C(R)C=CH2、
C6H5OCH2CH(OH)CH2OC(=O)C(R)C=CH2、
HOCH2CH=CH2、
HO(CH2)kCH=CH2、
(CH3)3SiCH(OH)CH=CH2、
HOC6H4CH=CHC6H5。
ただし、Rは、水素原子またはメチル基であり、iは、2~10の整数であり、kは、2~20の整数である。
ポリイソシアネート(c)は、2つ以上のイソシアナート基を有する化合物である。
イソシアナート基は、化合物(a1)の活性水素含有基、化合物(a2)の活性水素含有基および化合物(b)の活性水素含有基と反応し、ポリイソシアネート(c)の構造を含フッ素化合物(X)の構造の一部として組み入れるためのものである。
イソシアナート基の数は、2~4が好ましく、3が特に好ましい。
ジイソシアネートとしては、無黄変ジイソシアネート(すなわち、芳香核に直接結合したイソシアネート基を有しないジイソシアネート)が好ましく、アルキレンジイソシアネートや脂環式ジイソシアネートが好ましい。
ジイソシアネートの変性体としては、イソシアヌレート変性体、ビュレット変性体、3価または4価のアルコールで変性した多価アルコール変性体などが挙げられる。3価または4価のアルコールとしては、グリセリン、トリメチロールプロパン、ペンタエリスリトール等が挙げられる。
下式(6-1)で表されるイソシアヌレート変性アルキレンジイソシアネート(アルキレンジイソシアネートの環状3量体)、
下式(6-2)で表されるイソシアヌレート変性トリレンジイソシアネート(トリレンジイソシアネートの環状3量体)、
下式(6-3)で表されるイソシアヌレート変性イソホロンジイソシアネート(イソホロンジイソシアネートの環状3量体)、
下式(6-4)で表されるビュレット変性アルキレンジイソシアネート、
下式(6-5)で表されるグリセロール変性アルキレンジイソシアネート。
ただし、s、tおよびuは、それぞれ独立に2~10の整数である。
含フッ素化合物(X)は、ウレタン化触媒の存在下、ポリイソシアネート(c)に、活性水素含有基を有する化合物(化合物(a1)、化合物(a2)および化合物(b))を同時に、またはポリイソシアネート(c)に、化合物(a1)および化合物(a2)と、化合物(b)とを順次反応させることによって製造される。
よって、活性水素含有基を有する化合物を過剰に用いる際には、まず、化合物(a1)および化合物(a2)と、過剰当量のポリイソシアネート(c)とを反応させ、化合物(a1)および化合物(a2)の活性水素基をすべてイソシアネート基と反応させた後、残存ずるイソシアネート基に対して等当量以上の化合物(b)を反応させることが好ましい。
したがって、含フッ素化合物(X)の製造においては、化合物(a1)に由来する部分と前記化合物(a2)に由来する部分の割合を上記割合とすべく、化合物(a1)と化合物(a2)との合計(100質量%)のうち化合物(a1)の割合は、60~99.9質量%であることが好ましく、70~99質量%がより好ましく、80~95質量%が特に好ましい。
含フッ素化合物(X)を製造する際には、製造に必要な添加剤(以下、「製造用添加剤」とも記す。)を用いてもよい。製造用添加剤としては、重合禁止剤等が挙げられる。
有機溶媒は、フッ素系有機溶媒であっても、非フッ素系溶媒であってもよく、両溶媒を併用してもよい。各原料および含フッ素化合物(X)が溶解しやすい点で、フッ素系有機溶媒としては、フルオロアルカン、クロロフルオロアルカン、フルオロ芳香族化合物、フルオロアルキルエーテルが好ましく、クロロフルオロアルカンおよびフルオロアルキルエーテルが好ましく、非フッ素系溶媒としては、グリコールエーテル系有機溶媒およびケトン系有機溶媒が好ましい。
含フッ素化合物(X)の数平均分子量は、1,200~8,000が好ましく、1,200~7,000がより好ましく、1,200~5,000が特に好ましい。数平均分子量が該範囲内であれば、対象物(ハードコート層等)に防汚性および防汚性の擦れ耐性を充分に付与できるとともに、硬化性組成物において含フッ素化合物と他の成分との相溶性に優れる。
含フッ素化合物の数平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)によって求めたポリメチルメタクリレート換算の数平均分子量である。
