WO2023248880A1 - フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 - Google Patents
フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 Download PDFInfo
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- WO2023248880A1 WO2023248880A1 PCT/JP2023/022017 JP2023022017W WO2023248880A1 WO 2023248880 A1 WO2023248880 A1 WO 2023248880A1 JP 2023022017 W JP2023022017 W JP 2023022017W WO 2023248880 A1 WO2023248880 A1 WO 2023248880A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- the present invention relates to fluoropolyether group-containing polymers, etc., and specifically relates to a linker portion containing at least one phenylene group in the molecule and a silanol group (hydroxyl group bonded to a silicon atom) or hydration group connected to the linker portion.
- the present invention relates to a surface treatment agent containing the above-mentioned surface treatment agent, and an article surface-treated with the surface treatment agent.
- 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. .
- the fluoropolyether group-containing polymer of the present invention has a silanol group and/or a hydrolyzable silyl group, and has a fluorooxyalkylene group-containing polymer residue (Rf) in the main chain and a silanol group and/or a hydrolyzable silyl group. It has an o-, m- or p-phenylene group in the connecting group (linker) with the silyl group (-SiX a (R) 3-a ).
- Articles surface-treated with a surface treatment agent containing the polymer and/or its partial (hydrolyzed) condensate exhibit excellent slipperiness in addition to water and oil repellency.
- articles surface-treated with the above-mentioned surface treatment agent have improved adhesion to the substrate and excellent chucking properties, and especially can exhibit its effect more effectively on the lens base material.
- the fluoropolyether group-containing polymer of the present invention has at least one, preferably 1 to 12, more preferably 1 to 8 groups represented by the following formula (1) at at least one terminal in the molecule. It is a fluoropolyether group-containing polymer (or a fluorooxyalkylene group-containing polymer).
- Y is a divalent organic group containing an o-, m- or p-phenylene group
- R is an alkyl group having 1 to 4 carbon atoms or a phenyl group
- X is independently a hydroxyl group or a hydrolyzable (a is 2 or 3)
- Y is a divalent organic group containing an o-, m-, or p-phenylene group, and preferred examples include those represented by the following formula (5).
- g is an integer from 0 to 20
- h is an integer from 1 to 3
- i1, j1, k1 are integers from 1 to 10
- i2, j2, k2 are integers from 0 to 5.
- k3 is an integer from 1 to 10
- each repeating unit may be randomly bonded to each other, and when (CH 2 ) g exists in multiple units, the (CH 2 ) unit divided into multiple units (The number of repetitions may be the same or different.)
- Examples of such Y include the following groups. Note that it is preferable that the bond on the right side bonds with the silicon atom of formula (1).
- X is independently a hydroxyl group, or a group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, etc.
- alkoxy groups alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy groups, methoxyethoxy groups, ethoxymethoxy groups, and ethoxyethoxy groups; acyloxy groups having 2 to 10 carbon atoms such as acetoxy groups and propionoxy groups; vinyloxy groups; It is a hydrolyzable group selected from the group consisting of alkenyloxy groups having 2 to 10 carbon atoms such as allyloxy group, propenoxy group, and isopropenoxy group, and halogen atoms such as chloro group, bromo group, and iodo group.
- R is independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.
- a is 2 or 3, preferably 3.
- the groups represented by formula (1) may be the same or different. Good too.
- the fluoropolyether group-containing polymer of the present invention is preferably a fluoropolyether group-containing polymer represented by the following formula (2).
- Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following formula (3)
- W is a fluoroalkylene group containing one or more hydrogen atoms.
- D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 -, CF 2 H- or CH 2 F- and may contain an oxygen atom, or A, where A is represented by the following formula (4). is the group represented.
- U is a single bond or a di- to tetravalent organic group
- Z is independently a single bond or a carbon atom, silicon atom, nitrogen atom, or a tri- to nine-valent organic group
- Y' is independently is an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, a are the same as above, and b is 1 is an integer from 1 to 8, and c is an integer from 1 to 3.
- Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following formula (3).
- W is a fluoroalkylene group containing one or more hydrogen atoms, such as CF 2 , C 2 F 4 , C 3 F 6 , C 4 F 8 , C 5 F 10 , C 6 F
- perfluoroalkylene groups such as 12 in which one or two fluorine atoms are replaced with hydrogen atoms.
- d is an integer of 1 to 3 independently for each unit, preferably 1 or 2.
- p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably p is an integer of 0 to 440, q is an integer of 0 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, v is an integer of 0 to 100, p+q+r+s+t+u+v is 20 to 450, preferably 20 to 200, and p+q+r+s+t+u+v is If it is smaller than the above upper limit, the adhesion and curability will be good, and if it is larger than the above lower limit, the characteristics of the fluoropolyether group can be fully exhibited, so it is preferable.
- Each unit may be linear or branched. Furthermore, the repeating units shown in
- Rf the following can be exemplified as Rf.
- p', q', r', s', t', and u' are each an integer of 1 or more, and their upper limit is the same as the upper limit of p, q, r, s, t, and u above.
- the total of these p', q', r', s', t', and u' is 20 to 450.
- r1' is an integer of 20 to 180.
- r2' and r3' are each 1 to 100. is an integer, and the sum of r2' and r3' is 20 to 180.
- each repeating unit shown in parentheses with p', q', r', s', t', and u' may be randomly combined.
- D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 -, CF 2 H- or CH 2 F- and which may contain an oxygen atom, or A (described below).
- a monovalent fluorine-containing hydrocarbon group which is a group represented by formula (4) and has a terminal of CF 3 -, CF 2 H- or CH 2 F- and may contain an oxygen atom,
- a fluoroalkyl group having 1 to 6 carbon atoms is used, particularly one in which the terminal end of the polymer is CF 3 -- or CF 2 H-.
- Examples of the monovalent fluorine-containing hydrocarbon group whose terminal end of D is CF 3 --, CF 2 H -- or CH 2 F -- and which may contain an oxygen atom include the following groups.
- D is preferably a fluorine atom, CF 3 --, CF 3 CF 2 -- or A.
