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    • 专利摘要:
    patent: surface treatment composition, process for producing same, and surface treated article. The present invention relates to a surface treatment composition comprising (i) an organosilicon compound having a functional alkoxysilane group at the end of a fluorine-containing polyether chain and (ii) fluorine-containing polyether compounds, wherein a content of the Fluorine-containing polyether compounds in a surface treatment composition is less than 25 mol% based on a surface treatment composition.
    公开号:BR112012011306B1
    申请号:R112012011306-2
    申请日:2010-11-10
    公开日:2019-10-08
    发明作者:Grégory HERVIEU；Pierre-Jean Calba；Don Lee Kleyer；Masayuki Hayashi；Peter Cheshire Hupfield；Tomohiro Yoshida；Yasuo Itami；Masahiko Maeda；Tetsuya Masutani
    申请人:Daikin Industries, Ltd.；Essilor International；Dow Corning Corporation；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for COMPOSITION FOR SURFACE TREATMENT, ITS PRODUCTION PROCESS, AND ARTICLE TREATED ON THE SURFACE.
    TECHNICAL FIELD [001] The present invention relates to (i) a surface treatment composition comprising an organosilicon compound for use in the formation of a low surface energy layer or an anti-dust layer on the surface of various materials, (ii ) a process for producing it and iii) an article treated on the surface to which it is applied.
    BACKGROUND [002] Anti-reflective coatings, optical filters, optical lenses, eyeglass lenses, ray dividers, prisms, mirrors and other optical elements and sanitary articles are likely to be stained with fingerprints, skin oil, sweat, household products, etc. when used. Once adhered, such stains are not easily removed, and, in particular, stains that adhere to optical members with anti-reflective coatings are easily noticeable and present problems.
    [003] To solve such problems related to dust control, techniques using various surface treatment compositions have been proposed so far.
    [004] For example, publication JP1994-29332 proposed an anti-subject, low-reflective plastic that has, on its surface, an anti-reflective coating that comprises 7mono- and disilane compounds, containing polyfluoroalkyl group and halogen-, alkyl- or alkoxysilane.
    [005] Recently, WO2006 / 107083 proposed a surface treatment composition comprising compounds of
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    2/44 organosilicon carrying an alkoxysilyl functional group at the end of a polyropolymer chain. This surface treatment composition provides a low-energy surface layer that prevents moisture or dirt from adhering to the surface of various materials, especially anti-reflective films and as optical members and glasses.
    [006] However, the anti-dust coatings formed by the hitherto known processes are not necessarily sufficient in anti-dust properties, and in particular, their stain resistance reasonably reduces when they are used over a longer period of time. Therefore, if you want to develop an anti-dust coating with excellent anti-dust properties and excellent durability.
    DESCRIPTION OF THE INVENTION [007] The present invention should solve the problems of the prior art techniques described above and provide a composition for surface treatment that forms a layer treated by low surface energy, superior of high durability that prevents moisture or dirt, such as fingerprints, skin oil, sweat, and household goods from sticking to the surface of various materials, especially anti-reflective films, optical members and glasses, and which allows dirt and moisture, once adhered, to be easily removed.
    [008] Another objective of the present invention is to provide a process for the production of the surface treatment composition that can form a low energy layer of upper surface having a high durability.
    [009] An object of the present invention is to provide a method for easily forming a low energy layer of upper surface having a high durability.
    [0010] Yet another objective of the present invention is to provide
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    3/44 optical members (eg anti-reflective films, optical filters, optical lenses, eyeglass lenses, ray dividers, prisms and mirrors) and various materials supplied with the upper surface low-energy layer having a high durability.
    [0011] The present invention provides a surface treatment composition comprising an organosilicon compound represented by the General Formula (A):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-C3H6-Si (X ') 3- a (R 1 ) a (A) [0012] where q is an integer from 1 to 3; m, n, and o are independently whole numbers from 0 to 200; p is 1 or 2; X is oxygen or a divalent organic group; r is an integer from 0 to 17; R 1 is a straight or branched C1-C22 hydrocarbon group that does not have an unsaturated aliphatic bond; a is an integer from 0 to 2; and X 'is an independently selected hydrolyzable group, [0013] in which a content of fluorine-containing compounds represented by the General Formulas (B) and (C):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-F (B) [0014] where q, m, n and o are the same as described above,
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-CH = CHCH3 (C) [0015] where q, m, n, o , p, r and X are the same as described above, [0016] a surface treatment composition is less than
    25 mol% based on a surface treatment composition.
    [0017] The present invention especially provides a surface treatment composition comprising the organosilicon compound in which, in General Formula (A), the hydrolyzable group X 'is at least one selected from an alkoxy group (-OR) and one alkylamino group (-NHR or -NR2) where R is independently a straight or branched C1-C22 alkyl group and two R groups can form a cyclic amine, and the integer a is 0.
    [0018] The present invention especially provides a
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    4/44 surface treatment composition comprising the organosilicon compound represented by any of the General Formulas (A-1), (A-2) and (A-3):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-C3H6-Si (OR) 3 (A-1), F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-C3H6-Si- (HNR) 3 (A-2) [0019] and
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-C3H6-Si (NR2) 3 (A-3) [0020] where q , m, n, o, p, X and r are the same as described above, and R is independently a straight or branched C1-C22 alkyl group, and two R groups can form a cyclic amine, [0021] in which a content of compounds containing fluorine represented by the General Formulas (B) and (C) a surface treatment composition is less than 25 mol% based on a surface treatment composition.
    [0022] The present invention most preferably provides a surface treatment composition comprising the organosilicon compound in which, in General Formula (A), the hydrolyzable group X 'is the alkylamino group (-NHR or -NR2) in which R is equal to that described above, and the integer a is 0, where a content of fluorine-containing compounds represented by the General Formulas (B) and (C) a surface treatment composition is less than 25 mol% based on a composition for surface treatment.
    [0023] The present invention more specifically provides a surface treatment composition, wherein the organosilicon compound represented by the General Formula (A) is represented by a General Formula (i-d-i) or (i-d-ii):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si- (HNR) 3 (i-d-i) [0024] or
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (NR2) 3 (id-ii) [0025] where q, m, n, o, r and R are the same as described above, and fluorine-containing compounds represented by the General Formulas (B) and
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    5/44 (C) are represented respectively by the General Formulas (ii) and (i-c-
    d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-F (ii) [0026] and
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (i-c-d).
    [0027] The present invention provides a process for the production of a surface treatment composition comprising an organosilicon compound, comprising the steps of:
    [0028] (a) contacting a mixture comprising (D) perfluoropolyether acid fluorides and (E) nonreactive perfluoropolyether with a reducing agent to react acid fluorides thereby producing a reaction mixture comprising (F) hydroxyl perfluoropolyether thereby generated and non-reactive perfluoropolyether (E); [0029] (b) purify the reaction mixture prepared in step (a) by column chromatography to produce a purified material in which the content of the perfluoropolyether hydroxyl (F) in the purified material is greater than the content of the perfluoropolyether hydroxyl (F) in reaction mixture;
    [0030] (c) contacting the purified material obtained in step (b) with allyl halide to react the hydroxyl perfluoropolyether (F) thereby producing a reaction mixture comprising (G) ally perfluoropolyether thus generated and non-reactive perfluoropolyether (E ); and [0031] (d) contacting the reaction mixture obtained in step (c) with hydrosilane in the presence of an isomer reducing agent and a transition metal catalyst to react the perfluoropolyether ally thereby producing a surface treatment composition comprising :
    [0032] (I) organosilicon compounds each having a functional alkoxysilane group at one end of the fluorine-containing polyether chain, non-reactive perfluoropolyether (F), and (H) allyl isomer
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    6/44 perfluoropolyether (G), wherein a non-reactive perfluoropolyether (E) and isomer (H) content in a surface treatment composition is less than 25 mol% based on a surface treatment composition.
    [0033] The present invention also provides a process for producing a surface treatment composition that comprises an organosilicon compound, comprising the steps of:
    [0034] (a) contacting a mixture of raw material comprising compounds represented by the following General Formulas (i) and (ii):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-C (= O) F (i) [0035] where q is an integer from 1 to 3; m, n and o are independently whole numbers from 0 to 200;
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) oF (ii) [0036] where q, m, neo are the same as described above, with a reducing agent to react the compound ( i) thereby producing a reaction mixture comprising thus prepared alcohols represented by the following General Formula (ib):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2OH (i-b) [0037] where q, m, n, and o are the same as described above; and the compound represented by the General Formula (ii);
    [0038] (b) purifying the reaction mixture obtained in the step by column chromatography to remove at least part of the fluorine-containing compound represented by the General Formula (ii), and thereby producing a purified material in which a content of the compound represented by the Formula General (ib) in the purified material is greater than a content in the reaction mixture;
    [0039] (c) contact the purified material produced in step (b) with
    Z- (CH2) r-CH2CH = CH2 [0040] where Z is a halogen atom; r is an integer
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    7/44 from 0 to 17, to react the compound (i-b) in this way producing a reaction mixture comprising thus prepared allyl compounds represented by the following General Formula (i-c):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (ic) [0041] where q, m, n, oer are equal to described above; and the compound represented by the General Formula (ii), [0042] where a content of the compound represented by the Formula
    General (ii) in this intermediate composition is preferably less than 5 mol% based on the intermediate composition; and [0043] (d) contacting the reaction mixture obtained in step (c) with hydrosilane compound represented by the General Formula (iii):
    H-Si (X ') 3- a (R 1 ) to (iii) [0044] where R 1 , a, and X' are the same as described above, and an isomer reducing agent in the presence of a catalyst of transition metal and then, if necessary, contact alkali metal alkoxide to react the compound (ic) thereby producing a surface treatment composition comprising:
    [0045] an organosilicon compound represented by the Formula
    General (i-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (X ') 3- a (R 1 ) a (id) [0046] where q, m, n, o, a, r, X 'and R 1 are the same as described above;
    [0047] fluorine-containing compounds represented by
    General Formulas (ii) and (i-c-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (icd) [0048] where q, m, n, oer are equal to described above, [0049] wherein a content of fluorine-containing compounds represented by the General Formulas (ii) and (icd) a surface treatment composition is less than 25 mol% based on a surface treatment composition.