以上説明した本発明の含フッ素化合物(X)にあっては、化合物(a1)に由来する部分と化合物(a2)に由来する部分との合計のうち化合物(a1)に由来する部分の割合が60質量%以上であるため、化合物(a1)に由来する部分の構造(特に末端のCF3-)によって、対象物(ハードコート層等)の表面の表面エネルギーが低下する。その結果、防汚性を対象物に付与できる。
また、化合物(a1)に由来する部分と化合物(a2)に由来する部分との合計のうち化合物(a2)に由来する部分の割合が0.1質量%以上であるため、化合物(a2)に由来する部分の構造が含フッ素化合物に充分に導入される。そのため、含フッ素化合物(X)が高分子量化し、該含フッ素化合物(X)を含む硬化性組成物から形成される硬化膜(ハードコート層等)に含フッ素化合物(X)が強固に固定される。その結果、対象物に防汚性の擦れ耐性を付与できる。
また、化合物(a1)と化合物(a2)との合計のうち化合物(a2)の割合が40質量%以下であるため、含フッ素化合物(X)の分子量が大きくなりすぎない。その結果、含フッ素化合物(X)と他の成分との相溶性にも優れる。
本発明の光硬化性組成物は、含フッ素化合物(X)と、光重合性化合物(ただし、含フッ素化合物(X)を除く。)と、光重合開始剤とを含む。本発明の光硬化性組成物は、必要に応じて光硬化性組成物用添加剤をさらに含んでいてもよい。
光重合性化合物は、後述する光重合開始剤の存在下、光を照射することによって重合反応を開始するモノマーである。
光重合性化合物としては、多官能性モノマー、単官能性モノマーが挙げられる。対象物(ハードコート層等)に耐摩耗性を付与する点から、多官能性モノマーを必須成分として含むものが好ましい。
光重合性化合物は、1種を単独で用いてもよく、2種以上を併用してもよい。
多官能性モノマーとしては、対象物に充分な耐摩耗性を付与する点から、(メタ)アクリロイル基の3つ以上を有し、(メタ)アクリロイル基1つあたりの分子量が120以下であるモノマー、またはウレタン結合および(メタ)アクリロイル基の3つ以上を有するモノマーが好ましい。
光重合開始剤としては、公知の光重合開始剤、たとえば、アリールケトン系光重合開始剤(アセトフェノン類、ベンゾフェノン類、アルキルアミノベンゾフェノン類、ベンジル類、ベンゾイン類、ベンゾインエーテル類、ベンジルジメチルケタール類、ベンゾイルベンゾエート類、α-アシルオキシムエステル類等)、含硫黄系光重合開始剤(スルフィド類、チオキサントン類等)、アシルホスフィンオキシド類(アシルジアリールホスフィンオキシド等)、その他の光重合開始剤が挙げられる。
光重合開始剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
光重合開始剤は、アミン類等の光増感剤と併用してもよい。
光硬化性組成物用添加剤としては、コロイダルシリカ、光増感剤、紫外線吸収剤、光安定剤、熱硬化安定剤、酸化防止剤、レベリング剤、消泡剤、増粘剤、沈降防止剤、顔料、染料、分散剤、帯電防止剤、界面活性剤(防曇剤、レベリング剤等)、金属酸化物粒子、各種樹脂(エポキシ樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂等)等が挙げられる。
含フッ素化合物(溶媒)の含有量は、光硬化性組成物(ただし、溶媒を除く。)(100質量%)のうち、0.01~5質量%が好ましく、0.02~4質量%がより好ましく、0.05~3質量%が特に好ましい。含フッ素化合物(X)の含有量が前記範囲内であれば、光硬化性組成物の貯蔵安定性、対象物(ハードコート層等)の外観、耐摩耗性、防汚性および防汚性の擦れ耐性に優れる。
不純物のうち、化合物(a1)、化合物(a2)および化合物(e1)は、他の成分との相溶性が低いため、硬化性組成物に化合物(a1)、化合物(a2)および化合物(e1)が残存した場合、硬化性組成物が白濁する。よって、化合物(a1)、化合物(a2)および化合物(e1)の合計の含有量は、含フッ素化合物(X)(100質量%)に対して10質量%以下が好ましく、5質量%以下が特に好ましい。
不純物のうち、ポリイソシアネート(c)は、他の成分との反応性が高いため、硬化性組成物にポリイソシアネート(c)が残存した場合、硬化性組成物の貯蔵安定性が低下する。よって、ポリイソシアネート(c)の含有量は、含フッ素化合物(X)(100質量%)に対して4質量%以下が好ましく、1質量%以下が特に好ましい。
不純物の同定および定量は、1H-NMRおよび19F-NMRあるいはガスクロマトグラフィによって行う。
