Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C09D171/12—Polyphenylene oxides
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
  • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

• the present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), and more particularly, to a fluoropolyether group-containing polymer composition that forms a film having excellent water and oil repellency, abrasion resistance, and anti-slip properties, a coating agent containing the composition, an article having a layer composed of a cured product of the coating agent, and a method for modifying the surface of the article.
• a fluoropolyether group-containing polymer a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule
• fluoropolyether group-containing compounds have very low surface free energy, so they have water and oil repellency, chemical resistance, lubricity, releasability, and antifouling properties. Utilizing its properties, it is widely used industrially as a water- and oil-repellent antifouling agent for paper and textiles, a lubricant for magnetic recording media, an anti-oil agent for precision equipment, a release agent, a cosmetic, and a protective film. However, its properties also mean that it is non-sticky and non-adhesive to other substrates, and although it can be applied to the surface of substrates, it is difficult to adhere the film.
• Patent Documents 1 to 6 JP-A-2008-534696, JP-A-2008-537557, JP-A-2012- 072272, JP 2012-157856, JP 2013-136833, JP 2015-199906).
• a coating agent containing the fluoropolyether group-containing polymer composition can form a cured film having excellent water and oil repellency and abrasion resistance, as well as anti-slip properties due to a high friction coefficient, by using a combination of two types of specific fluoropolyether group-containing polymers described later in a specific ratio in the above-mentioned fluoropolyether group-containing polymer composition, and completed the present invention.
• the present invention provides the following fluoropolyether group-containing polymer composition, coating agent and article, and method for modifying the surface of the article.
• Rf1 is a monovalent or divalent fluorooxyalkylene group-containing polymer residue containing a group represented by -(C 3 F 6 O) d - (repeating unit C 3 F 6 O consists of a branched structure, and d is an integer of 2 to 200), V is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at its terminal and having no polar group, and ⁇ is 1 or 2.)
• a fluoropolyether group-containing polymer and / or a partial (hydrolysis) condensate thereof represented by (II) the following general formula (2) W-Rf2-W (2) ( ⁇ Rf2 ⁇ -(C 3 F 6 ⁇ )
• a fluoropolyether group-containing polymer composition [2] (I) component is the following general formula (3) (Wherein, Rf1 and ⁇ are the same as above, L is independently a single bond or a divalent heteroatom, Y is independently a divalent to hexavalent hydrocarbon group and may have a silicon atom and/or a siloxane bond.R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, and m is an integer of 1 to 5.)
• the fluoropolyether group-containing polymer composition according to [1] which is a fluoropolyether group-containing polymer represented by and/or a partial (hydrolysis) condensate thereof.
• one L is an oxygen atom
• the other L is a single bond
• Y is independently an alkylene group having 3 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, and each alkylene group has a silalkylene structure or a silarylene structure.
• X is independently a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.
• X is independently a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.
• a coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [7].
• a method for modifying the surface of an article comprising the step of applying a coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [7] to the entire or part of the surface of the article by a dry method or a wet method, and curing the coating to form a layer.
• the fluoropolyether group-containing polymer composition of the present invention it is possible to provide a cured film that exhibits excellent abrasion resistance despite having excellent water and oil repellency and a high coefficient of friction.
• articles for example, portable electronic device terminals, etc.
• a coating agent containing the composition of the present invention have excellent water and oil repellency, abrasion durability, and high slip resistance.
• the fluoropolyether group-containing polymer composition of the present invention contains two specific types of fluoropolyether group-containing polymers in a specific ratio.
• one component (I) is a polymer having a fluoropolyether group and a reactive functional group in the molecule
• the other component (II) is a polymer having a fluoropolyether group in the molecule and no reactive functional group.
• the polymer having a fluoropolyether group and a reactive functional group in the molecule which is the component (I)
• Rf1 [CH(V) 2 ] ⁇ (1)
• Rf1 is a monovalent or divalent fluorooxyalkylene group-containing polymer residue containing a group represented by -(C 3 F 6 O) d - (repeating unit C 3 F 6 O consists of a branched structure, and d is an integer of 2 to 200), V is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at its terminal and having no polar group, and ⁇ is 1 or 2.