- A is a group represented by the following formula (4).
- U is a single bond or a di- to tetravalent organic group
- Z is independently a single bond or a carbon atom, silicon atom, nitrogen atom, or a tri- to nine-valent organic group
- Y' is independently is an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, a are the same as above, and b is 1 is an integer from 1 to 8, and c is an integer from 1 to 3.
- U is a single bond or a divalent to tetravalent organic group, preferably a single bond, a carbonyl group, an amide group, a group represented by the following formula, (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- linear divalent organopolysiloxane residues having 2 to 100 silicon atoms, preferably 2 to 50 silicon atoms, which may be included in the divalent to tetravalent hydrocarbon group include those shown below. can.
- 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 may be different.
- n is an integer from 1 to 99, preferably an integer from 1 to 49.
- U examples include the following groups. Note that it is preferable that the bond on the left side is bonded to Rf, and the other bonds are bonded to Z. (In the formula, f is independently an integer of 1 to 4, l1 and l2 are integers of 1 to 4, n is an integer of 1 to 99, and e is an integer of 1 to 30.)
- 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
- R 1 may be the same
- R 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, ethylene group, propylene group, or butylene group, or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.
- Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, and at least one Y' in the molecule is Y.
- aliphatic divalent hydrocarbon groups having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octa Examples include alkylene groups such as methylene group, and propylene group is preferred.
- Y is the same as Y in the above formula (1). At least one Y' in the molecule may be Y, but it is preferable that all Y' be Y. Note that when a plurality of Y's are included in the above formula (4), these Y's may be the same or different.
- Examples of the fluoropolyether group-containing polymer represented by the above formula (2) include the following structures.
- Y' is the same as above, D' is F, CF 3 or CF 3 CF 2 , p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is 20 to 450 preferably an integer from 20 to 200, r1 is an integer from 20 to 180, r2 is an integer from 1 to 100, r3 is an integer from 1 to 100, and r2+r3 is an integer from 20 to 180.
- Each repeating unit shown in parentheses with p1 and q1 may be combined randomly.
- fluoropolyether group-containing polymer represented by the above formula (2) include the following structures.
- Rf, D, and A in the above formula (2) fluoropolyether group-containing polymers having several types of silanol groups and/or hydrolyzable silyl groups can be obtained.
- D' is F, CF 3 or CF 3 CF 2
- p1 is an integer of 5 to 440
- q1 is an integer of 5 to 250
- p1+q1 is an integer of 20 to 450, preferably 20 to 440.
- r1 is an integer of 20 to 180
- r2 is an integer of 1 to 100
- r3 is an integer of 1 to 100
- r2+r3 is an integer of 20 to 180.
- Each repeating unit shown in parentheses labeled p1 and q1 may be randomly linked.
- Examples of the method for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) include the following methods.
- a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and o-, m- or p- - Mixing an organosilicon compound having a phenylene group, a SiH group and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.), and adding a hydrosilylation reaction catalyst such as chloroplatinic acid/vinyl Aging in the presence of a toluene solution of the siloxane complex at a temperature of 40 to 120°C, preferably 60 to 100°C
- a hydrosilylation reaction catalyst such as chloroplatinic acid/vinyl Aging in the presence of a toluene solution of the siloxane complex
- the terminal of D 1 is CF 3 -, CF 2 H- or CH 2 F-, and as a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, the terminal of D is CF 3 -, CF 2 H- or CH 2 F-, and the same monovalent fluorine-containing hydrocarbon groups which may contain an oxygen atom can be exemplified.
- D 1 is preferably a fluorine atom, CF 3 --, CF 3 CF 2 -- or A 1 .
- a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) it has an o-, m- or p-phenylene group in the molecule, and a SiH group and a silanol group.
- organosilicon compounds having a hydrolyzable silyl group include the following.
- a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) it has an o-, m- or p-phenylene group in the molecule, and a SiH group and a silanol group.
- the amount of the organosilicon compound having a hydrolyzable silyl group is based on 1 mole of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).
- the SiH group can be used in an amount of 1 to 4 moles, preferably 1 to 2.5 moles.
- a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) it is preferable to have an o-, m-, or p-phenylene group in the molecule, and to form a polymer with an SiH group.
- organosilicon compounds having a silanol group or a hydrolyzable silyl group an organosilicon compound that does not have an o-, m-, or p-phenylene group in its molecule and has an SiH group and a silanol group or a hydrolyzable silyl group. It is also possible to react compounds.
- the fluoropolyether group-containing polymer having an olefin moiety preferably has two or more olefin moieties (alkenyl group).
- examples of the organosilicon compound having no o-, m- or p-phenylene group in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group include, for example, trimethoxysilane.
- the reaction rate is 1 mole or more of an organosilicon compound having an o-, m-, or p-phenylene group in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group reacts with 1 mole of the polyether group-containing polymer.
- Organosilicon compounds that have a phenylene group and have a SiH group and a silanol group or a hydrolyzable silyl group; It is preferable to use the organosilicon compound having a decomposable silyl group so that the total amount of SiH groups in the organosilicon compound is 1 to 4 moles, preferably 1 to 2.5 moles.
- examples of the solvent include fluorine-based solvents.
- fluorine-based solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1 , 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, product name: Novec series) ), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), Asahikl
- examples of hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, and alcohol modification of chloroplatinic acid. Examples include complexes of chloroplatinic acid and olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
- the amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, preferably 0.1 to 50 ppm in terms of transition metal (mass), based on the mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group). Use the amount.
- organosilicon compound having an o-, m- or p-phenylene group in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group
- those having a halogen atom as the hydrolyzable silyl group When an organosilicon compound is used, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group.
- This usage amount is based on the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) and the organosilicon polymer having an o-, m-, or p-phenylene group in the molecule and having a SiH group and a halogenated silyl group. It can be used in an amount of 10 to 200 parts by weight, preferably 40 to 100 parts by weight, per 100 parts by weight of the addition reaction product with the compound.
- a fluoropolyether group-containing polymer having an olefin moiety alkenyl group
- a compound represented by the following formula A silane compound represented by the following formula as an organosilicon compound having an o-, m- or p-phenylene group in the molecule, and a SiH group and a silanol group or a hydrolyzable silyl group.
