WO2021117688A1 - Article doté d'une couche hydrofuge et oléofuge et procédé de production d'un article doté d'une couche hydrofuge et oléofuge - Google Patents

Article doté d'une couche hydrofuge et oléofuge et procédé de production d'un article doté d'une couche hydrofuge et oléofuge Download PDF

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Publication number
WO2021117688A1
WO2021117688A1 PCT/JP2020/045527 JP2020045527W WO2021117688A1 WO 2021117688 A1 WO2021117688 A1 WO 2021117688A1 JP 2020045527 W JP2020045527 W JP 2020045527W WO 2021117688 A1 WO2021117688 A1 WO 2021117688A1
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group
water
oil
repellent
repellent layer
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PCT/JP2020/045527
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English (en)
Japanese (ja)
Inventor
将幸 原口
豊和 遠田
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Ａｇｃ株式会社
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Priority to CN202080087185.8A priority Critical patent/CN114845862A/zh
Priority to JP2021563954A priority patent/JPWO2021117688A1/ja
Publication of WO2021117688A1 publication Critical patent/WO2021117688A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to an article with a water-repellent oil-repellent layer and a method for manufacturing an article with a water-repellent oil-repellent layer.
  • Fluorine-containing having a poly (oxyperfluoroalkylene) chain and a reactive silyl group in order to impart water repellency, oil repellency, fingerprint stain removal property, lubricity (smoothness when touched by a finger), etc. to the surface of the base material. It is known that a water- and oil-repellent layer made of a condensate of a fluorine-containing ether compound is formed on the surface of a base material by surface treatment using an ether compound.
  • Patent Document 1 discloses that a silicon oxide layer is provided between a base material and a water-repellent oil-repellent layer.
  • an object of the present invention is to provide an article with a water-repellent oil-repellent layer and an article with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer having excellent abrasion resistance.
  • the present inventors have found that in an article with a water-repellent oil-repellent layer having a base material, a base layer, and a water-repellent oil-repellent layer in this order, the surface of the base material in contact with the base layer is gold.
  • Silver, copper and other metallic materials formed from an organic sulfur compound having at least one group selected from the group consisting of a thiol group, a disulfide group and a thiourea group, and a reactive silyl group. It has been found that an article with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer having excellent abrasion resistance can be obtained by using the prepared base layer, and the present invention has been made.
  • the surface of the base material in contact with the base layer is a surface made of metal.
  • the underlayer is a layer formed of an organic sulfur compound having at least one group selected from the group consisting of a thiol group, a disulfide group and a thiourea group, and a reactive silyl group.
  • An article with a water / oil repellent layer wherein the water / oil repellent layer is a layer formed of a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group.
  • the surface made of the metal material is a surface made of a metal material containing at least one metal selected from the group consisting of gold, silver and copper.
  • the AS2 is an alkyl group having 1 to 4 carbon atoms or ⁇ Z S2- Si ( RS2 ) n2 ( LS2 ) 3-n2
  • the Z S2 is an alkylene group having 1 to 3 carbon atoms.
  • the n2 is 0, wherein L S2 is an alkoxy group having 1 to 4 carbon atoms, water- and oil-repellent layer article with the [6] or [7].
  • the n32 is 0, the L S3 is an alkoxy group having 1 to 4 carbon atoms, water- and oil-repellent layer article with the [9] or [10].
  • the compound represented by the formula (1A) is referred to as compound (1A).
  • Compounds represented by other formulas are also described in the same manner.
  • the group represented by the formula (A) is referred to as a group (A).
  • the groups represented by other formulas are also described in the same manner.
  • the alkylene group may have an A group
  • the alkylene group may have an A group between carbon atoms in the alkylene group, or the alkylene group-. It may have an A group at the end, such as A group.
  • the "aryl group” in the “aryloxy group” includes not only an aryl group but also a heteroaryl group.
  • the meanings of the terms in the present invention are as follows.
  • the "divalent organopolysiloxane residue" is a group represented by the following formula.
  • R x in the following formula is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or a phenyl group.
  • g1 is an integer of 1 or more, preferably 1 to 9, and particularly preferably 1 to 4.
  • the "number average molecular weight" of a compound is calculated by determining the number (average value) of oxyfluoroalkylene groups based on the terminal groups by 1 H-NMR and 19 F-NMR.
  • the article with a water- and oil-repellent layer of the present invention is an article with a water- and oil-repellent layer having a base material, a base layer, and a water- and oil-repellent layer in this order, and the surface of the base material in contact with the base layer is a surface.
  • the water- and oil-repellent layer is a layer formed of a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group.
  • the article with a water-repellent oil-repellent layer of the present invention has excellent abrasion resistance of the water-repellent oil-repellent layer. The details of this reason have not been clarified, but it is presumed to be due to the following reasons.
  • the base material is glass
  • silicon oxide is used as the material for forming the base layer
  • the silanol groups derived from the silicon oxide of the base layer and the silanol groups derived from the glass of the base layer are condensed.
  • the reaction improves the adhesion between the base layer and the base material.
  • the surface of the base material is metal, even if silicon oxide is used as the material for forming the base layer, there is no reaction point between the base material and the base layer, so that the base material and the base layer are used. Adhesion becomes poor.
  • the water-repellent oil-repellent layer formed on the base layer is rubbed, there is a problem that the water-repellent oil-repellent layer is peeled off from the base material together with the base layer.
  • the present inventors have found that when the above-mentioned organic sulfur compound is used for forming the base layer, the friction resistance of the water-repellent oil-repellent layer formed on the base layer is improved. It is presumed that the reason for this is that the sulfur atoms contained in the organic sulfur compound bond or interact with the metal contained on the surface of the base material to improve the adhesion between the base layer and the base material.
  • the base material is a base material whose surface on which the water-repellent and oil-repellent layer is formed via the base layer is a metal surface.
  • the base material body including the surface on which the water- and oil-repellent layer is formed via the base layer A composite base material or base material whose main body is made of a non-metal material and whose main body is a metal surface of a metal layer on which a water-repellent and oil-repellent layer is formed via a base layer.
  • a composite metal base material, etc., in which the main body is a metal and the surface on which the water- and oil-repellent layer is formed via the base layer is a metal surface of a metal layer made of a metal different from the metal of the main body provided on the main body.
  • the surface metal on which the water- and oil-repellent layer is formed via the base layer at least one metal selected from the group consisting of gold, silver and copper because the water- and oil-repellent layer has better abrasion resistance. It is preferably made of a metal material containing.
  • the metal material containing these metals include simple substances of these metals, alloys composed of two or more kinds of these metals, alloys of at least one kind of these metals with other metals, and the like.
