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WO2009151141A1 - Composition de traitement de surface, son procédé de fabrication et article traité en surface - Google Patents

Composition de traitement de surface, son procédé de fabrication et article traité en surface Download PDF

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Publication number
WO2009151141A1
WO2009151141A1 PCT/JP2009/060969 JP2009060969W WO2009151141A1 WO 2009151141 A1 WO2009151141 A1 WO 2009151141A1 JP 2009060969 W JP2009060969 W JP 2009060969W WO 2009151141 A1 WO2009151141 A1 WO 2009151141A1
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Prior art keywords
expressed
compound
formula
surface treatment
treatment composition
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English (en)
Inventor
Tomohiro Yoshida
Masahiko Maeda
Tetsuya Masutani
Akinobu Wakabayashi
Kazunori Shirai
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Daikin Industries Ltd
Moresco Corp
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Daikin Industries Ltd
Moresco Corp
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Publication of WO2009151141A1 publication Critical patent/WO2009151141A1/fr
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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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—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
    • 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
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to surface treatment composition comprising a fluorine-containing polymer, a process for producing the same, and surface- treated article to which the same is applied.
  • fluorine-containing polymers provide a good property of antifouling when they are used for surface treatment of glass, plastic or the like.
  • fluorine-containing polymers are, for example, a fluoropolymer having a part comprising a Si atom or a metal atom at its molecular end (see Patent Document 1 listed below) , or a compound prepared by combining a monomer having perfluoropolyether and a carbon-carbon double bond with a triisocyanate (see Patent Document 2 listed below) .
  • a surface treatment composition comprising such fluorine-containing polymer (hereinafter which is also refereed to as a "fluorine-containing polymer surface treatment composition” or just as a “surface treatment composition”) is used to, for example, improve a property of antifouling of a spectacle lens
  • the surface treatment composition is applied to a surface of the lens to form a antifouling layer (thin film) on the surface of the lens, and thus obtained surface-treated lens is subjected to a grinding process to fit into a desired frame shape while it is held with a chucking (or clamping) tool and rotated (see Patent Documents 3 and 4 listed below) .
  • Patent Document 1 WO 98/49218
  • Patent Document 2 WO 03/002628
  • Patent Document 3 Japanese Patent Laid-open (Kokai) Publication No. 2006-95657
  • Patent Document 4 Japanese Patent Laid-open (Kokai) Publication No. 2007-152439
  • Patent Document 3 a porous adhesive sheet between the lens and the chucking tool
  • Patent Document 4 a chucking pressure depending on a load applied to the lens
  • the present inventors has focused on a fluorine- containing surface treatment composition itself, and aimed to produce a surface treatment composition which can give a hard-to-slip surface when being applied and thus can improve processability, a process for producing such surface treatment composition, and a surface-treated article to which it is applied.
  • a surface treatment composition comprising a fluorine-containing polymer, which comprises as a reactive fluorine-containing polymer a compound expressed by any of the following general formulas (I) and (II) :
  • Rf represents a perfluoroalkyl group having a carbon number of 1 to 16;
  • R 1 is a group expressed by the following formula:
  • a, b and c are integers not less than 0 but not larger than 200 independently; the sum of a, b and c is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ;
  • R 2 is a group expressed by the following formula:
  • Y is an oxygen atom or a divalent polar group
  • d, e and f are integers not less than 0 but not larger than 50 independently; the sum of d, e and f is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula
  • P represents a hydrolyzable polar group
  • R 3 represents an alkyl group having a carbon number of 1 to 22
  • n is an integer from 1 to 3;
  • R 4 is a group expressed by the following formula:
  • g is an integer not less than 0 but not larger than 50
  • X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom; m is an integer not less than 1 but not larger than 10], wherein a content of a compound of a non-reactive fluorine-containing polymer expressed by the following general formula (III) : Rf-R 1 ⁇ -F (III) [wherein Rf, R 1 and R 2 are the same as described above] in the surface treatment composition is less than 25 mol% (on the basis of the total amount) .
