Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • 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 coating composition, and more specifically to a fluorine-containing coating composition that forms a cured coating film that has excellent water and oil repellency and abrasion resistance, a surface treatment agent that contains the composition, a cured coating film made of a cured product of the surface treatment agent, and an article having the cured coating on its surface.
• 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 surface of substrates such as glass, 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 or the like, resulting in a strong and durable coating.
• compositions have been disclosed that use fluoropolyether group-containing polymer-modified silanes, in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, to form coatings that are easy to adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance on the substrate surface (Patent Documents 1 to 8: JP 2003-238577 A, JP 9-202648 A, JP 2000-308846 A, JP 2008-534696 A, JP 2008-537557 A, JP 2012-072272 A, JP 2012-157856 A, and JP 2013-136833 A).
• Patent Document 9 proposes that a fluorine-containing coating composition using a specific mixture ratio of a hydroxyl- or hydrolyzable-group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer and perhydropolysilazane can form a cured coating layer that exhibits excellent water and oil repellency on resin and metal surfaces.
• the fluorine-containing coating composition described in Patent Document 9 can provide a surface treatment layer with excellent functionality, but it is subject to wear and tear during actual use, resulting in a decrease in antifouling properties, and therefore does not have a wear resistance that is satisfactory for practical use. There is a demand for a surface treatment layer with even greater durability.
• the present invention has been made in consideration of the above circumstances, and aims to provide a fluorine-containing coating composition capable of forming a cured coating film with excellent water and oil repellency and abrasion resistance, a surface treatment agent containing said composition, a cured coating film consisting of a cured product of the surface treatment agent, and an article having said cured coating on its surface.
• a surface treatment agent containing a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the general formula (1) described below and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal
• a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the general formula (2) described below and a hydroxyl group-containing silyl group and/or a hydrolyzable silyl group at the terminal) and/or a partial (hydrolyzed) condensate thereof mixed with polysilazane in a specific blending ratio
• a partial (hydrolyzed) condensate thereof mixed with polysilazane in a specific blending ratio can form a water- and oil-repellent layer
• a fluorine-containing coating agent composition comprising (A) a fluoropolyether group-containing polymer represented by the following general formula (1) and/or a partial (hydrolyzed) condensate thereof, and (B) a polysilazane, wherein the mixing mass ratio of component (A) to component (B) is 0.1:99.9 to 95:5: Rf[Q-CH(V) 2 ] ⁇ (1)
• Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
• Q is a single bond or a divalent organic group
• V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group and/or a hydrolyzable silyl group
• each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.
• Rf is a divalent fluoropolyether group represented by the following general formula (4):
• W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms
• d is an integer of 1 to 3 independently for each unit
• p, q, r, s, t, u, and v are each an integer of 0 to 200
• the total of p, q, r, s, t, u, and v is 3 to 200, and 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 randomly bonded.
• L is independently a group selected from the group consisting of 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.
• G is independently represented by any of the following formulas.
• k is independently an integer of 2 to 8 for each unit.
• the component (B) is represented by the following general formula (16): -(SiH 2 -NH)- (16) and/or a perhydropolysilazane having a base unit represented by the following general formula (17): -(SiR s 2 -NH)- (17)
• Rs are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a vinyl group, except for the case where all Rs are hydrogen atoms.
• a surface treatment agent comprising the fluorine-containing coating composition according to any one of [1] to [12].
• a cured coating comprising a cured product of the surface
• the surface treatment agent containing the fluorine-containing coating composition of the present invention which contains the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate and polysilazane in a specific blend ratio, can form a water- and oil-repellent layer with excellent abrasion resistance on the surface of resin or metal, and the article surface-treated with the surface treatment agent has excellent water- and oil-repellency and abrasion resistance, especially resistance to cloth abrasion.
• numeric value refers to a numeric value (approximate number) that is rounded off, and if the lowest digit of the displayed numeric value is not "0", the lowest digit is rounded off to the nearest digit, and the displayed numeric value includes the range of the numeric value.
• “about 3 equivalents” refers to 2.5 equivalents or more and 3.4 equivalents or less
• “about 0.02 equivalents” refers to 0.015 equivalents or more and 0.024 equivalents or less.
• the lowest digit of the displayed numeric value is "0"
• the lowest digit is rounded off to the nearest digit
• the displayed numeric value includes the range of the numeric value.
• partial (hydrolyzed) condensate refers to a partial condensate or partial hydrolyzed condensate, and means an organosiloxane oligomer having at least two, preferably three or more residual hydrolyzable groups and/or residual hydroxyl groups in the molecule, which is produced by partial condensation or hydrolysis condensation of one or more fluoropolyether group-containing polymers represented by the following general formula (1).
