WO2002074878A1 - Produit hydrophobe - Google Patents

Produit hydrophobe Download PDF

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Publication number
WO2002074878A1
WO2002074878A1 PCT/JP2002/002168 JP0202168W WO02074878A1 WO 2002074878 A1 WO2002074878 A1 WO 2002074878A1 JP 0202168 W JP0202168 W JP 0202168W WO 02074878 A1 WO02074878 A1 WO 02074878A1
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WO
WIPO (PCT)
Prior art keywords
group
water
monomer
copolymer
cross
Prior art date
Application number
PCT/JP2002/002168
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English (en)
Japanese (ja)
Inventor
Akira Nakajima
Kazuhito Hashimoto
Norio Yoshino
Original Assignee
Center For Advanced Science And Technology Incubation, Ltd.
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Publication date
Application filed by Center For Advanced Science And Technology Incubation, Ltd. filed Critical Center For Advanced Science And Technology Incubation, Ltd.
Priority to JP2002573875A priority Critical patent/JPWO2002074878A1/ja
Publication of WO2002074878A1 publication Critical patent/WO2002074878A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds

Definitions

  • the present invention relates to a water-repellent material that can form a water-repellent film, preferably a super water-repellent film, by being applied. Background art.
  • a method of obtaining a water-repellent film, preferably a super-water-repellent film, by lowering the surface energy by coating is roughly divided into two materials, a) a method of applying a coupling agent, and b) a water-repellent containing fluorine.
  • a method of applying a polymer material has been proposed. .
  • the method using a coupling agent has the advantage of providing high water repellency, but has the advantage of high cost, short pot life, low durability, and The disadvantage is that the selection range is narrow.
  • the method using a water-repellent polymer material containing fluorine has the advantages that the pot life is relatively long, the selection range of the substrate on which coating can be performed is wide, and the film is easily formed. It has the disadvantage of being low and / or expensive.
  • T i 0 2 be supported on the superhydrophobic surface (coated surface).
  • T i 0 2 be supported on the superhydrophobic surface (coated surface).
  • some of the present inventors have proposed that the problem can be solved by using a surface having two levels of surface roughness (Japanese Patent Application No. 2000-268). 0 26). Disclosure of the invention
  • an object of the present invention is to provide a water-repellent material for products used outdoors, particularly a durable water-repellent material.
  • Another object of the present invention is to provide a water-repellent material in which peeling or detachment from a surface to be coated is suppressed in addition to or in addition to the above-mentioned objects.
  • an object of the present invention is to provide a water-repellent material which has a high level of water repellency in addition to or in addition to the above-mentioned objects, and which has a reduced production cost.
  • Another object of the present invention is to provide a water-repellent material capable of reversibly controlling the adhesiveness to a surface to be coated, in addition to the above object or in addition to the above object.
  • the second site may be derived from a plurality of types of monomers.
  • the first portion repels the material to be applied.
  • the first site may be derived from a plurality of monomers.
  • the polymer may further have a cross-linking site, and the polymer may be cross-linked via the cross-linking site.
  • the crosslinking site may be derived from a plurality of monomers.
  • the cross-linking site may be heat-responsive, thermoplastic or thermoplastic. Is preferably thermosetting.
  • the crosslinked site may be formed by heating.
  • the crosslinked portion is preferably formed by ultraviolet irradiation.
  • the crosslinked site may be formed by drying the solvent.
  • the crosslink may be formed by a photoacid generator.
  • a water-repellent material in which the first and second monomers have a polymerizable group
  • the second monomer has a group corresponding to a site capable of binding and / or adsorbing to the material to be coated with the water-repellent material.
  • the second monomer is preferably composed of a plurality of types.
  • the plurality is at least two kinds, and at least one kind of the second monomer corresponds to a part capable of binding to a substrate as a material to be coated and Z or adsorbing. It is preferable that the other second monomer has a group corresponding to a site capable of bonding and Z or adsorbing to the copolymer.
  • the first monomer has a group that repels the material to be coated.
  • the first monomer may be composed of a plurality of types.
  • the first and / or the second monomer may have a crosslinking group, and the copolymer may be crosslinked via the crosslinking group. Good.
  • the copolymer may further include a third monomer, the third monomer having a cross-linking group, and It is preferred that the copolymer is cross-linked via the polymer.
  • the crosslinking group has a plurality of types.
  • the crosslinking group may be thermoresponsive, thermoplastic or thermosetting.
  • the crosslinking group may be reacted by heating.
  • the crosslinking group reacts by irradiation with ultraviolet light.
  • the crosslinking group may react with the drying of the solvent.
  • the crosslinking group may be reacted with a photoacid generator.
  • a water-repellent film comprising:
  • the polymer further has a crosslinking site, and the polymer is crosslinked via the crosslinking site.
  • the first portion repels the substrate.