    [0050] The present invention especially provides the process for producing a composition for surface treatment, wherein the
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    8/44 organosilicon compound is represented by the General Formula (i-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-SÍ (X ') 3- a (R 1 ) a (id) [0051] where r is 0, X 'is chlorine or alkoxy, and a is 0, eq, m, neo are the same as described above, and [0052] the hydrosilylation reaction is conducted between trichlorosilane (HSiCl3) or trialkoxysilane (HSi (OR ) 3) and a compound represented by the General Formula (ic):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (ί-θ) [0053] where q, m, n, oer are same as described above.
    [0054] The present invention also especially provides the process for producing a composition for surface treatment, wherein step (d) comprises contacting the reaction mixture obtained in step (c) with trichlorosilane (HSiCl3) and a reducing agent isomer in the presence of a transition metal catalyst and then contacting alkylamine thereby producing the surface treatment composition comprising:
    [0055] an organosilicon compound represented by the Formula
    General (i-d-i) or (i-d-ii):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si- (HNR) 3 (idi) or F- (CF2) q- (OC3F6 ) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (NR2) 3 (id-ii) [0056] where q, m, n, o, r and R are equal to described above, and fluorine-containing compounds represented by the General Formulas (ii) and (ic-d).
    [0057] The present invention especially provides the process for producing the composition for surface treatment, in which the purification operation is conducted by column loaded with silica gel and a hydrocarbon as a solvent.
    [0058] The present invention provides a low surface energy surface having a high durability using a surface treatment composition.
    [0059] The present invention provides an optical member,
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    9/44 especially an anti-reflective optical member, and a display device, which are provided with a treated layer containing the surface treatment composition.
    [0060] The present invention provides sanitary articles and automobile and aeronautical glass and having an inorganic material having the aforementioned surface.
    MODE FOR CARRYING OUT THE INVENTION [0061] The present inventors have intensively studied components of the conventional surface treatment composition comprising organosilicon compounds and the reactivity of each of the components when the surface treatment composition is applied to a base material such as a lens. As a result, it was found that the conventional surface treatment composition comprising organosilicon compounds contains, in addition to the organosilicon compounds described by (A), fluorine-containing compounds represented by the General Formulas (B) and (C):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-F (B) [0062] where q, m, n and o are the same as described above,
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-CH = CHCH3 (C) [0063] where q, m, n, o , p, r and X are the same as described above, [0064] in large quantities, usually about 35 to 60 mol% based on a surface treatment composition, and fluorine-containing compounds are contained relatively freely in a layer of the surface treatment composition whose layer is formed on the base material by the reaction of the organosilicon compound, and therefore, fluorine-containing compounds decrease the durability of anti-dust properties.
    On the contrary, according to the surface treatment composition of the present invention, a content of the compounds containing
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    10/44 fluorine (B) and (C) in the composition is reduced to less than 25 mol% based on a surface treatment composition, therefore, the use of this surface treatment composition provides a high quality of anti-dust properties and high durability of anti-dust properties. The present invention was carried out based on the exclusive knowledge of the present inventors as described above.
    [0066] Among the fluorine-containing compounds, component (ii) is now present in the mixture of raw starting material that comprises the component represented by General Formula (i):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-C (= O) F (i) [0067] where q, m, n, and o are the same as described above. The other component (C) and / or (i-c-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-CH = CHCH3 (C) [0068] where q, m, n, o , p, r, and X are the same as described above;
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (icd) [0069] where q, m, n, oer are equal to described above, [0070] is a by-product of an isomer produced during hydrosilylation of the terminal allyl compound represented by the General Formula (ic):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (Í-O) [0071] where q, m, n, oer are same as described above.
    [0072] A content of fluorine-containing compounds (B) and / or (ii) and (C) and / or (icd) a surface treatment composition of the present invention is less than 25 mol% (based on the total amount , which is also applied hereinafter), preferably about 20 mol% or less, more preferably about 10 mol% or less, and especially less than 5 mol%. Among fluorine-containing compounds, the content of (C) and / or (i-c-d) is generally at least 0.1 mol%, for example, 1 mol%.
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    [0073] The surface treatment composition for anti-dust layers of the present invention comprises an organosilicon compound represented by the General Formula (A):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) r-C3H6-Si (X ') 3- a (R 1 ) a (A) [0074] In General Formula (A), q is an integer from 1 to 3; m, n, and o are independently whole numbers from 0 to 200; p is 1 or 2; X is oxygen or a divalent organic group; r is an integer from 0 to 17; R 1 is a straight or branched C1-C22 hydrocarbon group that does not have an unsaturated aliphatic bond; a is an integer from 0 to 2; and X 'is an independently selected hydrolyzable group. [0075] Preferably, in General Formula (A), [0076] m, n, and o are independently whole numbers from 1 to
    150, [0077] X is an oxygen atom or a divalent organic group such as linear or branched C1-C22 alkylene group;
    [0078] R 1 is a straight or branched C1-C22 alkyl group, more preferably a straight or branched C1-C12 alkyl group; and [0079] X 'is an independently selected chlorine atom, an alkoxy group (-OR), an alkylamino group (-NHR or -NR2) or a dialkyliminoxy group (-ON = CR2) where R is independently a C1 group -C22 straight or branched alkyl, and two R groups can form a cyclic amine or cyclic ketoxime, and the integer a is 0. In General Formula (A), -C3H6- includes - (CH2) 3-, -CH2-CH (CH3) - and -C (CH3>.
    [0080] The hydrolyzable group, X ', of General Formula (A) can be independently selected and is exemplified by groups of the following formulas: alkoxy or alkoxy-substituted alkoxy groups such as methoxy, ethoxy, propoxy and methoxyethoxy groups, acyloxy groups such such as acetoxyoxy, propionyloxy and benzoyloxy groups, alkenyloxy groups such as isopropenyloxy and isobutenyloxy groups, iminoxyl groups such as dimethyl ketoxime groups, methyl ethyl ketooxy, diethyl ketooxy, cyclohexanoxime, substituted amino groups such as groups
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    12/44 methylamino, ethylamino, dimethylamino, diethylamino, pyrrolidine and piperidino, starch groups such as N-methyl acetamido and N-ethylamido groups, substituted aminoxy groups such as dimethyl aminoxy and diethyl aminoxy, halogen groups, such as chlorine and so on .
    [0081] Among such hydrolyzable groups, the acyloxy, iminoxoxy, alkoxy and dialkylamino groups such as acetoxy (-OAc), dimethyl ketooxide (-ON = CMe2), methoxy (-OCH3), ethoxy (-OC2H5), dimethylamino (-N ( CH3) 2), diethylamino (-N (C2H5) 2) and di-i-propylamino (-N (iC3H7) 2) are preferable and methoxy (-OCH3) and dimethylamino (-N (CH3) 2) are particularly preferable. Even more preferred is dimethylamino (N (CH3) 2). Such hydrolyzable groups can be contained in the organosilicon compound of the surface treatment composition of the present invention as one species or as a combination of two or more species.
    [0082] The content of the fluorine-containing compound represented by
    General Formula (C) is 1.0 mol% or more based on a surface treatment composition.
    [0083] The content of fluorine-containing compounds, represented by
    General Formula (B) and (C) is preferably less than 15 mol%.
    [0084] In the General Formulas (A) and (C), p is 1 and X is oxygen, which represent the General Formulas (i-d) and (i-c-d), respectively:
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (X ') 3- a (R 1 ) a (id) [0085] where q, m, n, o, a, r, X 'and R 1 are the same as described above,
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (icd) [0086] where q, m, n, oer are equal to described above.
    [0087] Preferably, in the General Formulas (A), (B), (C) and (icd), q is 3, m is an integer from 10 to 200, n is 1, o is 0, p is 1, X is oxygen, r is 0 and a is 0 or 1.
    [0088] In General Formula (A), the sum of m, n, and o is preferably or more, and particularly preferably 10 or more. X is preferably oxygen and r is preferably 0. In General Formula (A),
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    13/44 a is preferably 0.