- a compound represented by the following formula is obtained.
- a compound represented by the following formula as a fluoropolyether group-containing polymer having an olefin moiety alkenyl group
- trimethoxysilane trimethoxysilane
- fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) include the following methods.
- Preparation method 2 A fluoropolyether group-containing polymer having a carbonyl group is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and o-, m-, or p-phenylene groups are added to the molecule.
- a solvent for example, a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and o-, m-, or p-phenylene groups are added to the molecule.
- 20 to 100°C, preferably 25 to 50°C, more preferably Aging is performed at a temperature of about 25° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
- organosilicon compounds having an o-, m- or p-phenylene group in the molecule, and an amino group and a silanol group or a hydrolyzable silyl group
- an organosilicon compound having a halogen atom as the hydrolyzable silyl group When a compound is used, the substituent (halogen atom) on the silyl group may then be converted into another hydrolyzable group, such as an alkoxy group such as a methoxy group.
- the fluoropolyether group-containing polymer having a carbonyl group is as follows.
- An example is a fluoropolyether group-containing polymer represented by formula (14).
- D 2 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 -, CF 2 H- or CH 2 F- and may contain an oxygen atom, or A 2
- a 2 is a group represented by the following formula (15). (Wherein, Q is OH, OCH 3 , OCH 2 CH 3 or F.)]
- the terminal of D 2 is CF 3 -, CF 2 H- or CH 2 F-, and as a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, the terminal of D is CF 3 -, CF 2 H- or CH 2 F-, and the same monovalent fluorine-containing hydrocarbon groups which may contain an oxygen atom can be exemplified.
- D 2 is preferably a fluorine atom, CF 3 --, CF 3 CF 2 -- or A 2 .
- Examples of the fluoropolyether group-containing polymer having a carbonyl group represented by the above formula (14) include the following. (In the formula, D', p1, q1, p1+q1, r1, r2, r3, r2+r3 are the same as above. Each repeating unit shown in parentheses with p1 and q1 may be randomly combined. .)
- a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 2), having an o-, m- or p-phenylene group in the molecule
- organosilicon compound having an amino group and a silanol group or a hydrolyzable silyl group include p-aminophenyltrimethoxysilane, (4-trimethoxysilylphenyl)methanamine, and the like.
- a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 2), having an o-, m- or p-phenylene group in the molecule
- the amount of the organosilicon compound having an amino group and a silanol group or a hydrolyzable silyl group is based on the amino group in the organosilicon compound per mole of carbonyl group in the fluoropolyether group-containing polymer having a carbonyl group. can be used in an amount of 1 to 4 mol, preferably 1 to 2.5 mol.
- the solvent may be the same as that exemplified for the solvent in preparation method 1 above. can be used.
- the amount of the solvent to be used can be 10 to 300 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the fluoropolyether group-containing polymer having a carbonyl group.
- the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group, and
- reagents that can be used to convert a substituent (halogen atom) into another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.
- This usage amount is based on the addition of a fluoropolyether group-containing polymer having a carbonyl group and an organosilicon compound having an o-, m- or p-phenylene group in the molecule and an amino group and a halogenated silyl group. It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the reaction product.
- a fluoropolyether group-containing polymer having a carbonyl group a compound represented by the following formula p-aminophenyltrimethoxysilane was used as an organosilicon compound having an o-, m- or p-phenylene group in the molecule and an amino group and a silanol group or a hydrolyzable silyl group.
- a compound represented by the following formula is obtained.
- fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) include the following methods.
- Preparation method 3 A fluoropolyether group-containing polymer having SiH groups is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and o-, m-, or p-phenylene groups are added to the molecule.
- a hydrosilylation reaction catalyst such as chloroplatinic acid/vinyl Aging in the presence of a toluene solution of the siloxane 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 10 to 36 hours, more preferably about 12 hours.
- organosilicon compounds having an o-, m- or p-phenylene group in the molecule an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group
- a halogen atom is used as the hydrolyzable silyl group.
- the substituent (halogen atom) on the silyl group may be converted into another hydrolyzable group, such as an alkoxy group such as a methoxy group.
- the fluoropolyether group-containing polymer having an SiH group is as follows.
- An example is a fluoropolyether group-containing polymer represented by formula (16).
- Rf is the same as above
- D 3 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 -, CF 2 H- or CH 2 F- and may contain an oxygen atom, or A 3
- a 3 is a group represented by the following formula (17). (In the formula, U, Z, b, and c are the same as above.)]
- the terminal of D 3 is CF 3 -, CF 2 H- or CH 2 F-, and as a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, the terminal of D is CF 3 -, CF 2 H- or CH 2 F-, and the same monovalent fluorine-containing hydrocarbon groups which may contain an oxygen atom can be exemplified.
- D 3 is preferably a fluorine atom, CF 3 -, CF 3 CF 2 - or A 3 .
- organosilicon compounds having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group include p-styryltrimethoxysilane, p-styrylethyltrimethoxysilane, 2-(4-ethynylphenyl)ethyl Examples include trimethoxysilane.
- the hydrolyzable silyl group when an organosilicon compound having a halogen atom is used, the substituent on the silyl group (halogen atom) may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group.
- Examples of reagents that can be used to convert substituents (halogen atoms) on silyl groups into other hydrolyzable groups include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. Can be mentioned. This usage amount is based on a fluoropolyether group-containing polymer having an SiH group and an organosilicon polymer having an o-, m-, or p-phenylene group in the molecule, an olefin moiety (alkenyl group), and a halogenated silyl group. It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the addition reaction product with the compound.
- a fluoropolyether group-containing polymer having an SiH group a compound represented by the following formula p-styryltrimethoxysilane is used as an organosilicon compound having an o-, m- or p-phenylene group in the molecule, an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group.
- a compound represented by the following formula is obtained.
- fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) include the following methods.
- Preparation method 4 A fluoropolyether group-containing polymer having a hydroxyl group is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and a polymer having an o-, m-, or p-phenylene group in the molecule is dissolved.
