Classifications

• • 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
  • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

• the present invention relates to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer (a compound having a fluoropolyether group in the molecule), and more specifically to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface peelability and eraser abrasion resistance, a surface treatment agent containing the fluorine-containing ether composition, and an article surface-treated with the surface treatment agent.
• a fluorine-containing ether composition containing a fluoropolyether group-containing polymer (a compound having a fluoropolyether group in the molecule)
• touch panels have exposed screens and are often in direct contact with fingers or cheeks, which makes them susceptible to dirt such as sebum.
• the surface of touch panel displays is prone to fingerprints, there is a demand for the provision of a water- and oil-repellent layer.
• conventional water- and oil-repellent layers are highly water- and oil-repellent and easy to wipe off, there is a problem in that their anti-fouling performance deteriorates during use.
• fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and although they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.
• silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates.
• Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule.
• the hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating.
• the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc., resulting in a strong, durable coating.
• compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, and that can form coatings on the substrate surface that are easily adhered to the substrate surface and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).
• Patent Document 7 International Publication No. 2021/054202.
• Patent Document 7 International Publication No. 2021/054202
• the present invention has been made in consideration of the above circumstances, and aims to provide a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or a partial (hydrolyzed) condensate thereof, capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface peelability and eraser abrasion resistance, a surface treatment agent containing the fluorine-containing ether composition, and an article surface-treated with the surface treatment agent.
• a surface treatment agent containing a fluorine-containing composition containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof in which a hydrolyzable silyl group has been introduced into a fluoropolyether group-containing compound and/or a surface treatment agent containing a fluorine-containing composition containing a partial (hydrolyzed) condensate thereof, can form a cured coating having high performance in terms of water and oil repellency, heat resistance, and abrasion resistance, by considering the molar ratio in the composition of the fluoropolyether group contained in the fluoropolyether group-containing compound, particularly the fluorooxymethylene group and the fluorooxyethylene group adjacent to the terminal fluorooxyalkyl group.
• a surface treatment agent containing a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or a partial (hydrolyzed) condensate thereof which is represented by the average composition formula (1) described below, in which the molar ratio of the terminal groups fluorooxymethyl group and fluorooxyethyl group is within a specific range, can form a cured coating that is water- and oil-repellent, as well as excellent stain resistance, heat resistance, surface peelability, and eraser abrasion resistance, and have been able to complete the present invention.
• a fluorine-containing ether composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the following average composition formula (1), and/or a partial (hydrolyzed) condensate thereof:
• RF 1 is CF 3 O- or CF 3 CF 2 O-
• the molar ratio of CF 3 O- to CF 3 CF 2 O- (CF 3 CF 2 O-/CF 3 O-) is 0.01 or more and 0.17 or less
• RF 2 is --CF 2 O- or --CF 2 CF 2 O-
• Rf is a group represented by the following formula (2):
• W is a fluoroalkylene group containing one or more hydrogen atoms.
• d is an integer of 1 to 6.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.
• U is a single bond or a divalent to pentavalent organic group
• Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom
• -SiR' (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group
• Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and 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
• a is independently 2 or 3 for each unit bonded to a silicon atom
• b is independently an integer of 1 to 8
• c is an integer of 1 to 4.
• U is a single bond, a carbonyl group, an amide group, a group represented by the following formula:
• B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group
• B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• a di- to pentavalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group.
• Y is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups having 1 to 10 carbon atoms and containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.
• d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) is a divalent fluoropolyether group represented by the following formula: [8] The fluorine-containing ether composition according to any one of [1] to [7], further comprising 30 mass% or less of a fluoropolyether group-containing polymer represented by the following general formula (5): A-Rf'-A (5) In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group having a terminal group of CF 3 —, CF 2 H—, CF 3 CF 2 —, or CF 3 CFH— and which may contain an oxygen atom.
• Rf′ is a group represented by the following formula (4): (In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.
• the fluorine-containing ether composition of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, and is represented by the above average composition formula (1) taking into account the molar ratio of the terminal groups, fluorooxymethyl group and fluorooxyethyl group, and/or a partial (hydrolyzed) condensate thereof.