    [0089] The present invention also provides a process for producing a surface treatment composition containing the organosilicon compound, which comprises the steps of:
    [0090] (a) an alcohol formation reaction of a mixture of crude material comprising an acid fluoride compound represented by the General Formula (i):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) oC (= O) F (i) [0091] where q, m, n, oea are the same as described above, and the polymer containing fluorine represented by the General Formula (ii):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) oF (ii) [0092] where q, m, neo are the same as described above, to obtain a reaction mixture that comprises alcohol in this way formed represented by the General Formula (ib)
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2OH (ib) [0093] where q, m, n, and o are the same as described above, and the fluorine-containing compound represented by the General Formula (ii);
    [0094] (b) a step of purifying the reaction mixture obtained in step (a) by column chromatography to remove at least part of the fluorine-containing compound represented by General Formula (ii);
    [0095] (c) subjecting the purified material obtained in step (b) to an allylation reaction with a compound represented by the General Formula Z- (CH2) r-CH2CH = CH2: where Z er are the same as described above, for obtain a reaction mixture comprising the compound thus generated represented by the following General Formula (ic):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (ic) [0096] where q, m, n, oer are equal to described above, and the fluorine-containing compound represented by the General Formula (ii);
    [0097] (d) subjecting the reaction mixture obtained in step (c) to a hydrosilylation reaction with the represented hydrosilane compound
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    14/44 by the General Formula (iii):
    H-Si (X ') 3-a (R 1 ) to (iii) [0098] where R 1 , a and X' are the same as described above and an isomer reducing agent, and then, if necessary, a ( d-1) an alkoxylation reaction in the presence of a neutralizing agent with an aliphatic alcohol, or a (d-2) an alkoxylation reaction with a metal alkoxide having an alkoxyl group, to obtain a reaction mixture comprising:
    [0099] an organosilicon compound represented by the Formula
    General (i-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (X ') 3-a (R1) to (id) [00100] in that q, m, n, o, r, a, X 'and R 1 are the same as described above, and [00101] fluorine-containing compounds represented by the General Formulas (ii) and (icd):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-F (ii) [00102] where q, m, n and o are the same as described above,
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (icd) [00103] where q, m, n, oer are equal to described above, [00104] where the content of fluorine-containing compounds represented by the General Formulas (ii) and (icd) a surface treatment composition is less than 25 mol% (in total amount).
    [00105] In step (a), the mixture of crude material generally does not comprise only the acid fluoride compound represented by formula (i):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) oC (= O) F (i) [00106] where q, m, neo are the same as described above, but also the represented compound by the General Formula (ii). In the crude material mixture, a ratio of the compound represented by the General Formula (i) is, for example, from about 45 to 85 mol%, and typically from about 65 to 75 mol%, a ratio of the represented compound
    Petition 870190035159, of 12/12/2019, p. 18/59
    15/44 by the General Formula (ii) is, for example, about 25 to 35 mol%, and typically about 25 to 30 mol% (with the proviso that it does not exceed 100 mol% in total ). Since the compound represented by General Formula (i) has a boiling point close to that of the compound represented by General Formula (ii), it is very difficult to distill the compound of General Formula (ii) by subjecting the mixture of crude material to a distillation. Therefore, in the reaction mixture in step (a) contains the compound of General Formula (ii), which must be purified in the next purification step (b).
    [00107] The alcohol formation reaction is conducted in the presence of a reducing agent, such as NaBH4, diborane complex and LiAlH4. The reaction is preferably conducted in a non-protic solvent, especially in an ether solvent such as diglyme (diethylene glycol dimethyl ether), tetrahydrofuran, toluene, xylene and hydrofluoroether. The molar ratio of the reducing agent to the acid fluoride compound represented by the General Formula (i) is 0.9-4.0, preferably 1.0 to 2.0, more preferably 1.05 to 1.5. The reaction temperature is in the range of 10 to 250 ° C, preferably 20 to 200 ° C, more preferably 40 to 150 ° C. The reaction time is 1 to 24 hours, preferably 3 to 20 hours, more preferably 5 to 12 hours.
    [00108] In step (b), the reaction mixture obtained in step (a) is subjected to a purification operation using column chromatography. Whereas the alcohol of the General Formula (ib) is: F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2OH (ib) [00109] where q, m, n, and o are the same as described above, have a different polarity than the compound of the General Formula (ii), the compound of the General Formula (ii) can be removed by using column chromatography. By such a purification operation, the compound represented by the General Formula (ii) is at least partially removed, and the purified material in which a content of the compound
    Petition 870190035159, of 12/12/2019, p. 19/59
    16/44 represented by the General Formula (i-b) in the purified material is greater than a content in the above reaction material is obtained. In the purified material, a ratio of the compound represented by the General Formula (ib) is, for example, from about 80 to 100 mol%, and typically from about 90 to 100 mol%, a ratio of the compound represented by the General Formula (ii) is, for example, from about 0 to 20 mol%, and typically from about 0 to 10 mol% (with the proviso that it does not exceed 100 mol% in total), however the present invention it is not limited to these.
    [00110] The purification operation can be conducted by column loaded with a material such as a solid absorbent, for example, silica gel, surface modified silica gel, active alumina, and magnesium oxide. A solvent for the reaction mixture is, for example, fluorocarbon and hydrofluoroether, and an eluting solvent is, for example, hydrofluorocarbon based fluids such as Vertrel®, perfluoroexane and hydrofluoroether such as HFE®.
    [00111] In step (c), the purified material obtained in step above (b) is subjected to an allylation reaction with a compound represented by the General Formula Z- (CH2) r-CH2CH = CH2: where Z and r are equal to that described above, to obtain a reaction mixture which thus comprises the compound represented by the General Formula (ic):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (Í-O) [00112] where q, m, n, oer are equal to that described above, and the fluorine-containing compound represented by the General Formula (ii).
    [00113] In the allylation reaction, hydrogen halide is released, therefore, in order to accelerate the reaction, an alkaline material such as an inorganic or organic base is preferably used. Examples of the base are NaOH, KOH, Et3N, i-Pr3N, n-Bu3N, i-Bu3N, t-Bu3N, and n-OctihN. The reaction is conducted using a solvent, for example, hydrofluorocarbon, hydrofluoroether and 1,3-bis-trifluoromethylbenzene. The reaction temperature is in the range of 20 to 120 ° C, preferably 40
    Petition 870190035159, of 12/12/2019, p. 20/59
    17/44 at 90 ° C, more preferably 50 to 80 ° C. The reaction time is 1 to 24 hours, preferably 3 to 20 hours, more preferably 5 to 12 hours.
    [00114] In step (d), the reaction mixture obtained in step (c) is subjected to a hydrosilylation reaction with hydrosilane compound represented by the General Formula (iii):
    H-Si (X ') 3- a (R 1 ) to (iii) [00115] where R 1 , a, and X' are the same as described above, and an isomer reducing agent in the presence of a catalyst of transition metal. Among the reaction mixture in step (c), only the terminal olefinic compound represented by the General Formula (ic):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH2CH = CH2 (Í-O) [00116] where q, m, n, oer are equal to that described above, can react with the hydrosilane compound, and then, if necessary, after (d1) alkylation in the presence of a neutralizing agent with a linear or branched C1C22 aliphatic alcohol, or (d-2) alkoxylation with an alkali metal alkoxide having a linear or branched C1-C22 alkoxy alkoxy group;
    [00117] the organosilicon compound represented by the General Formula (i-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-C3H6-Si (X ') 3- a (R 1 ) a (id) [00118] where q, m, n, o, r, a, X 'and R 1 are the same as described above, is obtained.
    [00119] It is particularly preferable that the hydrosilylation reaction is conducted between trichlorosilane and a compound represented by the General Formula (i-c) in the presence of an isomer reducing agent and a transition metal catalyst. And then, if necessary, hydrosilylation can be followed by dehydrochlorination by alcohol (for example, methanol, ethanol: alkoxylation reaction) resulting in the formation of the organosilicon compound (i-d) having a terminal trialoxysilane.
    Petition 870190035159, of 12/12/2019, p. 21/59
    18/44 [00120] A preferable compound is produced according to the following reaction schemes.
    [0001]
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX-CH2CH = CH2 + HSiCb F- (CF2) q- (OC3F6) m- (OC2F4) n- ( OCF2) o- (CH2) pX- (CH2) 3-SiCl3 | + 3CH3OH - 3HCl F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) 3-Si (OCH3) 3 [00121] In the reaction scheme above, q is an integer from 1 to 3; m, n, and o are independently whole numbers from 0 to 200; p is 1 or 2; X is oxygen, or a divalent organic group.
    [00122] Other preferable schemes are prepared by replacing HSi (OMe) 3 or HSi (OEt) 3 with HSiCh in the above reaction scheme with the additional advantage of not requiring dehydrochlorination as a second step.
    [00123] Dehydrochlorination is preferably conducted using alkylamine (for example, mono- or di-methylamine, mono- or diethylamine or mono- or diisopropylamine: amination reaction) resulting in the formation of the organosilicon compound (id) having a tris (alkylamino) terminal silyl.
    [00124] Specifically, a particularly preferable compound is produced according to the following reaction schemes.
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX-CH2CH = CH2 + HSiCl3 F- (CF2) q- (OC3F6) m- (OC2F4) n- ( OCF2) o- (CH2) pX- (CH2) 3-SiCl3 | + 3HN (CH3) 2 -3HCl
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o- (CH2) pX- (CH2) 3-Si (N (CH3) 2) 3 [00125] In the reaction scheme above, q, m, n, o, p and X are the same as described above.