- a toluene solution of the acid/vinyl siloxane 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 10 to 36 hours, more preferably about 12 hours. Let time mature.
- an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule if an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used, then The substituent (halogen atom) may be converted into another hydrolyzable group, such as an alkoxy group such as a methoxy group.
- D 4 is preferably a fluorine atom, CF 3 -, CF 3 CF 2 - or A 4 .
- Examples of the fluoropolyether group-containing polymer having a hydroxyl group represented by the above formula (18) include the following. (In the formula, D', p1, q1, p1+q1, r1, r2, r3, r2+r3 are the same as above. Each repeating unit shown in parentheses with p1 and q1 may be randomly combined. .)
- the amount of the organic compound having a halogen group and an olefin moiety (alkenyl group) to be used is preferably 1 to 4 moles of halogen group in the organic compound per mole of hydroxyl group in the fluoropolyether group-containing polymer having a hydroxyl group. can be used in an amount of 1 to 2.5 moles.
- the basic reagent is preferably sodium hydroxide or potassium hydroxide.
- the basic reagent can be used in an amount of 0.5 to 15 moles, preferably 0.8 to 7 moles, per mole of the fluoropolyether group-containing polymer having a hydroxyl group.
- This usage amount is based on a fluoropolyether group-containing polymer having an SiH group and an organosilicon polymer having an o-, m-, or p-phenylene group in the molecule, an olefin moiety (alkenyl group), and a halogenated silyl group. It can be used in an amount of 10 to 300 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of the addition reaction product with the compound.
- a fluoropolyether group-containing polymer having a hydroxyl group a compound represented by the following formula and 1-(bromomethyl)-3-allylbenzene was used as an organic compound having an o-, m- or p-phenylene group in the molecule, and a halogen group and an olefin moiety (alkenyl group).
- a compound represented by the following formula is obtained.
- trimethoxysilane is used as an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the compound represented by the following formula is obtained.
- the present invention further provides a fluoropolyether group-containing polymer having at least one group represented by the above formula (1) at at least one end of the molecule, particularly a silanol group represented by the above formula (2).
- a surface treatment agent containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group as a main component is provided.
- the surface treatment agent may contain as a main component the above-mentioned fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group. It may contain unreacted raw materials and reaction intermediates before introducing the terminal silanol group or the terminal hydrolyzable silyl group.
- the surface treatment agent is obtained by condensing the hydroxyl group of the fluoropolyether group-containing polymer or the hydroxyl group of the terminal hydrolyzable silyl group of the fluoropolyether group-containing polymer partially hydrolyzed in advance by a known method.
- the obtained partial (hydrolysis) condensate may also be included.
- the "partial (hydrolyzed) condensate” refers to a partial condensate or a partially hydrolyzed condensate.
- Examples of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by formula (20) include the following. (In the formula, p4, q4, and r4 are each independently an integer of 1 to 450, and the total of p4, q4, and r4 is 20 to 450, and r5 and r6 are each an integer of 20 to 450. Each repeating unit shown in parentheses with p4, q4, r6 may be combined randomly.)
- the surface treatment 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.), or an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added.
- 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, usually 0.01 to 5 parts by weight, particularly 0.01 to 5 parts by weight, per 100 parts by weight of the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate of the present invention. It is 0.1 to 1 part by mass.
- the surface treatment agent may contain a suitable solvent.
- suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluorohexane, perfluoroheptane, perfluorooctane, tridecafluorooctane, 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), methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, 1,1, 2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, 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, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, and tridecafluorooctane are preferred.
- the substrate 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 and their oxides, glass, plastics, ceramics, and quartz.
- the surface treatment agent of the present invention can impart water and oil repellency to the base material. In particular, it can be suitably used as a surface treatment agent for SiO 2 -treated glass or film.
- the surface treatment agent of the present invention can be applied to antifouling coatings for sanitary products such as bathtubs and wash basins, antifouling coatings for window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc., and antifouling coatings for building materials for external walls.
- Water and oil repellent coatings anti-oil coatings for kitchen building materials, antifouling and anti-paper/graffiti coatings for telephone booths, anti-fingerprint coatings for works of art, anti-fingerprint coatings for compact discs, DVDs, etc. It is also useful as a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersion modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.
- the surface treatment agent of the present invention can provide a lens substrate with a cured film that is excellent in water and oil repellency, slipperiness, and abrasion resistance, as well as excellent chucking performance.
- the chucking property here refers to the degree to which the board to be processed is fixed when processing is performed with the board fixed with adhesive tape. For example, when a lens is fixed with lens blocking tape for rounding processing. Judgment is made based on the strength of adhesion between the lens blocking tape and the lens (tensile shear adhesion strength). Good chucking performance is when the adhesive tape and the substrate can be firmly fixed to the extent that the substrate can be processed with high precision.
- the repeating units shown in parentheses with p1 and q1 are randomly bonded.
- the film thickness is a value measured by a spectroscopic ellipsometric measurement method using a spectroscopic ellipsometer.
- Example 9 A surface treatment agent was prepared by dissolving the compound obtained in Synthesis Example 9 in Opteon SF10 (manufactured by Mitsui Chemours Fluoro Products, methyl perfluoroheptenyl ether) to a concentration of 20% by mass.
- a surface treatment agent was prepared by dissolving the compound obtained in Synthesis Example 18 in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) to a concentration of 20% by mass.
- results were improved (evaluation A, B) by introducing a phenylene group into the linking group between the fluorooxyalkylene group-containing polymer residue in the main chain and the silanol group and/or hydrolyzable silyl group.