• the polymer having a fluoropolyether group in the molecule and having no reactive functional group which is the component (II)
• the content of component (I) in the total of component (I) and component (II) is 55 to 85% by mass, preferably 65 to 75% by mass. If the content of component (I) is less than 55% by mass, the cured coating (hardened coating) has poor dynamic friction coefficient and wear resistance, and if it exceeds 85% by mass, the cured coating (hardened coating) has poor wear resistance.
• Component (I) is, as described above, a fluoropolyether group-containing polymer represented by the following general formula (1) and/or a partial (hydrolyzed) condensate thereof.
• Rf1[CH(V) 2 ] ⁇ (1)
• Rf1 is a monovalent or divalent fluorooxyalkylene group-containing polymer residue containing a group represented by -(C 3 F 6 O) d - (repeating unit C 3 F 6 O has a branched structure, and d is an integer of 2 to 200)
• V is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at its terminal and having no polar group, and ⁇ is 1 or 2.
• the fluoropolyether group-containing polymer represented by the formula (1) has a structure in which a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group (i.e., a monovalent or divalent fluorooxyalkylene group-containing polymer residue) and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group having no polar group, and two or more hydrolyzable silyl groups such as an alkoxysilyl group or a hydroxyl group-containing silyl group are present in the molecule, and the hydrolyzable group is present.
• a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group i.e., a monovalent or divalent fluorooxyalkylene group-containing polymer residue
• a hydrolyzable silyl group such as an alkoxysilyl group or a
• the main chain structure is composed of a group represented by -(C 3 F 6 O) d - (repeating unit C 3 F 6 O has a branched structure, and d is an integer of 2 to 200), which is characterized by a high coefficient of friction (hard to slip).
• Rf1 is -(C 3 F. 6 O) d - (repeating unit C 3 F. 6 ⁇ is -CF (CF 3 ) CF 2 It consists of a branched structure represented by O-- (that is, a repeating unit structure in which hexafluoropropylene oxide is ring-opened), and d is an integer of 2-200, preferably an integer of 8-60. ) is a monovalent or divalent fluorooxyalkylene group-containing polymer residue containing a group represented by (a repeating structure of hexafluoropropylene oxide) as a main structure. 5) is preferably a divalent fluoropolyether group.
• A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group having a terminal —CF3 group
• p is an integer of 1 to 200
• q and r are each an integer of 1 to 199
• q+r is an integer of 2 to 398.
• A is a fluorine atom , a hydrogen atom , or a fluoroalkyl group having a terminal —CF 3 group .
• CF2CF2OCF2CFH- CF3OCF2CF2CF2OCF2CFH- and the like , preferably CF3CF2CF2- .
• p is an integer of 1-200, preferably an integer of 3-100, more preferably an integer of 5-50.
• p is the above upper limit or less, adhesion and curability are good, and handling is easy.
• q+r is equal to or less than the above upper limit value, adhesion and curability are good, and handling is easy.
• Rf1 examples include the following. (In the formula, p1 is an integer of 1 to 199, preferably an integer of 3 to 100, and q and r are the same as above.)
• V is a monovalent group independently having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal and having no polar group, preferably a monovalent group consisting of a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal and a linking group having no polar group that connects the silyl group and the CH group, more preferably a monovalent organic group into which a plurality of hydroxyl groups or hydrolyzable groups bonded to silicon atoms are introduced at the terminal.
• Such V is preferably -LY-(Si(R) 3-n (X) n ) m in formula (3) described later (wherein L is a single bond or a divalent hetero atom, Y is a silicon atom and/or a divalent to hexavalent hydrocarbon group optionally having a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 5), and examples thereof include groups represented by the following formulas (6a) to (6e).
• L is a single bond or a divalent heteroatom
• D is an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms
• R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
• X is independently a hydroxyl group or a hydrolyzable group
• n is an integer of 1 to 3
• a is an integer of 2 to 6
• b is independently an integer of 1 to 10
• c is an integer of 1 to 50.