本発明のコーティング液は、本発明の光硬化性組成物と、溶媒とを含む。
本発明のコーティング液は、本発明の光硬化性組成物を基材に塗布しやすくするために調製される。
溶媒としては、有機溶媒が好ましい。有機溶媒としては、塗布方法に適した沸点を有する有機溶媒が好ましい。
有機溶媒は、フッ素系有機溶媒であっても、非フッ素系有機溶媒であってもよく、両溶媒を併用してもよい。
フッ素系有機溶媒としては、含フッ素化合物(X)が溶解しやすい点から、フルオロアルカン、フルオロ芳香族化合物、フルオロアルコール、フルオロアルキルエーテルが好ましく、フルオロアルコールまたはフルオロアルキルエーテルが特に好ましい。
非フッ素系有機溶媒としては、含フッ素化合物(X)が溶解しやすい点から、グリコールエーテル系有機溶媒およびケトン系有機溶媒が特に好ましい。
溶媒の含有量は、コーティング液(100質量%)のうち、5~80質量%が好ましく、10~70質量%がより好ましく、20~60質量%が特に好ましい。
本発明のハードコート層形成用組成物は、本発明の光硬化性組成物または本発明のコーティング液からなる。
本発明の光硬化性組成物およびコーティング液は、これらから形成された塗膜の硬化に際して加熱が不要であるため、ガラス等に比較して耐熱性の低い樹脂からなる基材に、ハードコート層を形成する際に好適に用いられる。
以上説明した本発明の光硬化性組成物、コーティング液およびハードコート層形成用組成物にあっては、含フッ素化合物(X)を含むため、防汚性および防汚性の擦れ耐性に優れる対象物(ハードコート層等)を形成できる。
本発明の物品は、基材と、本発明のハードコート層形成用組成物から形成したハードコート層とを有する。
ハードコート層は、基材の少なくとも1つの表面に直接形成されていてもよく、基材の少なくとも1つの表面に後述するプライマ層を介して形成されたものであってもよい。
ハードコート層の厚さは、耐摩耗性および防汚性の点から、0.5~20μmが好ましく、1~15μmが特に好ましい。
基材は、耐摩耗性および防汚性が必要とされる種々の物品(光学レンズ、ディスプレイ、光記録媒体等)の本体部分、または該物品の表面を構成する部材である。
基材の表面の材料としては、金属、樹脂、ガラス、セラミック、石、これらの複合材料等が挙げられる。光学レンズ、ディスプレイ、光記録媒体における基材の表面の材料としては、ガラスまたは透明樹脂基材が好ましい。
本発明の物品は、基材とハードコート層との密着性を向上させる点から、基材とハードコート層との間にプライマ層をさらに有していてもよい。
プライマ層としては、公知のものが挙げられる。プライマ層は、たとえば、溶媒を含むプライマ層形成用組成物を基材の表面に塗布し、溶媒を蒸発除去することによって形成される。
本発明の物品は、タッチパネルを構成する部材として好適である。タッチパネルとは、指等による接触によってその接触位置情報を入力する装置と表示装置とを組み合わせた入力/表示装置(タッチパネル装置)の、入力装置である。タッチパネルは、基材と、入力検出手段等とから構成される。入力検出手段は、たとえば、透明導電膜、電極、配線、IC等から構成される。物品のハードコート層を有する面をタッチパネルの入力面とすることによって、防汚性および防汚性の擦れ耐性に優れるタッチパネルが得られる。
物品は、たとえば、下記の工程(I)および工程(II)を経て製造される。
工程(I):必要に応じて、プライマ層形成用組成物を基材の表面に塗布してプライマ層を形成する工程。
工程(II):ハードコート層形成用組成物を基材またはプライマ層の表面に塗布して塗膜を得て、ハードコート層形成用組成物が溶媒を含む場合は溶媒を除去し、光硬化させてハードコート層を形成する工程。
以上説明した本発明の物品にあっては、ハードコート層形成用組成物から形成したハードコート層を有するため、防汚性および防汚性の擦れ耐性に優れる。
例2、3、6、8、9は実施例であり、例1、4、5、7、10、11は比較例である。
AC-2000:C6F13H(旭硝子社製、アサヒクリン(登録商標)AC-2000)、
AE-3000:CF3CH2OCF2CF2H(旭硝子社製、アサヒクリン(登録商標)AE-3000)、
AK-225:CF3CF2CHCl2とCClF2CF2CHClFとの混合物(旭硝子社製、アサヒクリン(登録商標)AK-225)、
DBTDL:ジブチル錫ジラウレート、
L:リットル、
Mn:数平均分子量。
(化合物(a1)、化合物(a2)および化合物(e1)のMn)