  • a surface treatment composition comprising a fluorine-containing polymer, which comprises as a reactive fluorine-containing polymer an alkene compound essentially consisting of the following (A) and (B) : (A) a triisocyanate of trimerized diisocyanate; and
  • the "reactive" means that a component is able to chemically react with a surface of a base material, and/or by itself or with other component on the surface of the base material, and the
  • non-reactive means that a component does not bring about such reaction.
  • What a material comprises a compound expressed by "any" of two general formulas means that the material comprises at least one of the compound expressed by one general formula and the compound expressed by the other general formula, and may comprise both of the compound expressed by one general formula and the compound expressed by the other general formula.
  • the "content” means a content ratio.
  • the present inventors intensively studied components of the conventional fluorine-containing surface treatment composition and reactivity of each of the components when the surface treatment composition is applied to a base material such as a lens.
  • the conventional fluorine-containing surface treatment composition contains, in addition to a reactive fluorine-containing polymer, a non-reactive fluorine- containing polymer at a large amount, generally about 30 to 40 mol% (on the basis of the total amount) , and the non- reactive fluorine-containing polymer is contained relatively freely in a layer of the fluorine-containing polymer surface treatment composition which layer is formed on the base material by a reaction of the reactive fluorine-containing polymer, and therefore make the surface being likely to slip.
  • a content of the non-reactive fluorine-containing polymer in the composition is reduced to 25 mol% or less (on the basis of the total amount) , thereby use of this surface treatment composition can provide a hard-to-slip surface and thus can improve processability .
  • the present invention has been accomplished based on the unique knowledge by the present inventors as described above.
  • a content of the non-reactive fluorine-containing polymer in the surface treatment composition of the present invention is, although the content of 25 mol% or less (on the basis of the total amount, which is also applied hereafter) can cause substantial effects, preferably about 20 mol% or less, more preferably about 15 mol% or less, and ideally substantially zero mol% (in other words, less than 1 mol%, which is a general lower limit of analysis) .
  • the non-reactive fluorine-containing polymer is a compound having a reactive part of silicon (Si) at one end or both ends, the compound having it at one end is expressed by the general formula (I), and the compound having it at both ends is expressed by the general formula (II) .
  • Rf represents a linear or branched perfluoroalkyl group having a carbon number of 1 to 16, and preferably a linear or branched perfluoroalkyl group having a carbon number of 1 to 3 (CF 3 -, C 2 F 5 -, C3F7-) .
  • R 1 is a group expressed by the following formula:
  • a, b and c represent, respectively, the numbers of the three-type repeating units of perfluoropolyethers constituting the main skeleton of the fluorine-containing polymer, wherein a, b and c are integers independently not less than 0 but not larger than 200, preferably from 1 to 100, and the sum of a, b and c is at least 1, preferably 1 to 100.
  • a, b and c are integers independently not less than 0 but not larger than 200, preferably from 1 to 100, and the sum of a, b and c is at least 1, preferably 1 to 100.
  • the unit -(OC 3 F 6 )- may be either (OCF 2 CF 2 CF 2 )- or -(OCF(CF 3 )CF 2 )-, preferably -(OCF 2 CF 2 CF 2 )-.
  • the unit -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.
  • R 2 is a group expressed by the following formula: - (Y) d - (CF 2 ) e - (CH 2 ) f -
  • Y is an oxygen atom or a divalent polar group.
  • the divalent polar group may include - C00-, -0C0-, -CONH-, -OCH 2 CH(OH)CH 2 -, -CH 2 CH(OH)CH 2 O-, -COS-, -SCO- and -0-, and preferably Y is -COO-, -CONH-, CH 2 CH(OH)CH 2 O- or -0- .
  • d, e and f are integers independently not less than 0 but not larger than 50, preferably from 0 to 20, and the sum of d, e and f is at least 1, preferably 1 to 10.