  • the surface of the water-repellent film preferably has a water contact angle of 110 ° or more.
  • the thickness of the layer is preferably from 20 to 800 nm.
  • the layer is preferably transparent in the visible region.
  • the water contact angle is 100 ° or more after 300 cycles of sliding with a dry cloth under a load of 100 g. Is good.
  • the second monomer preferably has a group corresponding to a site capable of bonding and / or adsorbing to the substrate.
  • the second monomer is preferably composed of a plurality of types.
  • the plural kinds are at least two kinds, and at least one kind of the second monomer has a group corresponding to a site capable of binding and / or adsorbing to the substrate, It is preferable that the other one kind of second monomer has a group corresponding to a site capable of binding to or adsorbing to the copolymer.
  • the first monomer may have a group that repels the material to be coated.
  • the first monomer is preferably composed of a plurality of types.
  • the first and the Z or the second monomer may have a crosslinking group, and the copolymer may be crosslinked via the crosslinking group. Is good.
  • the copolymer may further have a third monomer, wherein the third monomer has a crosslinking group, and It is preferred that the copolymer is cross-linked via the polymer.
  • the crosslinking group has a plurality of types.
  • the cross-linking group may be thermoresponsive, thermoplastic or thermosetting.
  • the cross-linking group may be reacted by heating.
  • the crosslinking group reacts by irradiation with ultraviolet rays.
  • the crosslinking group may react with the drying of the solvent.
  • the pendant group may be reacted with a photoacid generator.
  • the surface of the water-repellent film preferably has a water contact angle of 110 ° or more.
  • the layer may preferably have a thickness of 20 to 800 rim.
  • the layer is preferably transparent in the visible region.
  • the water contact angle is 100 ° or more after 300 cycles of sliding with a dry cloth under a load of 100 g. Is good.
  • a step of performing a polymerization reaction by mixing the first monomer and the second monomer, and a polymerization initiator, a step of diluting the obtained polymer, and a step of applying a diluent to the substrate surface A method for preparing a surface having water repellency, characterized in that the first monomer has a group corresponding to a site providing water repellency, and the first monomer and the second monomer are polymerizable. Method having various groups.
  • the second monomer has a group corresponding to a site capable of bonding to and / or adsorbing to the substrate surface.
  • the second monomer may have a group corresponding to a site capable of adsorbing the polymer coated on the substrate surface.
  • the second monomer is preferably composed of a plurality of types.
  • the first monomer may be composed of a plurality of kinds.
  • the first monomer preferably has a group that repels the substrate surface.
  • the first and / or second monomer has a crosslinking group, and the polymer is crosslinked via the crosslinking group after the coating step.
  • the method further includes a step.
  • the method further includes a step of mixing a third monomer having a crosslinking group, and crosslinking the polymer via the crosslinking group after the coating step.
  • the crosslinking group has a plurality of types.
  • the cross-linking group may be thermoresponsive, thermoplastic or thermosetting.
  • the crosslinking group may react by heating.
  • the cross-linking group may react by ultraviolet irradiation.
  • the crosslinking group may react with the drying of the solvent.
  • the crosslinking group may be reacted with a photoacid generator.
  • the concentration of the polymer is preferably adjusted to 100 gZ1 or less.
  • a water-repellent material having a copolymer comprising a first monomer, a second monomer and a third monomer, wherein the first, second and third monomers are polymerizable.
  • the first monomer has a group corresponding to a portion that repels the material to be coated with the water repellent material and provides water repellency
  • one of the second and third monomers Is a water-repellent material having a group corresponding to a site capable of bonding to a material to be coated with a water-repellent material, and the other having a group corresponding to a site capable of adsorbing with a copolymer.
  • Water contact angle on the surface is 110 ° or more, transparent in the visible region, sliding with a dry cloth under a load of 100 g, water contact angle of 10
  • the copolymer comprises: a first monomer containing fluorine; and a second monomer that binds to and Z or adsorbs to the surface of the substrate; and the concentration of the copolymer is: A water-repellent coating composition of 100 g Z dm 3 or less.
  • the first monomer does not have a site for binding to the surface of the base material and for adsorbing Z or adsorbing.
  • the copolymer may have a cross-linking site, and may be cross-linked between and / or within the copolymer via the cross-linking site. Is good.
  • the cross-linking site is preferably thermoresponsive, thermoplastic or thermosetting.
  • the cross-links may be formed by heating.
  • the crosslinking may be formed by irradiation with ultraviolet rays.
  • the crosslinking may be formed by drying the solvent.
  • the cross-link may be formed by a photoacid generator.
  • the first monomer may be composed of a plurality of types.
  • the second monomer may be composed of a plurality of types.
  • the base material is glass or ceramic
  • the second monomer interacts with the glass or ceramic to form a bond and / or Alternatively, it may have an adsorbing group.