• the fluorine-containing coating composition of the present invention is characterized in that it contains (A) a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the general formula (1) described below and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal, and (B) a polysilazane, and the mixture mass ratio of the (A) component to the (B) component is 0.1:99.9 to 95:5, preferably 0.5:99.5 to 90:10.
• A a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the general formula (1) described below and a
• Component (A) is a fluoropolyether group-containing polymer represented by the following general formula (1) and/or a partial (hydrolyzed) condensate thereof, and the fluoropolyether group-containing polymer has a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal.
• a polyvalent polysiloxane structure a polysiloxane structure having a valence of three or more
• a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal.
• Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
• Q is a single bond or a divalent organic group
• V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal
• ⁇ is 1 or 2.
• component (A) is a fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate represented by the above-mentioned general formula (1), a surface treatment agent is obtained that can form a cured coating with excellent abrasion resistance that is unlikely to lose its antifouling properties even when the surface is worn.
• the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate of component (A) have multiple hydroxyl groups and/or hydrolyzable groups, which increases the number of reaction sites with polysilazane and results in strong adhesion, so that even when the surface is worn, the loss of the fluoropolyether group-containing polymer derived from component (A) is suppressed, and a cured coating with excellent abrasion resistance can be formed.
• the fluoropolyether group-containing polymer of component (A) and/or its partial (hydrolyzed) condensate contain polyvalent polysiloxane, compatibility with polysilazane is improved, and the fluoropolyether group-containing polymer derived from component (A) is present not only on the outermost surface of the cured coating but throughout the entire cured coating. Even if the surface is worn down and the film thickness is reduced, the fluoropolyether group-containing polymer derived from component (A) can still be present on the surface, so it is presumed that a cured coating that maintains its antifouling properties and has excellent abrasion resistance can be formed.
• Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
• ⁇ is 1 (i.e., when Rf is a monovalent fluoropolyether group-containing polymer residue)
• it is preferably a monovalent fluoropolyether group represented by the following general formula (3)
• ⁇ is 2 (i.e., when Rf is a divalent fluoropolyether group-containing polymer residue)
• it is preferably a divalent fluoropolyether group represented by the following general formula (4).
• A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms
• W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms
• d is an integer of 1 to 3 independently for each unit
• p, q, r, s, t, u, and v are each an integer of 0 to 200
• the sum of p, q, r, s, t, u, and v is 3 to 200, and 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 randomly bonded.
• A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and more preferably a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.
• W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, and examples thereof include perfluoroalkylene groups such as CF2 units, C2F4 units, C3F6 units, C4F8 units , C5F10 units , and C6F12 units in which one or two fluorine atoms have been replaced by hydrogen atoms.
• d is independently an integer of 1 to 3 for each unit, and is preferably 1 or 2.
• p, q, r, s, t, u, and v are each an integer of 0 to 200, preferably p is an integer of 0 to 100, q is an integer of 0 to 100, r is an integer of 0 to 100, 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 the sum of p, q, r, s, t, u, and v is 3 to 200, preferably 10 to 100.
• the adhesion and curability of the obtained cured coating are good, and if it is larger than the lower limit value, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.
• r, s, t, u and v are all 0, p and q each represent an integer of 5 to 100, and the sum of p and q is preferably 10 to 105, particularly preferably 15 to 60.
• 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. (In the formulae, p', q', r', s', t', u', q1', r1', and r2' each represents an integer of 1 or more, and the total of p', q', r', s', t', u', q1', r1', and r2' in each formula is 3 to 200. In addition, each repeating unit shown in parentheses with p', q', r', s', t', and u' may be bonded randomly.)
• Rf the following is preferable. (In the formula, p', q', r' and the sum thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.)
• the molecular weight of Rf is sufficient as long as the number average molecular weight of the corresponding structural portion is within the range of 400 to 40,000, preferably 2,000 to 25,000, and the molecular weight distribution (or polymerization degree distribution) is not particularly limited.
• the molecular weight (or polymerization degree or number of repeating units) can be determined as the polystyrene-equivalent number average molecular weight (or number average polymerization degree) by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent, but is preferably the number average molecular weight (or number average polymerization degree) calculated from the characteristic peak intensity ratio 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 (hereinafter the same).
• GPC gel permeation chromatography
• Q is a single bond or a divalent organic group, preferably a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, and silicon atoms, and more preferably a single bond.
• Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, and silicon atoms include the following. (In the formula, * is a bond bonded to Rf in the above formula (1), and ** is a bond bonded to a carbon atom in the above formula (1).)
