CN105985501B - 包含涂有防油扩散剂的表面的基质和该基质的防油扩散方法 - Google Patents
包含涂有防油扩散剂的表面的基质和该基质的防油扩散方法 Download PDFInfo
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- CN105985501B CN105985501B CN201610150966.2A CN201610150966A CN105985501B CN 105985501 B CN105985501 B CN 105985501B CN 201610150966 A CN201610150966 A CN 201610150966A CN 105985501 B CN105985501 B CN 105985501B
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- 125000005842 heteroatom Chemical group 0.000 claims abstract description 11
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- 239000000047 product Substances 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/005—Coating layers for jewellery
- A44C27/007—Non-metallic coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/28—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/48—Lubricating compositions characterised by the base-material being a macromolecular compound containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
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- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/023—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
- C10M2209/0845—Acrylate; Methacrylate used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
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Abstract
本发明涉及包含至少一部分涂有防油扩散剂的表面的基质,所述防油扩散剂包含至少一种嵌段共聚物形式的化合物,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链共价键连接的N单元嵌段,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:M为N为其中R1、R2可以为相同或不同的,为H、C1‑C10烷基、C1‑C10烯基,Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的烃链形成的间隔臂,A可以为相同或不同的,形成对基质的锚定结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫酰胺、硅烷醇、烷氧基硅烷、硅烷卤化物、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环、羧酸、酐、儿茶酚的组,L可以为相同或不同的,为卤化C1‑C20碳结构部分。本发明还涉及该基质的防油扩散方法,和包含含有该基质的元件的时钟或珠宝件。
Description
发明领域
本发明涉及力学领域,特别是钟表或珠宝领域。更特别地涉及基质,特别是包含至少部分涂有防油扩散(epilamization)剂的表面的时钟或珠宝件的元件用基质。还涉及将该基质防油扩散化的方法,和包含含有该基质的元件的时钟或珠宝件。
发明背景
存在通过使用合适的试剂处理以具体地改进某些表面性能而改进基质的表面状态的多种方法。例如,在力学领域中,特别是在钟表领域中,以及在珠宝领域中,通常将件或元件的表面用防油扩散剂防油扩散化以控制和降低使用期间所述表面的表面能。更具体而言,防油扩散剂的目的是通过形成疏水性和疏油性表面,从而容许润滑剂保留在处理表面上的预定位置上而防止油或润滑剂在钟表的元件或珠宝件上的散布。
然而,目前用于防油扩散的物质具有各种缺点。更具体而言,已知的防油扩散剂,例如FK/BS或3MTM FluoradTM系列对钟表制造商的清洗操作具有较差的抗性。美国专利申请No 2012/0088099通过提议使用具有儿茶酚链端官能的防油扩散剂部分地解决该问题,该儿茶酚官能能够确保附着在基质的表面上。然而,这些防油扩散剂对钟表制造商的清洗操作的抗性未在所有基质,特别是金和钢上改进,所述金和钢是钟表和珠宝领域中非常常见的基质。因此,已知防油扩散剂的使用通常限于某些材料,这要求使用者取决于待处理表面的性质得到各类防油扩散剂。克服该问题的一种解决方法公开于例如WO专利申请2012/085130中。该解决方法在于对于防油扩散组合物,使用不同类型的化合物(硫醇和双膦酸型)的混合物,其协同作用增强防油扩散剂(epilame)在基质上的附着力。然而,这些化合物各自的合成要求至少4个步骤,使得合成整个防油扩散组合物的方法是长且复杂的。