• An article that has been surface-treated with a surface treatment agent containing the fluorine-containing ether composition has improved properties in terms of water and oil repellency, as well as stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.
• the number average molecular weight (Mn) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or its partial (hydrolyzed) condensate, or the fluorinated ether composition can be calculated from the characteristic peak intensity ratio of 19F -NMR analysis.
• the "partial (hydrolyzed) condensate" of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group is obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer having a silanol group, or the hydroxyl groups of the fluoropolyether group-containing polymer having a hydrolyzable silyl group, which have been partially hydrolyzed in advance by a known method.
• the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one terminal, represented by the following average composition formula (1), and/or a partial (hydrolyzed) condensate thereof:
• RF 1 is CF 3 O- or CF 3 CF 2 O-
• the molar ratio of CF 3 O- to CF 3 CF 2 O- (CF 3 CF 2 O-/CF 3 O-) is 0.01 or more and 0.17 or less
• RF 2 is --CF 2 O- or --CF 2 CF 2 O-
• Rf is a group represented by the following formula (2):
• W is a fluoroalkylene group containing one or more hydrogen atoms.
• d is an integer of 1 to 6.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.
• U is a single bond or a divalent to pentavalent organic group
• Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom
• -SiR' (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group
• Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and 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
• a is independently 2 or 3 for each unit bonded to a silicon atom
• b is independently an integer of 1 to 8
• c is an integer of 1 to 4.
• RF 1 is CF 3 O- or CF 3 CF 2 O-
• the molar ratio of CF 3 O- to CF 3 CF 2 O- is 0.01 or more and 0.17 or less, more preferably 0.04 or more and 0.16 or less. If the molar ratio is less than 0.01, the resulting cured coating cannot maintain high heat resistance. If it exceeds 0.17, the antifouling performance and eraser abrasion durability of the resulting cured coating are reduced.
• the resulting cured coating can simultaneously exhibit all the required characteristics of antifouling, heat resistance, surface peelability, and eraser abrasion durability.
• the molar ratio can be calculated from the characteristic peak intensity ratio of 19 F-NMR analysis.
• RF2 is -CF2O- or -CF2CF2O-
• the molar ratio of -CF2O- to -CF2CF2O- is preferably 1.05 or more and 1.2 or less, more preferably 1.1 or more and less than 1.2. If the molar ratio is less than 1.05, the heat resistance of the obtained cured coating may decrease, and if it exceeds 1.2, the release properties of the surface of the obtained cured coating may decrease.
• the molar ratio can be calculated from the characteristic peak intensity ratio of 19F -NMR analysis.
• Rf is a divalent fluoropolyether group represented by the following formula (2).
• W is a fluoroalkylene group containing one or more hydrogen atoms.
• d is an integer of 1 to 6.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.
• W is a fluoroalkylene group containing one or more hydrogen atoms, and examples thereof include perfluoroalkylene groups such as CF2 , C2F4 , C3F6 , C4F8 , C5F10 , and C6F12 , in which one or two fluorine atoms are replaced by hydrogen atoms.
• d is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.
• p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably p is an integer of 5 to 440, q is an integer of 5 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and p+q+r+s+t+u+v is 10 to 450, preferably 20 to 200, and p+q is 20 to 450, particularly preferably 20 to 200.
• each unit may be linear or branched.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.
• Rf examples include the following.
• p', q', and r' are each an integer of 1 or more, the upper limit of which is the same as the upper limit of p, q, and r above, and the sum of p', q', and r' is 20 to 450.
• each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• U is a single bond or a divalent to pentavalent organic group, and is preferably a single bond, a carbonyl group, an amide group, or a group represented by the following formula:
• B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group
• B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for B and B' include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, and thexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, and propenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups.
• the monovalent polyether group for B those represented by the formula --(C e1 H 2e1 O) e --CH 3 (e1 is an integer of 1 to 6, and e is
• Examples of the linear divalent organopolysiloxane residue having 2 to 100, preferably 2 to 50, silicon atoms which may be contained in the divalent to pentavalent hydrocarbon group include those shown below.
• R 1 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group, and R 1 may be the same or different.