  • the metal material containing these metals a simple substance of these metals and an alloy containing at least one of these metals as a main component are preferable, and in particular, a simple substance of gold and an alloy containing gold are preferable from the viewpoint of high designability.
  • the base material body may be made of a metal material other than the above-mentioned preferable metal material.
  • the material of the base material body made of a non-metallic material include resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened.
  • the metal layer on the base material surface includes formation of a thin metal layer on the base material body surface by plating, vapor deposition, etc., and metal on the base material body surface.
  • a metal layer formed by laminating films or the like is preferable.
  • the base material a surface that comes into contact with human skin, such as an article that may be held by a human finger (for example, a stylus) or an article that may be used by touching the human finger during operation (for example, a touch panel).
  • a substrate having a stylus is particularly suitable.
  • the surface of the base material on which the water- and oil-repellent layer is formed at least on the surface of the base material in contact with human skin and the water- and oil-repellent layer is formed via the base layer is a metal surface as described above. is there.
  • a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable.
  • the base material for the touch panel preferably has translucency.
  • the material of the base material for the touch panel is preferably glass or a transparent resin. Further, as the base material, there is also a base material whose main body is made of glass or a resin film, which constitutes an exterior part (excluding the display part) of a device such as a mobile phone (for example, a smartphone), a mobile information terminal, a game machine, or a remote controller. preferable.
  • the underlayer is a layer formed of an organic sulfur compound having at least one group selected from the group consisting of a thiol group, a disulfide group and a thiourea group, and a reactive silyl group.
  • group SX the thiol group, the disulfide group and the thiourea group.
  • groups SX Two or more kinds of organic sulfur compounds may be used in combination.
  • the reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH). Specific examples of the hydrolyzable silyl group include groups L S group T described later is a hydrolyzable group.
  • the thickness of the base layer is preferably 0.1 to 100 nm, more preferably 0.1 to 50 nm, and particularly preferably 1 to 20 nm.
  • the thickness of the base layer is at least the above lower limit value, the adhesiveness of the water-repellent oil-repellent layer by the base layer is further improved, and the friction resistance of the water-repellent oil-repellent layer is more excellent.
  • the thickness of the base layer is not more than the above upper limit value, the friction resistance of the base layer itself is excellent.
  • the thickness of the base layer is measured by a spectroscopic method such as an X-ray reflectivity (XRR).
  • the organic sulfur compound has a group SX and a reactive silyl group.
  • the number of groups SX contained in the organic sulfur compound is 1 or more, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.
  • the plurality of group SXs may be the same or different. From the viewpoint of easy availability of raw materials and easy production of organic sulfur compounds, they are preferably the same.
  • the reactive silyl group is preferably a group represented by the following formula (hereinafter, also referred to as group T). -Si (R S) ns (L S) 3-ns
  • group T -Si (R S) ns (L S) 3-ns
  • the number of groups T contained in the organic sulfur compound is 1 or more, preferably 1 to 3, and particularly preferably 1 to 2.
  • the plurality of groups T may be the same or different. From the viewpoint of easy availability of raw materials and easy production of organic sulfur compounds, they are preferably the same.
  • RS is a monovalent hydrocarbon group.
  • a monovalent hydrocarbon group (which may be saturated or unsaturated) and a monovalent aromatic hydrocarbon group are preferable, and a monovalent aliphatic hydrocarbon group is preferable.
  • Hydrocarbon groups are more preferred, and alkyl groups are particularly preferred.
  • the monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.
  • L S is a hydrolyzable group or a hydroxyl group.
  • L hydrolyzable group S is a hydroxyl group by hydrolysis reaction group. That is, a silyl group having a hydrolyzable represented by Si-L S becomes a silanol group represented by Si-OH by hydrolysis reaction.
  • the silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by dehydration condensation reaction with a silanol group derived from a fluorine-containing ether compound used for forming a water-repellent oil-repellent layer.
  • L S an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and isocyanate group (-NCO) is.
  • alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • aryloxy group an aryloxy group having 3 to 10 carbon atoms is preferable.
  • halogen atom a chlorine atom is preferable.
  • the acyl group an acyl group having 1 to 6 carbon atoms is preferable.
  • an acyloxy group having 1 to 6 carbon atoms is preferable.
  • the L S from the viewpoint of manufacturing an organic sulfur compound is easier, preferably an alkoxy group or a halogen atom having 1 to 4 carbon atoms.
  • the L S, less outgassing during application, from the viewpoint of storage stability of the organic sulfur compound is more excellent, preferably an alkoxy group having 1 to 4 carbon atoms, if need long-term storage stability of the organic sulfur compounds
  • the ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.
  • ns is an integer from 0 to 2. As for ns, 0 or 1 is preferable, and 0 is particularly preferable.
  • L S there are a plurality, adhesion between the base layer and the water-repellent oil repellent layer becomes stronger. If ns is 1 or less, more L S present in one molecule may be different even in the same. From the viewpoint of easy availability of raw materials and easy production of organic sulfur compounds, they are preferably the same. If ns is 2, a plurality structured R S present in one molecule may be different even in the same. From the viewpoint of easy availability of raw materials and easy production of organic sulfur compounds, they are preferably the same.
  • the organic sulfur compound contains at least one compound selected from the group consisting of compound (S1), compound (S2), compound (S3) and compound (S4) from the viewpoint of better adhesion to a substrate. Is preferable. Among these, compound S1 has particularly excellent adhesion to the substrate.
  • each R S1, L S1 and n the same meanings as R S, L S and nS defined in group T.
  • Z S1 is a linking group of (q1 + 1) valence. As will be described later, 1 is preferable as q1, and when q1 is 1, Z S1 represents a divalent linking group.
  • Specific examples of the (q1 + 1) -valent linking group include -C (O) NR SA- , -C (O)-, between carbon-carbon atoms in a hydrocarbon group and a hydrocarbon group having 2 or more carbon atoms. Examples include groups having —NR SA ⁇ or —O—, preferably hydrocarbon groups.
  • R SA is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • an aliphatic hydrocarbon group (which may be saturated or unsaturated) or an aromatic hydrocarbon group is preferable, an aliphatic hydrocarbon group is more preferable, and an alkylene group is particularly preferable. ..
  • the hydrocarbon group may be linear, branched or cyclic, preferably linear or branched.
  • the hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • q1 is an integer of 1 or more, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly preferably 1.
  • the plurality of RS1s may be the same as or different from each other.
  • the plurality of LS1s may be the same as or different from each other.
  • Specific examples of the compound (S1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylethyldiethoxysilane.
