Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
  • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule), and in particular, to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule).
• a fluoropolyether group-containing polymer composition capable of forming an excellent cured film, a coating agent containing the composition, and an article having a layer consisting of a cured product of the coating agent, and further applying and curing the coating agent.
• the present invention relates to a method for modifying the surface of an article, including a step of forming a layer.
• fluoropolyether group-containing compounds have water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, etc. because their surface free energy is very small.
• it is widely used industrially as water-, oil-, and stain-proofing agents for paper and textiles, lubricants for magnetic recording media, oil-proofing agents for precision equipment, mold release agents, cosmetics, and protective films.
• its properties also mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of the substrate, it is difficult to make the film adhere to it. .
• silane coupling agents are well known as agents that bond organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for the surfaces of various substrates.
• a silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups cause a self-condensation reaction with moisture in the air to form a film. The coating becomes a durable and strong coating due to the hydrolyzable silyl group chemically and physically bonding to the surface of glass, metal, or the like.
• the antifouling thin film layer on the surface of a touch panel display has been given importance not only for its ability to prevent stains, but also for its usability (good slippage and smooth feel) when using a touch panel. Good feeling in use is related to a low coefficient of friction (Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906).
• the low coefficient of friction on the casing surface of a portable electronic device terminal may be disadvantageous.
• the coefficient of friction is low, there is a high possibility that the device will fall or vibrate during use. Therefore, it is important to control the coefficient of friction while maintaining antifouling performance and durability when applying antifouling coating thin film layers to various applications including portable electronic device terminals (Patent Document 7: JP 2019-131808A).
• the present invention was made in view of the above circumstances, and provides a fluoropolyether group-containing polymer composition capable of forming a cured film having excellent water and oil repellency and abrasion resistance and a high coefficient of friction, and the composition.
• An object of the present invention is to provide a coating agent containing the above-mentioned coating agent, an article having a layer made of a cured product of the coating agent, and a method for surface modification of an article, which further includes a step of applying and curing the coating agent to form a layer. .
• the present inventors have found that, in the fluoropolyether group-containing polymer composition, two specific types of fluoropolyether group-containing polymers described below are used in combination in a specific ratio.
• a fluoropolyether group-containing polymer composition (particularly a coating agent containing the composition) formed by using the polymer and/or its partial (hydrolyzed) condensate has excellent water and oil repellency and abrasion durability.
• the present invention has been completed based on the discovery that it is possible to form a cured film having anti-slip properties due to a high coefficient of friction.
• Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.)
• J is a single bond or a carbonyl group
• Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom
• L is independently is a single bond or a divalent heteroatom
• M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond
• X is independently a hydroxyl group or a hydrolyzable group
• R are independently an alkyl group or phenyl group having 1 to
• W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.
• [2] (II) component is represented by the following general formula (3)
• Rf2 contains a unit represented by -(C c F 2c O) -
• the C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching.
• R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
• X is independently a hydroxyl group or a hydrolyzable group
• n is bonded to a silicon atom.
• Each unit is independently an integer of 1 to 3
• Y is independently a divalent to hexavalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond.
• n is independently 1 It is an integer between ⁇ 5.
• A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is -CF 3 group, and b1 is an integer from 1 to 200.
• X independently represents 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, or an alkenyloxy group having 2 to 10 carbon atoms.
• the fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
• each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.
• the above Rf2 is the following formula (In the formula, p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.
• each repeating unit shown in parentheses with p', q', r', s', t', and u' is random.
• X independently represents 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, or an alkenyloxy group having 2 to 10 carbon atoms.
• a coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [9].
• a coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [9] is applied to the entire or part of the surface of the article by a dry method or a wet method and cured to form a layer.
• a method for surface modification of an article including a process.
• the fluoropolyether group-containing polymer composition of the present invention it is possible to provide a cured film that has excellent water and oil repellency and exhibits high abrasion durability despite having a high coefficient of friction.
• Articles for example, portable electronic device terminals, etc.
• having a layer made of a cured product of the composition particularly a coating agent containing the composition
• the "partial (hydrolyzed) condensate” refers to a partial condensate or a partially hydrolyzed condensate.
• the fluoropolyether group-containing polymer composition of the present invention contains two specific types of fluoropolyether group-containing polymers in a specific ratio, and for each of the fluoropolyether group-containing polymers, one of them contains One component (I) is a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, and the other component (II) has a fluorooxyalkylene group in the molecule. It is a polymer having reactive functional groups at both ends of the polymer.