发明概述
本发明的目的是克服已知防油扩散剂的各个缺点。
更具体而言,本发明的目的是提供与已知防油扩散剂相比提供提高的耐清洗性的防油扩散剂。
本发明的目的还有提供能够用于任何类型的材料的通用防油扩散剂。
本发明的目的还有提供在几个步骤中简单地生产的防油扩散剂。
为此,本发明涉及包含至少一部分涂有防油扩散剂的表面的基质。
根据本发明,所述防油扩散剂包含至少一种嵌段共聚物形式的化合物,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为
其中R1、R2可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,优选H、CH3基团,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且
可包含至少一个杂原子的线性或支化烃链形成的间隔臂,A可以为相同或不同的,形成对基质的结合结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫代酰胺、硅烷醇、烷氧基硅烷、卤化硅烷、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环、羧酸、酐、儿茶酚的组,
L可以为相同或不同的,为卤化,优选氟化C1-C20碳结构部分。
该防油扩散剂提供改进的耐清洗性且具有通用特征,使得它用于任何类型的材料。
本发明还涉及至少一部分基质表面的防油扩散方法,其包括步骤:
a)制备包含至少一种如上文所定义的嵌段共聚物的防油扩散剂,
b)任选制备基质表面,
c)使基质表面与防油扩散剂接触,
d)干燥。
本发明还涉及嵌段共聚物,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,所述嵌段以线性序列(linear sequences)通过其主链通过共价键相互连接,其中:
M为N为
其中R1、R2可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,优选H、CH3基团,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A可以为相同或不同的,形成对基质的结合结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫代酰胺、硅烷醇、烷氧基硅烷、卤化硅烷、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环、羧酸、酐、儿茶酚的组,
L可以为相同或不同的,为卤化,优选氟化C1-C20碳结构部分,
以下共聚物除外:
本发明还涉及嵌段共聚物作为至少一部分基质表面(特别是意欲用于时钟或珠宝)的防油扩散剂的用途,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个通过其主链通过共价键连接的P单元,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为P为
其中R1、R2、R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,优选H、CH3基团,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A可以为相同或不同的,形成对基质的结合结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫代酰胺、硅烷醇、烷氧基硅烷、卤化硅烷、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环、羧酸、酐、儿茶酚的组,
L可以为相同或不同的,为卤化,优选氟化C1-C20碳结构部分,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至
少一个杂原子的线性或支化、饱和或不饱和烃链。
本发明还涉及具有包含如上文所定义的基质的元件的时钟或珠宝件。
发明详述
根据本发明,基质,特别是用于时钟或珠宝件的元件的基质具有至少一部分涂有防油扩散剂的表面,所述防油扩散剂包含至少一种嵌段共聚物形式的化合物,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个通过其主链通过共价键连接的P单元,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为P为
其中R1、R2、R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,优选H、CH3基团,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A可以为相同或不同的,形成对基质的结合结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫代酰胺、硅烷醇、烷氧基硅烷、卤化硅烷、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环如咪唑或吡啶、羧酸、酐、儿茶酚的组,
L可以为相同或不同的,为卤化,优选氟化C1-C20碳结构部分,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至少一个杂原子的线性或支化、饱和或不饱和烃链。