    [00126] In the case of alkoxylation, the use of acid receptors such as sodium methoxide or trimethylorto-formate is preferred to facilitate dehydrochlorination. On the other hand, in the case of amination, the very
    Petition 870190035159, of 12/12/2019, p. 22/59
    19/44 alkylamine functions as an acid receptor, so the amount of alkylamine must be greater than 2 molar equivalents of chlorine atom.
    [00127] Group VIII catalytic transition metals in hydrosylation are preferably platinum or rhodium. Platinum is more preferred. It is preferable to provide platinum as a chloroplatinic acid or as a platinum complex with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane or rhodium as tris- (triphenylphosphino) Rh I Cl.
    [00128] An isomer reducing agent is also used during a hydrosilylation step. In certain embodiments, the isomer reducing agent comprises a carboxylic acid compound. The carboxylic acid compound can comprise (a) a carboxylic acid, (b) a carboxylic acid anhydride, (c) a silylated carboxylic acid, and / or (d) a substance that will produce the aforementioned carboxylic acid compounds ( that is, (a), (b), and / or (c)) through a reaction or decomposition in the reaction of the method. It should be appreciated that a mixture of one or more carboxylic acid compounds can be used as the isomer reducing agent. For example, a silylated carboxylic acid can be used in combination with a carboxylic acid anhydride as the isomer reducing agent. In addition, a mixture within one or more types of carboxylic acid compounds can be used as the isomer reducing agent. For example, two different silylated carboxylic acids can be used together, or two silylated carboxylic acids can be used together with a carboxylic acid anhydride.
    [00129] When the isomer reducing agent comprises (a) carboxylic acid, any carboxylic acid having carboxyl groups can be used. Suitable examples of carboxylic acids include suitable carboxylic acids, unsaturated carboxylic acids,
    Petition 870190035159, of 12/12/2019, p. 23/59
    20/44 monocarboxylic, and dicarboxylic acids. A saturated or unsaturated hydrocarbon group, halogenated hydrocarbon group, hydrogen atom, or the like are generally selected as the different portion of the carboxyl groups in these carboxylic acids. Specific examples of suitable carboxylic acids include saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, hexanoic acid, cyclohexanoic acid, lauric acid, and stearic acid; saturated dicarboxylic acids such as oxalic acid and adipic acid; aromatic carboxylic acids such as benzoic acid and para-phthalic acid; carboxylic acids in which the hydrogen atoms of the hydrocarbon groups of these carboxylic acids have been replaced with a halogen atom or an organosilyl group, such as chloroacetic acid, dichloroacetic acid, trifluoroacetic acid, parachlorobenzoic acid, and trimethylsilylacetic acid; unsaturated fatty acids such as acrylic acid, methacrylic acid, and oleic acid; and compounds having hydroxy groups, carbonyl groups, or amino groups in addition to the carboxyl groups, i.e., hydroxy acids such as lactic acid, keto acids such as acetoacetic acid, aldehyde acids such as glyoxylic acid, and amino acids such as glutamic acid.
    [00130] When the isomer reducing agent comprises (b) carboxylic acid anhydrides, suitable examples of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, and benzoic anhydride. These anhydrides of carboxylic acids can be obtained through a reaction or decomposition in the reaction system include acetyl chloride, butyryl chloride, benzoyl chloride, and other carboxylic acid halides, metal salts of carboxylic acid such as zinc acetate 10 and thallium acetate, and carboxylic esters that are decomposed by light or heat, such as (2-nitrobenzyl) propionate.
    Petition 870190035159, of 12/12/2019, p. 24/59
    21/44 [00131] In embodiments where the isomer reducing agent comprises (c) a silylated carboxylic acid, suitable examples of silylated carboxylic acids include trialkylsilylated carboxylic acids, such as trimethylsilyl formate, trimethylsilyl acetate, triethylsilyl propionate, benzoate trimethylsilyl, and trimethylsilyl trifluoroacetate; and di-, tri-, or tetracarboxysilylates, such as dimethyldiacetoxy silane, diphenyldiacetoxy silane, methyltriacetoxy silane, ethyl triacetoxy silane, vinyl triacetoxy silane, di-t-butoxydiacetoxy silane, and silicon tetrabenzoate. [00132] The isomer reducing agent is typically used in an amount of 0.001 to 20, alternatively from 0.01 to 5, alternatively from 0.01 to 1 percent by weight, based on the total amount of the terminal olefinic compound represented by the General Formula (ic). Examples of commercially available silylated carboxylic acids suitable as the isomer reducing agent are DOW CORNING® ETS 900 and XIAMETER® OFS-1579 Silane, available from Dow Corning Corporation of Midland, MI.
    [00133] The hydrosilylation reaction proceeds by reacting a compound described by the General Formula (ic) for a period of time and temperature with an excess of silicon hydride in the presence of an isomer reducing agent and sufficient transition metal catalyst to conduct the reaction to the conclusion. As an option, an appropriate solvent can be added to facilitate mixing. Various instrumental methods such as nuclear magnetic resonance or infrared spectroscopy are used to monitor the progress of the reaction. For example, preferred conditions are 30 to 90 ° C for 1 to 10 hours with 1.05 to 30 mol of trichlorosilane per mol of fluorine compound using 0.001 to 10 mmol of Pt supplied as a platinum complex with 1.3 catalyst -divinyl-1,1,3,3tetramethyldisiloxane, that is, a group VIII transition metal and 0.01 to 1 percent by weight of an isomer reducing agent based on
    Petition 870190035159, of 12/12/2019, p. 25/59
    22/44 amount of the fluorine compound (i-c). Any excess silicon hydride can easily be removed from the reaction product by vacuum distillation.
    [00134] If trichlorosilane is used for hydrosilylation, the second reaction (alkoxylation) is preferably carried out by reacting a molar excess of 0.05 to 10 of a mixture of trimethylortoformate and methanol at 30 to 70 ° C for 1 to 10 hours per mol of the compound obtained in the first reaction. Various instrumental methods such as nuclear magnetic resonance or infrared spectroscopy can be used to monitor the progress of the reaction. Any excess trimethylorthoformate and methanol can easily be removed from the reaction product by vacuum distillation. In the case of amination as a second reaction, more than 6 molar equivalents of excess alkylamine are required, since 3 molar equivalents of amine is for the chlorine atom replacement reaction and an additional 3 molar equivalents of amine is for neutralizing the 3 molar equivalents eluted from HCl per 1 mole of SiCl3.
    [00135] The fluorine-containing compounds represented by the General Formula (ii):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-F (ii) [00136] where q, m, n and o are the same as described above, cannot react with the hydrosilane compound. Therefore, they remain unreacted in the reaction mixture.
    [00137] In the hydrosilylation reaction, it was found that some part of the terminal olefinic compound represented by the General Formula (i-c) is isomerized in an internal olefinic compound represented by the General Formula (i-c-d):
    F- (CF2) q- (OC3F6) m- (OC2F4) n- (OCF2) o-CH2O- (CH2) r-CH = CHCH3 (icd) [00138] where q, m, n, oer are equal to described above. The reactivity of this internal-olefinic compound with respect to the
    Petition 870190035159, of 12/12/2019, p. 26/59
    23/44 hydrosilane is very low. Therefore, this compound generally remains unreacted in the reaction mixture, and can decrease the durability property. The amount of the internal olefinic by-product (i-c-d) of the hydrosilylation step can be around 10 to 20 mol% based on a surface treatment composition.
    [00139] Therefore, in the present invention, the total content of fluorine-containing compounds (B) + (C) or (ii) + (icd) must be controlled to be less than 25 mol% based on a treatment composition of surface.
    [00140] The surface treatment composition according to the present invention can include any other suitable compound (s) such as a bleaching agent, an anti-aesthetic agent, an ultraviolet absorbent, a plasticizer, a leveling agent, a pigment, a catalyst and so on.
    [00141] According to another method of the present invention, a surface-treated article is provided, comprising:
    [00142] a base material, and [00143] a layer (or a thin film) formed by the surface treatment composition of the present invention on a surface of the base material.
    [00144] The layer formed by a composition for surface treatment on the surface of the base material has good anti-dirt (or dirt resistant) properties and high durability. Furthermore, since this layer shows a light transmittance such as transparency and light transmittance, the surface treatment composition of the present invention is suitable for use for optical materials that require transmittance.
    [00145] Optional catalysts can be used, if necessary, to promote surface modification by composition for
    Petition 870190035159, of 12/12/2019, p. 27/59
    24/44 surface treatment of the present invention. This catalyst promotes the reaction between the functional organosilic group and the surface of the base material. They can be used alone or as a combination of two or more species to form the surface modifier of the present invention. Examples of suitable catalytic compounds include acids, bases, metal salts of organic acids such as dibutyl tin dioctoate, iron sterate, lead octoate and others, titanate esters such as tetraisopropyl titanate, tetrabutyl titanate, chelate compounds such as acetylacetonate titanium and the like. It is preferable to use an amount of the optional catalyst in the range of 0 to 5 parts by weight, more preferably 0.01 to 2 parts by weight based on 100 parts by weight of a surface treatment composition of the present invention.