• g is an integer of 1 to 99, preferably an integer of 1 to 49.
• silalkylene group and silarylene group examples include those shown below.
• R 1 is the same as above, and R 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.
• U examples include the following groups in addition to a single bond: It is preferable that the left bond is bonded to Rf and the other bond is bonded to Z. (In the formula, f is independently an integer of 1 to 4, l1 and l2 are integers of 1 to 4, n is an integer of 1 to 100, and e is an integer of 1 to 30.)
• Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom
• -SiR' (R' is an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group), or a trivalent to nonavalent, preferably trivalent to heptavalent, organic group, preferably a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanuric group or a trivalent triazine ring-containing group.
• Examples of the linear, branched or cyclic tri- to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms include those represented by the following general formula: [In the formula, R 1 and R 2 are the same as above, and R 1 and R 2 may be the same or different.
• R 3 independently represents R 1 or a group represented by the following general formula (6): (In the formula, R 1 is the same as above, and R 1 may be the same or different.
• m8 is an integer of 1 to 6, preferably 1, and the left bond is bonded to Si.)
• At least one of R3 is represented by formula (6).
• R4 is independently a single bond or a group represented by the following general formula (7): (In the formula, R 2 and R 3 are the same as above, and R 2 and R 3 may be the same or different.
• m9 is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 1.
• m10 is an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and m9+m10 ⁇ 0.
• Each repeating unit shown in parentheses may be bonded randomly.
• m1 is an integer of 1 to 9, preferably an integer of 1 to 4
• m2 is an integer of 0 to 9, preferably an integer of 0 to 3
• m3 is an integer of 2 to 6, preferably an integer of 3 to 5
• m4 is an integer of 0 to 8, preferably 0 or 1
• m3+m4 is an integer of 3 to 10, preferably an integer of 3 to 5
• m5 is 2 or 3
• m6 is an integer of 3 to 9, preferably an integer of 3 to 7
• m7 is an integer of 0 to 9, preferably an integer of 0 to 3, and each repeating unit shown in parentheses may be bonded randomly.
• the number of silicon atoms in each organopolysiloxane residue is 3 to 13.]
• Z examples include the following groups in addition to a single bond: It is preferable that the left bond is bonded to U, and the other bond is bonded to Y.
• b is independently an integer from 1 to 8, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3, and c is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 or 2.
• Y is a divalent hydrocarbon group which may have one or more independently selected from fluorine atoms, silicon atoms, and siloxane bonds.
• the divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds include alkylene groups having 1 to 10 carbon atoms, such as methylene groups, ethylene groups, propylene groups, butylene groups, hexylene groups, and octylene groups, alkylene groups having 1 to 10 carbon atoms and containing fluorine atoms, It is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene groups having 1
• examples of the silalkylene group and silarylene group include those similar to those shown for U.
• examples of the divalent organopolysiloxane residue which is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms include those shown below.
• R 1 is the same as above, and R 1 may be the same or different.
• g1 is an integer of 1 to 9, preferably an integer of 1 to 3
• g2 is an integer of 1 to 8, preferably an integer of 1 to 3.
• Y include the following: In the following structure, it is preferable that the left bond is bonded to Z and the right bond is bonded to Si.
• 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 group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy group and propionoxy group; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy group, allyloxy group, propenoxy group, and isopropenoxy group; and halogen groups, such as chlorine group, bromo group, and iodo group.
• R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, of which the methyl group and the ethyl group are preferred.
• a is independently 2 or 3 for each unit bonded to a silicon atom, with 3 being preferred from the standpoint of reactivity and adhesion to the substrate.
• the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end may have the following structure.
• Rf, U, Z, Y, R, X, and a in the above formula (1) several types of fluoropolyether group-containing polymers having a silanol group or a hydrolyzable silyl group at one end can be obtained.
• RF 1 and RF 2 are the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1 + q1 is an integer of 20 to 450, and each repeating unit shown in parentheses with p1 and q1 may be randomly bonded.
• Examples of methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), include those described in Japanese Patent No. 6451279, Japanese Patent No. 6119656, Japanese Patent No. 6828744, Japanese Patent No. 6524955, and Japanese Patent No. 6521091, and further include the following methods.