  • P and R 3 are groups linked to Si, and n is an integer from 1 to 3.
  • P represents a hydrolyzable polar group.
  • R 3 represents a linear or branched alkyl group having a carbon number of 1 to 22, preferably a linear or branched alkyl group having a carbon number of 1 to 3 (CH3-,
  • R 4 is a group expressed by the following formula:
  • g is an integer not less than 0 but not larger than 50, preferably an integer not less than 1 but not larger than 20.
  • a bond extending from the repeating units in parentheses with a subscript g is linked to Si.
  • X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom, preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 4.
  • m is an integer not less than 1 but not larger than 10, preferably an integer not less than 1 but not larger than 5.
  • X, Y, m and n are the same as described above, unless otherwise specified.
  • a process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of:
  • the raw material mixture used for the step (p) what is subjected to the reaction is the compound expressed by any of the above general formulas (i) and (ii) .
  • the raw material mixture generally comprises not only the compound expressed by the formulas (i) and (ii) but also the compound expressed by the general formula (III) .
  • a ratio of the compound expressed by any of the general formulas (i) and (ii) (when it comprises both, the sum of ratios of the respective compounds) is, for example, about 65 to 75 mol%, and typically about 70 to 75 mol%
  • a ratio of the compound expressed by the general formula (III) is, for example, about 25 to 35 mol%, and typically about 25 to 30 mol% (with the proviso that they do not exceed 100 mol% in total), but the present invention does not limited to these.
  • each of the compounds expressed by the general formulas (i) and (ii) has a boiling point close to that of the compound expressed by the general formula (III), it is very difficult to distill off the compound of the general formula (III) by subjecting the raw material mixture to a distillation operation.
  • step (p) such raw material mixture is used, and the compound expressed by any of the general formulas (i) and (ii) is subjected to an iodination reaction to generate a compound expressed by any of the following general formulas (i-a) and (ii-a) : Rf-R 1 ⁇ -I (i-a) I-R ⁇ R ⁇ R 2 -! (ii-a)
  • the iodination reaction can proceed by reacting the compound expressed by any of the formulas (i) and (ii) with I 2 in the presence of, for example, K 2 CO 3 .
  • the reaction conditions are not particularly limited, but may be, for example, at about 160 to 210 0 C in the stream of nitrogen.
  • the reaction mixture obtained by the iodination reaction comprises not only the compound expressed by any of the general formulas (i-a) and (ii-a) , but also the unreacted compound expressed by the general formula (III) .
  • -Step (q) the reaction mixture obtained by the iodination reaction comprises not only the compound expressed by any of the general formulas (i-a) and (ii-a) , but also the unreacted compound expressed by the general formula (III) .
  • the reaction mixture obtained from the step (p) is subjected to a purifying operation using column chromatography. Since the iodinated compounds of the general formulas (i-a) and (ii-a) have a different polarity from that of the compound of the general formula (III), the compound of the general formula (III) can be removed off by the use of column chromatography. By such purifying operation, the compound expressed by the general formula (III) is at least partially removed, and the purified material in which .the content of the compound expressed by any of the general formulas (i-a) and (ii-a) is higher than that in the above reaction material can be obtained.
  • a ratio of the compound expressed by any of the general formulas (i-a) and (ii-a) is, for example, about 80 to 100 mol%, and typically about 90 to 100 mol%
  • a ratio of the compound expressed by the general formula (III) is, for example, about 0 to 20 mol%, and typically about 0 to 10 mol% (with the proviso that they do not exceed 100 mol% in total) , but the present invention does not limited to these.
  • z is a halogen atom which is the same as or different from iodine (I), for example, Cl, Br, I, and preferably Cl.
  • I iodine
  • the reaction conditions are not particularly limited, but the first stage reaction may be, for example, at about 100 to 150 0 C, and the second stage reaction may be, for example, at about 40 to 70 0 C.