化合物(a1)、化合物(a2)および化合物(e1)の数平均分子量は、核磁気共鳴装置(NMR)によって内部標準物質と化合物(a1)、化合物(a2)および化合物(e1)の末端官能基の積分比をそれぞれ比較することにより求めた。
分子量測定用の標準試料として市販されている重合度の異なる数種の単分散ポリメチルメタクリレートのGPCを、GPC測定装置(東ソー社製、HLC-8220GPC)にて、溶離液にAK-225:ヘキサフルオロイソプロパノール=99:1(体積比)の混合溶媒を用いて測定し、ポリメチルメタクリレートの分子量と保持時間(リテンションタイム)との関係をもとに検量線を作成した。
含フッ素化合物を前記混合溶媒で1.0質量%に希釈し、0.5μmのフィルタに通過させた後、含フッ素化合物についてのGPCを、GPC測定装置を用いて測定した。
検量線を用いて、含フッ素化合物のGPCスペクトルをコンピュータ解析することによって含フッ素化合物のMnを求めた。
下記の基準にしたがい、目視によって調製直後のハードコート層形成用組成物の外観を評価した。
○(良好):溶液が均一で濁りがない。
×(不良):濁りが確認できる。
ハードコート層形成用組成物を室温で3ヶ月静置した後、目視によってハードコート層形成用組成物の外観を評価した。
○(良好):溶液が均一で濁りがない。
×(不良):濁りが確認できる。
下記の基準にしたがい、目視によってハードコート層の外観を評価した。
○(良好):異物が確認できず、膜厚が均一である。
△(可) :異物は確認できないが、膜厚にムラがある。
×(不良):異物が確認され、膜厚にムラがある。
人工指紋液(オレイン酸とスクアレンとからなる液)を、シリコンゴム栓の平坦面に付着させた後、余分な油分を不織布(旭化成社製、ベンコット(登録商標)M-3)にて拭き取り、指紋のスタンプを準備した。該指紋スタンプを、ハードコート層を有する物品上に乗せ、荷重:9.8Nにて10秒間押しつけた。指紋が付着した箇所について、ティッシュペーパを取り付けた、往復式トラバース試験機(ケイエヌテー社製)を用い、荷重:4.9Nにて拭き取りを行った。拭き取り一往復毎にヘーズを目視で観察し、10往復後までのヘーズを目視で観察することによって評価した。評価基準は下記の通りである。
○(良好):ヘーズを目視で確認できない。
△(可) :ヘーズを目視でわずかに確認できる。
×(不可):ヘーズを目視で明らかに確認できる。
ハードコート層の表面にフェルトペン(ゼブラ社製、マッキー極太黒色)で線を描き、油性インクの付着状態を目視で観察することによって評価した。評価基準は下記の通りである。
◎(優良):油性インクを玉状にはじく。
○(良好):油性インクを玉状にはじかず、線状にはじき、線幅がフェルトペンのペン先の幅の50%未満である。
△(可) :油性インクを玉状にはじかず、線状にはじき、線幅がフェルトペンのペン先の幅の50%以上100%未満である。
×(不良):油性インクを玉状にも線状にもはじかず、表面にきれいに線が描ける。
ハードコート層を有する物品について、往復式トラバース試験機(ケイエヌテー社製)を用い、スチールウール(日本スチールウール社製、ボンスター(登録商標)#0000)を荷重:9.8Nにて500回往復させた後、ハードコート層の表面にフェルトペン(ゼブラ社製、マッキー極太黒色)で線を描き、油性インクの付着状態を目視で観察することによって評価した。評価基準は前記「油性インクはじき性」と同じである。
ハードコート層の表面の鉛筆硬度を、JIS K5600-5-4:1999(ISO 15184:1996)「引っかき硬度(鉛筆法)」に準じて測定した。
(化合物(13-1-1)、化合物(23-1-1)の製造)
特開2011-116947号公報の段落[0061]、[0062]に記載の方法にしたがい、化合物(53-1-1)(ソルベイ・ソレクシス社製、FLUOROLINK(登録商標) C)から、化合物(13-1-1)、化合物(23-1-1)および化合物(33-1-1)からなる混合物を得た。
HO-C(=O)-CF2O{(CF2O)p(CF2CF2O)q}-CF2C(=O)-OH ・・・(53-1-1)
CF3-O-{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(13-1-1)
HO-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(23-1-1)