优选,嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个通过其主链通过共价键连接的P单元,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为P为
其中R1、R2、R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,优选H、CH3基团,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且
可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A可以为相同或不同的,形成对基质的结合结构部分,并且选自包含硫醇、硫醚、硫酯、硫化物、硫代酰胺、硅烷醇、烷氧基硅烷、卤化硅烷、羟基、磷酸酯、保护或未保护膦酸、保护或未保护膦酸酯、胺、铵、氮化杂环如咪唑或吡啶、羧酸、酐、儿茶酚的组,
L可以为相同或不同的,为卤化,优选氟化C1-C20碳结构部分,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至少一个杂原子的线性或支化、饱和或不饱和烃链。
优选,嵌段共聚物包含或者仅由M单元嵌段和N单元嵌段形成,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个P单元。
任选包含至少一个P单元的单元M和N嵌段以线性序列通过其主链通过共价键相互连接,使得嵌段共聚物以以下形式书写:
优选,嵌段共聚物包含单一M单元嵌段和单一N单元嵌段,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个P单元。当存在时,M单元嵌段中的P单元数目z可与N单元嵌段中的P单元数目w不同。
优选,P单元结合并分布在例如通过P单元与N单元统计共聚而由N单元形成的嵌段内,以形成主要由N单元形成并结合在N单元嵌段中的单一嵌段。
有利地,相同或不同的Y、X结构部分选自包含C1-C20酯基团,优选C2-C10酯基团,更优选C2-C6酯基团,甚至更优选C2-C5酯基团,优选烷基酯基团,优选线性酰胺基团和苯乙烯衍生物基团的组。
有意义的A官能团能够与待防油扩散化的基质表面反应以在基质表面上形成用于防油扩散剂的结合结构部分。有利地,A基团可在M单元嵌段的末端提供。
有利地,M单元嵌段包含至少两个不同的A结合结构部分。
有意义的L官能团造成防油扩散效果。它们包含至少一个卤原子,优选氟原子。优选,L为碳结构部分,即C2-C20,优选C4-C10,更优选C6-C9烷基链,其可以为环状的,优选不具有杂原子。L为部分或完全卤化的。有利地,L为至少部分氟化,优选完全氟化结构部分。L还可包含在端基中的氢原子。L优选为全氟化烷基链。
P单元的有意义的R4官能团用于改进防油扩散剂的性能和/或提供其它功能。例如,R4可以为用于改进所得接触角的烷基链,优选C8-C20烷基链,或者能够在补充交联步骤(步骤e)中形成交联点的链。例如,P单元可衍生自甲基丙烯酸硬脂基酯。显然,存在于M单元嵌段中的R4可以与存在于N单元嵌段中的R4不同。
优选,嵌段共聚物包含0.1%至50%,优选5%至30%,更优选5%至20%M单元,1%至99.9%,优选50%至99.9%,更优选80%至95%N单元,和0%至50%,优选0%至30%,更优选0%至10%P单元,其中百分数相对于单元(x+y+z+w)的总数表示。
有利地,嵌段共聚物包含10-350个单元(x+y+z+w)。
以特别有利的方式,选择M、N、P单元以带有几个不同类型的A基团、几个L基团(优选相同类型)以及可能一个或多个R4基团(可以为相同或不同类型),以精炼和改进防油扩散剂的性能,以便更具体地得到具有改进的与基质的亲合力的通用防油扩散剂。
优选,至少一部分涂有防油扩散剂的基质表面由选自包含金属、掺杂或未掺杂金属氧化物、聚合物、蓝宝石、红宝石、硅、硅氧化物、硅氮化物、硅碳化物、DLC(类金刚石碳)及其合金的组的材料制成。
更具体而言,基质表面可由钢,由贵金属如金、铑、钯、铂,或者铝、锆、钛、铬、锰、镁、铁、镍、铜、锌、钼、银、钨的掺杂或未掺杂金属氧化物,或者由聚甲醛或丙烯酰胺,及其合金制成。
本发明还涉及至少一部分基质表面的防油扩散方法,其包括步骤:
a)制备包含至少一种如上文所定义的嵌段共聚物的防油扩散剂,
b)任选,特别是通过根据标准钟表制造商的方法清洗而制备基质表面,
c)使基质表面与防油扩散剂接触,
d)干燥。
优选,防油扩散剂的制备通过能够形成至少一个M单元嵌段的单体和能够形成至少一个N单元嵌段的单体嵌段共聚而实现,其中能够形成至少一个M单元嵌段或至少一个N单元嵌段的单体的嵌段共聚任选用能够形成至少一个P单元的单体进行。
共聚技术是本领域技术人员熟知的,且不需要详细描述。特别合适的共聚方法为以下单体的可控连续共聚:
-能够形成至少一个M单元嵌段的单体以及任选与能够形成至少一个P单元的单体,
-能够形成至少一个N单元嵌段的单体以及任选与能够形成至少一个P单元的单体,其中P为相同或不同的。
两种特别合适的聚合方法是在溶液或乳液中原子转移自由基聚合(ATRP)和可逆加成断裂链转移聚合(RAFT)。
根据第一变化方案,嵌段共聚物可通过使带有Y-A侧链的单体可能与带有R4侧链的单体聚合,优选可控自由基聚合,其后使带有X-L侧链的单体可能与带有R4侧链的单体共聚,优选可控自由基聚合而得到,其中R4为相同或不同的。