• V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group (i.e., a hydroxysilyl group, a silanol group, or a hydroxyl-containing silyl group) and/or a hydrolyzable silyl group bonded to a silicon atom at the end, preferably a monovalent group consisting of a linking group having a polyvalent polysiloxane structure (i.e., a polysiloxane structure having a valence of 3 or more, preferably a valence of 3 to 10) that has a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the end and connects these terminal groups to a CH group, and more preferably a monovalent organic group having a plurality of hydroxyl groups and/or hydrolyzable silyl groups (specifically 2 to 9, particularly 2 to 7) bonded to a silicon atom at the end
• X is independently a single bond or a divalent heteroatom
• D and D' are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms
• R1 is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms
• R2 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms
• a is an integer of 0 to 6
• a1 is an integer of 1 to 6
• a2 is an integer of 2 to 7
• b is an integer of 2 to 9, and
• c is 1.
• the repeating units shown in parentheses with a, a2, and c may be bonded randomly.
• L is independently a hydroxyl group or a hydrolyzable group; and n is independently an integer of 1 to 3 for each silicon atom to which it is bonded.
• X is a single bond or a divalent heteroatom, and examples of divalent heteroatoms include an oxygen atom, a nitrogen atom, and a sulfur atom.
• the X in one V is a single bond
• the X in the other V is a divalent heteroatom, particularly an oxygen atom.
• D and D' are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms.
• the divalent hydrocarbon group include alkylene groups such as methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups, and octamethylene groups, arylene groups such as phenylene groups, and combinations of two or more of these groups (alkylene-arylene groups, etc.).
• D and D' are preferably ethylene groups, propylene groups, butylene groups, hexamethylene groups, octamethylene groups, and phenylene groups.
• R 1 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., or a phenyl group, with a methyl group being preferred.
• L is a hydroxyl group or a hydrolyzable group which may be different from each other.
• L examples include hydroxyl group, alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy group, methoxyethoxy group, acyloxy groups having 1 to 10 carbon atoms such as acetoxy group, alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy group, halogen groups such as chlorine group, bromo group, iodo group, etc. Among them, methoxy group, ethoxy group, isopropenoxy group, and chlorine group are preferable.
• R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 20 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 2 may be the same or different, and among them, a methyl group is preferable.
• n is an integer of 1 to 3, preferably 2 or 3, for each silicon atom to which it is bonded, and 3 is more preferable from the viewpoints of reactivity and adhesion to the substrate.
• a is an integer of 0 to 6, preferably 2 to 6, a1 is an integer of 1 to 6, preferably 2 to 6, a2 is an integer of 2 to 7, preferably 3 to 7, and b is an integer of 2 to 9, preferably 3 to 5.
• ⁇ is 1 or 2, preferably 1.
• the fluoropolyether group-containing polymer of component (A) is more preferably one represented by the following general formula (2).
• Rf, X, R1 , L, n, and ⁇ are the same as above, Y1 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, Z is independently an (m+1)-valent linking group having a polyvalent polysiloxane structure, Y2 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, and m is independently an integer of 2 to 9.
• Rf and ⁇ are the same as Rf and ⁇ in the above formula (1), and examples thereof include the same as those described above.
• R 1 , L and n are the same as R 1 , L and n in the above formulas (7a) to (7f), and examples thereof include the same as those described above.
• Y 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may independently contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms.
• Y 1 include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups and octamethylene groups, arylene groups having 6 to 20 carbon atoms, such as phenylene groups, combinations of two or more of these groups (for example, alkylene groups having 2 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (alkylene-arylene groups having 8 to 18 carbon atoms) and the like), and combinations of these groups with an amide bond (for example, an unsubstituted amide bond, an N-methyl
• alkylene group examples include those which are linked or interposed with one or more bonds selected from the group consisting of an N-phenyl-substituted amide bond, an N-phenyl-substituted amide bond, an urethane bond, an ether bond, a carbonyl bond, an ester bond, a diorganosilylene group (for example, a dialkylsilylene group such as a dimethylsilylene group), a silarylene bond (for example, a silphenylene bond), and a silalkylene bond (for example, a silethylene bond), and are preferably an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, and more preferably a linear alkylene group having 3 to 6 carbon atoms.
• bonds selected from the group consisting of an N-phenyl-substituted amide bond, an N-phenyl-sub
• Y 1 include the following groups. (In the formula, * is a bond bonded to X in the above formula (2), and ** is a bond bonded to Z in the above formula (2).)
• Z is independently a (m+1)-valent, i.e., 3-10 valent linking group having a polyvalent polysiloxane structure (i.e., a polysiloxane structure having 3 or more valences, preferably 3-10 valences), and is preferably a linear, branched or cyclic 3-10 valent organopolysiloxane residue having 3-10 silicon atoms.
• a polyvalent polysiloxane structure i.e., a polysiloxane structure having 3 or more valences, preferably 3-10 valences
• Z include the following groups. (In the formula, R2 , a, a1, a2, b, and c are the same as above, and each repeating unit shown in parentheses with a, a2, and c may be bonded randomly. * is a bond bonded to Y1 in formula (2), and ** is a bond bonded to Y2 in formula (2).)