• component (I) a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, is represented by the following general formula (1). fluoropolyether group-containing polymers and/or partial (hydrolyzed) condensates thereof.
• Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.)
• J is a single bond or a carbonyl group
• Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom
• L is independently is a single bond or a divalent heteroatom (preferably an oxygen atom in an ether bond)
• M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond
• X is independently is a hydroxyl group or a hydrolyzable group
• R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
• n is an integer of 1 to 3 for each unit bonded to the silicon atom
• a is 2
• the component (II), a polymer having a fluorooxyalkylene group in the molecule and having reactive functional groups at both ends of the polymer has the following general formula (2 ) is a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof.
• W-O-CH 2 -Rf2-CH 2 -O-W (2) (In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching.
• W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
• the content of component (I) in the total of components (I) and (II) is 65 to 95% by mass, preferably 65 to 90% by mass.
• the content is preferably 65 to 85% by mass. If the content of component (I) in the total of components (I) and (II) is less than 65% by mass, the friction coefficient and wear durability of the cured film will decrease, and if it is more than 95% by mass, the friction coefficient will be high. The abrasion durability of the hardened coating on the product decreases.
• the fluoropolyether group-containing polymer of formula (1) has a structure in which a fluorooxyalkyl group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group. There are two or more hydrolyzable silyl groups or hydroxyl group-containing silyl groups in the molecule.
• the main chain structure is composed of a group represented by -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.) It is characterized by a high coefficient of friction (hard to slip).
• Rf1 is -(C 3 F 6 O) b - (the repeating unit C 3 F 6 O is a branched structure represented by -CF(CF 3 )CF 2 ⁇ - (i.e., hexafluoropropylene
• b is an integer of 2 to 200, preferably an integer of 3 to 100.
• A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is -CF 3 group, and b1 is an integer from 1 to 200.
• A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is a -CF 3 group
• the fluoroalkyl group whose terminal is a -CF 3 group is CF 3 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 -, CF 3 CF 2 -, CF 3 -, CF 3 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2
• Examples include CFH-, and CF 3 CF 2 CF 2 - is preferred.
• b1 is an integer of 1 to 200, preferably an integer of 3 to 100, more preferably an integer of 5 to 50. If b1 is smaller than the above upper limit, the adhesiveness and curability will be good, and it will be easy to handle, and if b1 is larger than the above lower limit, the characteristics of the fluorooxyalkyl group can be fully exhibited, which is preferable.
• Rf1 is an integer from 1 to 199, preferably from 3 to 100.
• Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, and specific examples of Q other than a single bond include The following groups may be mentioned. Note that it is preferable that the bond on the left side be bonded to J, and the bond on the right side be bonded to a carbon atom. (In the formula, e1 is an integer of 1 to 4, preferably 1 or 2, and e2 is an integer of 1 to 4, preferably 1, 2 or 3.)
• L is independently a single bond or a divalent heteroatom, and examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably an oxygen atom (in an ether bond) oxygen atom). L is preferably a single bond or an oxygen atom.
• M is independently a divalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, and specific examples of M include a propylene group, a butylene group, a hexamethylene group, etc.
• Alkylene groups having 3 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms such as phenylene groups (for example, alkylene/arylene groups having 8 to 16 carbon atoms), carbon atoms
• Examples include divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a polysiloxane residue, preferably alkylene groups having 3 to 10 carbon atoms, and phenylene groups containing 3 to 10 carbon atoms.
• an alkylene group with 3 to 10 carbon atoms a divalent group in which alkylene groups with 3 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and a bond of a divalent organopolysiloxane residue with 2 to 10 carbon atoms
• R 1 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, 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.
• R 2 is an alkylene group having 1 to 6 carbon atoms, such as a methylene group, ethylene group, or propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.
• linear divalent organopolysiloxane residue having 2 to 10 silicon atoms preferably 2 to 5 silicon atoms
• the following can be exemplified.
• R 1 is the same as above.
• g is an integer of 1 to 9, preferably an integer of 1 to 4.
• M examples include groups represented by the following formulas. (wherein, f1 is an integer of 3 to 10, preferably 3 to 6, f2 is an integer of 1 to 6, preferably 2 to 4, and f3 is an integer of 3 to 10, preferably g is an integer of 3 to 6, and g is an integer of 1 to 9, preferably 1 to 4.)