• a fluoropolyether group-containing polymer having an olefin moiety is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.) is mixed, and aged for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C.
• a hydrosilylation reaction catalyst for example, a toluene solution of a chloroplatinic acid/vinylsiloxane complex
• the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.
• the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) can be exemplified by the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the following average composition formula (8) or (9).
• RF 1 , RF 2 , Rf, U, Z, b, and c are the same as above, and U′ is a divalent to pentavalent, preferably divalent or trivalent, hydrocarbon group having 1 to 18 carbon atoms which may contain an ether group.
• U' is a divalent to pentavalent, preferably divalent or trivalent, hydrocarbon group having 1 to 18 carbon atoms which may contain an ether group. Specific examples include those shown below. (In the formula, l1 is an integer of 1 to 4, l2' is an integer of 0 to 2, and f' is independently an integer of 0 to 2.)
• fluoropolyether group-containing polymer having an olefin moiety represented by the above average composition formula (8) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)
• fluoropolyether group-containing polymer having an olefin moiety represented by the above average composition formula (9) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)
• Y 1 include the following groups.
• Examples of the compound represented by the above general formula (10) include the following.
• the amount of the organosilicon compound used when reacting a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) with an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group is such that the amount of SiH group in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents per equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.
• a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (8) is used as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group)
• a compound represented by the above general formula (10) is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group
• a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (9) is used as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group)
• a compound represented by the above general formula (11) is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group.
• the solvent may be, for example, a fluorine-based solvent.
• fluorine-based solvent examples include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, product name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, product name: Fluorinert series).
• HFE hydrofluoroether
• the amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).
• examples of the hydrosilylation reaction catalyst include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, etc. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
• the amount of the hydrosilylation catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass) based on the mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).
• the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.
• reagents that can be used when converting the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol.
• the amount of the compound used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, based on 100 parts by mass of an addition reaction product of a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group) in the molecule.
• a fluoropolyether group-containing polymer having an olefin moiety is a compound represented by the following formula: and when trimethoxysilane is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.
• a fluoropolyether group-containing polymer having a SiH group is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having, for example, an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.), and aged for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours, in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid/vinylsiloxane complex, at a temperature of 40
• the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.
• fluoropolyether group-containing polymer having a SiH group is a compound represented by the following average composition formula (12). (In the formula, RF 1 , RF 2 , Rf, U, Z, b, and c are the same as above.)
• Examples of the compound represented by the above average composition formula (12) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)
• An example of an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group is a compound represented by the following general formula (13).
• R, X, and a are the same as above.
• Y2 is a monovalent hydrocarbon group having an alkenyl group at the terminal and which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.
• Y2 is a monovalent hydrocarbon group which has an alkenyl group at its terminal and which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, and examples of such a monovalent hydrocarbon group include those represented by the following formula:
• Examples of the compound represented by the above general formula (13) include the following.
• the amount of the organosilicon compound used when reacting the fluoropolyether group-containing polymer having a SiH group with an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group can be such that the amount of the olefin moiety (alkenyl group) in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents, per equivalent of the SiH group in the fluoropolyether group-containing polymer.
• the solvent may be, for example, a fluorine-based solvent.
• the fluorine-based solvent include the same ones as those exemplified in Preparation method 1.
• the amount of the solvent used may be 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having SiH groups.
• examples of the hydrosilylation reaction catalyst include those similar to those exemplified in Preparation Method 1. Preferred are platinum-based compounds such as vinylsiloxane coordination compounds.
• the amount of the hydrosilylation catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass) based on the mass of the fluoropolyether group-containing polymer having SiH groups.
• the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group, and examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include those similar to those exemplified in Preparation Method 1.
• the amount used may also be the same as in Preparation Method 1.
• the fluoropolyether group-containing polymer having a SiH group may be a compound represented by the following formula: and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.
• the compound represented by the above formula is used as the fluoropolyether group-containing polymer having a SiH group, and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, the compound represented by the following formula is obtained.