• a2 and c are the same as above, and each repeating unit shown in parentheses with a2 and c may be bonded randomly. * is a bond bonded to Y1 in formula (2), and ** is a bond bonded to Y2 in formula (2).
• Y2 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms independently selected from oxygen, nitrogen, silicon and sulfur atoms.
• Y2 include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene and octamethylene groups, arylene groups having 6 to 20 carbon atoms, such as phenylene, combinations of two or more of these groups (e.g., alkylene groups having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups having 8 to 18 carbon atoms) and the like), and combinations of these groups having an amide bond (e.g., unsubstituted amide bond, N-methyl substituted amide bond, etc.).
• alkylene group examples include those which are linked or interposed with one or more bonds selected from the group consisting of an N-phenyl-substituted amide bond, an N-phenyl-substituted amide bond, an urethane bond, an ether bond, a carbonyl bond, an ester bond, a diorganosilylene group (for example, a dialkylsilylene group such as a dimethylsilylene group), a silarylene bond (for example, a silphenylene bond), and a silalkylene bond (for example, a silethylene bond), and are preferably an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, and more preferably a linear alkylene group having 3 to 8 carbon atoms.
• bonds selected from the group consisting of an N-phenyl-substituted amide bond, an N-phenyl-sub
• Y2 include the following groups. (In the formula, * is a bond bonded to Z in general formula (2), and ** is a bond bonded to the silicon atom in general formula (2).)
• m is independently an integer from 2 to 9, preferably an integer from 2 to 7, and more preferably an integer from 2 to 5. If m is 10 or more, the number of hydroxyl groups and/or hydrolyzable silyl groups bonded to the terminal silicon atoms will be too large, adversely affecting water repellency and stain resistance.
• fluoropolyether group-containing polymer of the component (A) represented by the above formula (2) those represented by the following general formulas (5) and (6) are preferred.
• d is independently an integer of 1 to 3 for each unit
• p", q", r", and s are each an integer of 0 to 200, preferably 0 to 100
• the total of p", q", r", and s" in each formula is 3 to 200, preferably 10 to 100
• each repeating unit shown in parentheses with p", q", r", and s" may be randomly bonded.
• i and j are independently an integer of 2 to 10 for each unit. Each of these units may be linear or branched.
• G is independently represented by any of the following formulas. (In the formula, k is independently an integer of 2 to 8 for each unit.)
• fluoropolyether group-containing polymer represented by the above formula (2) examples include those represented by the following formula. (In the formula, p', q', r', and the sum thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.)
• the fluoropolyether group-containing polymer represented by the above formula (2) can be prepared, for example, by the following method.
• M is a removable monovalent group, examples of which include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, and an acyl group.
• M include the following groups.
• fluoropolyether group-containing polymer having a carbonyl group at its terminal represented by the above formula (8)
• fluoropolyether group-containing polymer having a carbonyl group at its terminal represented by the above formula (8)
• examples of the fluoropolyether group-containing polymer having a carbonyl group at its terminal include those shown below.
• p', q', r', and the total thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• r3' and r4' are each an integer of 1 or more, and the sum of r3' and r4' is 2 to 199.
• organometallic reagent having an aliphatic unsaturated double bond at the terminal and a ⁇ -hydrogen atom include organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, and organotin reagents, and from the viewpoint of ease of handling, it is preferable to use Grignard reagents and organozinc reagents.
• organometallic reagents the following can be particularly suitably used.
• the amount of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and a ⁇ -hydrogen atom is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalents, per equivalent of the reactive terminal group (removable monovalent group) of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8).
• a solvent can be used for the reaction between the fluoropolyether group-containing polymer having a carbonyl group at the end represented by the above formula (8) and the organometallic reagent having an aliphatic unsaturated double bond at the end and having a ⁇ -hydrogen atom.
• the solvent used at this time is not particularly limited, but it is preferable to use a fluorine-based solvent because the reaction compound is a fluorine compound.
• fluorine-based solvents examples include 1,3-bistrifluoromethylbenzene, trifluoromethylbenzene, perfluoro-based solvents sold by AGC (such as Asahiklin AC2000 and Asahiklin AC6000), hydrofluoroether (HFE)-based solvents sold by 3M (such as NOVEC7100: C4F9OCH3 , NOVEC7200 : C4F9OC2H5, NOVEC7300: C2F5-CF(OCH3)-CF(CF3)2 ) , and perfluoro - based solvents sold by 3M (such as PF5080, PF5070, and PF5060 ) .