• M include the following groups. Note that it is preferable that the bond on the left side is bonded to L, and the bond on the right side is bonded to the silicon atom.
• X independently represents a hydroxyl group or a hydrolyzable group, specifically a group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc.
• R is independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a phenyl group, of which a methyl group is preferred.
• n is an integer of 1 to 3 independently for each unit bonded to a silicon atom, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.
• -SiX n (R) 3-n includes a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tri(isopropoxy)silyl group, a tributoxysilyl group, a tri(isobutoxysilyl group) ) silyl group, tri(sec-butoxy)silyl group, tri(tert-butoxy)silyl group, and other trialkoxysilyl groups are preferred.
• a is 2 or 3.
• all are single bonds, or one L is an oxygen atom, and the remaining one or two
• L is a single bond, particularly when a is 2, it is preferable that one of the two Ls present in one molecule is an oxygen atom and the other L is a single bond,
• a is 3, it is preferable that all three L's present in one molecule are single bonds.
• Examples of the fluoropolyether group-containing polymer represented by the formula (1) include those represented by the following formula.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• In the formula, b1' is an integer from 1 to 199.
• In the formula, b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• b1' is an integer from 1 to 199.
• the fluoropolyether group-containing polymer represented by the formula (1) is preferably one represented by the following formula. (In the formula, b1' is an integer from 1 to 199.)
• the fluoropolyether group-containing polymer of formula (2) is a polymer in which a fluorooxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group that does not have a polar group. structure, and one or more hydrolyzable silyl groups such as alkoxysilyl groups or hydroxyl group-containing silyl groups are present at each end, and two or more in total in the molecule, and the hydrolyzable silyl group or hydroxyl group-containing silyl group is present in the molecule.
• the silyl group there is no polar group in the molecule, specifically a carbonyl group, -NH- group, amide group, or hydroxyl group, resulting in a simpler bonding style.
• Rf2 is represented by the formula: -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6.) It is a linear fluorooxyalkylene group containing units and having no branching. By using a straight-chain fluorooxyalkylene group with no branching, high abrasion durability of the cured film can be obtained.
• the fluorooxyalkylene group for Rf2 is preferably one represented by the following formula (5).
• d is an integer from 0 to 5 independently for each unit
• p, q, r, s, t, and u are each an integer from 0 to 200
• p+q+r+s+t+u an integer from 10 to 250
• Each of these units is linear.
• each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.
• d is an integer of 0 to 5 independently for each unit, preferably an integer of 0 to 2, and more preferably 1 or 2.
• p, q, r, s, t, and u are each an integer of 0 to 200, preferably p is an integer of 10 to 150, q is an integer of 10 to 150, r is an integer of 0 to 20, and s is an integer of 0 to 20.
• t is an integer of 0 to 20
• u is an integer of 0 to 20
• p+q+r+s+t+u is an integer of 10 to 250, preferably an integer of 20 to 150.
• each of these units is linear. Further, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly combined.
• Such a fluorooxyalkylene group of Rf2 can be represented by the following structure, for example.
• p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.
• each repeating unit shown in parentheses with p', q', r', s', t', and u' is random.
• d' is an integer from 0 to 5 independently for each unit, and each of these units is linear.
• Rf2 preferably the following can be used.
• p" and q" are each an integer of 1 to 199, and the sum of p"+q" is an integer of 10 to 200, and the repeating unit (CF 2 CF 2 O) and (The arrangement of CF 2 O) is random.
• W is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal and having no polar group, preferably a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal.
• Examples of such W include groups represented by the following formulas (6a) to (6e).
• D is a divalent organic group having 1 to 20 carbon atoms and may be substituted with fluorine, v1 is an integer of 2 to 6, are independently integers from 2 to 10, and g1 is an integer from 1 to 9.
• D is an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, preferably 1 to 20 carbon atoms, More preferably, it is a divalent hydrocarbon group having 2 to 8 carbon atoms which may be substituted with fluorine, and examples of the divalent hydrocarbon group include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group.
• D is preferably an ethylene group, a propylene group, a butylene group, a hexamethylene group, or a phenylene group.
• v1 is an integer of 2 to 6, preferably an integer of 2 to 4
• v2 is independently an integer of 2 to 10, preferably an integer of 3 to 6
• g1 is an integer of 1 to 9, preferably an integer of 1 to 4.