• L is a single bond or a divalent heteroatom
• the divalent heteroatom includes an oxygen atom, a nitrogen atom, and a sulfur atom.
• one of the two Ls present in the two Vs is a single bond, and the other L is preferably a divalent heteroatom.
• D is an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, which may be optionally fluorine-substituted.
• An alkylene group such as an octamethylene group, an arylene group such as a phenylene group, a combination of two or more of these groups (such as an alkylene-arylene group), and the like, and those in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms.
• D is preferably an ethylene group, a propylene group, a butylene group, a hexamethylene group, or a phenylene group.
• R is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl, or a phenyl group, preferably methyl group.
• X is a hydroxyl group or a hydrolyzable group which may be different from each other.
• Examples of such X include alkoxy groups having 1 to 10 carbon atoms such as hydroxyl, methoxy, ethoxy, propoxy, isopropoxy and butoxy groups, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups, acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups, alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy groups, and halogen groups such as chloro, bromo and iodine groups. . Among them, methoxy group, ethoxy group, isopropenoxy group and chloro group are preferable.
• n is an integer of 1 to 3, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.
• a is an integer of 2-6, preferably 2-4;
• b is independently an integer of 1-10, preferably 3-6;
• c is an integer of 1-50, preferably 1-9.
• ⁇ is 1 or 2, preferably 1.
• the fluoropolyether group-containing polymer of formula (1) is represented by the following general formula (3).
• Rf1, L, R, X, n, and ⁇ are the same as above, and Y is independently a divalent to hexavalent hydrocarbon group, which may have a silicon atom and/or a siloxane bond.
• m is an integer of 1 to 5.
• L is independently a single bond or a divalent heteroatom in the same manner as L described above, and the divalent heteroatom includes an oxygen atom, a nitrogen atom, and a sulfur atom.
• the divalent heteroatom includes an oxygen atom, a nitrogen atom, and a sulfur atom.
• one L is an oxygen atom and the other L is a single bond at each end of the molecular chain. is desirable.
• Y is independently a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may have a silicon atom and/or a siloxane bond. By not including a polar group in the molecule, a coating film with excellent water and oil repellency can be obtained.
• Y is preferably a divalent to hexavalent hydrocarbon group including the above D (an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms).
• the above D preferably an alkylene group having 3 to 10 carbon atoms such as a propylene group, a butylene group, and a hexamethylene group, an alkylene group including an arylene group having 6 to 8 carbon atoms such as a phenylene group (for example, an alkylene arylene group having 8 to 16 carbon atoms), a divalent group in which the above D and an alkylene group, preferably an alkylene group, are bonded to each other via a silalkylene structure or a silarylene structure, 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms.
• an alkylene group having 3 to 10 carbon atoms such as a propylene group, a butylene group, and a hexamethylene group
• an alkylene group including an arylene group having 6 to 8 carbon atoms such as a phenylene group (for example, an alkylene arylene group having 8 to 16 carbon atoms)
• D preferably a divalent to hexavalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of one linear, branched or cyclic divalent to hexavalent organopolysiloxane residue, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group containing a phenylene group, a divalent group in which the alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure, a straight chain having 2 to 10 silicon atoms or a branched group having 3 to 10 silicon atoms, or It is a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a cyclic divalent to tetravalent organopolysiloxane residue, and more preferably an alkylene group having 3 to 6 carbon atoms.
• R 1 is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, and an aryl group having 6 to 10 carbon atoms such as phenyl group, and R 1 may be the same or different.
• R 2 is an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group and propylene group (trimethylene group, methylethylene group), and an arylene group having 6 to 10 carbon atoms such as phenylene group.
• linear, branched or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10, preferably 2 to 5, silicon atoms are shown below.
• R 1 is the same as above, g is an integer of 1 to 9, preferably 1 to 4, h is an integer of 2 to 6, preferably 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.
• Examples of Y include groups represented by the following formulae. (Wherein, D, a, and b are the same as above, and c' is an integer of 1 to 9.)
• Y include the following groups.
• n is an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate decreases, and if it is 6 or more, the terminal alkoxy value is too high and adversely affects the performance.