• AGC such as Asahiklin AC2000 and Asahiklin AC6000
• HFE hydrofluoroether
• 3M such as NOVEC7100: C4F9OCH3 , NOVEC7200 : C4F9OC2H5, NOVEC7300: C2F5-CF(
• the fluorine - based solvents may be used alone or in combination.
• an organic solvent can be used in addition to the above-mentioned fluorine-based solvents.
• an ether-based solvent such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc. can be used.
• THF tetrahydrofuran
• monoethylene glycol dimethyl ether diethylene glycol dimethyl ether
• triethylene glycol dimethyl ether tetraethylene glycol dimethyl ether
• dioxane dioxane
• the amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 200 to 350 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a carbonyl group at its terminal, represented by the above formula (8).
• the reaction conditions for the fluoropolyether group-containing polymer having a carbonyl group at its terminal, as represented by the above formula (8), and the organometallic reagent having an aliphatic unsaturated double bond at its terminal and a ⁇ -hydrogen atom can be 0 to 80°C, preferably 45 to 70°C, more preferably about 50°C, for 1 to 12 hours, preferably 5 to 7 hours.
• Y 1' is independently a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 2 to 12 carbon atoms, which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, and specific examples thereof include single bonds, alkylene groups having 1 to 18 carbon atoms such as methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups, and octamethylene groups, and alkylene groups including arylene groups having 6 to 8 carbon atoms such as phenylene groups (for example, alkylene-arylene groups having 7 to 18 carbon atoms).
• Y 1' is preferably a linear alkylene group having 1 to 4 carbon atoms.
• Y 1' examples include the following groups. (In the formula, * is a bond bonded to the carbon atom bonded to Rf in formula (9), and ** is a bond bonded to the vinyl group in formula (9).)
• fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (9) include those shown below. (In the formula, p', q', r', r3', r4', and the sum thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.)
• the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (9) obtained above and the olefin introducing agent are aged in the presence of a base, if necessary with an additive or solvent that improves reactivity, at a temperature of 0 to 90°C, preferably 40 to 60°C, more preferably about 50°C, for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours.
• a halide can be used, and specific examples thereof include allyl bromide, allyl chloride, and 3-butenyl bromide.
• the amount of the olefin introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 4 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9).
• Examples of the base used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9) with the olefin introducing agent include amines and alkali metal bases, and specific examples of the amines include triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc.
• alkali metal bases examples include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc.
• the amount of the base used is 1 to 20 equivalents, more preferably 4 to 8 equivalents, and even more preferably about 6 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9).
• tetrabutylammonium halide In the reaction between the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9) and the olefin introducing agent, tetrabutylammonium halide, alkali metal halide, etc. may be used as an additive for improving reactivity.
• the additive include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether, etc.
• additives improve reactivity by catalytically exchanging halogen with the olefin introducing agent in the reaction system, and crown ether improves reactivity by coordinating with metal.
• the amount of the additive used is 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9).
• a solvent may be used in the reaction between the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9) and the olefin introducing agent.
• the solvent include fluorine-based solvents such as fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 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).
• fluorine-based solvents such as fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluor
• examples of the organic solvent that can be used include dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, and tetrahydrofuran (THF).
• 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 a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (9).
• fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by formula (10) the following may be preferably exemplified.
• p', q', r', r3', r4', and the sum thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals and represented by formula (10) obtained above 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 three or more SiH groups in the molecule, such as 2,4,6,8-tetramethylcyclotetrasiloxane, and aged 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, for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
• a solvent for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having three or
• organosilicon compound having three or more SiH groups in the molecule to be reacted with the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (10) a compound represented by the following formula is preferred. (In the formula, R2 , a, a1, a2, b, and c are the same as above.)
• organosilicon compounds having three or more SiH groups in the molecule include compounds such as 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, methyltris(dimethylsiloxy)silane, tetrakis(dimethylsilyloxy)silane, and 1,1,1,3,5,7,9,11,13,15,17,19,19,19-tetradecamethyldecasiloxane.
• the amount of the organosilicon compound having three or more SiH groups in the molecule can be 2 to 10 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 5 equivalents per equivalent of the reactive terminal group (terminal olefin moiety) of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain end.
• the solvent used is preferably 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 50 to 200 parts by mass, and more preferably 100 to 150 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (10).
• examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium.
• platinum compounds such as vinylsiloxane coordination compounds.
• the amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (10).
• a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal represented by the above formula (10) By reacting a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal represented by the above formula (10) with an organosilicon compound having three or more SiH groups in the molecule, a fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain terminal represented by the following general formula (11) can be obtained.
• Rf, Y 1 and ⁇ are the same as above, and Z′ is independently a monovalent group having two or more SiH groups.
• Z' is a monovalent group having two or more SiH groups, and is preferably a monovalent group having a linear, branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, and specific examples of Z' include the following groups.