  • each R S2, L S2 and n2 the same meanings as R S, L S and nS defined in group T.
  • Z S2 is a divalent linking group.
  • the divalent linking group include -C (O) NR SA- , -C (between carbon-carbon atoms in a divalent hydrocarbon group and a divalent hydrocarbon group having 2 or more carbon atoms). Examples thereof include a group having O)-, -NR SA- or -O-, and a divalent hydrocarbon group is preferable.
  • R SA is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • the divalent hydrocarbon group an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkylene group.
  • the divalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
  • AS2 is a monovalent hydrocarbon group which may have a substituent, or —Z S2- Si ( RS2 ) n2 ( LS2 ) 3-n2 .
  • the monovalent hydrocarbon group an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkyl group is preferable. Is particularly preferable.
  • the monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 4.
  • the substituent include a hydroxyl group, an amino group, and a carboxy group.
  • the plurality of RS2s may be the same as or different from each other.
  • the plurality of LS2s may be the same as or different from each other.
  • the plurality of Z S2s may be the same as or different from each other.
  • a commercially available product may be used as the compound (S2), and examples thereof include CG-Si75 (bis (triethoxysilylpropyl) disulfide) manufactured by ChenGung.
  • Z S31 is a divalent linking group.
  • the divalent linking group include -C (O) NR SA- , -C (between carbon-carbon atoms in a divalent hydrocarbon group and a divalent hydrocarbon group having 2 or more carbon atoms). Examples thereof include a group having O)-, -NR SA- or -O-, and a divalent hydrocarbon group is preferable.
  • R SA is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkylene group. Is particularly preferable.
  • the divalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
  • a S31 is substituent having optionally may be monovalent hydrocarbon group, a monovalent aromatic heterocyclic group, or,, -Z S31 -Si (R S3 ) n32 (L S3) is 4-n32 ..
  • the monovalent hydrocarbon group an aliphatic hydrocarbon group (which may be saturated or unsaturated) and an aromatic hydrocarbon group are preferable, an aliphatic hydrocarbon group is more preferable, and an alkyl group is preferable. Is particularly preferable.
  • the monovalent hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
  • the substituent include a hydroxyl group, an amino group, and a carboxy group.
  • Specific examples of the monovalent aromatic heterocyclic group include a pyridyl group, a pyrrolyl group, a frill group and a pyranyl group.
  • n31 is 1 or 2, preferably 1.
  • n32 is an integer of 0 to 2, preferably 0 or 1, and particularly preferably 0.
  • n31 + n32 is an integer of 1 to 3, and 1 or 2 is preferable, and 1 is particularly preferable, because the adhesion between the base layer and the water-repellent oil-repellent layer is more excellent.
  • the plurality of RS3s may be the same as or different from each other.
  • the plurality of LS3s may be the same as or different from each other.
  • the plurality of Z S31s may be the same as or different from each other.
  • the compound (S3) a commercially available product may be used, and examples thereof include X-12-1016M, X-12-1111, X-12-1116, and X-12-1117 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Compound (S4) is a hydrolysis condensate of one or more selected from compound (S1), compound (S2) and compound (S3) and a silane compound (S5) having no sulfur atom.
  • the no silane compound sulfur atom (S5), Si (R S1 ) n11 (L S1) compound represented by the 4-n11 is preferred.
  • n11 is 0, 1 or 2, preferably 0.
  • the plurality of RS1s may be the same as or different from each other.
  • the plurality of LS1s may be the same as or different from each other.
  • Specific examples of the compound (S5) include the compound of the following formula. However, x and y in the following formula represent integers of 1 or more.
  • the water- and oil-repellent layer is a layer formed by using a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group, and specifically, it is composed of a condensate of a fluorine-containing ether compound. Two or more kinds of fluorine-containing ether compounds may be used in combination.
  • the reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH), and specific examples of the hydrolyzable silyl group are as described above.
  • the hydrolyzable silyl group becomes a silanol group represented by Si-OH by the hydrolysis reaction.
  • the silanol groups further undergo a dehydration condensation reaction between the silanol groups to form a Si—O—Si bond. Further, the silanol group forms a chemical bond (Si—O—Si bond) by a condensation reaction with the silanol group on the surface of the underlying layer. That is, the water- and oil-repellent layer contains a condensate in which some or all of the reactive silyl groups of the fluorine-containing ether compound are hydrolyzed and dehydrated and condensed.
  • the thickness of the water-repellent and oil-repellent layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm.
  • the thickness of the water-repellent oil-repellent layer is at least the lower limit, the effect of the water-repellent oil-repellent layer can be sufficiently obtained. If the thickness of the water-repellent and oil-repellent layer is not more than the upper limit, the utilization efficiency is high.
  • the thickness obtained by the X-ray diffractometer for thin film analysis is defined as the thickness of the water-repellent oil-repellent layer.
  • the thickness of the water- and oil-repellent layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G manufactured by RIGAKU), and the vibration cycle of the interference pattern. Can be calculated from.
  • the poly (oxyfluoroalkylene) chain contains a plurality of units represented by the formula (1).
  • X is a fluoroalkylene group having one or more fluorine atoms.
  • the number of carbon atoms of the fluoroalkylene group is preferably 1 to 6 and particularly preferably 2 to 4 from the viewpoint of more excellent weather resistance and corrosion resistance of the water- and oil-repellent layer.
  • the fluoroalkylene group may be linear, branched or cyclic.
  • the number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, more preferably 1.7 to 2 times, the number of carbon atoms, from the viewpoint of more excellent corrosion resistance of the water-repellent oil-repellent layer.
  • As the fluoroalkylene group a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group is preferable.
  • (OX) is, -OCHF -, - OCF 2 CHF -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF 2- , -OCF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2- , -OCF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CF 2 CH 2- , -OCH 2 CF 2 CF 2 CF 2 CF 2- , -OCF 2 CF 2 CF 2 CF 2 CH 2- , -
  • -cycloC 4 F 6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group.
  • -CycloC 6 F 10- means a perfluorocyclohexanediyl group, and specific examples thereof include a perfluorocyclohexane-1,4-diyl group.
  • the number of repetitions m of unit 1 contained in the poly (oxyfluoroalkylene) chain is an integer of 2 or more, preferably 2 to 200, more preferably 5 to 150, particularly preferably 5 to 100, and 10 to 50. The integer of is most preferred.
  • the poly (oxyfluoroalkylene) chain may contain only one type of (OX) or may contain two or more types of (OX).