    [00146] The surface treatment composition of the present invention can contain a liquid medium such as an organic solvent. The concentration of the surface treatment composition including the organosilicon compound and the fluorine compounds is preferably 0.01 to 80% by weight. The organic solvent can be various solvents that preferably dissolve the composition for surface treatment as long as the organic solvent does not react with components (particularly, the reactive organic silicon compound) contained in the composition of the present invention. Examples of the organic solvent include a fluorine-containing solvent such as a fluorine-containing alkane, a fluorine-containing haloalkane, fluorine-containing aromatics and a fluorine-containing ether (e.g., hydrofluoroether (HFE)).
    [00147] The material to be treated with the surface treatment composition of the invention to form a surface treated layer is not particularly limited. Examples thereof include optical members comprising: inorganic materials such as
    Petition 870190035159, of 12/12/2019, p. 28/59
    25/44 glass plates, glass plates comprising an inorganic layer, ceramics, and the like; and organic materials such as transparent plastic materials and transparent plastic materials that comprise an inorganic layer; etc. Optical members that can comprise such material are not limited, and as an example we can mention anti-reflective films, optical filters, optical lenses, eyeglass lenses, ray dividers, prisms, mirrors, etc.
    [00148] Examples of inorganic materials include glass plates. Examples of inorganic compounds for forming glass plates comprising an inorganic layer include metal oxides (silicon oxides (silicon dioxide, silicon monoxide, etc.), magnesium oxide, titanium oxide, tin oxide, oxide of zirconium, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (indium tin oxide) and the like.
    [00149] The inorganic layer or inorganic material comprising such an inorganic compound can be single layer or multiple layers. The inorganic layer acts as an anti-reflective layer, and can be formed by known methods such as wet coating methods, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), and the like. Examples of wet coating methods include dip coating, centrifugal coating, flow coating, spray coating, cylinder coating, engraving coatings, and the like. Examples of PVD methods include vacuum evaporation, reactive deposition, ion beam aided deposition, spraying, ion coating, and the like.
    [00150] Among organic materials, examples of transparent plastic materials include materials that comprise various organic polymers. From the point of view of transparency, refractive index,
    Petition 870190035159, of 12/12/2019, p. 29/59
    26/44 dispersibility and similar optical properties, and various other properties such as shock resistance, heat resistance and durability, materials used as optical members generally comprise polyolefins (polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene terephthalate, etc. ), polyamides (nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimides, polyvinyl alcohol, ethylene vinyl alcohol, acrylics, celluloses (triacetylcellulose, diacetylcellulose, cellophane, etc.), or copolymers of such organic polymers . These materials can be mentioned as examples of transparent plastic materials to be in the invention. More particularly, these materials can be understood by optical components as ophthalmic elements. Non-limiting elements of ophthalmic elements include corrective and non-corrective lenses, including single vision or multiple vision lenses such as bifocal, trifocal and progressive lenses, which can be segmented or non-segmented, as well as other elements used to correct, protect, or enhance vision, including without limitation contact lenses, intraocular lenses, magnifying lenses and protective lenses or visors. Preferred materials for ophthalmic elements comprise one or more polymers selected from polycarbonates, polyamides, polyimides, polysulfones, polyethylene terephthalate and polycarbonate copolymers, polyolefins, especially polynorbornenes, diethylene glycol bis (allyl carbonate) polymers - known as CR39 - and copolymers , (meth) acrylic polymers and copolymers, especially (meth) acrylic polymers and copolymers derived from bisphenol A, thio (meth) acrylic polymers and copolymers, urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, and polymers and copolymers of epoxy and copolymers .
    [00151] Examples of materials include those prepared by adding known additives such as antistatic agents,
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    27/44 UV absorbers, plasticizers, lubricants, coloring agents, antioxidants, flame retardants, etc. to the organic polymers of these organic materials.
    [00152] The material to be used in the invention can be a material prepared by forming an inorganic layer in an organic material. In this vessel, the inorganic layer acts as an anti-reflective layer and can be formed in an organic material by methods as mentioned above.
    [00153] The inorganic material or organic material to be treated is not particularly limited. Transparent plastic materials used as optical members are usually in the form of films or sheets. Such materials in the form of films or sheets can also be used as the material of the invention. A material in the form of a film or sheet can be a monolayer or a laminate of a plurality of organic polymers. The thickness is not particularly limited, but is preferably 0.01 to 5 mm.
    [00154] The material having a hard coating layer between the transparent plastic material and the inorganic layer can be used for the base material of the present invention. The hard coating layer improves the material's surface hardness and also smooths and smooths the material's surface, thereby improving the adhesion between the transparent plastic material and the inorganic layer. Therefore, scratching caused by loads of pencils or similar can be prevented. In addition, the hard coating layer can inhibit cracking in the inorganic layer caused by the flexing of the transparent plastic material, thereby improving the mechanical intensity of the optical member.
    [00155] The material of the hard coating layer is not particularly limited as long as it has transparency, appropriate hardness, and mechanical intensity. For example, resins
    Petition 870190035159, of 12/12/2019, p. 31/59
    28/44 thermosetting and resins cured by ionizing radiation or ultraviolet radiation are UV curing acrylic resins and organic silicon resins, and thermosetting polysiloxane resins are particularly preferable. The refractive index of such resins is preferably equivalent to or close to that of the transparent plastic material. [00156] Materials as mentioned above can be used as the transparent material of the antireflective optical member of the invention. In particular, such materials that comprise an anti-reflective layer on the surface can be transparent materials that comprise an anti-reflective layer. An anti-reflective optical member of the invention can be obtained by forming an anti-dust layer on the surface of such material.
    [00157] In addition to such optical members, the surface treatment composition of the invention can be applied to window members for automobiles or airplanes, thereby providing advanced functionality. To also improve the surface hardness, it is also possible to carry out the surface modification by a so-called solution-gel process using a combination of the inventive surface treatment composition and TEOS (tetraethoxysilane). [00158] Using the surface treatment composition of the invention as a mold release agent in a nanoprint process, accurate mold release can be easily achieved. When the surface is treated with the surface treatment composition of the invention, the treatment composition diffuses almost to the state of a monolayer, so that the resulting layer is only several nanometers thick. Despite such a thickness, it is possible to form a surface with a water contact angle of 110 ° or more, as shown later in the examples.
    [00159] The surface treatment composition of the invention
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    29/44 has excellent liquid repellency and can therefore be applied to lithography and device formation.
    [00160] In addition, by treating the surface of materials, it is also possible to produce sanitary articles and exterior walls easily maintained.
    [00161] The method of forming a treated layer is not particularly limited. For example, wet coating methods and dry coating methods can be used.
    [00162] Examples of wet coating methods include dip coating, centrifugal coating, flow coating, spray coating, cylinder coating, engraving coatings, and the like.
    [00163] Examples of dry coating methods include vacuum evaporation, spraying, CVD, and the like methods. Specific examples of vacuum evaporation methods include resistive heating methods, electron beam, high frequency heating, ion beam and the like. Examples of CVD methods include plasma CVD, optical CVD, thermal CVD, and the like.
    [00164] In addition, coating by atmospheric pressure plasma methods is also possible.
    [00165] When using wet coating methods, thinner solvents are not particularly limited. In view of the stability and volatility of the composition, the following compounds are preferable: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms, such as perfluoroexane, perfluoromethylcyclohexane, and perfluoro-1,3dimethylcyclohexane; polyfluorinated aromatic hydrocarbons such as bis (trifluoromethyl) benzene; polyfluorinated aliphatic hydrocarbons, perfluorobutyl methyl ether and similar HFEs, etc. Such a solvent can be used separately or as a mixture of two or more.
    Petition 870190035159, of 12/12/2019, p. 33/59
    30/44 [00166] A coating method is preferably used for materials having large areas and / or complicated shapes.
    [00167] On the other hand, in consideration of the working environment at the time of formation of an anti-dust layer, dry coating methods, which do not require diluting solvent, are preferable. Vacuum evaporation methods are particularly preferable.
    [00168] After the formation of an anti-dust layer on the material by a wet or dry coating method, if necessary, heating, humidification, post catalytic treatment, photo-radiation, electron beam irradiation, etc. can be accomplished.
    [00169] The thickness of the anti-dust layer formed using the anti-dust agent of the invention is not particularly limited. A range of 1 to 30 nm is preferable in terms of anti-dust properties, more preferably 1 to 10 nm, anti-scratch properties and optical performance of the optical member.
    [00170] The present invention is also explained specifically by the following examples, however the present invention is not limited to these examples.
    [00171] A composition of the organosilicon compound or the fluorine-containing compound in the present description is analyzed as follows.
    [00172] Polymer composition (per 1H-NMR, 19F-NMR, IR) [00173] An average molecular weight is calculated from the results of assessments of 19 F NMR and molar ratios (mol%) of the respective components in a mixture are calculated from the 1 H NMR evaluation results. The average molecular weight throughout the description means a number average molecular weight.
    [00174] A production is calculated with the proviso that an ideal case matches with respect to both the precursors of an organosilicon compound and a fluorine-containing compound are established at
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    31/44
    100% in which the entire process of a reactive compound containing fluorine is converted into a targeted reaction product.