• the number average molecular weight of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate represented by the above average composition formula (1) is preferably 1,000 to 53,000, more preferably 2,000 to 23,000, even more preferably 2,500 to 13,000, and particularly preferably 3,000 to 8,300. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may decrease, and if it exceeds 53,000, the surface properties of the resulting cured coating may become unstable.
• the above number average molecular weight can be achieved by rectification or molecular distillation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate represented by the above average composition formula (1).
• the amount of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate, represented by the above-mentioned average composition formula (1), in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer), is preferably 70 to 100 mass %, more preferably 80 to 100 mass %. If it is less than 70 mass %, the heat resistance decreases, and it may not be possible to obtain a cured coating that has both stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.
• the fluorine-containing ether composition of the present invention may further contain, if necessary, a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and/or a partial (hydrolyzed) condensate thereof (polymer containing functional fluoropolyether groups at both ends), which has the effect of further improving heat resistance.
• a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends represented by the following general formula (3), and/or a partial (hydrolyzed) condensate thereof (polymer containing functional fluoropolyether groups at both ends), which has the effect of further improving heat resistance.
• Rf′ is represented by the following formula (4):
• W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above.
• d' is an integer of 1 to 6.
• Each of these units may be linear or branched.
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.
• Rf' is a divalent fluoropolyether group represented by the above formula (4)
• W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v in formula (4) can be exemplified as those exemplified for Rf in the above formula (1).
• d' is an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1 or 2.
• Rf' include the following.
• p', q', and r' are each integers of 1 or more, the upper limit of which is the same as the upper limit of p, q, and r above, and the sum of p', q', and r' is 20 to 450.
• r2' and r3' are each integers of 1 or more, and the sum of r2' and r3' is 35 to 180.
• each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• Examples of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends represented by the general formula (3) include the following. (In the formula, p2 is an integer of 5 to 440, q2 is an integer of 5 to 250, and p2+q2 is an integer of 20 to 450, and each repeating unit shown in parentheses with p2 and q2 may be randomly bonded.)
• the number average molecular weight of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate represented by the above general formula (3) is preferably 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,600 to 16,000, and particularly preferably 3,100 to 14,000. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may decrease, and if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable.
• the above number average molecular weight can be achieved by rectification or molecular distillation of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate represented by the above general formula (3).
• the amount of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate (both-end functional fluoropolyether group-containing polymer) represented by the general formula (3) is preferably 0 to 25 mass %, particularly 0 to 15 mass %, in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer).
• the surface peelability decreases, and it may not be possible to obtain a cured coating that has both antifouling properties, heat resistance, surface peelability, and eraser abrasion resistance.
• it is preferably 5 mass % or more, particularly 8 mass % or more in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer).
• the fluorine-containing ether composition of the present invention may further contain a fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the following general formula (5) if necessary, which can further improve the surface peelability.
• a fluoropolyether group-containing polymer represented by the following general formula (5) if necessary, which can further improve the surface peelability.
• A-Rf'-A (5) ( In the formula, Rf' is the same as defined above.
• A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group which terminates in CF3- , CF2H- , CF3CF2- , or CF3CFH- and which may contain an oxygen atom.)
• Rf' is the same as Rf' in the above formula (3), and examples of Rf' include those similar to those exemplified as Rf' (the divalent fluoropolyether group represented by formula (4)). Rf' may be the same as or different from Rf' in formula (3).
• A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- , CF2H- , CF3CF2- , or CF3CFH- and which may contain an oxygen atom , and specific examples include a fluorine atom, a hydrogen atom, CF3- , CF2H- , CF2CF3- , CF3CFH- , CF3O- , CF3CF2O- , etc.
• Examples of the fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the general formula (5) include the following. (In the formula, p3, q3, and r3 are each independently an integer of 0 to 450, the sum of p3, q3, and r3 is 20 to 450, and r4 and r5 are each an integer of 20 to 450. Each repeating unit shown in parentheses with p3, q3, and r3 may be bonded randomly.)