• fluoropolyether group-containing polymer represented by the formula (3) examples include those represented by the following formula.
• Component (II) is, as described above, a fluoropolyether group-containing polymer represented by the following general formula (2).
• the repeating unit C3F6O contained in the main chain structure has a branched structure, and the polymer of the formula (1), which is the component (I), has high compatibility and large interaction. Moreover, since it does not have a reactive functional group, it does not form a chemical bond between polymers or with a substrate. Therefore, the prevention of excessive condensation of component (I) improves the stability, and the lubricating effect improves wear durability.
• z is an integer that makes the weight average molecular weight of the fluoropolyether group-containing polymer 1,500 to 20,000.
• W is independently a fluorine atom , a hydrogen atom , or a fluoroalkyl group having a terminal -CF3 group
• the fluoroalkyl groups having a terminal -CF3 group include CF3CF2CF2CF2- , CF3CF2CF2- , CF3CF2- , CF3- , CF3OCF2CFH- , and CF.
• W is preferably a fluorine atom or CF3-
• Rf2 contains a group represented by -( C3F6O ) d'- as a main structure
• W is preferably a fluorine atom or CF3-
• Rf2 contains a group represented by -( C3F6O ) e ( CF20 ) f- as a main structure
• W is preferably a fluorine atom or CF3- .
• the fluoropolyether group-containing polymer represented by the formula (2) preferably has a weight average molecular weight of 1,500 to 20,000, preferably 2,500 to 12,000. If the weight-average molecular weight is less than 1,500, it may be difficult to obtain the effect of improving the abrasion resistance of the cured film, and if it exceeds 20,000, the coefficient of dynamic friction of the cured film may be remarkably lowered.
• the weight average molecular weight is a value measured as a polyethylene-equivalent weight average molecular weight in molecular weight distribution measurement by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent (hereinafter the same).
• fluoropolyether group-containing polymer represented by the formula (2) which is the component (II) of the present invention
• compounds represented by the following formulas are preferably used.
• x and y are integers of 1 or more
• x + y and z are integers that make the weight average molecular weight of the fluoropolyether group-containing polymer 1,500 to 20,000.
• Each repeating unit shown in parentheses with x and y may be randomly combined.
• FOMBLIN Y (trade name manufactured by Solvay Solexis, FOMBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100)
• KRYTOX trade name manufactured by DuPont
• KRYTOX 143AB weight average molecular weight: 3,500
• KRYTOX 143AX weight average molecular weight: 4,700
• KRYTOX 143AC weight average molecular weight: 5,500
• KRYTOX 143AD (weight average molecular weight: 7,000)
• the fluoropolyether group-containing polymer composition of the present invention can contain optional components within a range that does not impair the object of the present invention.
• this optional component include hydrocarbon oils, silicone oils, silane coupling agents, surfactants, and the like.
• the present invention provides a coating agent containing a fluoropolyether group-containing polymer composition containing a fluoropolyether group-containing polymer having a hydroxyl group-containing silyl group or a hydrolyzable silyl group represented by formula (1), particularly a fluoropolyether group-containing polymer having a hydroxyl group-containing silyl group or a hydrolyzable silyl group represented by formula (3), and a fluoropolyether group-containing polymer having no hydroxyl group-containing silyl group or hydrolyzable silyl group represented by formula (2), in a specific ratio. do.
• the coating agent may contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by the formula (1) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance by a known method.
• a hydrolytic condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added to the coating agent.
• acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acids, and the like are particularly desirable.
• the amount of the hydrolytic condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer and/or partial (hydrolytic) condensate thereof as component (I) of the present invention.
• the coating agent may contain a suitable solvent.
• suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methylperfluorobutyl ether, ethylperfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), Ton-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified.
• fluorine-modified solvents are desirable in terms of solubility and wettability, and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.
• the optimum concentration of the fluoropolyether group-containing polymer composition of the present invention to be dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to weigh. In the case of direct coating, it is preferably 0.01 to 10 parts by mass (concentration 0.01 to 10% by mass), particularly 0.05 to 5 parts by mass (concentration 0.05 to 5% by mass). It is preferably 1 to 50 parts by mass (concentration of 1 to 50% by mass), particularly preferably 3 to 30 parts by mass (concentration of 3 to 30% by mass), per 100 parts by mass of the polyether group-containing polymer composition.