    EXAMPLES
    EXAMPLE 1 [00175] The present example relates to a composition for surface treatment, according to the present invention described above and to a process for producing it.
    Step (a):
    [00176] A mixture of crude material used was a mixture of 700 g (0.175 mole) of ω-fluoro poliperfluorooxetano acyl fluoride (average molecular weight: 4000) represented by the following chemical formula:
    F- (CF2CF2CF2O) n-CF2CF2-COF [00177] and 300 g (0.075 mole) of perfluoropolioxethane (average molecular weight: 4200) represented by the following chemical formula:
    F- (CF2CF2CF2O) n-CF2CF3 [00178] Under a stream of nitrogen gas, a 3.0 L four-necked flask equipped with an agitator, a drip funnel, a reflux condenser and a thermometer was loaded with 330 g of diglyme, and 11.4 g (0.3 mole) of NaBH4 were added to it with stirring. The crude material mixture described above was added dropwise to it at a rate of 10 ml / minutes. After completion of the dropwise addition, the temperature of the liquid phase was raised to about 110 ° C and a reaction was allowed to proceed for 8 hours at this reaction temperature. After the reaction, the contents of the flask were cooled to 40 ° C less, 700 g of perfluoroexane was added to it followed by stirring for 10 minutes. It was also cooled to 5 ° C less, 140 ml of ion-exchanged water was added dropwise. Then, after 1000 g of a 3N HCl solution was added dropwise, the liquid phase was separated into two phases
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    32/44 (upper and lower) using a separating funnel, and the lower phase (organic phase) was obtained separately. The organic phase thus obtained was washed with a 3N HCl / acetone solution (340 g / 340 g) three times. As a result of complete removal of a volatile portion by distillation under reduced pressure, 950 g (95% yield) of a reaction mixture was obtained.
    [00179] According to IR analysis of the obtained reaction mixture, the absorption at 1890 cm -1 derived from -C (= O) F completely disappeared, and the absorption at 3300 cm -1 derived from -CH2OH again appeared. Therefore, the reaction mixture was recognized as a mixture of perfluoropolioxethane alcohol represented by the following chemical formula:
    CF3CF2CF2- (OCF2CF2CF2) a-O-CF2CF2-CH2OH [00180] and perfluoropolyethane represented by the following chemical formula:
    CF3CF2CF2- (OCF2CF2CF2) aO-CF2CF3 [00181] In this reaction mixture, the alcohol content of perfluoropolyethane (average molecular weight 4000) was 70% by mol, and the content of perfluoropolyethane (average molecular weight 4200) was 30% in mol.
    Step (b): Purification step by chromatography:
    [00182] The reaction mixture obtained from step (a) was subjected to separation by column chromatography loaded with silica gel (solvent: Vertrel XF from DuPont), and thereby 660 g (98 mol% purity) of a material substantially purified consisting of perfluoropolyethane alcohol represented by the chemical formula below were obtained:
    CF3CF2CF2- (OCF2CF2CF2) a-O-CF2CF2-CH2OH [00183] In the purified material, the perfluoropolioxethane content represented by the chemical formula below was 2 mol%:
    Petition 870190035159, of 12/12/2019, p. 36/59
    33/44
    CF3CF2CF2- (OCF2CF2CF2) a-O-CF2CF3
    Step (c): Allylation reaction:
    [00184] Under a stream of nitrogen gas, to a 3.0 L four-neck flask equipped with a stirrer, a drip funnel, a reflux condenser and a thermometer were added 500 g (0.125 mol) of a mixture (CF3CF2CF2 (OCF2CF2CF2) aO-CF2CF2-CH2OH / CF3CF2CF2- (OCF2CF2CF2) a-OCF2CF3 = 98 mol% / 2 mol%), and 300 g of 1.3 bis (trifluoromethyl) benzene were added to it with stirring. After adding 10 g (0.25 mol) of sodium hydrate, the temperature of the liquid phase was raised to about 65 ° C and a reaction was allowed to proceed for 4 hours at this reaction temperature. After 4 hours, 30 g (0.24 mol) of allylbromide was added. After adding allylbromide, the reaction was allowed to proceed for 8 hours at 65 ° C. After the reaction, the contents of the flask were cooled to 40 ° C less, and 200 g of perfluoroexane were added to it followed by stirring for 10 minutes. It was also cooled to 5 ° C less, 150 g of 3N HCl solution was added dropwise, the liquid phase was separated into two phases (upper and lower) using a separating funnel, and the lower phase (organic phase) was obtained separately. The organic phase thus obtained was washed with 3 N HCl / acetone solution (150 g / 150 g) three times. As a result of complete removal of a volatile portion by distillation under reduced pressure, 480 g (96% yield) of a reaction mixture was obtained.
    [00185] According to the analyzes of 1H-NMR and 19F-NMR, the reaction mixture obtained was recognized as a mixture of CF3CF2CF2 (OCF2CF2CF2) 22OCF2CF2CH2OCH2CH = CH2 and
    CF3CF2CF2 (OCF2CF2CF2) 22OCF2CF3 (the ratio is 98 mol% / 2 mol%).
    Petition 870190035159, of 12/12/2019, p. 37/59
    34/44 [00186] Step (d) (1): Silylation by trichlorosilane then alkoxylation:
    [00187] To a 3-necked flask of 300 mL equipped with magnetic stir bar, reflux condenser cooled by water, temperature control and dry nitrogen-free top purge was added 80.0 g of
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH = CH2 e
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 (mixing ratio is 98 mol% / 2 mol%, FW 4521 g / mole), 40.0 g 1.3bis (trifluoromethyl) benzene, 0.24 g Dow Corning® ETS 900 and 4.06 g of trichlorosilane. The contents were heated to 60 ° C before incremental addition over 80 minutes of Pt metal complexed with
    1,3-divinyl-1,1,3,3-tetramethyl-disiloxane. The contents were maintained at 65 ° C for a further 120 minutes to mix CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2SiCl3, CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3. Residual trichlorosilane and solvent were removed in vacuo from the reaction mixture before the addition of 10.0 g of trimethylorthoformate, 10.0 g of methanol and 20.0 g of 1.3bis (trifluoromethyl) benzene. The contents of the flask were maintained at 60 ° C for 3 hours to facilitate the methoxylation of chlorosilane. The excess reagent was removed in vacuo. Activated carbon, 4.0 g, was added. The product was filtered through a celite filter bed aided in a 0.5 micron membrane. The product mixture (X), CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2Si (OCH3) 3,
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 and
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 (the mixing ratio is 81 mol% / 17 mol% / 2 mol%), was isolated as the filtrate. Analysis by infrared spectroscopy and nuclear magnetic resonance showed the complete disappearance of
    Petition 870190035159, of 12/12/2019, p. 38/59
    35/44
    CH2 = CHCH2O and SiCl.
    [00188] The following steps (i) - (iii) refer to an anti-dust treatment of ophthalmic lenses and the lenses thus obtained.
    (i) Pre-treatment of ophthalmic lenses:
    [00189] The coatings are obtained on substrates that are ophthalmic lenses based on CR39.RTM. comprising, on both sides, a polysiloxane type anti-abrasion coating corresponding to example 3 in Patent Publication EP614957. The lenses are washed in an ultrasound cleaning vessel, sprayed for a minimum of 3 hours at a temperature of 100 ° C. They are then ready to be treated. Treated lenses are round lenses.
    (ii) Preparation of the Lenses (Preparation of the Lenses having a Non-Relative and Hydrophobic / Oleophobic Coating:
    [00190] The vacuum treatment machine used is a Syrus 3 machine from Leybold Optics supplied with an electron gun, an ion cannon and an evaporation source with a Joule effect. The lenses are placed in a carousel provided with circular openings designed to accommodate the lenses to be treated, the concave side covering the evaporation sources and the ion cannon.
    [00191] A vacuum extraction is performed until a secondary vacuum is obtained.
    [00192] Then, a successive evaporation is performed, with the electron gun with 4 non-reflective optical layers, high index (IH), low index (BI), HI, BI: ZrO2, SiO2, ZrO2, SO [00193] Finally, the hydrophobic and oleophobic coating layer of reaction mixture (X) obtained above is deposited by evaporation.
    [00194] A certain amount of the reaction mixture (X) obtained above is placed in a copper capsule with a diameter of 18
    Petition 870190035159, of 12/12/2019, p. 39/59
    36/44 mm, successively placed in a joule crucible (tantalum crucible). A thickness of 1 to 5 nm of hydrophobic and oleophobic coating is deposited through evaporation.
    [00195] The deposited thickness is evaluated using a quartz monitor.
    [00196] Subsequently, the room is heated again and the treatment chamber is fixed again in an atmosphere.
    [00197] The lenses are then turned upside down and the convex side oriented towards the treatment area. The convex side is treated identically to the concave side (reproducing steps (ii) above).
    (iii) Tests & evaluations:
    (iii-1) Durability procedure A:
    [00198] A Microfiber M840S 30X40 of FACOL is immersed in water at 25 ° C for 1 minute and then removed in air. This Microfiber is then used to mechanically rub the surface of the plastic lens having a repellent film 1200 times (ie, 600 cycles), 2400 times (ie, 1200 cycles), 3600 times (ie, 1800 cycles), 4800 times (that is, 2400 cycles), and 6000 times (that is, 3000 cycles), in an anterograde and retrograde movement (1 cycle corresponds to a more retrograde anterograde movement) while applying a load of 3.5 kg. (in air of 25 ° C, 40 to 60% humidity), and the static contact angle is assessed every 600 mop cycles. The mechanical mop equipment is fixed to obtain 600 cycles in 7 minutes.