• the number average molecular weight of the fluoropolyether group-containing polymer represented by the above general formula (5) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, even more preferably 2,500 to 10,000, and particularly preferably 3,000 to 8,000. If the number average molecular weight is less than 1,000, the fluoropolyether group-containing polymer represented by the above formula (5) in the obtained cured coating may volatilize in a heating environment, and if it exceeds 50,000, the surface properties of the obtained cured coating may become unstable.
• the above number average molecular weight can be obtained by rectifying or molecular distilling the fluoropolyether group-containing polymer represented by the above general formula (5).
• the amount of the fluoropolyether group-containing polymer (nonfunctional fluoropolyether group-containing polymer) represented by general formula (5) is desirably 0 to 30 mass %, and especially 0 to 20 mass %, in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers). If it exceeds 30 mass %, the eraser abrasion resistance decreases, and it may not be possible to obtain a cured coating that has both stain resistance, heat resistance, surface peelability, and eraser abrasion resistance. If it is added, it is preferably 0.1 mass % or more, and especially 1 mass % or more in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers).
• the fluorine-containing ether composition of the present invention can be prepared by uniformly mixing predetermined amounts of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or a partial (hydrolyzed) condensate thereof, which is represented by the above-mentioned average composition formula (1), and, if necessary, a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at both ends and/or a partial (hydrolyzed) condensate thereof, which is represented by the general formula (3), or a fluoropolyether group-containing polymer represented by the general formula (5), in accordance with a conventional method.
• the fluorine-containing ether composition of the present invention preferably has a number average molecular weight of 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,500 to 16,000, and particularly preferably 3,000 to 8,600. If the number average molecular weight is less than 1,000, the stain resistance and heat resistance of the resulting cured coating may decrease, and if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable.
• the above number average molecular weight can be achieved by rectifying or molecular distilling the fluorine-containing ether composition.
• the present invention further provides a surface treatment agent comprising the above fluorinated ether composition.
• the surface treatment agent may contain a hydrolysis condensation catalyst, for example, an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium 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.).
• a hydrolysis condensation catalyst for example, an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an in
• acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferable.
• the amount of the hydrolysis and 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 fluorine-containing ether composition (particularly the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group in the composition and/or its partial (hydrolysis) condensate).
• the surface treatment agent may contain a suitable solvent.
• suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropene trimer, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether,
• fluorine-modified solvents are preferable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are particularly preferable.
• the optimal concentration of the fluorinated ether composition to be dissolved in the solvent varies depending on the processing method, and may be any amount that is easy to weigh. In the case of direct coating, however, it is preferable that the concentration is 0.01 to 10 parts by mass, and particularly 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluorinated ether composition in total, and in the case of vapor deposition processing, it is preferable that the concentration is 1 to 100 parts by mass, and particularly 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluorinated ether composition in total.
• the surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition.
• the heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited.
• the curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferable to apply the agent at 25 to 200°C, especially 25 to 150°C, for 30 minutes to 36 hours, especially 1 to 18 hours. Furthermore, when applying the agent by vapor deposition, it is preferable to apply the agent at a temperature in the range of 20 to 200°C for 1 to 24 hours. It may also be cured under humidification.
• the agent in the case of spray coating, is diluted in a fluorine-based solvent to which moisture has been added beforehand, and then hydrolyzed, i.e., Si-OH is generated, and then spray coating is performed, which results in rapid curing after coating.
• the thickness of the cured coating is selected appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 20 nm.
• the thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.
• the substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc.
• the surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO2- treated glass or film.
• Articles that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films and other optical articles.
• the surface treatment agent of the present invention can prevent the adhesion of fingerprints and sebum to the above-mentioned articles and can also impart scratch resistance, making it particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflective films and the like.
• the surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, as an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc., as a water- and oil-repellent coating for exterior wall building materials, as a coating to prevent oil stains for kitchen building materials, as an anti-fouling and anti-posting/anti-graffiti coating for telephone booths, as a coating to prevent fingerprints from adhering to artworks, etc., as a fingerprint-preventing coating for compact discs, DVDs, etc., as a release agent or paint additive for molds, as a resin modifier, as a flowability modifier or dispersibility modifier for inorganic fillers, and as a lubricity improver for tapes, films, etc.