• R 2 , a, a1, a2, b, and c are the same as above, and the repeating units shown in parentheses with a, a2, and c may be bonded randomly.
• the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals represented by formula (11)
• the following may be preferably exemplified.
• p', q', r', r3', r4', and the total thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• Z" is independently represented by any of the following formulas. (In the formula, a2 and c are the same as above, and the repeating units shown in parentheses with a2 and c may be bonded randomly.)
• the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain end and represented by formula (11) obtained above is dissolved in a solvent, for example a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group) bonded to a silicon atom in the molecule, such as 7-octenyltrimethoxysilane or 7-octenyltrichlorosilane, is mixed, and the resulting mixture is aged 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
• the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.
• organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule to be reacted with the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminal represented by the above formula (11) a compound represented by the following general formula (12) is preferred.
• R 1 , L, and n are the same as above, and Y 2' is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms.
• Y 2' is a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, and specific examples thereof include single bonds, alkylene groups having 1 to 18 carbon atoms such as methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups, and octamethylene groups, and alkylene groups including arylene groups having 6 to 8 carbon atoms such as phenylene groups (for example, alkylene/arylene groups having 7 to 18 carbon atoms).
• Y 2' is preferably an alkylene group having 1 to 6 carbon atoms.
• Examples of Y 2′ include the following groups. (In the formula, * is a bond bonded to the vinyl group in formula (12), and ** is a bond bonded to the silicon atom in formula (12).)
• organosilicon compounds having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule include the following.
• the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain end represented by the above formula (11) is subjected to an addition reaction with an organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule
• the amount of the organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule can be 0.9 to 5 equivalents, more preferably 0.95 to 3 equivalents, and even more preferably 0.98 to 1.4 equivalents per equivalent of the reactive end group (Si-H moiety) of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups.
• the solvent used is preferably 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 50 to 200 parts by mass, and more preferably about 150 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminal represented by the above formula (11).
• the hydrosilylation reaction catalyst can be 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, chlorotris(triphenylphosphine)rhodium, etc.
• platinum compounds such as vinylsiloxane coordination compounds.
• the amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals, as represented by the above formula (11).
• a compound represented by the following formula can be used as a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminal: and 7-octenyltrimethoxysilane is used as the organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule, the compound represented by the following formula is obtained.
• a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at a molecular chain terminal a compound represented by the following formula is and 7-octenyltrimethoxysilane is used as the organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule, the compound represented by the following formula is obtained.
• the following method can be mentioned.
• an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule is used in place of the organosilicon compound having an olefin moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule.
• the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals, represented by formula (11), obtained above, is dissolved in a solvent, for example a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule is mixed therewith.
• a solvent for example a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene
• the mixture is aged at a temperature of 40 to 120° C., preferably 60 to 100° C., and more preferably about 80° C., for 0.5 to 24 hours, preferably 1 to 20 hours, and more preferably 1.5 to 16 hours.
• a hydrosilylation reaction catalyst for example a toluene solution of a chloroplatinic acid/vinylsiloxane complex
• U is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, and is preferably an alkylene group having 1 to 6 carbon atoms which may contain an oxygen atom.
• Examples of such alcohols having an olefin moiety and a terminal hydroxyl group in the molecule include allyl alcohol, ethylene glycol monoallyl ether, ethylene glycol monovinyl ether, tetramethylene glycol monoallyl ether, and tetramethylene glycol monovinyl ether.
• the amount of the alcohol having an olefin moiety and a terminal hydroxyl group in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and even more preferably 1 to 2 equivalents per equivalent of the reactive terminal group (Si-H moiety) of the fluoropolyether group-containing polymer having two monovalent groups with two or more SiH groups.
• the solvent used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include those exemplified above.
• the amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 150 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminal represented by the above formula (11).
• the hydrosilylation reaction catalyst may be the same as those exemplified above.
• it is a platinum-based compound such as a vinylsiloxane coordination compound.
• the amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals, as represented by the above formula (11).
• the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain terminals represented by formula (14) may be preferably exemplified.
• U, m, p', q', r', r3', r4', and the sum thereof in each formula are the same as above, and each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.
• Z1 is independently represented by any of the following formulas. (In the formula, ** is a bond bonded to the terminal carbon atom in the unit enclosed by m, and * is a bond bonded to the remaining carbon atom.)
• the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain terminals represented by formula (14) obtained above and an organosilicon compound having an isocyanate moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule, such as 3-(isocyanatopropyl)trimethoxysilane, are dissolved and mixed in a solvent, for example a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged in the presence of a Lewis acid catalyst, for example tetrakis(2-ethylhexyloxy)titanium, at a temperature of 20 to 80°C, preferably 40 to 60°C, more preferably about 50°C, for 1 to 24 hours, preferably 1 to 10 hours, more preferably about 3 hours, to obtain a fluoropolyether group-containing polymer represented by formula (2) above.