    (iii-2) Durability procedure B:
    [00199] A Microfiber M840S 30X40 of FACOL is immersed in water at 25 ° C for 1 minute and then removed in air. This Microfiber is then used to mechanically rub the surface of the plastic lens having a water-repellent film 2400 times (ie 1200
    Petition 870190035159, of 12/12/2019, p. 40/59
    37/44 cycles), 4800 times (that is, 2400 cycles), 7200 times (that is, 3600 cycles), 9600 times (that is, 4800 cycles), and 12000 times (that is, 6000 cycles), in one motion anterograde and retrograde (1 cycle corresponds to a more retrograde anterograde movement) while applying a load of 3.5 kg. (in air of 25 ° C, 40 to 60% humidity), and the static contact angle is assessed every 1200 mop cycles. The mechanical mop equipment is fixed to obtain 1200 cycles in 14 minutes.
    (iii-3) Static contact angle to water:
    [00200] Using a meter of contact angle (DSA 100, manufactured by KRUSS Advancing Surface Science), a doublet of water having a volume of 4 micro-liters is deposited in the highest portion of the convex side of the lens using a 25 needle ° C. The angle between the doublet and the surface is defined as the angle of static contact with water. This angle is evaluated using the DSA 100 drop shape analysis software. Using this technique and equipment, the evaluation uncertainty is +/- 1.3 °.
    EXAMPLE 2 [00201] A cycle was performed following the process described above. Three lenses were tested using a durability test procedure A described above and for each lens at each step 3, static contact angle assessments were performed. Table 1 shows the average value calculated using the 3 assessments made on the 3 lenses:
    Table 1 (using durability procedure A, product mix X) Number of cycles no cycle 600 cycles @ 3.5 kg 1200 cycles@ 3.5 kg 1800 cycles@ 3.5 kg 2400 cycles3.5 kg @ 3000 cycles@ 3.5 kg Static contact angle(°) Average over 3 lenses 120 ° 112 ° 112 ° 112 ° 112 ° 113 °
    Note: @ 3.5 kg means the load applied for each cycle.
    [00202] The example shows that the anti-dust coating is a
    Petition 870190035159, of 12/12/2019, p. 41/59
    38/44 little damaged after 600 cycles, however it demonstrates the very high durability of the coating. In fact, the contact angle is stable from 1200 to 3000 cycles and remains at a high level.
    COMPARATIVE EXAMPLE EMPLOUS 1 [00203] A product mixture (XX) was obtained according to procedures similar to Example 1, except that step (b) was not carried out, the reaction mixture obtained from step (a) was used for step (c) in place of the purified material obtained from step (b) and the reaction mixture obtained from the above was used for step (d), however Dow Corning® ETS 900 was not added.
    [00204] In the product mixture (XX), the perfluoropolyether content of silane functional was 28 mol%,
    CF3CF2CF2 (OCF2CF2CF2) 22OCF2CF3 was 30 mol% and CF3CF2CF2 (OCF2CF2CF2) 22OCF2CF2CH2O-CH = CHCH3 was 42 mol%.
    EXAMPLE 3 [00205] A product mixture (XXX) was obtained according to procedures similar to Example 1. The product mixture (XXX) contained,
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2Si (OCH3) 3, CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 e
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 (the mixing ratio is 77 mol% / 21 mol% / 2 mol%).
    [00206] The surface treated lenses were prepared according to the same procedure as Example 2, except that the reaction mixture (XX) of comparative example 1 or (XXX) of example 3 was used. Durability procedure B was used to compare treatments. The results are shown in table 2.
    Petition 870190035159, of 12/12/2019, p. 42/59
    Table 2 (Durability procedure B) Number of cycles no cycle 1200 cycles @ 3.5kg 2400 cycles @ 3.5kg 3600 cycles @3.5kg 4800 cycles @ 3.5kg 6000 cycles@ 3.5kg Angle ofaverage static contact (°) in 3 lenses Product mix (XXX) 119 ° 120 ° 106 ° 105 ° 105 ° 104 ° Comparative Example1, Product mix (XX) 104 ° 100 ° OCOCD 97 ° 95 ° 94 °
    Note: 3.5 kg means the load applied for each cycle.
    39/44
    Petition 870190035159, of 12/12/2019, p. 43/59
    40/44 [00207] By comparing the results of Example 2, using product mixture (XXX) and comparative example 1 (product mixture (XX)) in table 2, it is clearly understood that the purification step (b) contributes greatly for decreasing surface energy and increasing the durability of the anti-dust layer.
    EXAMPLE 4 [00208] A reaction mixture (YY) was obtained according to procedures similar to Example 1, except that the alkylation reaction in step (d) (1) was replaced by the amination reaction as follows:
    [00209] Step (d) (1): Trichlorosilane silylation after amination:
    [00210] To a 3-neck flask of 100 mL equipped with magnetic stir bar, reflux condenser cooled by water, temperature control and dry nitrogen free top purging were added 36.78 g of
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH = CH2 e
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 (mixing ratio is 98 mol% / 2 mol%, FW 4070 g / mole), 18.91 g 1.3bis (trifluoromethyl) benzene, 0.0879 g Dow Corning® ETS 900 and 7.72 g of trichlorosilane. The contents were heated to 60 ° before incremental addition for 3.25 hours of Pt metal complexed with 1,3-divinyl-
    1,1,3,3-tetramethyl-disyloxane. The contents were maintained at 60 ° C for another 30 minutes to prepare the mixture of
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2SiCl3, CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 e
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3. The residual trichlorosilane and solvent were vacuum extracted from the reaction mixture.
    [00211] The mixture was transferred to a 250 ml 3-neck flask equipped with magnetic stir bar, dry ice (CO2)
    Petition 870190035159, of 12/12/2019, p. 44/59
    41/44 reflux condenser, thermometer and dry nitrogen free top purge with 87.04 g of perfluoroexanes before condensation in 37 g of anhydrous dimethylamine which cooled the reaction mixture to 7 ° C. The dry ice was allowed to evaporate and the contents heated overnight to room temperature which resulted in the purging of excess dimethylamine. Activated carbon, 0.33 g, was added. The product was filtered through a celite filter bed aided in a 5 micron membrane. The product mixture (YY), CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2Si (NMe2) 3,
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 and
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 (the mixing ratio is 85 mol% / 2 mol% / 13 mol%), was isolated as the filtrate. Analysis by infrared spectroscopy and nuclear magnetic resonance showed the complete disappearance of CH2 = CHCH2O and SiCl functionalities.
    EXAMPLE 5 [00212] The synthesis was repeated according to the procedure of example 1 with the exception that step (d) of hydrosilylation was completed by trimethoxysilane, avoiding having to methoxylate in an additional step.
    [00213] To a bottle of 3 necks of 100 mL equipped with magnetic stir bar, reflux condenser cooled by water, temperature control and dry nitrogen free top purge were added 20.5 g of
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH = CH2 e
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3 (mixing ratio is 98 mol% / 2 mol%, FW 4521 g / mole), 10.0 g 1.3bis (trifluoromethyl) benzene, 0.06 g Dow Corning® ETS 900 and 1.94 g of trimethoxysilane. The contents were heated to 60 ° before incremental addition during 0.5 hours of Pt metal complexed with 1.3 Petition 870190035159, from 12/04/2019, p. 45/59
    42/44 divinyl-1,1,3,3-tetramethyl-disiloxane. The levels were maintained at
    60 ° CFor a further 50 minutes to prepare the mixture of CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2Si (OCH3) 3, CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 and
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3. The residual trimethoxysilane and solvent were vacuum extracted from the reaction mixture before the addition of 1.1 g of activated carbon. The product was filtered through a celite filter bed aided in a 0.5 micron membrane. The product mixture [00214] CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH2CH2CH2Si (O
    CH3) 3, CF3CF2CF2 (OCF2CF2CF2) xOCF2CF2CH2OCH = CHCH3 and
    CF3CF2CF2 (OCF2CF2CF2) xOCF2CF3. (the mixing ratio is 81 mol% / 17 mol% / 2 mol%), it was isolated as the filtrate. Analysis by infrared spectroscopy and nuclear magnetic resonance showed the complete disappearance of CH2 = CHCH2O functionalities.
    [00215] The surface treated lenses were prepared according to the same procedure as Example 2, except that the Example 4 reaction mixture (YY) was used. Three lenses were tested using the durability procedure B described above and for each lens at each step, 3 static contact angle assessments were performed. Table 3 shows the average value calculated using the 3 assessments made on the 3 lenses:
    Petition 870190035159, of 12/12/2019, p. 46/59
    Table 3 (Durability procedure B)
    Number of cycles no cycle 1200 cycles@ 3.5 kg Static contact angle and (°) Average over 3 lenses 114 °
    2400 cycles@ 3.5 kg 3600 cycles@ 3.5 kg 4800 cycles@ 3.5 kg 6000 cycles@ 3.5 kg 112 ° 112 ° 109 ° 109 °
    Note: 3.5 kg means the load applied for each cycle.