  • the reaction mixture obtained from the above reaction comprises not only the compound expressed by any of the general formulas (I) and (II), but also the unreacted compound expressed by the general formula (III) .
  • the compound expressed by any of the general formulas (I) and (II) is a reactive fluorine-containing polymer
  • the compound expressed by the general formula (III) is a non-reactive fluorine-containing polymer.
  • a ratio of the compound expressed by any of the general formulas (I) and (II) in this reaction mixture is similar to the ratio of the compound expressed by any of the general formulas (i-a) and (ii-a) in the above purified material (when it comprises both, the sum of ratios of the respective compounds)
  • a ratio of the compound expressed by the general formula (III) in this reaction mixture is similar to its ratio in the purified material.
  • the reaction mixture can be obtained as a surface treatment composition.
  • a content of the unreacted compound expressed by the general formula (III) as the non- reactive fluorine-containing polymer is less than 25 mol%, and therefore the surface treatment composition according to the first aspect of the present invention can be produced.
  • a way of obtaining a surface treatment composition according to the first aspect of the present invention is not limited to that reaction, but it can also be obtained by a reaction of the above raw material mixture (i) , (ii) and (III) with, for example, a silane coupling agent (e.g. HOCH 2 CH 2 CH 2 Si (OCH 3 ) 3) .
  • a silane coupling agent e.g. HOCH 2 CH 2 CH 2 Si (OCH 3 ) 3
  • a reactive fluorine-containing polymer is a compound having a reactive part of a carbon-carbon double bond, which is an alkene compound essentially consisting of the following (A) and (B) :
  • (B-2) a monomer having an active hydrogen and a carbon-carbon double bond.
  • a hydrogen in a hydroxyl group (-0H) is an active hydrogen.
  • a process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of: (s) using a raw material mixture which comprises a compound expressed by any of the following general formulas (i) and (ii) : Rf-R ⁇ -I ⁇ -COF (i) FOC- ⁇ -I ⁇ -F ⁇ -COF (ii) [wherein Rf, R 1 , and R 2 are the same as described above, which are also applied hereafter] ; and a compound expressed by the following general formula
  • step (s) As the raw material mixture used for the step (p) , a similar raw material mixture to that explained in the above with respect to the step (p) can be used. [0041] In the step (s) , such raw material mixture is used, and the compound expressed by any of the general formulas (i) and (ii) is subjected to an alcohol-forming reaction to generate a compound expressed by any of the following general formulas (i-b) and (ii-b) : Rf-R ⁇ R ⁇ CHaOH (i-b) HOCH 2 -R 2 -R 1 -R 2 -CH 2 OH (ii-b)
  • the alcohol-forming reaction can proceed by reducing the compound expressed by any of the formulas (i) and (ii) with, for example, NaBH 4 .
  • the reaction conditions are not particularly limited, but may be, for example, at about 90 to 130 0 C.
  • the reaction mixture obtained by the alcohol-forming reaction comprises not only the compound expressed by any of the general formulas (i-b) and (ii-b), but also the unreacted compound expressed by the general formula (III) • [0044] -Step (t)
  • the reaction mixture obtained from the step (s) is subjected to a purifying operation using column chromatography. Since the alcoholic compounds of the general formulas (i-b) and (ii-b) have a different polarity from that of the compound of the general formula (III), the compound of the general formula (III) can be removed off by the use of column chromatography. By such purifying operation, the compound expressed by the general formula
  • a ratio of the compound expressed by any of the general formulas (i-b) and (ii-b) (when it comprises both, the sum of ratios of the respective compounds) is, for example, about 80 to 100 mol%, and typically about 90 to 100 mol%
  • a ratio of the compound expressed by the general formula (III) is, for example, about 0 to 20 mol%, and typically about 0 to 10 mol% (with the proviso that they do not exceed 100 mol% in total) , but the present invention does not limited to these.