  • the binding order of two or more types of (OX) is not limited, and may be randomly, alternately, or arranged in blocks. Including two or more kinds of (OX) means that two or more kinds of (OX) having different carbon atoms are present in the fluorine-containing ether compound, and two or more kinds of (OX) having different hydrogen atom numbers are present.
  • m25 is a m25 amino (OCF 2 CF 2) and m25 amino (OCF 2 CF 2 CF 2 CF 2) Indicates that they are arranged alternately.
  • -cycloC 4 H mg F (6- mg) represents a fluorocyclobutane diyl group, and a fluorocyclobutane-1,2-diyl group is preferable.
  • -CycloC 6 H mh F (10-mh) represents a fluorocyclohexanediyl group, preferably a fluorocyclohexane-1,4-diyl group.
  • ma is 0 or 1
  • mb is an integer of 0 to 3
  • mc is an integer of 0 to 5
  • md is an integer of 0 to 7
  • me is an integer of 0 to 9
  • mf is an integer of 0 to 9.
  • m11, m12, m13, m14, m15, m16, m17 and m18 are each independently an integer of 0 or more, preferably 100 or less.
  • m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 are integers of 2 or more, preferably an integer of 2 to 200, more preferably 5 to 150, further preferably 5 to 100, and particularly preferably 10 to 50.
  • m12 is preferably 2 or more, and particularly preferably 2 to 200.
  • C 3 H mc F (6-mc) , C 4 H md F (8-md) , C 5 H me F (10-me) and C 6 H mf F (12-mf) are linear. However, it may have a branched chain shape, and a linear shape is preferable from the viewpoint of more excellent friction resistance of the water-repellent oil-repellent layer.
  • m11 (OCH ma F (2-ma) ), m12 (OC 2 H mb F (4-mb) ), m13 (OC 3 H mc F (6-mc) ), m14 (OC 4 H md F (8-md) ), m15 (OC 5 H me F (10-me) ), m16 (OC 6 H mf F (12-mf) ), m17 ( The binding order of O-cycloC 4 H mg F (6- mg) ) and m18 (O-cycloC 6 H mh F (10-mh) ) is not limited. When m11 is 2 or more, a plurality of (OCH ma F (2-ma) ) may be different.
  • a plurality of (OC 2 H mb F (4-mb) ) may be different.
  • a plurality of (OC 3 H mc F (6-mc) ) may be different.
  • a plurality of (OC 4 H md F (8-md) ) may be different.
  • m15 is 2 or more, a plurality of (OC 5 H me F (10-me) ) may be different.
  • a plurality of (OC 6 H mf F (12-mf) ) may be different.
  • a plurality of (O-cycloC 4 H mg F (6- mg) ) may be different.
  • a plurality of (O-cycloC 6 H mh F (10-mh) ) may be different.
  • (OX) m preferably has the following structure. ⁇ (OCF 2) m21 ⁇ ( OCF 2 CF 2) m22 ⁇ , (OCF 2 CF 2 ) m23 , (OCF 2 CF 2 CF 2 ) m24 , (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) m25, ⁇ (OCF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 CF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) m26 ⁇ (OCF 2 ) m27 ⁇ , ⁇ (OCF 2 CF 2 CF
  • m21 is an integer of 1 or more
  • m22 is an integer of 1 or more
  • m21 + m22 is an integer of 2 to 500
  • m23 and m24 are independently integers of 2 to 500
  • m25 is 1 It is an integer of ⁇ 250
  • m26 and m27 are each independently an integer of 1 or more
  • m26 + m27 is an integer of 2 to 500
  • m28 is an integer of 1 to 250.
  • (OX) m is more preferably having the following structure from the viewpoint that a fluorine-containing ether compound can be easily produced. ⁇ (OCF 2) m21 ⁇ ( OCF 2 CF 2) m22 ⁇ , (OCF 2 CF 2 CF 2 ) m24 , (OCF 2 CF 2) 2 ⁇ (OCF 2) m21 ⁇ (OCF 2 CF 2) m22-2 ⁇ , (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) m25-1 OCF 2 CF 2, (OCF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2) m28, (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -OCF 2) m28, (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2) m28, (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2 CF 2) m28, (OCF 2 CF 2 -
  • the numbers of m22, m25 and m28 are selected so as to be an integer of 1 or more.
  • (OX) m is, ⁇ (OCF 2) m21 ⁇ (OCF 2 CF 2) m22 ⁇ is preferably.
  • ⁇ (OCF 2) m21 ⁇ ( OCF 2 CF 2) m22 ⁇ , m22 / m21 from that friction resistance of the water-repellent and oil-repellent layer and fingerprint stain removal properties more excellent preferably 0.1 to 10, 0 .2 to 5.0 is more preferable, 0.2 to 2.0 is further preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.
  • the number average molecular weight of (OX) m is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 3,000 to 10,000.
  • the number average molecular weight is at least the lower limit value, the molecular chain of the fluorine-containing ether compound becomes long, so that the flexibility of the molecular chain of the fluorine-containing ether compound is improved.
  • the reaction probability between the silanol group derived from the reactive silyl group of the fluorine-containing ether compound and the silanol group of the base layer is increased, so that the adhesiveness between the water-repellent oil-repellent layer and the base layer is further improved.
  • the abrasion resistance of the water-repellent and oil-repellent layer is more excellent. Further, since the fluorine content of the water-repellent and oil-repellent layer is improved, the water- and oil-repellent properties are more excellent. Further, when the number average molecular weight is not more than the upper limit value, the handleability at the time of film formation is more excellent.
  • the reactive silyl group is preferably a group represented by the formula (2). -Si (R) n L 3-n (2)
  • R is a monovalent hydrocarbon group.
  • a monovalent aliphatic hydrocarbon group (which may be saturated or unsaturated) and a monovalent aromatic hydrocarbon group are preferable, and a monovalent aliphatic hydrocarbon group is preferable.
  • Hydrocarbon groups are more preferred, and alkyl groups are particularly preferred.
  • the monovalent aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched.
  • the number of carbon atoms of the monovalent aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.
  • L is a hydrolyzable group or a hydroxyl group.
  • the hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolyzing reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by the hydrolysis reaction.
  • the silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by dehydration condensation reaction with a silanol group derived from an organic sulfur compound used for forming the underlying layer.
  • L which is a hydrolyzable group
  • L include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO).
  • alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • aryloxy group an aryloxy group having 3 to 10 carbon atoms is preferable.
  • halogen atom a chlorine atom is preferable.
  • the acyl group an acyl group having 1 to 6 carbon atoms is preferable.
  • acyloxy group an acyloxy group having 1 to 6 carbon atoms is preferable.
  • an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable from the viewpoint that the fluorine-containing ether compound can be more easily produced.