• the surface treatment agent of the present invention can impart a cured coating that is excellent in water and oil repellency, as well as stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.
• the present invention will be described in more detail below with reference to synthesis examples, working examples, and comparative examples, but the present invention is not limited to the following working examples.
• the repeating units shown in parentheses with p1 and q1, p2 and q2, and p3 and q3 are randomly bonded.
• the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
• the number average molecular weights (Mn) of the fluoropolyether group-containing polymer and the fluorinated ether composition are values calculated from the characteristic peak intensity ratios of the terminal structure and main chain structure of the fluoropolyether group-containing polymer based on 1 H-NMR analysis and 19 F-NMR analysis.
• the RF1 molar ratio (CF 3 CF 2 O-/CF 3 O-), RF2 molar ratio (-CF 2 CF 2 O-/-CF 2 O-), p1, q1, p2, q2, p3, and q3 were calculated from the characteristic peak intensity ratios of 19 F-NMR analysis.
• the obtained product was confirmed to be a compound represented by the average composition formula (VII-c) below by 1 H-NMR.
• the RF 1 molar ratio and RF 2 molar ratio in formula (VII-c) were the same as the RF 1 molar ratio and RF 2 molar ratio in raw material polymer D.
• the obtained product was confirmed by 1 H-NMR to be a polymer containing a functional fluoropolyether group at one end represented by the following average composition formula (VII).
• the RF 1 molar ratio and RF 2 molar ratio in formula (VII) were the same as the RF 1 molar ratio and RF 2 molar ratio in raw material polymer D.
• the number average molecular weight was 6,490.
• non-functional fluoropolyether polymer As a non-functional fluoropolyether polymer, a non-functional fluoropolyether group-containing polymer L (number average molecular weight 4,300) represented by the following general formula (L) was prepared.
• the list of the one-terminal functional fluoropolyether group-containing polymers obtained in Synthesis Example 1-6 of the one-terminal functional fluoropolyether group-containing polymer is shown in Table 2.
• the one-terminal functional fluoropolyether group-containing polymer A-II is a one-terminal functional fluoropolyether group-containing polymer having a structure represented by the above average composition formula (II) obtained by using the raw material polymer A represented by the average composition formula (I) having the composition in Table 1 as the starting material.
• a polyester adhesive tape No. 31B (manufactured by Nitto Denko Corporation) was attached to the glass on which the cured coating film was formed as described above, and the glass was left standing for 3 days in a state of being pressed with a load of 1 kgf.
• the peel strength was then evaluated using an autograph AGS-X10N (manufactured by Shimadzu Corporation).
• the test environment conditions were a temperature of 25°C, a relative humidity of 50%, a crosshead speed of 300 mm/min, and a test piece width of 19 mm.
• B peeling force 0.08 N or more and less than 0.11 N
• C peeling force 0.11 N or more
• the results of evaluation according to the above evaluation criteria are shown in Table 4.
• the glass on which the cured coating was formed was rubbed 3,000 times under the following conditions using a reciprocating abrasion tester (Tribogear, manufactured by Shinto Scientific Co., Ltd.), and the contact angle of the cured coating with water was measured in the same manner as above to evaluate the abrasion resistance.
• the test environment conditions were 25°C and 40% relative humidity.
• Comparative Examples 1 to 3 and 5 the decrease in the water contact angle after heating is kept below 6° compared to the initial water contact angle (i.e., the water contact angle is kept above 100°), but the number of times of rubbing until the ink is wiped off increases, and the water contact angle after eraser wear is greatly reduced.
• Comparative Examples 4 and 6 the ink can be wiped off immediately, and the decrease in the water contact angle after eraser wear is kept below 6° (i.e., the water contact angle is kept above 100°), but the heat resistance is weak and the peel value is high.
• Examples 1 to 25 by adjusting the molar ratio of CF 3 CF 2 O- and CF 3 O-, which are the terminal groups of the one-terminal functional fluoropolyether group-containing polymer, to within the range of 0.01 to 0.17, good results were obtained in four properties, namely water and oil repellency, antifouling property, heat resistance, surface peelability and eraser wear resistance.

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