CF3-O-{(CF2O)p(CF2CF2O)q}-CF3 ・・・(33-1-1)
ただし、p/q=0.6、p+q≒15である。
化合物(13-1-1)のMnは1,540であり、化合物(23-1-1)のMnは1,570であり、化合物(33-1-1)のMnは1,540であった。
500mLの3つ口丸底フラスコに、水酸化カリウムの1.04gを取り入れ、tert-ブタノールの83gと1,3-ビス(トリフルオロメチル)ベンゼンの125gを加えた。室温で撹拌して水酸化カリウムを溶解させ、これに化合物(23-1-2)(ソルベイ・ソレクシス社製、FLUOROLINK(登録商標) D10/H)の250gを加えて1時間撹拌した。室温のまま、ペルフルオロ(n-プロピルビニルエーテル)(CF3CF2CF2-O-CF=CF2)の38.2gを加え、さらに24時間撹拌した。塩酸水溶液を加えて中和し、さらに水を加えて分液処理を行った。3回の水洗後、有機相を回収し、エバポレータで濃縮することによって、化合物(12-1-1)、化合物(23-1-2)および化合物(32-1-1)からなる混合物の288.0gを得た。
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(12-1-1)
HO-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-OH ・・・(23-1-2)
CF3-CF2CF2-O-CHFCF2-O-CH2-CF2O{(CF2O)p(CF2CF2O)q}-CF2CH2-O-CF2CHF-O-CF2CF2-CF3 ・・・(32-1-1)
ただし、p/q=0.6、p+q≒15である。
化合物(12-1-1)のMnは1,830であり、化合物(23-1-2)のMnは1,570であった。
(化合物(b))
(b-1):HOCH2CH2OC(=O)CH=CH2(日本触媒社製、2-ヒドロキシエチルアクリレート)。
(c-1):式(6-1)で表されるイソシアヌレート変性ヘキサメチレンジイソシアネート(s、tおよびu=6)(旭化成ケミカルズ社製、DURANATE(登録商標) TKA-100、ヘキサメチレンジイソシアネートの環状3量体、イソシアネート基含有量:21.8質量%)。
(m-1):ジペンタエリスリトールヘキサアクリレート(モノマー(m11)に該当)、
(m-2):トリス(アクリロイルオキシエチル)イソシアヌレート(モノマー(m12)に該当)。
(i-1):2-メチル-1-{4-(メチルチオ)フェニル}-2-モルホリノプロパン-1-オン。
(s-1):2,2,3,3-テトラフルオロプロパノール、
(s-2):プロピレングリコールモノメチルエーテル。
(含フッ素化合物の製造)
撹拌機を装着した50mLの2つ口フラスコに、トリイソシアネート(c-1)の1.0g、AK-225の6.0gを入れ、DBTDLの7.5mgおよび2,6-ジ-tert-ブチル-p-クレゾールの0.3mgを加えた。窒素雰囲気中、室温で撹拌しながら1時間かけて、混合物(p1-1)の0.98gをAK-225の1.0gに溶かした溶液を滴下し、室温で12時間撹拌した。40℃に加温し、化合物(b-1)の0.76gを2分間で滴下し、12時間撹拌した。赤外吸収スペクトルによってイソシアナート基の吸収が完全に消失していることを確認できたため、得られた反応溶液をエバポレータで濃縮して目的の含フッ素化合物を得た。
30mLのバイアル管に、含フッ素化合物の1mg、光重合性化合物(m-1)の94mg、光重合性化合物(m-2)の94mg、光重合開始剤(i-1)の11mg、有機溶媒(s-1)の18mg、有機溶媒(s-2)の117mgを入れ、常温および遮光にした状態で、1時間撹拌して、ハードコート層形成用組成物を得た。
ポリエチレンテレフタレート基材の表面にハードコート層形成用組成物をバーコートにより塗布し、塗膜を形成し、50℃のホットプレートで1分間乾燥させ、基材の表面に乾燥膜を形成した。高圧水銀ランプを用いて紫外線(光量:300mJ/cm2、波長365nmの紫外線積算エネルギー量)を照射し、基材の表面に厚さ5μmのハードコート層を形成した。
含フッ素化合物のMn、ハードコート層形成用組成物およびハードコート層の評価結果を表3に示す。
混合物(p1-1)を混合物(p1-2)~(p1-6)に変更した以外は、例1と同様にして含フッ素化合物を製造し、ハードコート層形成用組成物を調製し、ハードコート層を形成した。含フッ素化合物のMn、ハードコート層形成用組成物およびハードコート層の評価結果を表3に示す。