  • an alkoxy group having 1 to 4 carbon atoms is preferable and a long-term storage stability of the fluorine-containing ether compound is required because there is little outgassing during coating and the storage stability of the fluorine-containing ether compound is more excellent.
  • the ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.
  • n is an integer of 0 to 2. As n, 0 and 1 are preferable, and 0 is particularly preferable.
  • the presence of a plurality of L makes the water- and oil-repellent layer more firmly adhered to the underlying layer.
  • n is 0 or 1
  • the plurality of Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of fluorine-containing ether compounds, they are preferably the same.
  • n is 2
  • the plurality of Rs present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of fluorine-containing ether compounds, they are preferably the same.
  • the fluorine-containing ether compound is preferably a fluorine-containing ether compound represented by the formula (1A) because the water- and oil-repellent layer has more excellent abrasion resistance.
  • Compound 1A may be used alone or in combination of two or more. [A- (OX) m- O-] j Y 1 [-Si (R) n L 3-n ] g (1A)
  • A is a perfluoroalkyl group or -Y 2 [-Si (R) n L 3-n ] k .
  • the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer.
  • the perfluoroalkyl group may be linear, branched or cyclic. However, when A is ⁇ Y 2 [ ⁇ Si (R) n L 3-n ] k , j is 1.
  • Perfluoroalkyl groups include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF (CF 3 )-and the like can be mentioned.
  • Y 2 is a linking group of (k + 1) valence.
  • Y 2 may be a group that does not impair the effects of the present invention, for example, an alkylene group that may have an ethereal oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, and silicon. Examples include atomic, 2- to 8-valent organopolysiloxane residues, groups g2-1 to group g2-9 and groups g3-1 to group g3-9, which will be described later.
  • Y 1 is a (j + g) -valued linking group.
  • Y 1 may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, or a silicon atom that may have an ethereal oxygen atom or a divalent organopolysiloxane residue. Examples thereof include 2- to 8-valent organopolysiloxane residues, and groups (g2-1) to groups (g2-9) and groups (g3-1) to groups (g3-9), which will be described later.
  • j is an integer of 1 or more, preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the water and oil repellent layer, and 1 from the viewpoint of easy production of compound (1A).
  • g is an integer of 1 or more, and is preferably 1 to 15, more preferably 1 to 8, and preferably 2 to 6 from the viewpoint of better abrasion resistance of the water- and oil-repellent layer. More preferably, it is particularly preferably 2 or 3, and most preferably 3.
  • k is an integer of 1 or more, and is preferably 1 to 15, more preferably 1 to 8, and particularly preferably 2 to 6, from the viewpoint of better abrasion resistance of the water- and oil-repellent layer.
  • the k + g is preferably 2 to 30, more preferably 2 to 20, further preferably 3 to 18, and 4 to 15 from the viewpoint of more excellent friction resistance of the water- and oil-repellent layer. It is particularly preferable to have.
  • a plurality of [-Si (R) n L 3 -n] may be different.
  • the compound (1A) is preferable from the viewpoint of being excellent in the abrasion resistance of the water-repellent oil-repellent layer.
  • X, m, R, n and L are synonymous with the definitions of X, m, R, n and L in formula (1A), respectively.
  • R f1 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above.
  • Y 11 is a linking group having a (g1 + j1) valence, and a specific example thereof is the same as that of Y 1 in the formula 1A.
  • j1 is an integer of 1 or more and is synonymous with the definition of j in the formula (1A).
  • g1 is an integer of 1 or more and is synonymous with the definition of g in the formula (1A).
  • X, m, R, n and L are synonymous with the definitions of X, m, R, n and L in formula (1A), respectively.
  • Y 22 is a linking group having a (k2 + 1) valence, and a specific example thereof is the same as that of Y 2 in the formula (1A).
  • Y 21 is a linking group having a (g2 + 1) valence, and a specific example thereof is the same as that of Y 1 in the formula (1A).
  • k2 is an integer of 1 or more, preferably 1 to 4, more preferably 2 or 3, and particularly preferably 3.
  • g2 is an integer of 1 or more, preferably 1 to 4, more preferably 2 or 3, and particularly preferably 3.
  • a 1 is connected to the (OX) m side, and Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28. Is connected to the [-Si (R) n L 3-n ] side.
  • a 1 is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -C (O) NR 6- , -C (O)-, -OC (O) O-,-between carbon atoms.
  • the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
  • Q 11 represents a single bond, -O-, alkylene group or a carbon of an alkylene group having 2 or more carbon atoms - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - Alternatively, it is a group having —O—.
  • Q 22 represents an alkylene group, a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - or a group having -O-, alkylene A group having -C (O) NR 6- , -C (O)-, -NR 6- or -O- at the end of the group not connected to Si, or a carbon-carbon of an alkylene group having 2 or more carbon atoms.
  • the two or more Q 22s may be different.
  • Q 23 the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - or -O- a group having a Yes, two of Q 23 may be different.
  • Q 24 when atom in Z 1 to Q 24 is attached is a carbon atom, a Q 22, when atoms in Z 1 to Q 24 is attached is a nitrogen atom, a Q 23, in each formula, Q 24 If there are two or more, the Q 24s of two or more may be different.
  • Q 25 the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - or -O- a group having a Yes, if there are two or more Q 25s in each equation, the two or more Q 25s may be different.
  • Q 26 the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - or -O- a group having a is there.
  • R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • Q 27 is a single bond or an alkylene group.
  • Q 28 represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an organopolysiloxane residue of the ethereal oxygen atom or a divalent between carbon atoms.
  • Z 1 is a group having an h1 + h2 valent ring structure having a carbon atom or nitrogen atom to which A 1 is directly bonded and a carbon atom or nitrogen atom to which Q 24 is directly bonded.
  • R e1 is a hydrogen atom or an alkyl group, and when two or more Re1s are present in each formula, two or more Re1s may be different.
  • Re2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
  • Re3 is an alkyl group.
  • Re4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom from the viewpoint of easy production of a compound. When two or more Re 4s are present in each equation, the two or more Re 4s may be different.
  • Re5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.
  • d1 is an integer of 0 to 3, preferably 1 or 2.
  • d2 is an integer of 0 to 3, preferably 1 or 2.
  • d1 + d2 is 1 to 3.
  • d3 is an integer of 0 to 3, preferably 0 or 1.
  • d4 is an integer of 0 to 3, preferably 2 or 3.
  • d3 + d4 is an integer of 1 to 3.
  • d1 + d3 in Y 11 represents an integer of 1 to 5, preferably 1 or 2, in Y 21 and Y 22 is 1.