  • the purified material obtained from the step (t) is used, and a combination (B) of at least first and second active hydrogen-containing compounds wherein the first active hydrogen-containing compound (B-I) is the compound expressed by any of the general formulas (i-b) and (ii-b) and the second active hydrogen-containing compound (B-2) is a monomer having an active hydrogen and a carbon- carbon double bond, reacts with a triisocyanate (A) of trimerized diisocyanate to generate an alkene compound.
  • a combination (B) of at least first and second active hydrogen-containing compounds wherein the first active hydrogen-containing compound (B-I) is the compound expressed by any of the general formulas (i-b) and (ii-b) and the second active hydrogen-containing compound (B-2) is a monomer having an active hydrogen and a carbon- carbon double bond, reacts with a triisocyanate (A) of trimerized diisocyanate to generate an alkene compound.
  • This alkene compound is resulted by reacting the three isocyanate groups of the triisocyanate of the component (A) with active hydrogens of the active hydrogen- containing compounds of the component (B) , and has at least one carbon-carbon double bond. It is only necessary that two of the three isocyanate groups (a NCO group) in the triisocyanate (A) react respectively with two kinds of the active hydrogen-containing compounds (B-I) and (B-2) . The remaining one isocyanate group may react with the active hydrogen-containing compound (B-I) or (B-2), or may react with the third active hydrogen-containing compound (B-3) which is different from them.
  • the triisocyanate (A) is a triisocyanate prepared from trimerizing a diisocyanate .
  • diisocyanate used for giving the triisocyanate (A) include diisocyanates having aliphatically bonded isocyanate groups, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate and dicyclohexylmethane diisocyanate; and diisocyanates having aromatically bonded isocyanate groups, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylenepolyphenyl polyisocyanate, tolidine diisocyanate and naphthalene diisocyanate.
  • HOCH 2 -R 2 -R 1 -R 2 -CH 2 OH (ii-b) is a fluorine-containing polymer wherein Rf, R 1 and R 2 are the same as described above.
  • the monomer (B-2) having an active hydrogen and a carbon-carbon double bond is preferably a (meth) acrylate ester or vinyl monomer having a hydroxyl group as a active hydrogen.
  • the monomer (B-2) include the following: hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate,
  • the third active hydrogen- containing compound (B-3) which is optionally used
  • the third component is preferably a compound which has neither a perfluoropolyether group nor a carbon-carbon double bond and which has at least one active hydrogen.
  • the third component (B-3) include the following: a monohydric alcohol composed of a linear or branched hydrocarbon having a carbon number of 1 to 16,
  • alkene compound obtained by using the third component include a compound of the following chemical formula:
  • a reacting ratio of the component (A) and the component (B) (i.e. (B-I) and (B-2), and (B-3) when used) may be appropriately selected.
  • the obtained alkene compound is preferably by reacting the first isocyanate group of the component (A) with the first component (B-I), reacting the second isocyanate group with the second component (B-2) , and reacting the third isocyanate group with any of the first component (B-I), the second component (B-2) and the third component (B-3) .
  • the reaction mixture obtained by the above reaction comprises not only the alkene compound, but also the unreacted compound expressed by the general formula (III) .
  • the alkene compound is a reactive fluorine-containing polymer
  • the compound expressed by the general formula (III) is a non-reactive fluorine- containing polymer.
  • a ratio of the alkene compound in this reaction mixture is similar to the ratio of the compound expressed by any of the general formulas (i-b) and (ii-b) in the above purified material (when it comprises both, the sum of ratios of the respective compounds) , and a ratio of the compound expressed by the general formula (III) in this reaction mixture is similar to the ratio in the purified material.
  • the reaction mixture can be obtained as a surface treatment composition.
  • a content of the unreacted compound expressed by the general formula (III) as the non- reactive fluorine-containing polymer is less than 25 mol%, and therefore the surface treatment composition according to the second aspect of the present invention can be produced.