混合物(p1-1)を混合物(p2-1)~(p2-5)に変更した以外は、例1と同様にして含フッ素化合物を製造し、ハードコート層形成用組成物を調製し、ハードコート層を形成した。含フッ素化合物のMn、ハードコート層形成用組成物およびハードコート層の評価結果を表4に示す。
例1、7の含フッ素化合物は、化合物(a1)の割合が100質量%であり、化合物(a2)の割合が0質量%であるため、防汚性の擦れ耐性がやや劣る。
例4、10の含フッ素化合物は、化合物(a1)の割合が60質量%未満であり、化合物(a2)の割合が40質量%超であるため、相溶性が悪い。また、防汚性が劣る。
例5、11の含フッ素化合物は、化合物(a1)の割合が0質量%であり、化合物(a2)の割合が100質量%であるため、含フッ素化合物の製造の際に不溶物が生成した。
なお、2015年4月30日に出願された日本特許出願2015-092928号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (13)
- ポリ(オキシペルフルオロアルキレン)鎖および1つの活性水素含有基を有する化合物(a1)と、
ポリ(オキシペルフルオロアルキレン)鎖および2つの活性水素含有基を有する化合物(a2)と、
重合性炭素-炭素二重結合および活性水素含有基を有する化合物(b)と、
ポリイソシアネート(c)と
の反応生成物であって、
前記化合物(a1)に由来する部分と前記化合物(a2)に由来する部分との合計(100質量%)に対する前記化合物(a1)に由来する部分の割合が、60~99.9質量%であることを特徴とする含フッ素化合物。 - 前記化合物(a1)の数平均分子量が、1,000~6,000であり、
前記化合物(a2)の数平均分子量が、1,000~6,000である、請求項1に記載の含フッ素化合物。 - 前記化合物(a1)が、下式(1)で表される化合物であり、
前記化合物(a2)が、下式(2)で表される化合物である、請求項1または2に記載の含フッ素化合物。
D1-(Cm1F2m1O)n1-E1 ・・・(1)
ただし、
D1は、D11-Rf1-O-CH2-またはD12-O-であり、
D11は、CF3-またはCF3-O-であり、
Rf1は、炭素数1~20のフルオロアルキレン基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のフルオロアルキレン基、炭素数1~20のアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~20のアルキレン基であり、
D12は、炭素数1~6のペルフルオロアルキル基であり、
m1は、1~6の整数であり、
n1は、2~200の整数であり、(Cm1F2m1O)n1は、m1の異なる2種以上のCm1F2m1Oからなるものであってもよく、
E1は、1つのヒドロキシ基を有する1価の有機基である。
E21-(Cm2F2m2O)n2-E22 ・・・(2)
ただし、
E21およびE22は、それぞれ独立に1つのヒドロキシ基を有する1価の有機基であり、
m2は、1~6の整数であり、
n2は、2~200の整数であり、(Cm2F2m2O)n2は、m2の異なる2種以上のCm2F2m2Oからなるものであってもよい。 - 前記(Cm1F2m1O)n1および前記(Cm2F2m2O)n2が、いずれも、{(CF2O)n11(CF2CF2O)n12}(ただし、n11は、1以上の整数であり、n12は、1以上の整数であり、n11+n12は、2~200の整数であり、n11個のCF2Oおよびn12個のCF2CF2Oの結合順序は限定されない。)である、請求項3に記載の含フッ素化合物。
- 前記D11-Rf1-O-CH2-が、RF2-O-CHFCF2-O-CH2-(ただし、RF2は、末端がCF3である、炭素数1~6のペルフルオロアルキル基である。)である、請求項3または4に記載の含フッ素化合物。
- 前記化合物(a1)が、前記化合物(a2)のE21またはE22をD1に変換して得られた化合物である、請求項3~5のいずれか一項に記載の含フッ素化合物。
- ポリ(オキシペルフルオロアルキレン)鎖および1つの活性水素含有基を有する化合物(a1)と、
前記化合物(a1)との合計(100質量%)に対する割合が0.1~40質量%となる量の、ポリ(オキシペルフルオロアルキレン)鎖および2つの活性水素含有基を有する化合物(a2)と、