  • d2 + d4 is an integer of 1 to 5, preferably 3 to 5, and particularly preferably 4 or 5.
  • e1 + e2 is 3 or 4.
  • e1 + e2 is 3 or 4.
  • e1 + e2 is 3 or 4.
  • e1 + e2 is 3 or 4.
  • e2 is an integer of 1 to 3, preferably 2 or 3.
  • h1 in Y 11 is an integer of 1 or more, the Y 21 and Y 22 is 1.
  • h2 is an integer of 1 or more, preferably 2 or more, and particularly preferably 2 or 3.
  • i1 + i2 is an integer of 2 to 4.
  • i1 is 1 to 3 in Y 11 and 1 in Y 21 and Y 22 .
  • i2 is 1 to 3 in Y 11 and 1 to 3 in Y 21 and Y 22 .
  • i3 is an integer of 0 to 3, preferably 1 to 3.
  • i4 is an integer of 1 or more, preferably 1 to 10, and particularly preferably 1 to 6.
  • i5 is an integer from 1 to 7.
  • the carbon number of the alkylene group of Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , and Q 28 the point that compounds (1A-1) and (compound 1A-2) can be easily produced, and the repulsion From the viewpoint of further excellent friction resistance, light resistance and chemical resistance of the water-repellent layer, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable.
  • the lower limit of the number of carbon atoms of the alkylene group is 2.
  • Examples of the ring structure in Z 1 include the above-mentioned ring structure, and the preferred form is also the same. Since A 1 and Q 24 are directly bonded to the ring structure in Z 1 , for example, an alkylene group is linked to the ring structure, and A 1 and Q 24 are not linked to the alkylene group.
  • Z a is a (i5 + 1) -valent organopolysiloxane residue, and the following groups are preferable.
  • Ra in the following formula is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or a phenyl group.
  • the number of carbon atoms of the alkyl group of R e1 , Re 2 , Re 3 or Re 4 is preferably 1 to 10 from the viewpoint of easy production of compound (1A-1) and compound (1A-2), and 1 to 6 is more preferable.
  • 1 to 3 is more preferable, and 1 to 2 is particularly preferable.
  • the number of carbon atoms in the alkyl group moiety of the acyloxy group R e2 from compound (1A-1) and compound (1A-2) that tends to produce, preferably 1-10, more preferably 1-6, 1-3 Is more preferable, and 1 to 2 are particularly preferable.
  • h1 is preferably 1 to 6 because it is easy to produce the compound (1A-1) and the compound (1A-2), and the water- and oil-repellent layer is more excellent in abrasion resistance and fingerprint stain removal property.
  • ⁇ 4 is more preferable, 1 or 2 is more preferable, and 1 is particularly preferable.
  • h2 is preferably 2 to 6 because it is easy to produce the compound (1A-1) and the compound (1A-2), and the water- and oil-repellent layer is more excellent in abrasion resistance and fingerprint stain removal property.
  • ⁇ 4 is more preferable, and 2 or 3 is particularly preferable.
  • a 1 is connected to the (OX) m side, and G 1 is connected to the [-Si (R) n L 3-n ] side.
  • G 1 is a group (g3), in each formula, if G 1 is present 2 or more, 2 or more G 1 may be be the same or different.
  • the codes other than G 1 are the same as the codes in the formulas (g2-1) to (g2-9).
  • -Si (R 8 ) 3-r1 (-Q 3- ) r1 (g3) Si is connected to the Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 sides, and Q 3 is [-Si (R) n L 3-n. ] Side is connected.
  • R 8 is an alkyl group.
  • Q 3 are carbon atoms in the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms (O) NR 6 -, - C (O) -, - NR 6 - or a group having -O- or, , - (OSi (R 9) 2) is a p -O-, 2 or more Q 3 are may be the same or different.
  • r1 is 2 or 3.
  • R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 9 is an alkyl group, a phenyl group or an alkoxy group, and the two R 9s may be the same or different.
  • p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R 9 ) 2 ) may be the same or different.
  • the lower limit of the number of carbon atoms of the alkylene group is 2.
  • the number of carbon atoms of the alkyl group of R 8 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3 from the viewpoint that the compound (1A-1) and the compound (1A-2) can be easily produced. 1 to 2 are particularly preferable.
  • the number of carbon atoms of the alkyl group of R 9 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3 from the viewpoint that the compound (1A-1) and the compound (1A-2) can be easily produced. 1 to 2 are particularly preferable. As the number of carbon atoms of the alkoxy group of R 9 , 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 3 is preferable from the viewpoint of excellent storage stability of the compound (1A-1) and the compound (1A-2). More preferably, 1 to 2 is particularly preferable. As p, 0 or 1 is preferable.
  • Examples of the compound (1A-1) and the compound (1A-2) include the compounds of the following formulas.
  • the compounds of the following formulas are industrially easy to manufacture and handle, and the water and oil repellent layer has better water and oil repellency, abrasion resistance, fingerprint stain removal, lubricity, chemical resistance, light resistance and chemical resistance. It is preferable because it is excellent, and above all, the light resistance is particularly excellent.
  • the R f in the compound of the following formula is the same as that of R f1- (OX) m- O- in the above-mentioned formula (1A-1), and the preferred embodiment is also the same.
  • the Q f in the compound of the following formula is the same as-(OX) m- O- in the formula (1A-2), and the preferred embodiment is also the same.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-1) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-2) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-2) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-3) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-4) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-5) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-6) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-7) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-1) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-2) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-3) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-4) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-5) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-6) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g3-7) include the compounds of the following formulas.
  • Examples of the compound (1A-1) having Y 11 as a group (g2-1) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-1) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-2) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-3) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-4) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-5) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-6) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g2-7) include the compounds of the following formulas.
  • Examples of the compound (1A-2) having Y 21 and Y 22 as a group (g3-2) include the compounds of the following formulas.
  • Compound 1A include those described in the following documents. Perfluoropolyether-modified aminosilane described in JP-A-11-209585, Silicon-containing organic fluoropolymers described in Japanese Patent No. 2874715, Organosilicon compounds described in JP-A-2000-144097, Perfluoropolyether-modified aminosilane described in JP-A-2000-327772, Fluorinated siloxanes described in JP-A-2002-506887, The organic silicone compound described in JP-A-2008-534696, Fluorinated modified hydrogen-containing polymer according to Japanese Patent No. 4138936, Compounds described in U.S. Patent Application Publication No. 2010/0129672, International Publication No.
  • the organic sulfur compound is used to form the base layer on the base material
  • the fluorine-containing ether compound is used to form the base layer on the base layer.