根据另一变化方案,嵌段共聚物可通过使带有合适的Y侧链的单体可能与带有意欲带有R4的侧链的单体聚合,优选可控自由基聚合,其后使带有合适的X侧链的单体可能与带有意欲带有R4的侧链的单体共聚,优选可控自由基聚合,然后将侧链例如通过点击化学(click chemistry)改进以引入有意义的A、L官能团和R4基团而得到。
优选,单体选自包含丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、乙烯基、二烯、苯乙烯和烯烃单体的组。
丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、乙烯基和苯乙烯单体是特别优选的。这些产品是已知的,并且多数在市场上可得到或者可在合成步骤中得到。
特别优选的单体是:
因此,用作防油扩散剂的共聚物可以容易地在有限数目的步骤中由市售产品得到。
优选用于本发明中的共聚物中的一种具有以下结构(I):
优选用于本发明中的另一共聚物具有以下结构(II):
用于本发明中的共聚物可以以粉末或粘性液体形式得到。然后可使它们以优选50mg/L至250mg/L的浓度放入在氟化溶剂如全氟化或氟化烃、全氟聚醚、氢氟烯烃、氢氟醚中的溶液中,以得到用于处理待防油扩散化的表面的防油扩散剂溶液。
在变化方案中,本发明防油扩散方法可进一步包括在步骤c)以后的补充交联步骤e),其特别通过在P单元的R4侧链中提供的合适的有意义官能团的存在而成为可能。
本发明基质具有涂有防油扩散剂的表面,所述防油扩散剂的合成是简单且经济的,显示出与任何基质类型的亲合力和与已知的防油扩散剂相比改进的耐清洗操作性。具有本发明基质的元件或件可用于力学领域中的任何应用类型,更特别是精密力学中,特别是钟表和珠宝中。
以下实施例阐述本发明,而不因此限制其范围。
实施例1
嵌段共聚物形式的防油扩散剂可根据以下程序通过:
-1H,1H,2H,2H-全氟癸基甲基丙烯酸酯,
-3-丙烯酰氧丙基甲基二甲氧基硅烷/3-丙烯酰氧丙基甲基硫醚(使用文献:Preparation of biomimetic polymer hydrogel materials for contact lenses,Bertozzi,Carolyn等人,美国专利6552103中所述程序得到),
可控自由基聚合而合成:
将RAFT剂(42μL)和1H,1H,2H,2H-全氟癸基甲基丙烯酸酯加入预先用氮气脱气的包含环己酮(1mL)和2mL 3MTM NovecTM氢氟醚HFE-7200的Schlenk管中。加入0.2mL的0.122摩尔/升偶氮双异丁腈(AIBN)溶液。将反应介质搅拌并加热至85℃6小时。将聚合物在甲醇中凝结,然后洗涤(3×30mL)。聚合物以浅黄色粉末的形式得到。将所得聚合物溶于预先用氮气脱气的环己酮(1mL)和2mL NovecTM氢氟醚HFE-7200(3MTM)中,然后加入3-丙烯酰氧丙基甲基二甲氧基硅烷(211μL)和3-丙烯酰氧丙基甲基硫醚(154μL)。加入0.2mL的0.122摩尔/升AIBN溶液。将反应介质搅拌并加热至85℃12小时。将聚合物在甲醇中凝结,然后洗涤(3×50mL)。聚合物以浅黄色粉末的形式得到(收率=76%)。
得到以下嵌段共聚物:
实施例2:耐清洗性
所用程序:
基质的制备
在防油扩散处理以前,使用标准钟表制造商的方法将不同类型的基质清洗。更具体而言,将部件在超声的存在下用Rubisol溶液清洗,用异丙醇漂洗3次,然后用热空气干燥。
基质的防油扩散处理
通过浸入防油扩散剂溶液(溶剂:250mg/L DuPontTM SuprionTM)中(约5分钟)而将基质防油扩散化,然后用热空气干燥。
耐清洗性
在对防油扩散化部件的3个连续清洗操作(标准钟表制造商的用Rubisol溶液清洗)以后评估防油扩散剂的耐清洗性。
接触角
通过沉积两种润滑剂:MOEBIUS3和9010油的滴而评估防油扩散剂的效力。对于各润滑剂和各防油扩散剂,用OCA Dataphysics仪器测量基质与润滑剂之间的接触角。
结果:
将不同的基质用实施例1的防油扩散剂防油扩散化。然后在钟表制造商的3个清洗操作中将基质清洗。
为了对比,将不同的基质:
-用FK/BS(市场上最常用的防油扩散剂中的一种),
-或者用下文提到的防油扩散剂M51,WO专利2014/009058所述,防油扩散化,其后是钟表制造商的3个清洗操作。
已知M51防油扩散剂是对钟表制造商清洗操作最具有抗性的防油扩散剂中的一种。
分别将3油和9010油滴沉积在各防油扩散化基质上并测量基质与润滑剂之间的接触角。
结果描述于下表中,所述表显示测量的接触角的值:
表1:用MOEBIUS 9010油测量的接触角
表2:用MOEBIUS3油测量的接触角
结论:
以上结果显示,对本发明防油扩散化基质而言,与用已知防油扩散剂防油扩散化的基质相比,在钟表制造商的3个清洗操作以后用两种油(3和9010)得到的接触角大得多。因此,用根据本发明防油扩散化的基质,在钟表制造商的3个清洗操作以后的防油扩散效果大得多。这证明根据本发明防油扩散化的基质提供改进的耐清洗性而无论其类型。
Claims (21)
1.包含至少一部分涂有防油扩散剂的表面的基质,其特征在于所述防油扩散剂包含至少一种嵌段共聚物形式的化合物,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段和至少一个通过其主链通过共价键连接的N单元嵌段,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为
其中R1、R2可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A形成对基质的结合结构部分,M单元嵌段包含至少两个不同的A结合结构部分,其中一个是硫醚,另一个是烷氧基硅烷,