• the coating agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and vapor deposition.
• a heating method during vapor deposition may be either a resistance heating method or an electron beam heating method, and is not particularly limited.
• the curing temperature is preferably 25 to 200°C.
• the temperature is preferably 40 to 120° C. for 30 minutes to 36 hours, particularly 1 to 24 hours.
• the film thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.
• spray coating for example, if the material is diluted with a fluorine-based solvent to which water has been added in advance, hydrolyzed, that is, Si--OH is generated, and then sprayed, curing after coating is accelerated.
• Substrates to be treated with the coating agent of the present invention are not particularly limited, and may be of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz.
• the coating agent of the present invention can impart water and oil repellency and steel wool abrasion resistance to the substrate. In particular, it can be suitably used as a coating agent for glass or film treated with SiO 2 .
• the articles to be treated with the coating agent of the present invention include optical articles such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio players, game machines, spectacle lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastrocameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films.
• optical articles such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio players, game machines, spectacle lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastrocameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films.
• the coating agent of the present invention can prevent fingerprints and sebum from adhering to the article, and can further impart scratch resistance (wear resistance), so it is particularly useful as a water- and oil-repellent layer for mobile phones, smartphones, PC housings, etc.
• the coating agent of the present invention is used as an antifouling coating for sanitary products such as bathtubs and washbasins, antifouling coatings for window glass or tempered glass for automobiles, trains, aircraft, etc., antifouling coatings for headlamp covers, etc., water and oil repellent coatings for building materials for exterior walls, anti-oil stain coatings for kitchen building materials, antifouling and anti-sticker/graffiti coatings for telephone boxes, anti-fingerprint coatings for works of art, anti-fingerprint coatings for compact discs, DVDs, etc., release agents or paint additives for molds, and resin modifiers.
• sanitary products such as bathtubs and washbasins, antifouling coatings for window glass or tempered glass for automobiles, trains, aircraft, etc., antifouling coatings for headlamp covers, etc., water and oil repellent coatings for building materials for exterior walls, anti-oil stain coatings for kitchen building materials, antifouling and anti-sticker/graffiti coatings
• the present invention by forming a layer of the cured coating agent of the present invention on the surface of the article, it is possible to modify the surface, specifically to prevent the adhesion of fingerprints and sebum, and to impart scratch resistance (abrasion resistance). That is, according to the present invention, it is possible to provide a method for modifying the surface of an article, which comprises the step of applying a coating agent containing the fluoropolyether group-containing polymer composition of the present invention to the entire surface or part of the article by a dry method or a wet method, and curing the coating to form a layer.
• the polymer composition was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a coating agent.
• 6 ⁇ l of each coating agent was vacuum-deposited on a glass (Gorilla manufactured by Corning Inc.) treated with 10 nm of SiO 2 on the outermost surface (treatment conditions: pressure: 3.0 ⁇ 10 ⁇ 3 Pa, heating temperature: 500° C.), allowed to stand in an atmosphere of 80° C. and humidity of 80% for 30 minutes, and then cured in an atmosphere of 25° C. and humidity of 50% for 12 hours or more to form a cured film with a thickness of 13 nm.
• the dynamic friction coefficient is 0.2 or more and ⁇ (excellent), 0.15 or more and less than 0.2 is ⁇ (good), 0.1 or more and less than 0.15 is ⁇ (acceptable), and less than 0.1 is x (improper), and shown in Tables 1 to 3.
• the number of abrasion reciprocations that maintains a water contact angle of 100° or more is defined as the steel wool abrasion durability number, and the steel wool abrasion durability number is 20,000 times as ⁇ (excellent), 10,000 times or more and less than 20,000 times as ⁇ (good), 5,000 times or more and less than 10,000 times as ⁇ (acceptable), and less than 5,000 times as x (improper), as shown in Tables 1 to 3.
• the test environmental conditions are 25° C. and 50% humidity.

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