前記化合物(a1)と前記化合物(a2)との合計(100質量%)に対する割合が10~50質量%となる量の、重合性炭素-炭素二重結合および活性水素含有基を有する化合物(b)と、
ポリイソシアネート(c)とを該ポリイソシアネート(c)のイソシアネート基が残存しない割合で反応させることを特徴とする含フッ素化合物の製造方法。 - 前記化合物(a1)と前記化合物(a2)の混合物に前記ポリイソシアネート(c)を反応させてイソシアネート基を有する反応中間体を製造し、次いで該反応中間体に前記化合物(b)を反応させる、請求項7に記載の製造方法。
- 前記化合物(a1)が前記化合物(a2)の活性水素含有基の1つを活性水素含有基以外の基に変換して得られた化合物であり、前記化合物(a1)と化合物(a2)の混合物が前記変換において得られた、生成した化合物(a1)と未変換の化合物(a2)との混合物である、請求項8に記載の製造方法。
- 請求項1~6のいずれか一項に記載の含フッ素化合物と、
光重合性化合物(ただし、前記含フッ素化合物を除く。)と、
光重合開始剤と
を含むことを特徴とする光硬化性組成物。 - 請求項10に記載の光硬化性組成物と、
溶媒と
を含むことを特徴とするコーティング液。 - 請求項10に記載の光硬化性組成物または請求項11に記載のコーティング液からなる、ハードコート層形成用組成物。
- 基材と、
請求項12に記載のハードコート層形成用組成物から形成したハードコート層と
を有することを特徴とする物品。
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KR1020177022579A KR20170141649A (ko) | 2015-04-30 | 2016-04-28 | 함불소 화합물, 광 경화성 조성물, 코팅액, 하드 코트층 형성용 조성물 및 물품 |
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JP2020033425A (ja) * | 2018-08-28 | 2020-03-05 | 株式会社東京セロレーベル | フッ素樹脂組成物 |
KR20200049815A (ko) * | 2017-09-01 | 2020-05-08 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 신규 (퍼)플루오로폴리에테르 중합체 및 이의 용도 |
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CN109963894B (zh) * | 2017-01-26 | 2022-05-13 | 昭和电工株式会社 | 含氟醚化合物、磁记录介质用润滑剂及磁记录介质 |
JP2020535260A (ja) * | 2017-09-27 | 2020-12-03 | アーケマ・インコーポレイテッド | ハロゲン化反応成分から調製される付加及び縮合ポリマー |
CN108864783A (zh) * | 2018-06-06 | 2018-11-23 | Ppg涂料(天津)有限公司 | 防水涂层 |
JP7338631B2 (ja) | 2018-09-12 | 2023-09-05 | 株式会社レゾナック | 含フッ素エーテル化合物、磁気記録媒体用潤滑剤および磁気記録媒体 |
US11214707B2 (en) * | 2018-09-21 | 2022-01-04 | The Boeing Company | Compositions and methods for fabricating coatings |
JP7435589B2 (ja) | 2019-03-12 | 2024-02-21 | 株式会社レゾナック | 含フッ素エーテル化合物、磁気記録媒体用潤滑剤および磁気記録媒体 |
CN114341094B (zh) | 2019-09-18 | 2024-01-12 | 株式会社力森诺科 | 含氟醚化合物、磁记录介质用润滑剂及磁记录介质 |
WO2021132252A1 (ja) | 2019-12-26 | 2021-07-01 | 昭和電工株式会社 | 含フッ素エーテル化合物、磁気記録媒体用潤滑剤および磁気記録媒体 |
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