  • a method of forming an oil repellent layer can be mentioned. More specifically, a composition containing the above-mentioned organic sulfur compound and a liquid medium (hereinafter, also referred to as “composition for forming a base layer”) is used to form a base layer on the surface of the base material.
  • composition for forming a water-repellent oil-repellent layer is used to surface a water-repellent oil-repellent layer on the surface of the base layer.
  • the liquid medium contained in the composition for forming an underlayer include water and an organic solvent.
  • the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.
  • the organic solvent may be used alone or in combination of two or more.
  • fluorinated organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
  • fluorinated alkane a compound having 4 to 8 carbon atoms is preferable, and for example, C 6 F 13 H (AC-2000: product name, manufactured by AGC Inc.), C 6 F 13 C 2 H 5 (AC-6000: product). Name, manufactured by AGC), C 2 F 5 CHFCHFCF 3 (Bertrel: product name, manufactured by DuPont).
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
  • fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable, and for example, CF 3 CH 2 OCF 2 CF 2 H (AE-3000: product name, manufactured by AGC), C 4 F 9 OCH 3 (Novec-7100).
  • fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
  • non-fluorine-based organic solvent a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
  • a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
  • Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent can be mentioned.
  • Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
  • Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ether-based organic solvent examples include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
  • ester-based organic solvent examples include ethyl acetate and butyl acetate.
  • alcohol-based organic solvent examples include methanol, ethanol, propanol, butanol and the like.
  • non-fluorine-based organic solvent a chlorine-based organic solvent such as dichloromethane is also suitable.
  • the content of the liquid medium is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.99% by mass, based on the total mass of the composition for forming the underlying layer.
  • the content of the organic sulfur compound is preferably 0.01 to 50.00% by mass, particularly preferably 0.01 to 30.00% by mass, based on the total mass of the composition for forming the underlying layer.
  • the content of the organic sulfur compound is preferably 50 to 100% by mass, particularly preferably 70 to 100% by mass, based on the total solid content mass of the composition for forming the underlying layer.
  • the base layer can be produced, for example, by the following method. -A method of obtaining the base layer by treating the surface of the base material by dry coating using the organic sulfur compound. -A method in which a composition for forming a base layer is applied to the surface of a base material by a wet coating method and dried to obtain the base layer.
  • the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method.
  • Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.
  • liquid medium contained in the composition for forming a water-repellent oil-repellent layer include water and an organic solvent.
  • the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.
  • the organic solvent may be used alone or in combination of two or more.
  • Specific examples of the fluorinated organic solvent and the non-fluorine-based organic solvent are the same as those of the liquid medium contained in the composition for forming the underlayer.
  • the composition for forming a water- and oil-repellent layer among specific examples of the non-fluorine-based organic solvent, a hydrocarbon-based organic solvent, a ketone-based organic solvent, an ether-based organic solvent, an ester-based organic solvent, and an alcohol-based organic solvent are used. preferable.
  • a fluorine-based organic solvent, an alcohol-based organic solvent, or a mixed solvent thereof is particularly preferable.
  • the content of the liquid medium is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.95% by mass, based on the total mass of the water- and oil-repellent layer forming composition.
  • the content of the fluorine-containing ether compound is preferably 0.01 to 50.00% by mass, particularly preferably 0.05 to 30.00% by mass, based on the total mass of the water- and oil-repellent layer forming composition.
  • the content of the fluorine-containing ether compound is preferably 30 to 100% by mass, particularly preferably 50 to 100% by mass, based on the total solid content mass of the water- and oil-repellent layer forming composition.
  • the water-repellent and oil-repellent layer can be produced, for example, by the following method.
  • the dry coating method and the wet coating method in the production of the water- and oil-repellent layer are the same as the specific examples given in the production of the base layer.
  • the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing ether compound and the simplicity of the apparatus.
  • a pellet-shaped porous metal containing a fluorine-containing ether compound obtained by impregnating a metal porous body such as iron or steel with a solution of a fluorine-containing ether compound (such as the composition for forming a water-repellent oil-repellent layer) and drying the metal porous body. May be used.
  • the water- and oil-repellent layer formed by the above procedure contains a condensate in which some or all of the reactive silyl groups of the fluorine-containing ether compound are hydrolyzed and dehydrated and condensed.
  • Example 1 is an example
  • Example 2 is a comparative example.
  • the blending amount of each component in the table described later indicates a mass standard.
  • the surface of the water-repellent oil-repellent layer was wiped 20 times with a Bencot (manufactured by Asahi Kasei Co., Ltd.) impregnated with a fluorine-based organic solvent (AGC, Asahi Clean AE3000), and then wiped 20 times with a Bencot impregnated with ethanol. Then, the water contact angle (water contact angle after the friction test) of the water-repellent and oil-repellent layer was measured by the above-mentioned method. The smaller the decrease in the water contact angle after the friction test, the better the friction resistance of the water- and oil-repellent layer.
  • Example 1 24 mg of the organic sulfur compound 1 (3-mercaptopropyltrimethoxysilane) and 106 g of dichloromethane were placed in a vial, and the organic sulfur compound 1 was uniformly dissolved in dichloromethane to form the underlayer composition 1 (solid content concentration). 0.023% by mass) was obtained. Further, 0.4 g of the compound (1A-1-1) and 39.6 g of a fluorine-based organic solvent (Novec 7200, manufactured by 3M) are mixed to form a water- and oil-repellent layer-forming composition 1 (solid content concentration). 1% by mass) was obtained.
  • a fluorine-based organic solvent Novec 7200, manufactured by 3M
  • the base material 1 After putting the base layer forming composition 1 in the stainless steel petri dish, the base material 1 was put into the stainless steel petri dish, and the base material was immersed in the base layer forming composition 1 at room temperature (about 23 ° C.) for 12 hours. Then, the base material 1 was taken out, and nitrogen gas was injected onto the base material 1 to remove the organic solvent. In this way, a base material 1 with a base layer having a base layer formed on the surface of the base material 1 was obtained.
  • Example 1 An evaluation sample of Example 1 (article with a water- and oil-repellent layer) was obtained.
  • Base material 1 A base material (diameter 25 mm, thickness 5 mm) in which the surface of glass is coated in the order of chromium (film thickness 50 to 60 nm) and gold (film thickness 200 nm), and gold is arranged on the outermost surface.
  • Example 2 30 g of silicon oxide was placed as a vapor deposition source on a copper hearth in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.), and 0.16 g of compound (1A-1-1) was placed as a vapor deposition source on a molybdenum boat. ..
  • the base material 1 was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became 5 ⁇ 10 -3 Pa or less.