  • the surface treatment composition according to the first or the second aspect of the present invention may include any suitable other component (s) such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst and so on.
  • a coupling agent such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst and so on.
  • a surface-treated article which comprises a base material, and a layer (or a thin film) formed by the surface treatment composition in the first or the second aspect of the present invention on a surface of the base material.
  • the layer formed by the surface treatment composition on the surface of the base material has a good antifouling property. Further, since this layer shows a high transmittance, the surface treatment composition of the present invention is suitable to the use for optic materials which require transmittancy.
  • the layer formed by the surface treatment composition may have a thickness of, for example, about 0.001 to 0.03 ⁇ m.
  • a reactive part of silicon (Si) in the reactive fluorine-containing polymer can be combined to a material consisting of the surface of the base material to form the layer derived from the surface treatment composition.
  • a reactive part of the carbon-carbon double bond in the reactive fluorine-containing polymer can polymerize with each other (optionally, with other polymerizable component) to form the layer derived from the surface treatment composition.
  • materials suitably used for the base material may include glass, resin, metal, ceramic, wood, pottery, porcelain, stone, leather and so on.
  • the base material may have any layer such as a hard coat layer or an antireflection layer on the surface of such material before the application of the surface treatment composition.
  • the surface-treated article obtained thereby may be, for example, lens such as spectacle lens; a front protective panel, a antireflection plate, a polarizing plate, an antiglare plate of a display such as PDP and LCD; a touch panel sheet of an instrument such as a cellular phone and a personal digital assistance; a disc plane of an optical disc such as a DVD disc, a CD-R and an MO; and an optical fiber.
  • the composition When applying the surface treatment composition, the composition may be applied in a state dissolved, suspended or dispersed in a fluorine-free solvent or a fluorine-containing solvent, and then the solvent may be removed off by drying and/or vaporization.
  • fluorine-free solvent examples include ketones (for example, methyl ethyl ketone and acetone), alcohols (for example, a monohydric alcohol such as ethanol and propanol, and polyhydric alcohol such as ethylene glycol, diethylene glycol and propylene glycol), esters (for example, ethyl acetate) , and ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monomethyl acetate, and propylene glycol monomethyl ether) .
  • examples of the fluorine-containing solvent include fluoroalcohols, fluoroethers, ditrifluoromethyl benzene, and perfluorohexane .
  • the surface-treated article obtained as described above shows that, a deviation angle of the base material from a rotational axis holding the base material in processing (or shaping) of the surface-treated article is preferably 2 degrees or less.
  • the "deviation angle" in the present invention is defined as an angular difference ⁇ (degree) (shown in Fig.
  • a basing point marked on a surface of a lens between before and after the lens is processed with an edger into a rectangle of 60 mm x 30 mm at a chucking pressure of 50 kg by using a lens processing tape (trade name: Leap lens blocking pad, from Sumitomo 3M Limited) and using SE9090 or LE9000 (both from NIDEK CO., LTD) as a processing apparatus.
  • a lens processing tape trade name: Leap lens blocking pad, from Sumitomo 3M Limited
  • SE9090 or LE9000 both from NIDEK CO., LTD
  • a deviation angle is generally 3 degrees or more.
  • a deviation angle is reduced to 2 degrees or less.
  • the surface-treated article obtained in accordance with the present invention is hard to slip and readily processable (or workable) as compared with the conventional article.
  • a surface treatment composition which can give a hard-to-slip surface when being applied and thus can improve processability (or workability) , a process for producing such surface treatment composition, and a surface-treated article to which it is applied.
  • Fig. 1 is a graph for explaining a deviation angle referred to in the present invention.
  • a polymer composition in the present description is measured as follows. Polymer Composition (IH-NMR, 19F-NMR, IR)
  • IR measurement apparatus from PerkinElmer Inc. An average molecular weight and molar ratios (mol%) of the respective components in a mixture are calculated from the results by the NMR measurement.