    43/44
    Petition 870190035159, of 12/12/2019, p. 47/59
    44/44 [00216] The results in table 3 demonstrate the very high durability of the coating. In fact, the contact angle is stable from 1200 to 6000 cycles and remains at a high level.
    [00217] Furthermore, the optically functional member obtained by attaching the optical element or antireflective optical member of the present invention to an optical functional member, such as a deflection plate, has a treated layer with the above-mentioned excellent functionality and high durability formed on its surface and therefore provides the display device with high image recognition of the present invention, when connected, for example, to the front panel of the display screen of various displays (liquid crystal displays, CRT displays, projection displays, plasma displays, EL displays, etc.).
    [00218] In addition, the treated layer formed on a material surface using the surface treatment composition of the present invention is extremely thin, and thus has excellent micro-treatment properties and highly accurate processability.
    INDUSTRIAL APPLICABILITY [00219] A surface treatment composition obtained by the present invention can be suitably used as a surface treatment agent for providing an anti-dust property to a surface of various base materials, especially optical materials that require transmittance.
    权利要求:
    Claims (15)
    [1]
    1. Suitable composition as a surface treatment composition, characterized by the fact that it comprises an organosilicon compound of Formula (A):

    in which
    X is O or a divalent organic group;
    R 1 is a C1-22 hydrocarbon group, linear or branched, which does not have an unsaturated aliphatic bond;
    X 'is hydrolyzable group, a is an integer from 0 to 2;
    m is an integer from 0 to 200;
    n is an integer from 0 to 200;
    o is an integer from 0 to 200;
    p is 1 or 2;
    q is an integer from 1 to 3;
    r is an integer from 0 to 17; and which contains, based on the composition, <25 mol% of fluorine-containing compounds of Formulas (B) and (C):
    F- (CF 2 ) g- (OC 3 F 6 ) m - (OC 2 F 4 ) n - (OCF 2 ) o -F (β) F- (CF 2 ) Q - (OC 3 F 6 ) m - (OC 2 F4) n - (OCF 2 ) o - (CH 2 ) p -X- (CH 2 ) r -CH = CHCH3 (C) in which
    m. n o, p, q, r and X are as defined above.
    [2]
    2. Composition, according to claim 1, characterized by the fact that, in Formula (A),
    X 'is at least one of -OR, -NHR and -NR2, where R is independently a straight or branched C1-C22 alkyl, and two groups R can form a cyclic amine, and
    Petition 870190035948, of 15/04/2019, p. 4/13
    2/5 a is 0.
    [3]
    Composition according to claim 1 or 2, characterized in that X 'is -NHR or -NR2.
    [4]
    4. Composition according to any one of claims 1 to 3, characterized by the fact that:
    (A) is a compound of Formula (i-d-i) or (i-d-ii):
    F- (CF 2 ) q - (OC 3 F 6 ) m - (OC 2 F 4 ) n - (OCF 2 ) o -CH 2 O- (CH 2 ) / --C 3 H 6 -Si (NHR) 3 (μό _ 0 F- (CF 2 ) Q - (OC 3 F 6 ) m - (OC 2 F 4 ) n - (OCF 2 ) o -CH 2 O- (CH 2 ) r -C 3 H 6 - Si (NR 2 ) 3 (μό _ Η) and
    (C) is a compound of Formula (i-c-d):
    F- (CF 2 ) < (0C 3 F 6 ) m - (0C 2 F 4 ) n - (0CF 2 ) o -CH 2 0- (CH 2 ) r -CH = CHCH 3 (j _ c _ d) where m, n, o, q, r and R are as defined in claim 1.
    [5]
    Composition according to any one of claims 1 to 4, characterized in that it contains> 0.1 mol%, preferably> 1.0 mol% of compound (C).
    [6]
    Composition according to any one of claims 1 to 5, characterized in that it contains <15 mol% of the compounds (B) and (C).
    [7]
    7. Composition according to any one of claims 1 to 6, characterized by the fact that in Formulas (A) and (C), p is 1 and X is O.
    [8]
    8. Process for producing a composition, as defined in any one of claims 1 to 7, characterized by the fact that it comprises the steps of:
    (a) contacting a mixture of raw material, which comprises compounds of Formulas (i) and (ii):
    Petition 870190035948, of 15/04/2019, p. 5/13
    3/5
    F- (CF 2 ) q - (OC 3 F 6 ) m - (OC 2 F 4 ) n - (OCF 2 ) o -C (= O) F (j) F- (CF 2 ) Q - (OC 3 F 6 ) / 77 - (OC 2 F 4 ) n - (OCF 2 ) o -F (jj) with a reducing agent to react compound (i) thereby producing a reaction mixture, which comprises alcohols of Formula (ib ):
    F- (CF 2 ) Q - (OC 3 F 6 ) m - (OC 2 F 4 ) n - (OCF 2 ) o -CH 2 OH (j _ b) in which m, n, o and q are as defined in the claim 1;
    and the compound of Formula (ii);
    (b) purifying the reaction mixture obtained by column chromatography to remove at least part of the compound (ii) to produce a purified material, the content of the compound (i-b) being greater than that of the reaction mixture;
    (c) contact the purified material produced in step (b) with
    Z- (CH 2 ) r -CH 2 CH = CH 2 in which
    Z is a halogen atom;
    r is an integer from 0 to 17, to react the compound (i-b) to produce a reaction mixture comprising allyl compounds of Formula (i-c):
    F- (CF 2 ) Q - (OC 3 F 6 ) m - (OC 2 F 4 ) / 1 - (OCF 2 ) o -CH 2 O- (CH 2 ) r -CH 2 CH = CH 2 (j _ c) in which m, n, o, q and r are as defined in claim 1;
    and the compound of Formula (ii) in an amount less than
    10 mol%, based on the reaction mixture produced; and
    Petition 870190035948, of 15/04/2019, p. 6/13
    4/5 (d) contact the reaction mixture obtained with the hydrosilane compound of Formula (iii):

    in which
    R 1 , a and X 'are as defined in claim 1, in the presence of a transition metal catalyst and an isomer reducing agent, and then, if necessary, contact alkali metal alkoxide to react the compound (ic ).
    [9]
    9. Process according to claim 8, characterized by the fact that step (d) comprises contacting the reaction mixture obtained in step (c) with trichlorosilane (HSiCh) in the presence of an isomer reducing agent and a catalyst of transition metal, and then contacting alkylamine, thereby producing the composition, as defined in claim 4.
    [10]
    10. Process according to claim 8 or 9, characterized by the fact that the reducing agent is NaBH4 or LiAlH4.
    [11]
    Process according to any one of claims 8 to 10, characterized in that step (c) is carried out in the presence of a base.
    [12]
    Process according to any one of claims 8 to 11, characterized in that the transition metal catalyst used in step (d) is either platinum, rhodium or palladium.
    [13]
    Process according to any one of claims 8 to 12, characterized in that the isomer reducing agent is a carboxylic acid compound, and is preferably selected from one or more of silylated carboxylic acids.
    [14]
    14. Article treated on the surface, characterized by the fact that it comprises:
    Petition 870190035948, of 15/04/2019, p. 7/13
    5/5 (i) a base material, preferably a transparent material, comprising an anti-reflective optical layer; and (ii) a layer formed by applying the composition, as defined in any one of claims 1 to 7, on a surface of the base material.
    [15]
    15. Article treated on the surface, according to claim 14, characterized by the fact that it is selected from corrective and non-corrective lenses, including single vision or multi-vision lenses such as bifocal, trifocal and progressive lenses, which can be segmented or not targeted.
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    同族专利:
    公开号 | 公开日
    AU2010319593A8|2012-06-07|
    EP2499209A1|2012-09-19|
    CA2779655C|2015-10-13|
    WO2011060047A8|2012-05-31|
    BR112012011306A2|2016-04-12|
    CN102666759A|2012-09-12|
    WO2011059430A1|2011-05-19|
    JP5774018B2|2015-09-02|
    KR101599655B1|2016-03-03|
    EP2499209B8|2019-09-25|
    KR101419153B1|2014-07-11|
    EA026635B1|2017-04-28|
    AU2010319593A1|2012-05-31|
    CA2779655A1|2011-05-19|
    CN102666759B|2015-07-15|
    EA201290313A1|2012-12-28|
    KR20120093343A|2012-08-22|
    AU2010319593B2|2014-04-24|
    WO2011060047A1|2011-05-19|
    KR20140082845A|2014-07-02|
    EP2499209B1|2019-08-21|
    JP2013510931A|2013-03-28|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-08-14| B25A| Requested transfer of rights approved|Owner name: DOW CORNING CORPORATION (US) ; DAIKIN INDUSTRIES, |
    2019-02-12| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-07-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/11/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/11/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    USPCT/US2009/64016|2009-11-11|
    PCT/US2009/064016|WO2011059430A1|2009-11-11|2009-11-11|Surface treatment composition, process for producing the same, and surface-treated article|
    PCT/US2010/056194|WO2011060047A1|2009-11-11|2010-11-10|Surface treatment composition, process for producing the same, and surface-treated article|
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