• the fluoropolyether group-containing polymer of formula (2) is more preferably one represented by the following general formula (3).
• Rf2, R, X, and n are the same as above, and Y is independently a divalent to hexavalent hydrocarbon group and may have a silicon atom and/or a siloxane bond.m are independently integers from 1 to 5.
• Y is independently a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond, By not containing a polar group in the molecule, a coating film with excellent water and oil repellency can be provided.
• Y is an alkylene group having 2 to 10 carbon atoms, including an alkylene group having 3 to 10 carbon atoms such as a propylene group, a butylene group, and a hexamethylene group, and an arylene group having 6 to 8 carbon atoms such as a phenylene group.
• alkylene/arylene groups having 8 to 16 carbon atoms divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and 2 to 16 silicon atoms.
• an alkylene group having 2 to 10 carbon atoms bonded to the bonds of the divalent to hexavalent organopolysiloxane residues.
• an alkylene group having 3 to 10 carbon atoms an alkylene group having 2 to 10 carbon atoms including a phenylene group, or an alkylene group having 2 to 10 carbon atoms connected to each other via a sylalkylene structure or a sylarylene structure.
• linear, branched, or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms include those shown below.
• R 1 is the same as above.
• g1 is an integer of 1 to 9, preferably an integer of 1 to 4
• h is an integer of 2 to 6, preferably 2 to 4
• j is an integer of 0 to 8.
• h+j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.
• Examples of Y include groups represented by the following formulas. (In the formula, v1, v2, and g1 are the same as above. v is an integer of 3 to 10, preferably an integer of 3 to 6, and v0 is an integer of 2 to 10, preferably an integer of 3 to 6. be.)
• Y include the following groups.
• n is independently an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate will decrease, and if it is 6 or more, the terminal alkoxy value will be too high, which will adversely affect the performance, so it is preferably 1 to 5. It is an integer of 3, and 1 is particularly preferred.
• fluoropolyether group-containing polymer represented by the above formula (3) examples include those represented by the following formula.
• p1 and q1 are each integers from 1 to 199, and the total of p1 and q1 is 10 to 200.
• the present invention provides a fluoropolyether group-containing polymer represented by the formula (1), a fluoropolyether group-containing polymer represented by the formula (2), and particularly a fluoropolyether group-containing polymer represented by the formula (3).
• a coating agent is provided that contains a fluoropolyether group-containing polymer composition in a specific proportion with a group-containing polymer.
• the hydroxyl group of the fluoropolyether group-containing polymer represented by the above formula (1) and the above formula (2), or the terminal hydrolyzable group of the fluoropolyether group-containing polymer is partially removed in advance by a known method. It may also contain a partial (hydrolysis) condensate obtained by condensing hydrolyzed hydroxyl groups.
• the coating agent may optionally contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methane, etc.). Sulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
• the amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight, based on 100 parts by weight of the fluoropolyether group-containing polymer composition.
• the coating agent may contain a suitable solvent.
• suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), and fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane).
• 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.
• fluorine-modified solvents are preferable in terms of solubility and wettability, and in particular, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), and perfluorotrifluorinated solvents are preferred. Butylamine and ethyl perfluorobutyl ether are preferred.
• Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate.
• the optimum concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the treatment method, and may be in an amount that is easy to weigh.
• 0.01 to 10 parts by mass per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) In particular, it is preferably 0.05 to 5 parts by mass, and in the case of vapor deposition treatment, the amount of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) It is preferably 1 to 100 parts by weight, particularly 3 to 30 parts by weight, based on a total of 100 parts by weight.
• the coating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition.
• the heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited.
• the curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1. It is preferable to set the time period to 24 hours. Further, when applying by vapor deposition, it is desirable to apply at a temperature range of 20 to 200°C, particularly 25 to 80°C for 30 minutes to 36 hours, particularly 30 minutes to 24 hours.
• the thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.
• spray coating if the material is diluted with a fluorine-based solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.
• the film thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry, fluorescence X-ray measurement, or the like.
• the substrate treated with the coating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz.
• the coating agent of the present invention can impart water and oil repellency and steel wool abrasion resistance to the base material. In particular, it can be suitably used as a coating agent for SiO 2 -treated glass or film.
• Articles treated with the coating agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, and sunglasses. , medical equipment such as a gastrocamera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an antireflection film, and other optical articles. In addition, from the viewpoint of preventing slippage, it can also be applied to the cases of mobile phones, smartphones, PCs, etc.