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Abstract
Description
なお、本発明に関連する従来技術として、上述した文献と共に下記文献が挙げられる。
〔1〕
分子中の少なくとも1個の末端に下記式(1)
で表される基を少なくとも1個有するフルオロポリエーテル基含有ポリマー。
〔2〕
前記式(1)において、Yが下記式(5)
で表される基である〔1〕に記載のフルオロポリエーテル基含有ポリマー。
〔3〕
前記式(1)において、Yが下記式で表される基から選ばれるものである〔1〕又は〔2〕に記載のフルオロポリエーテル基含有ポリマー。
〔4〕
前記式(1)において、Xが水酸基、炭素数1~10のアルコキシ基、炭素数2~10のアルコキシアルコキシ基、炭素数2~10のアシロキシ基、炭素数2~10のアルケニルオキシ基又はハロゲン原子である〔1〕~〔3〕のいずれかに記載のフルオロポリエーテル基含有ポリマー。
〔5〕
フルオロポリエーテル基含有ポリマーが、下記式(2)で表されるものである〔1〕~〔4〕のいずれかに記載のフルオロポリエーテル基含有ポリマー。
Dはフッ素原子、末端がCF3-、CF2H-もしくはCH2F-であり酸素原子を含んでもよい1価のフッ素含有炭化水素基、又はAであり、Aは下記式(4)で表される基である。
〔6〕
前記式(4)において、Zが単結合、又は炭素原子、ケイ素原子、窒素原子、ケイ素原子数3~13個の直鎖状、分岐状もしくは環状の3~8価のオルガノポリシロキサン残基、3価のイソシアヌル基もしくは3価のトリアジン環含有基である〔5〕に記載のフルオロポリエーテル基含有ポリマー。
〔7〕
前記式(4)において、Uが単結合、カルボニル基、アミド基、下記式で表される基、
又は酸素原子、硫黄原子、水酸基、ポリエーテル基、ジオルガノシリレン基、ケイ素原子数2~100個の直鎖状の2価のオルガノポリシロキサン残基、シルアルキレン基、シルアリーレン基、2級アミノ基、3級アミノ基、エーテル基、カルボニル基、アミド基及びエステル基から選ばれる1種又は2種以上の原子又は基を含んでいてもよい炭素数1~20の2~4価の炭化水素基である〔5〕又は〔6〕に記載のフルオロポリエーテル基含有ポリマー。
〔8〕
前記式(2)で表されるポリマーが、下記式のいずれかで表されるものである〔5〕~〔7〕のいずれかに記載のフルオロポリエーテル基含有ポリマー。
〔9〕
〔1〕~〔8〕のいずれかに記載のフルオロポリエーテル基含有ポリマー及び/又はその部分(加水分解)縮合物を主成分とする表面処理剤。
〔10〕
〔9〕に記載の表面処理剤で表面処理された物品。
〔11〕
レンズ基材である〔10〕に記載の物品。
上記式(1)において、aは2又は3であり、3であることが好ましい。
なお、本発明のフルオロポリエーテル基含有ポリマーにおいて、式(1)で表される基を分子中に2個以上有する場合、式(1)で表される基は同一であっても異なっていてもよい。
Dはフッ素原子、末端がCF3-、CF2H-もしくはCH2F-であり酸素原子を含んでもよい1価のフッ素含有炭化水素基、又はAであり、Aは下記式(4)で表される基である。
また、p、q、r、s、t、u、vはそれぞれ0~450の整数、好ましくは、pは0~440の整数、qは0~250の整数、rは0~180の整数、sは0~100の整数、tは0~100の整数、uは0~100の整数、vは0~100の整数であり、p+q+r+s+t+u+vは20~450、好ましくは20~200であり、p+q+r+s+t+u+vが上記上限値より小さければ密着性や硬化性が良好であり、上記下限値より大きければフルオロポリエーテル基の特徴を十分に発揮することができるので好ましい。各単位は直鎖状であっても分岐状であってもよい。また、p、q、r、s、t、u、vが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。
又は酸素原子、硫黄原子、水酸基、ポリエーテル基、ジメチルシリレン基等のジオルガノシリレン基、ケイ素原子数2~100個、好ましくは2~50個の直鎖状の2価のオルガノポリシロキサン残基、シルアルキレン基、シルアリーレン基、2級アミノ基、3級アミノ基、エーテル基、カルボニル基、アミド基及びエステル基から選ばれる1種又は2種以上の原子又は基を含んでいてもよい炭素数1~20の2~4価の炭化水素基である。
また、Bの1価のポリエーテル基としては、-(Ce1H2e1O)e-CH3(e1は1~6の整数であり、eは1~30の整数である。)で示されるものが好ましい。
で表される基であり、R4は独立に単結合又は下記式(7)
で表される基であり、R3の少なくとも1つは式(6)である。m1は1~9、好ましくは1~4の整数であり、m2は0~9、好ましくは0~3の整数であり、m3は2~6、好ましくは3~5の整数、m4は0~8の整数、好ましくは0又は1で、m3+m4は3~10、好ましくは3~5の整数であり、m5は2又は3であり、m6は3~9、好ましくは3~7の整数であり、m7は0~9、好ましくは0~3の整数であり、括弧内に示される各繰り返し単位はランダムに結合されていてよい。但し、それぞれのオルガノポリシロキサン残基のケイ素原子数は3~13個である。]
炭素数1~8の脂肪族2価炭化水素基としては、メチレン基、エチレン基、プロピレン基(トリメチレン基、メチルエチレン基)、ブチレン基(テトラメチレン基、メチルプロピレン基)、ヘキサメチレン基、オクタメチレン基等のアルキレン基が例示でき、プロピレン基が好ましい。
Yは上記式(1)のYと同じである。Y’としては、分子中の少なくとも1個がYであればよいが、Y’のすべてがYであることが好ましい。なお、上記式(4)にYが複数含まれる場合、これらのYは同一であっても異なっていてもよい。
上記式(4)において、bは1~8の整数、好ましくは1~4の整数であり、cは1~3の整数、好ましくは1又は2である。
[調製方法1]
オレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えば分子中にo-,m-もしくはp-フェニレン基を有し、SiH基とシラノール基又は加水分解性シリル基(ハロゲン化シリル基やアルコキシシリル基等)とを有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは10~36時間、より好ましくは約12時間熟成させる。なお、分子中にo-,m-もしくはp-フェニレン基を有し、SiH基とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物において、加水分解性シリル基としてハロゲン原子を有する有機ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として、例えばメトキシ基などのアルコキシ基等に変換してもよい。
ここで、分子中にo-,m-もしくはp-フェニレン基を有さず、SiH基とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物としては、例えばトリメトキシシラン等が例示できる。
溶剤の使用量は、オレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは30~150質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、オレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.01~100ppm、好ましくは0.1~50ppmとなる量で使用する。