  • the "average molecular weight” throughout the present description means a number average molecular weight.
  • a yield is calculated with the proviso that an ideal case with respect to both a precursor of a reactive fluorine-containing polymer and a non-reactive fluorine- containing polymer is set at 100% wherein the all of the precursor of a reactive fluorine-containing polymer is converted into an aimed reaction product.
  • the present example relates to a surface treatment composition according to the first aspect of the present invention described above and to a process for producing the same. [0072] -Step (p)
  • a raw material mixture used was a mixture of 2800 g (0.72 mole) of ⁇ -fluoro poly perfluorooxetane acyl fluoride (average molecular weight 3900) expressed by the following chemical formula:
  • reaction mixture obtained from the step (p) was subjected to chromatography separation by using a column filled with silica gel (solvent: Vertrel XF from
  • reaction mixture (A) was obtained. [0078] It was recognized by IR analysis and NMR analysis that this reaction mixture (A) contained a silicone- containing and fluorine-containing organic polymer which had iodine at its end.
  • this reaction mixture (B) contained a silicone-containing and fluorine-containing organic polymer of which end was hydrogenated .
  • Is means an integrated absorption intensity of the internal standard; and m means a polymerization degree
  • the content of a reactive fluorine-containing polymer having a reactive part of silicon was 95 mol%
  • reaction mixture (B) obtained above was dissolved in perfluorohexane to prepare a treatment solution of 0.1 wt%.
  • the used base material was a double-sided aspheric lens with a diameter of 80 mm (composed of an acrylic resin of which surface was coated with oxidized silicon) . It was dipped into the treatment solution for 10 seconds, and pulled up at a velocity of 5 mm/sec, so that surface treatment was performed on the lens.
  • Two surface-treated lenses were similarly prepared as Samples 1 and 2. These were evaluated with respect to contact angle, deviation angle, and ease in wiping off fingerprint as described below. The results are shown in Table 1.
  • Fingerprint wiping mark is extended and removal of the mark is difficult.
  • a reaction mixture (B) ' was obtained according to similar procedures to Example 1, except that the step (q) was not conducted and the reaction mixture obtained from the step (p) was used for the step (r) in place of the purified material obtained from the step (q) .
  • Example 2 As understood from Table 1, Samples 1 and 2 of Example 1 showed a remarkably reduced deviation angle while maintaining contact angles with water and with hexadecane and ease in wiping off fingerprint at levels equal to Samples 1 and 2 of Comparative Example 1. [0094] Example 2
  • a raw material mixture used was a mixture of 700 g (0.28 mole) of ⁇ -fluoro poly perfluorooxetane acyl fluoride (average molecular weight 2500) expressed by the following chemical formula: F- (CF 2 CF 2 CF 2 O) n -CF 2 CF 2 -COF and 300 g (0.12 mole) of perfluoropolyoxetane (average molecular weight 2500) expressed by the following chemical formula:
  • the reaction mixture obtained from the step (s) was subjected to chromatography separation by using a column filled with silica gel (solvent: Vertrel XF from DuPont) , and thereby 660 g (purity 95 mol%) of a purified material substantially consisting of perfluoropolyoxetane alcohol expressed by the chemical formula below was obtained:
  • reaction mixture (C) was considered as a 50 wt% HCFC- 225 solution of a perfluoropolyether urethane acrylate composition.
  • the solid portion ratio is a ratio of the solid portion of the reaction mixture (C) (50 wt% HCFC-225 solution) to the solid portion of Fulshade UV-S4 (50 wt% toluene solution) .
  • a reaction mixture (C) ' was obtained according to similar procedures to Example 2, except that the step (t) was not conducted and the reaction mixture obtained from the step (s) was used for the step (u) in place of the purified material obtained from the step (t) .