• the coating agent of the present invention can prevent fingerprints and sebum from adhering to the article, and can also provide scratch resistance (wear resistance), so it can be used especially for mobile phones, smartphones, PC casings, etc. It is useful as a water- and oil-repellent layer.
• the coating agent of the present invention can be used as an antifouling coating for sanitary products such as bathtubs and washstands, as an antifouling coating for window glasses or tempered glass for automobiles, trains, and airplanes, for headlamp covers, and as a repellent for building materials for exterior walls.
• Water and oil repellent coating anti-oil coating for kitchen building materials, anti-fouling and anti-paper/graffiti coating for telephone booths, anti-fingerprint coating for works of art, anti-fingerprint coating for compact discs, DVDs, etc., gold It is also useful as a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersibility modifier for inorganic fillers, and a water and oil repellent for tapes, films, and the like. Furthermore, from the viewpoint of being non-slip, it is also useful as a stain-preventing coating for building materials, especially flooring and wall materials.
• a coating agent containing the fluoropolyether group-containing polymer composition of the present invention is applied to the entire or part of the surface of an article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.). By coating and curing to form a layer, the surface of an article can be modified.
• the coefficient of kinetic friction on the surface of the article is preferably 0.13 or more, more preferably 0.18 or more under the measurement conditions described below. preferable. If the coefficient of dynamic friction is less than 0.13, the surface of the cured coating may be too slippery, resulting in insufficient retention or fixation of the coated article.
• the fluoropolyether represented by the formula (1) is used in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention. This can be achieved by controlling the content of the group-containing polymer to 65% by mass or more.
• the abrasion durability on the surface of the article is preferably 5,000 times or more, and preferably 7,500 times or more under the test conditions described below. It is more preferable.
• the fluoropolymer represented by the above formula (2) is used in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention. This can be achieved by controlling the content of the ether group-containing polymer to 10% by mass or more.
• the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
• Examples 1 to 54, Comparative Examples 1 to 39 Preparation of coating agent and formation of cured film
• component (I) a fluoropolyether group-containing polymer having a structure represented by the following formula (A), (B), or (C);
• component (II) As a component, a fluoropolyether group-containing polymer having a structure represented by the following formula (D), (E), (F), (G), (H), or (I); were mixed in the proportions shown in Tables 1, 2, and 3 to obtain a fluoropolyether group-containing polymer composition.
• a coating agent was prepared by dissolving the polymer composition in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass. 6 ⁇ l of each coating agent was vacuum-deposited on glass (Gorilla, manufactured by Corning Inc.) whose outermost surface had been treated with 10 nm of SiO 2 (processing conditions: pressure: 3.0 ⁇ 10 ⁇ 3 Pa, heating temperature: 500° C.), After being left in an atmosphere of 80% relative humidity at 25°C for 30 minutes, it was cured for 12 hours or more in an atmosphere of 25°C and 50% relative humidity to form a cured film with a thickness of 13 nm.
• the dynamic friction coefficient is ⁇ (excellent) if it is 0.23 or more, ⁇ (good) if it is 0.18 or more and less than 0.23, ⁇ (fair) if it is 0.13 or more and less than 0.18, and less than 0.13. are marked as ⁇ (impossible) and are shown in Tables 1, 2, and 3.
• the test environmental conditions are 25° C. and 50% relative humidity.
• ⁇ (Excellent) is when the steel wool abrasion durability is 10,000 times or more, and ⁇ (Good) is 7,500 times or more but less than 10,000 times. ), 5,000 times or more but less than 7,500 times is ⁇ (acceptable), and less than 5,000 times is ⁇ (impossible), as shown in Tables 1, 2, and 3.
• the test environmental conditions are 25° C. and 50% relative humidity.
• the component (II) When the fluoropolyether group-containing polymer of component (I) was used alone, the coefficient of dynamic friction was good, but the wear resistance was insufficient.
• the component (II) also has a fluorooxyalkylene group in the molecule, a reactive functional group at both ends of the polymer, and a polar group.
• the fluoropolyether group-containing polymer was used in the proportions shown in the examples, both the coefficient of dynamic friction and the abrasion resistance were good. There was a tendency for the dynamic friction coefficient and wear resistance to decrease as the mixing ratio of component (II) to component (I) increased.

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• 2023
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