• a solvent for example a
• an organosilicon compound having an isocyanate moiety and a hydrolyzable silyl group in the molecule if an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used, 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.
• organosilicon compound having an isocyanate moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule to be reacted with the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain terminal represented by the above formula (14) a compound represented by the following general formula (15) is preferred.
• R 1 , L, and n are the same as above, and U′ is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.
• U' is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.
• organosilicon compounds having an isocyanate moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule include 3-(isocyanatopropyl)trimethoxysilane, 3-(isocyanatopropyl)triethoxysilane, and 3-(isocyanatopropyl)trichlorosilane.
• the fluoropolyether group-containing polymer having 4 or more OH groups at the molecular chain terminal represented by the above formula (14) is subjected to an addition reaction with an organosilicon compound having an isocyanate moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule
• the amount of the organosilicon compound having an isocyanate moiety and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and even more preferably 1 to 2 equivalents per equivalent of the reactive terminal group (OH group) of the fluoropolyether group-containing polymer having 4 or more OH groups.
• the solvent used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include those exemplified above.
• the amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably 100 to 150 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having 4 or more OH groups at the molecular chain terminals represented by the above formula (14).
• examples of the Lewis acid catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and stannous dioctanoate, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-
• the Lewis acid catalyst include titanate esters or titanium chelate compounds such as tetrakis(2-ethylhe
• the component (A) may contain a partial (hydrolysis) condensate obtained by partially condensing the hydroxyl groups of the hydroxysilyl groups present at the terminals of the fluoropolyether group-containing polymer represented by the above-mentioned general formula (1), or by condensing the hydroxyl groups obtained by partially hydrolyzing the hydrolyzable groups of the hydrolyzable silyl groups present at the terminals of the fluoropolyether group-containing polymer in advance by a known method.
• the component (A) may be a single type, or a mixture of two or more types.
• Component (B) The fluorine-containing coating agent composition of the present invention is prepared by blending the fluoropolyether group-containing polymer as component (A) with polysilazane as component (B) in the specific ratio described above.
• the polysilazane of the component (B) is preferably a polysilazane represented by the following general formula (16): -(SiH 2 -NH)- (16) and/or a perhydropolysilazane having a base unit represented by the following general formula (17): -(SiR s 2 -NH)- (17)
• R are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a vinyl group, except for the case where all Rs are hydrogen atoms.
• Rs are independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, or a vinyl group, and among these, a methyl group is preferable.
• all of Rs cannot be hydrogen atoms.
• the degree of polymerization of the polysilazane of component (B) is preferably about 800 to 8,000, and more preferably about 1,000 to 5,000. This degree of polymerization can usually be measured as the weight average degree of polymerization in terms of standard polystyrene by gel permeation chromatography (GPC) analysis using toluene as the developing solvent.
• GPC gel permeation chromatography
• polysilazanes component (B)
• polysilazanes component (B)
• perhydropolysilazanes sold by Sanwa Chemical Co., Ltd. under the registered trademark "Tresmile” in the ANAX, ANP, and ANL series
• these products can also be obtained and used as organic solvent solutions of various solid concentrations.
• organic polysilazanes, sold by Sanwa Chemical Co., Ltd. under the registered trademark "Tresmile” in the HTA1500 and HTT1800 series and these products can also be obtained and used as organic solvent solutions of various solid concentrations.
• the polysilazane of component (B) may be dissolved in an organic solvent in advance in the form of a polysilazane solution and mixed with component (A) in a specific mixing mass ratio.
• the fluorine-containing coating composition of the present invention can be prepared by mixing components (A) and (B), but component (A) may also be synthesized in a state where component (B) is already contained in the raw material used to synthesize component (A).
• the fluorine-containing coating composition of the present invention is a mixture of a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the above general formula (1) and a hydroxyl group and/or a hydrolyzable silyl group bonded to a silicon atom at the terminal (particularly a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polysiloxane structure having a valence of three or more) represented by the above general formula (2) and a hydroxyl group-containing silyl group and/or a hydrolyzable silyl group at the terminal) and/or a partial (hydrolyzed) condensate thereof, and polysilazane, in a specific blending ratio.
• the polysilazane adheres to the substrate, and furthermore, the hydroxyl groups on the polysilazane layer react with the hydroxyl groups or hydrolyzable group portions of the fluoropolyether group-containing polymer, thereby strengthening the adhesion as a surface treatment agent.
• the fluorine-containing coating agent composition may contain a hydrolysis and 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.).
• acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable.
• the amount of the hydrolysis and condensation catalyst added is a catalytic amount, 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 its partial (hydrolysis) condensate, component (A).