  • This reaction mixture (C) ' had a solid portion (50 wt%) similar to that of the reaction mixture (C) in Example 2, and a ratio of the solid portion of the reaction mixture (C) ' to the solid portion of Fulshade UV-S4 was also similar to the ratio of the solid portion of the reaction mixture (C) to the solid portion of Fulshade UV-S4 in Example 2 (Table 2) .
  • a surface treatment composition obtained by the present invention can be suitably used as a surface treatment agent for giving an anti fouling property to a surface of various base materials, especially optic materials which require transmittancy.

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Abstract

Dans une composition de traitement de surface comprenant un polymère contenant du fluor, une teneur d'un polymère contenant du fluor non réactif est inférieure à 25 % en moles (sur la base de la quantité totale), lequel peut être présent conjointement avec un polymère contenant du fluor réactif dans la composition de traitement de surface et est exprimée par une formule : Rf-R1-R2-F (dans laquelle Rf représente un groupe perfluoroalkyle ayant un nombre de carbones de 1 à 16 ; R1 est un groupe exprimé par une formule : -(OC3F6)a-(OC2F4)b-(OCF2)c- ; R2 est un groupe exprimé par une formule : -(Y)d-(OCF2)e-(CH2)f- ; et Y est un atome d'oxygène ou un groupe polaire divalent). Conformément à la composition de traitement de surface de la présente invention, un article traité en surface obtenu par application de celui-ci sur une matière de base peut avoir une surface dure au glissement, de telle sorte que l'article traité en surface peut être maintenu avec un outil à mandrins de façon ferme et stable, et de ce fait l'aptitude au traitement est améliorée.
PCT/JP2009/060969 2008-06-10 2009-06-10 Composition de traitement de surface, son procédé de fabrication et article traité en surface Ceased WO2009151141A1 (fr)

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EP2641944A3 (fr) * 2011-11-30 2014-11-05 Shin-Etsu Chemical Co., Ltd. Agent de traitement de surface à base de fluor pour dépôt de vapeur et article fini avec l'agent de traitement de surface par dépôt de vapeur
WO2018038213A1 (fr) * 2016-08-25 2018-03-01 ダイキン工業株式会社 Procédé de séparation de composés de type alcool contenant un groupe perfluoro(poly)éther
CN109477628A (zh) * 2016-06-29 2019-03-15 皇家飞利浦有限公司 待在水中使用的具有涂层的光导

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EP1411073A1 (fr) * 2001-06-27 2004-04-21 Daikin Industries, Ltd. Composition d'agent de traitement de surface et procede de fabrication associe
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US3972856A (en) * 1969-03-10 1976-08-03 Minnesota Mining And Manufacturing Company Polyurethanes containing poly(perfluoroalkylene oxides) units
EP0435062A1 (fr) * 1989-12-12 1991-07-03 AUSIMONT S.p.A. Lubrifiants à base de perfluoropolyéther ayant des propriétés antiusures améliorÀ©es
EP0797111A2 (fr) * 1996-03-21 1997-09-24 Sony Corporation Composition pour revêtement à propriétés antisalissure, produit optique et dispositif d'affichage
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EP1411073A1 (fr) * 2001-06-27 2004-04-21 Daikin Industries, Ltd. Composition d'agent de traitement de surface et procede de fabrication associe
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2641944A3 (fr) * 2011-11-30 2014-11-05 Shin-Etsu Chemical Co., Ltd. Agent de traitement de surface à base de fluor pour dépôt de vapeur et article fini avec l'agent de traitement de surface par dépôt de vapeur
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CN109477628A (zh) * 2016-06-29 2019-03-15 皇家飞利浦有限公司 待在水中使用的具有涂层的光导
WO2018038213A1 (fr) * 2016-08-25 2018-03-01 ダイキン工業株式会社 Procédé de séparation de composés de type alcool contenant un groupe perfluoro(poly)éther
JP2018035348A (ja) * 2016-08-25 2018-03-08 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有アルコール化合物の分離方法

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