この使用量は、オレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーと、分子中にo-,m-もしくはp-フェニレン基を有し、SiH基とハロゲン化シリル基とを有する有機ケイ素化合物との付加反応生成物100質量部に対して、10~200質量部、好ましくは40~100質量部用いることができる。
[調製方法2]
カルボニル基を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えば分子中にo-,m-もしくはp-フェニレン基を有し、アミノ基とシラノール基又は加水分解性シリル基(ハロゲン化シリル基やアルコキシシリル基等)とを有する有機ケイ素化合物を混合し、20~100℃、好ましくは25~50℃、より好ましくは約25℃の温度で、1~72時間、好ましくは20~36時間、より好ましくは約24時間熟成させる。なお、分子中にo-,m-もしくはp-フェニレン基を有し、アミノ基とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物において、加水分解性シリル基としてハロゲン原子を有する有機ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として、例えばメトキシ基などのアルコキシ基等に変換してもよい。
溶剤の使用量は、カルボニル基を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは30~150質量部用いることができる。
この使用量は、カルボニル基を有するフルオロポリエーテル基含有ポリマーと、分子中にo-,m-もしくはp-フェニレン基を有し、アミノ基とハロゲン化シリル基とを有する有機ケイ素化合物との付加反応生成物100質量部に対して、10~300質量部、好ましくは50~200質量部用いることができる。
[調製方法3]
SiH基を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えば分子中にo-,m-もしくはp-フェニレン基を有し、オレフィン部位(アルケニル基)とシラノール基又は加水分解性シリル基(ハロゲン化シリル基やアルコキシシリル基等)とを有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは10~36時間、より好ましくは約12時間熟成させる。なお、分子中にo-,m-もしくはp-フェニレン基を有し、オレフィン部位(アルケニル基)とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物において、加水分解性シリル基としてハロゲン原子を有する有機ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として、例えばメトキシ基などのアルコキシ基等に変換してもよい。
溶剤の使用量は、SiH基を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは30~150質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、SiH基を有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.01~100ppm、好ましくは0.1~50ppmとなる量で使用する。
この使用量は、SiH基を有するフルオロポリエーテル基含有ポリマーと、分子中にo-,m-もしくはp-フェニレン基を有し、オレフィン部位(アルケニル基)とハロゲン化シリル基とを有する有機ケイ素化合物との付加反応生成物100質量部に対して、10~300質量部、好ましくは50~200質量部用いることができる。
[調製方法4]
水酸基を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えば分子中にo-,m-もしくはp-フェニレン基を有し、ハロゲン基とオレフィン部位(アルケニル基)を有する有機化合物を混合し、塩基性試薬、例えば水酸化ナトリウム水溶液存在下、40~120℃、好ましくは50~100℃、より好ましくは約60℃の温度で、1~72時間、好ましくは10~36時間、より好ましくは10~12時間熟成させる。得られたポリマーは、分子中にo-,m-もしくはp-フェニレン基とオレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーである。
次に、分子中にo-,m-もしくはp-フェニレン基とオレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーを、溶剤、例えば1,3-ビス(トリフルオロメチル)ベンゼンなどのフッ素系溶剤に溶解させ、例えば分子中にSiH基とシラノール基又は加水分解性シリル基(ハロゲン化シリル基やアルコキシシリル基等)とを有する有機ケイ素化合物を混合し、ヒドロシリル化反応触媒、例えば塩化白金酸/ビニルシロキサン錯体のトルエン溶液存在下、40~120℃、好ましくは60~100℃、より好ましくは約80℃の温度で、1~72時間、好ましくは10~36時間、より好ましくは約12時間熟成させる。分子中にオレフィン部位(アルケニル基)とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物において、加水分解性シリル基としてハロゲン原子を有する有機ケイ素化合物を用いた場合は、その後、シリル基上の置換基(ハロゲン原子)を、他の加水分解性基として、例えばメトキシ基などのアルコキシ基等に変換してもよい。
溶剤の使用量は、水酸基を有するフルオロポリエーテル基含有ポリマー100質量部に対して、0~300質量部、好ましくは30~150質量部用いることができる。
塩基性試薬の使用量は、水酸基を有するフルオロポリエーテル基含有ポリマー1モルに対して、塩基が0.5~15モル、好ましくは0.8~7モルとなるように用いることができる。
溶剤の使用量は、分子中にo-,m-もしくはp-フェニレン基とオレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマー100質量部に対して、10~300質量部、好ましくは30~150質量部用いることができる。
ヒドロシリル化反応触媒の使用量は、分子中にo-,m-もしくはp-フェニレン基とオレフィン部位(アルケニル基)を有するフルオロポリエーテル基含有ポリマーの質量に対して、遷移金属換算(質量)で0.01~100ppm、好ましくは0.02~50ppmとなる量で使用する。
この使用量は、SiH基を有するフルオロポリエーテル基含有ポリマーと、分子中にo-,m-もしくはp-フェニレン基を有し、オレフィン部位(アルケニル基)とハロゲン化シリル基とを有する有機ケイ素化合物との付加反応生成物100質量部に対して、10~300質量部、好ましくは50~200質量部用いることができる。
D5-Rf-D5 (20)
(式中、Rfは上記と同じであり、D5は独立にフッ素原子、水素原子、又は末端がCF3-、CF2H-もしくはCH2F-であり酸素原子を含んでもよい1価のフッ素含有炭化水素基である。)