L可以为相同或不同的,为卤化C1-C20碳结构部分。
2.根据权利要求1的基质,其特征在于R1、R2可以为相同或不同的,为H或CH3基团。
3.根据权利要求1的基质,其特征在于M单元嵌段和N单元嵌段中的至少一个包含至少一个P单元,其中P为:
R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至少一个杂原子的线性或支化、饱和或不饱和烃链。
4.根据权利要求3的基质,其特征在于R3可以为相同或不同的,为H或CH3基团。
5.根据权利要求1的基质,其特征在于Y、X可以为相同或不同的,选自包含C1-C20酯基团、酰胺基团的组。
6.根据权利要求5的基质,其特征在于Y、X可以为相同或不同的,为C2-C10酯基团。
7.根据权利要求1的基质,其特征在于L为卤化C2-C20碳结构部分。
8.根据权利要求7的基质,其特征在于L为卤化C4-C10碳结构部分。
9.根据权利要求1的基质,其特征在于L为至少部分氟化结构部分。
10.根据权利要求1的基质,其特征在于L为完全氟化结构部分。
11.根据权利要求3的基质,其特征在于嵌段共聚物包含0.1%至50%M单元,1%至99.9%N单元和0%至50%P单元,其中百分数相对于单元的总数。
12.根据权利要求11的基质,其特征在于共聚物包含5%至30%M单元,50%至99.9%N单元和0%至30%P单元,其中百分数相对于单元的总数。
13.根据权利要求1的基质,其特征在于嵌段共聚物包含10-350个单元。
14.根据权利要求1的基质,其特征在于其至少一部分涂有防油扩散剂的表面由选自包含金属、金属氧化物、聚合物、蓝宝石、红宝石、硅、硅氧化物、硅氮化物、硅碳化物、DLC及其合金的组的材料制成。
15.至少一部分基质表面的防油扩散方法,其包括步骤:
a)制备如权利要求1-14中定义的防油扩散剂,
b)任选制备基质表面,
c)使基质表面与防油扩散剂接触,
d)干燥。
16.根据权利要求15的防油扩散方法,其特征在于防油扩散剂的制备通过能够形成至少一个M单元嵌段的单体和能够形成至少一个N单元嵌段的单体嵌段共聚而实现。
17.根据权利要求16的防油扩散方法,其特征在于M单元嵌段和N单元嵌段中的至少一个包含至少一个P单元,并且能够形成至少一个M单元嵌段或至少一个N单元嵌段的单体的嵌段共聚在能够形成至少一个P单元的单体的存在下进行,其中P为
R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至少一个杂原子的线性或支化、饱和或不饱和烃链。
18.根据权利要求15的防油扩散方法,其特征在于在步骤c)以后,所述方法还包括补充交联步骤e)。
19.根据权利要求16的防油扩散方法,其特征在于单体选自包含丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、乙烯基和苯乙烯单体的组。
20.嵌段共聚物作为用于至少一部分基质表面的防油扩散剂的用途,所述嵌段共聚物包含至少一个通过其主链通过共价键连接的M单元嵌段、至少一个通过其主链通过共价键连接的N单元嵌段,其中M单元嵌段和N单元嵌段中的至少一个任选包含至少一个通过其主链通过共价键连接的P单元,所述嵌段以线性序列通过其主链通过共价键相互连接,其中:
M为N为P为
其中R1、R2、R3可以为相同或不同的,为H、C1-C10烷基、C1-C10烯基,
Y、X可以为相同或不同的,为由杂原子或者由包含至少一个碳原子并且可包含至少一个杂原子的线性或支化烃链形成的间隔臂,
A形成对基质的结合结构部分,M单元嵌段包含至少两个不同的A结合结构部分,其中一个是硫醚,另一个是烷氧基硅烷,
L可以为相同或不同的,为卤化C1-C20碳结构部分,
R4可以为相同或不同的,为H、CH3、包含至少2个碳原子并且可包含至少一个杂原子的线性或支化、饱和或不饱和烃链。
21.时钟或珠宝件,其包含含有根据权利要求1-14中任一项的基质的元件。
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- 2016-03-16 CN CN201610150966.2A patent/CN105985501B/zh active Active
- 2016-03-17 JP JP2016053417A patent/JP6364038B2/ja active Active
- 2016-03-17 RU RU2016109658A patent/RU2016109658A/ru not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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JP6364038B2 (ja) | 2018-07-25 |
US10253129B2 (en) | 2019-04-09 |
RU2016109658A (ru) | 2017-09-22 |
US20160272749A1 (en) | 2016-09-22 |
EP3070152B1 (fr) | 2018-02-28 |
RU2016109658A3 (zh) | 2018-08-01 |
EP3070152A1 (fr) | 2016-09-21 |
JP2016188358A (ja) | 2016-11-04 |
CN105985501A (zh) | 2016-10-05 |
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