• the fluorine-containing coating composition may contain a suitable solvent for dissolving the polyvalent polysiloxane represented by general formula (1) as component (A) and a fluoropolyether group-containing polymer having hydrolyzable groups and/or its partial (hydrolyzed) condensate, and the polysilazane as component (B).
• solvents examples include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (dipropyl ether, dibutyl ether, anisole, dioxane
• the above solvents may be used in combination of two or more kinds, and it is preferable to dissolve component (A) (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate) and component (B) (polysilazane) uniformly.
• component (A) fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate
• component (B) polysilazane
• concentration of component (A) (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate) and component (B) (polysilazane) to be dissolved in the solvent varies depending on the processing method, and may be any amount that is easy to measure, but it is preferably 0.01 to 50 parts by mass, particularly 0.05 to 25 parts by mass, per 100 parts by mass of the total of the solvent, component (A) (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate), and component (B) (polysilazane).
• the present invention further provides a surface treatment agent comprising a fluorine-containing coating composition comprising the above-mentioned fluoropolyether group-containing polymer represented by general formula (1) as component (A) and/or a partial (hydrolyzed) condensate thereof, and a polysilazane as component (B), in which the mixing mass ratio of component (A) to component (B) is 0.1:99.9 to 95:5.
• the surface treatment agent preferably consists of the above-mentioned fluorine-containing coating composition.
• the surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spin coating, spraying, etc.
• the curing temperature varies depending on the curing method, but for example, in the case of direct coating (brushing, dipping, spin coating, spraying, etc.), it is preferable to apply the agent at a temperature of 25 to 200°C, particularly 50 to 150°C, for 30 minutes to 36 hours, particularly 1 to 24 hours. Curing may also be performed under humid conditions.
• the thickness of the cured coating made of the cured product of the surface treatment agent of the present invention 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, metals such as duralumin and their oxides, glass, plastics such as polymethyl methacrylate resin (PMMA), polycarbonate resin (PC), and ABS resin, ceramics, and quartz.
• the surface treatment agent of the present invention can impart water and oil repellency, and abrasion resistance, particularly cloth abrasion resistance, to the substrate.
• Articles having a cured coating on their surface made of the cured product of 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 machines, 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-reflection films and other optical articles.
• the surface treatment agent of the present invention prevents the adhesion of fingerprints and sebum to the above-mentioned articles and further imparts scratch resistance, making it particularly useful as a water- and oil-repellent layer for the housing of smartphones due to its good adhesion to resins and metals.
• the surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins; an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc.; a water- and oil-repellent coating for exterior wall building materials; a coating to prevent oil stains for kitchen building materials; an anti-fouling and anti-posting/anti-graffiti coating for telephone booths; a coating to prevent fingerprints from adhering to artworks, etc.; a coating to prevent fingerprints from adhering to compact discs, DVDs, etc.; a release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.
• 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 in the fluoropolyether group in the formula may be randomly bonded.
• the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
• the polysilazanes used in component (B) were Tresmile ANAX 120-20 (manufactured by Sanwa Chemical), a 20% by mass dibutyl ether solution of perhydropolysilazane (PHPS), and Tresmile HTT1800 (manufactured by Sanwa Chemical), a 100% by mass product of organic polysilazane (OPS). Note that the mass of PHPS listed in Table 1 excludes the solvent.
• Each surface treatment agent was spin-coated on a substrate (polymethyl methacrylate resin (PMMA), polycarbonate resin (PC), ABS resin, or duralumin).
• the coating conditions were a rotation speed of 1,000 rpm and a rotation time of 30 seconds.
• the mixture was cured at 150° C. for 12 hours to form a cured coating having a thickness of about 100 nm.
• the proportion of component (A) in component (A) + component (B) and the solids content of the surface treatment agent are values calculated from the masses of components (A) and (B) excluding the solvent.
• the surface treatment agents of Examples 1 to 21 were prepared by mixing the fluoropolyether group-containing polymer represented by general formula (1) and polysilazane in a specific blend ratio, and the cured coatings of the surface treatment agents of Examples 1 to 21 maintained a water contact angle of 100° or more even after 8,000 cloth abrasions, demonstrating excellent abrasion resistance.
• the number of hydrolyzable groups in the fluoropolyether group-containing polymer of the surface treatment agents of Comparative Examples 1 to 4 was smaller than that of the fluoropolyether group-containing polymer represented by general formula (1), and therefore the cured coatings of the surface treatment agents of Comparative Examples 1 to 4 showed a significant decrease in water contact angle after 8,000 cloth abrasions and were inferior in abrasion resistance.

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• 2023
  • 2023-12-06 KR KR1020257024122A patent/KR20250124357A/ko active Pending
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