上記式(20)において、D5は独立にフッ素原子、水素原子、又は末端がCF3-、CF2H-もしくはCH2F-であり酸素原子を含んでもよい1価のフッ素含有炭化水素基である。このようなD5として、具体的には、CF3-、CF3CF2-、CF3CF2CF2-、C3F7O-CF(CF3)CH2-、C3F7O-CFHCF2OCH2-、CF3O-、CF3CF2O-、CF3CF2CF2O-等が例示できる。D5としては、中でも、フッ素原子、CF3-、CF3CF2-、CF3O-、CF3CF2O-、CF3CF2CF2O-が好ましい。
加水分解縮合触媒の添加量は触媒量であり、通常、本発明のフルオロポリエーテル基含有ポリマー及び/又はその部分(加水分解)縮合物100質量部に対して0.01~5質量部、特に0.1~1質量部である。
なお、膜厚は、例えば、分光反射率測定法、エックス線反射率測定法、分光エリプソメトリー測定法、蛍光エックス線測定法等の手段により測定できる。
ここでいうチャッキング性とは、加工対象の基板を接着テープで固定した状態で加工を行ったときの基板が固定される程度をいい、例えば玉摺り加工用のレンズブロッキングテープでレンズを固定した際のレンズブロッキングテープとレンズとの接着の強さ(引張せん断接着強さ)を目安に判断される。接着テープと基板との接着により基板を精度良く加工できる程度に強固に固定できる場合をチャッキング性がよいという。
反応容器に、下記式(1A)
反応容器に、下記式(2A)
反応容器に、上記式(2A)で表される化合物100g(2.32×10-2mol)、1,3-ビス(トリフルオロメチル)ベンゼン50g、下記式(3A)
反応容器に、下記式(4A)
反応容器に、下記式(5A)
反応容器に、下記式(6A)
反応容器に、下記式(7A)
反応容器に、下記式(8A)
反応容器に、下記式(9A)
反応容器に、下記式(10A)
反応容器に、下記式(11A-1)と(11A-2)
反応容器に、下記式(12A)
反応容器に、下記式(13A)
反応容器に、下記式(14A)
反応容器に、上記式(15A)
反応容器に、上記式(2A)で表される化合物100g(2.32×10-2mol)、1,3-ビス(トリフルオロメチル)ベンゼン50g、トリメトキシシラン3.31g(2.71×10-2mol)、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液8.30×10-2g(Pt単体として2.87×10-7molを含有)を混合し、80℃で24時間熟成させた。その後、溶剤及び未反応物を減圧留去後洗浄し、液状の生成物102gを得た。得られた化合物は、1H-NMRにより下記式(16A)で表される構造であることが確認された。
反応容器に、上記式(8A)で表される化合物100g(2.24×10-2mol)、1,3-ビス(トリフルオロメチル)ベンゼン50g、トリメトキシシラン9.40g(7.84×10-2mol)、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液8.30×10-2g(Pt単体として2.87×10-7molを含有)を混合し、80℃で12時間熟成させた。その後、溶剤及び未反応物を減圧留去後洗浄し、液状の生成物102gを得た。得られた化合物は、1H-NMRにより下記式(17A)で表される構造であることが確認された。
反応容器に、下記式(18A)
合成例1で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例2で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例3で得た化合物を、濃度20質量%になるようにアサヒクリンAE-3000(AGC社製、1,1,2,2-テトラフルオロエチル-2,2,2-トリフルオロエチルエーテル)に溶解させて表面処理剤を調製した。
合成例4で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例5で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例6で得た化合物を、濃度20質量%になるようにアサヒクリンAE-3000(AGC社製、1,1,2,2-テトラフルオロエチル-2,2,2-トリフルオロエチルエーテル)に溶解させて表面処理剤を調製した。
合成例7で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例8で得た化合物を、濃度20質量%になるようにオプテオンSF10(三井・ケマーズフロロプロダクツ社製、メチルパーフルオロヘプテニルエーテル)に溶解させて表面処理剤を調製した。
合成例9で得た化合物を、濃度20質量%になるようにオプテオンSF10(三井・ケマーズフロロプロダクツ社製、メチルパーフルオロヘプテニルエーテル)に溶解させて表面処理剤を調製した。
合成例10で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例11で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例12で得た化合物を、濃度20質量%になるようにNovec 7300(3M社製、メチルパーフルオロヘキシルエーテル)に溶解させて表面処理剤を調製した。
合成例13で得た化合物を、濃度20質量%になるようにアサヒクリンAC-6000(AGC社製、トリデカフルオロオクタン)に溶解させて表面処理剤を調製した。
合成例14で得た化合物を、濃度20質量%になるようにアサヒクリンAC-6000(AGC社製、トリデカフルオロオクタン)に溶解させて表面処理剤を調製した。
合成例15で得た化合物を、濃度20質量%になるようにアサヒクリンAC-6000(AGC社製、トリデカフルオロオクタン)に溶解させて表面処理剤を調製した。
合成例16で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例17で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
合成例18で得た化合物を、濃度20質量%になるようにNovec 7200(3M社製、エチルパーフルオロブチルエーテル)に溶解させて表面処理剤を調製した。
上記実施例及び比較例の通り、表面処理剤を調製した。最表面にSiO2層を有するAR処理プラスチックレンズ(サイズ:80mmφ)に、各表面処理剤を真空蒸着し(処理条件は、圧力:2.0×10-2Pa、加熱温度:700℃)、25℃、相対湿度50%の雰囲気下で12時間硬化させて膜厚10nmの硬化被膜を形成した。
[初期撥水性の測定]
上記にて作製した硬化被膜を形成したレンズについて、接触角計Drop Master(協和界面科学社製)を用いて、硬化被膜の水に対する接触角(撥水性)を測定した(液滴:2μl、温度:25℃、相対湿度:40%)。結果(初期水接触角)を表1に示す。
[動摩擦係数の測定]
上記にて作製した硬化被膜を形成したレンズについて、ベンコット(旭化成社製)に対する動摩擦係数を、表面性試験機14FW(新東科学社製)を用いて下記条件で測定した。
接触面積:10mm×30mm
荷重:100gf
A : 動摩擦係数が0.04以下
B : 動摩擦係数が0.04超0.08未満
C : 動摩擦係数が0.08以上
上記にて作製した硬化被膜を形成したレンズについて、ラビングテスター(新東科学社製)を用いて、下記条件で擦った後の硬化被膜の水に対する接触角(撥水性)を上記と同様にして測定し、耐布摩耗性の評価とした。試験環境条件は25℃、相対湿度40%である。
[耐布摩耗性の測定]