  • the hearth was heated to about 2000 ° C., and silicon oxide was vacuum-deposited on the surface of the base material to produce a base material with a silicon oxide layer having a silicon oxide layer having a thickness of about 20 nm.
  • the board was heated to about 1000 ° C., and the compound (1A-1-1) was vacuum-deposited on the surface of the silicon oxide layer, so that the thickness of the film on the silicon oxide layer became about 15 nm. At that point, the film formation was completed.
  • An evaluation sample article with a water-repellent oil-repellent layer in which an article on which the compound (1A-1-1) is deposited is heat-treated at 140 ° C. for 30 minutes, and a substrate, a silicon oxide layer and a water-repellent oil-repellent layer are laminated in this order.
  • Example 3 The same method as in [Example 1] was carried out except that the organic sulfur compound 2 (X-12-1200EP manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the organic sulfur compound, and the surface of the base material 1 with a base layer was water-repellent and repellent. An evaluation sample of Example 3 having an oil layer (article with a water-repellent oil-repellent layer) was obtained.
  • Example 4 The same method as in [Example 1] was carried out except that the organic sulfur compound 3 (X-12-1116 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the organic sulfur compound, and the surface of the base material 1 with an underlayer was repelled by water. An evaluation sample of Example 4 having an oil layer (article with a water-repellent oil-repellent layer) was obtained.
  • Organic sulfur compound 3 A compound represented by the following formula
  • Example 5 The same method as in [Example 1] was carried out except that the organic sulfur compound 4 (KR-518 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the organic sulfur compound, and a water- and oil-repellent layer was formed on the surface of the base material 1 with a base layer. An evaluation sample of Example 5 having a water- and oil-repellent layer was obtained.
  • Organic sulfur compound 4 A compound represented by the following formula (x is an average of about 3.2 per molecule, y is an average of about 1.2 per molecule).
  • the article with a water-repellent oil-repellent layer of the present invention can be used for various applications in which water-repellent and oil-repellent properties are required.
  • display input devices such as touch panels, transparent glass or transparent plastic members, lenses for glasses, antifouling members for kitchens, electronic devices, heat exchangers, water-repellent and moisture-proof members such as batteries, and antifouling members.
  • It can be used as an antifouling member for toiletries, a member that requires liquid repellency while conducting, a member for water repellency / waterproofing / sliding of a heat exchanger, a member for vibration sieving, a member for low surface friction such as inside a cylinder, and the like.
  • More specific examples of use include display front protective plates, antireflection plates, polarizing plates, antiglare plates, or those with antireflection film treatment applied to their surfaces, mobile phones (for example, smartphones), and personal digital assistants.
  • Game machines devices such as remote controls, touch panel sheets, touch panel displays, and other devices that have display input devices that operate on the screen with human fingers or palms (for example, glass or film used for display units, etc., and Glass or film used for exterior parts other than the display part).
  • decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof members for wiring boards, water-repellent / waterproof / sliding members for heat exchangers, water-repellent members for solar cells, printed wiring boards
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2019-225361 filed on December 13, 2019 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Abstract

L'invention concerne un article doté d'une couche hydrofuge et oléofuge ayant une excellente résistance au frottement ; et un procédé de production de l'article doté d'une couche hydrofuge et oléofuge.　Ledit article doté d'une couche hydrofuge et oléofuge comprend une base, une couche d'apprêt et la couche hydrofuge et oléofuge dans cet ordre, la surface de la base qui est en contact avec la couche d'apprêt étant une surface métallique, la couche d'apprêt étant une couche formée à partir d'un composé organosulfuré comprenant un groupe silyle réactif et au moins un groupe choisi dans le groupe consistant en un groupe thiol, un groupe disulfure et un groupe thiourée, et la couche hydrofuge et oléofuge étant une couche formée à partir d'un composé fluoroéther comprenant une chaîne poly(oxyfluoroalkylène) et un groupe silyle réactif.
PCT/JP2020/045527 2019-12-13 2020-12-07 Article doté d'une couche hydrofuge et oléofuge et procédé de production d'un article doté d'une couche hydrofuge et oléofuge WO2021117688A1 (fr)

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CN202080087185.8A CN114845862A (zh) 2019-12-13 2020-12-07 带拒水拒油层的物品及带拒水拒油层的物品的制造方法
JP2021563954A JPWO2021117688A1 (fr) 2019-12-13 2020-12-07

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WO2005069705A1 (fr) * 2004-01-15 2005-07-28 Matsushita Electric Industrial Co., Ltd. Modele metallique et procede de fabrication
JP2009138228A (ja) * 2007-12-06 2009-06-25 Kagawa Gakusei Venture:Kk 撥水撥油防汚性貴金属製品とその製造方法
JP2012098134A (ja) * 2010-11-01 2012-05-24 Utsunomiya Univ 熱伝導率測定用プローブ及びその製造方法
WO2014068688A1 (fr) * 2012-10-31 2014-05-08 株式会社 日立製作所 Élément métallique à surface modifiée obtenu au moyen d'un agent adhésif au silane contenant du fluor
JP2014218639A (ja) * 2012-11-05 2014-11-20 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
WO2019069642A1 (fr) * 2017-10-03 2019-04-11 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé pour fabriquer un élément hydrophobe et oléophobe

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US6284391B1 (en) * 1999-07-12 2001-09-04 Corning Incorporated Mercaptofunctional silanes to deposit sol-gel coatings on metals
KR101167476B1 (ko) * 2007-11-19 2012-07-27 니혼 파커라이징 가부시키가이샤 금속재료용 하지처리제 및 금속재료의 하지처리방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0586353A (ja) * 1990-10-25 1993-04-06 Matsushita Electric Ind Co Ltd 化学吸着単分子累積膜及びその製造方法
WO2005069705A1 (fr) * 2004-01-15 2005-07-28 Matsushita Electric Industrial Co., Ltd. Modele metallique et procede de fabrication
JP2009138228A (ja) * 2007-12-06 2009-06-25 Kagawa Gakusei Venture:Kk 撥水撥油防汚性貴金属製品とその製造方法
JP2012098134A (ja) * 2010-11-01 2012-05-24 Utsunomiya Univ 熱伝導率測定用プローブ及びその製造方法
WO2014068688A1 (fr) * 2012-10-31 2014-05-08 株式会社 日立製作所 Élément métallique à surface modifiée obtenu au moyen d'un agent adhésif au silane contenant du fluor
JP2014218639A (ja) * 2012-11-05 2014-11-20 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
WO2019069642A1 (fr) * 2017-10-03 2019-04-11 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé pour fabriquer un élément hydrophobe et oléophobe

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