布:ベンコット(旭化成社製)
接触面積:1cm2
移動距離(片道):40mm
移動速度:4,800mm/分
荷重:1kgf/1cm2
摩耗回数:30,000回
A : 水接触角が初期から0~2°低下
B : 水接触角が初期から3~5°低下
C : 水接触角が初期から6°以上低下
上記にて作製した硬化被膜を形成したレンズにレンズブロッキングテープ(3M社製:LEAP III 1695M)を貼り付け、引張せん断接着強さを測定した。具体的には、硬化被膜を形成したレンズと該レンズに貼り付けたレンズブロッキングテープとをその接着面にせん断応力が作用するように引張り、その接着接合部が破断したときの最大強さを測定した。
[引張せん断接着強さ測定]
接着面積:2.7cm2
引張速度:50mm/分
A : 引っ張りせん断接着強さ50N以上
B : 引っ張りせん断接着強さ30超50N未満
C : 引っ張りせん断接着強さ30N以下
Claims (11)
- 前記式(1)において、Xが水酸基、炭素数1~10のアルコキシ基、炭素数2~10のアルコキシアルコキシ基、炭素数2~10のアシロキシ基、炭素数2~10のアルケニルオキシ基又はハロゲン原子である請求項1に記載のフルオロポリエーテル基含有ポリマー。
- フルオロポリエーテル基含有ポリマーが、下記式(2)で表されるものである請求項1に記載のフルオロポリエーテル基含有ポリマー。
Dはフッ素原子、末端がCF3-、CF2H-もしくはCH2F-であり酸素原子を含んでもよい1価のフッ素含有炭化水素基、又はAであり、Aは下記式(4)で表される基である。
- 前記式(4)において、Zが単結合、又は炭素原子、ケイ素原子、窒素原子、ケイ素原子数3~13個の直鎖状、分岐状もしくは環状の3~8価のオルガノポリシロキサン残基、3価のイソシアヌル基もしくは3価のトリアジン環含有基である請求項5に記載のフルオロポリエーテル基含有ポリマー。
- 前記式(4)において、Uが単結合、カルボニル基、アミド基、下記式で表される基、
又は酸素原子、硫黄原子、水酸基、ポリエーテル基、ジオルガノシリレン基、ケイ素原子数2~100個の直鎖状の2価のオルガノポリシロキサン残基、シルアルキレン基、シルアリーレン基、2級アミノ基、3級アミノ基、エーテル基、カルボニル基、アミド基及びエステル基から選ばれる1種又は2種以上の原子又は基を含んでいてもよい炭素数1~20の2~4価の炭化水素基である請求項5に記載のフルオロポリエーテル基含有ポリマー。 - 請求項1~8のいずれか1項に記載のフルオロポリエーテル基含有ポリマー及び/又はその部分(加水分解)縮合物を主成分とする表面処理剤。
- 請求項9に記載の表面処理剤で表面処理された物品。
- レンズ基材である請求項10に記載の物品。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003238577A (ja) | 2001-10-05 | 2003-08-27 | Shin Etsu Chem Co Ltd | パーフルオロポリエーテル変性シラン及び表面処理剤、並びに反射防止フィルター |
JP2008144144A (ja) * | 2006-11-15 | 2008-06-26 | Shin Etsu Chem Co Ltd | コーティング剤組成物 |
JP2012072272A (ja) | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品 |
JP2012157856A (ja) | 2011-01-13 | 2012-08-23 | Central Glass Co Ltd | 防汚性物品及びその製造方法 |
JP2013136833A (ja) | 2011-11-30 | 2013-07-11 | Shin-Etsu Chemical Co Ltd | 蒸着用フッ素系表面処理剤及び該表面処理剤で蒸着処理された物品 |
JP2015199906A (ja) | 2014-03-31 | 2015-11-12 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品 |
WO2017077833A1 (ja) * | 2015-11-06 | 2017-05-11 | 信越化学工業株式会社 | 表面処理された樹脂製品 |
JP2021172702A (ja) * | 2020-04-21 | 2021-11-01 | 信越化学工業株式会社 | 被膜の耐候性を評価する方法、該被膜の製膜方法及び該被膜を有する物品 |
JP2022059417A (ja) * | 2020-10-01 | 2022-04-13 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品 |
WO2022131107A1 (ja) * | 2020-12-17 | 2022-06-23 | 信越化学工業株式会社 | 表面処理剤及び該表面処理剤で処理された物品 |
-
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Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003238577A (ja) | 2001-10-05 | 2003-08-27 | Shin Etsu Chem Co Ltd | パーフルオロポリエーテル変性シラン及び表面処理剤、並びに反射防止フィルター |
JP2008144144A (ja) * | 2006-11-15 | 2008-06-26 | Shin Etsu Chem Co Ltd | コーティング剤組成物 |
JP2012072272A (ja) | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品 |
JP2012157856A (ja) | 2011-01-13 | 2012-08-23 | Central Glass Co Ltd | 防汚性物品及びその製造方法 |
JP2013136833A (ja) | 2011-11-30 | 2013-07-11 | Shin-Etsu Chemical Co Ltd | 蒸着用フッ素系表面処理剤及び該表面処理剤で蒸着処理された物品 |
JP2015199906A (ja) | 2014-03-31 | 2015-11-12 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品 |
WO2017077833A1 (ja) * | 2015-11-06 | 2017-05-11 | 信越化学工業株式会社 | 表面処理された樹脂製品 |
JP2021172702A (ja) * | 2020-04-21 | 2021-11-01 | 信越化学工業株式会社 | 被膜の耐候性を評価する方法、該被膜の製膜方法及び該被膜を有する物品 |
JP2022059417A (ja) * | 2020-10-01 | 2022-04-13 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品 |
WO2022131107A1 (ja) * | 2020-12-17 | 2022-06-23 | 信越化学工業株式会社 | 表面処理剤及び該表面処理剤で処理された物品 |
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