  • the substrate is glass or ceramic
  • the second monomer is composed of one C1, one Br and one I.
  • the base material is glass or ceramics
  • the first monomer is bonded to the glass or ceramics and Z or adsorbs. It is good not to have a group.
  • the substrate may be glass or ceramic
  • the copolymer is preferably a block copolymer or a random copolymer.
  • the water-repellent film preferably has a water contact angle of 110 ° or more on the surface.
  • the water-repellent film is preferably transparent in the visible region.
  • the water-repellent film may have a water contact angle of 100 ° after sliding with a dry cloth under a load of 100 g. Should be more than
  • ⁇ 88> A composite material comprising the substrate surface coated with the water-repellent coating composition of any one of ⁇ 69> to ⁇ 83>.
  • ⁇ 8 9> a first monomer containing fluorine, binding and / 7 or adsorption with the substrate surface Performing a polymerization reaction with a second monomer to obtain a copolymer; and dissolving the obtained copolymer in a solvent to reduce the concentration of the copolymer to 100 gZdm 3 or less. Obtaining a water-repellent coating composition.
  • the first monomer does not have a site for binding and / or adsorbing to the substrate surface.
  • the copolymer may have a cross-linking site, and may be cross-linked between the copolymers and / or Z or the copolymer via the cross-linking site. Is good.
  • the cross-linking site may be thermoresponsive, thermoplastic or thermosetting.
  • the cross-links may be formed by heating.
  • the cross-linking may be formed by irradiation with ultraviolet rays.
  • the cross-linking may be formed by drying the solvent.
  • the crosslink may be formed by a photoacid generator.
  • the first monomer is preferably composed of a plurality of types.
  • the second monomer is preferably composed of a plurality of types.
  • the base material is glass or ceramic
  • the second monomer interacts with the glass or ceramic to form a bond and / or Alternatively, it may have an adsorbing group.
  • the base material is glass or ceramic
  • the substrate may be glass or ceramic, and the first monomer may bind to the glass or ceramic.
  • the substrate may be glass or ceramic
  • the copolymer may be a block copolymer or a random copolymer.
  • FIG. 1 is a diagram schematically showing the polymer of the present invention.
  • FIG. 2 is a graph showing the contact angles of the surfaces obtained in Examples 1 to 3 and Comparative Example 1.
  • FIG. 3 is a graph showing the film thicknesses of the coating films obtained in Examples 1 to 1 and Example 3—A to 3_F.
  • Fig. 4 shows the first embodiment.
  • 15 is a graph showing the contact angles of the surfaces obtained by Example 3-A to 3-F.
  • FIG. 5 is a graph showing the durability of the surface obtained in Example 4.
  • FIG. 6 is a graph showing that the water-repellent surface F 16 obtained in Example 5 has high durability.
  • FIG. 7 is a graph showing that the water-repellent surface F 16 obtained in Example 5 has higher durability than FAS-NCO which is said to have high durability.
  • FIG. 8 is a graph showing that the water repellent surfaces F 19 to 21, particularly F 21, obtained in Example 7 have high water repellency and excellent durability.
  • the water-repellent material of the present invention has a polymer.
  • the polymer has a) a first portion providing water repellency, and b) a second portion capable of bonding and Z or adsorbing to a material to be coated with the water repellent material.
  • the water-repellent material of the present invention may have other components in addition to the above-mentioned polymer, if desired.
  • the polymer of the present invention further preferably has c) a cross-linking site, and the polymer is cross-linked via the cross-linking site.
  • the cross-linking site can be cross-linked by various methods. For example, it can be formed by heating, by irradiation with ultraviolet light, or by drying a solvent.
  • the cross-linking sites can be thermo-responsive, thermoplastic or thermoset.
  • the position of the cross-linking site may be a part of the first and second sites, or may be a part of the first or the second, and c) the cross-linking site is the first or second site. It may be provided separately from the second part.
  • the present invention is based on the concept of a unique molecular chain structure determined by the characteristics of a substrate and a solvent when a polymer solution of a certain concentration having a portion having a high affinity for a solid surface and a portion having a low affinity is adsorbed on the solid surface.
  • the focus was on the property of self-organizing by forming an omension.
  • the parts responsible for water repellency are actively concentrated on the film surface to achieve high water repellency, and the durability of the film depends on the material to be coated inside. It is intended to achieve this by controlling the affinity of the polymer and, if necessary, forming a two-dimensional network in the film by thermal or optical treatment.
  • Each part of the polymer of the present invention may be derived from a monomer. That is, the first site is derived from the first monomer, the second site is derived from the second monomer, and the crosslinking site is derived from the third monomer. These copolymers may be used.
  • two or more sites may be included in one monomer. That is, the first site is derived from the first monomer, but the second site and the cross-linking site are the second monomer. It may be of origin. These will be described later, but these are merely examples, and the present invention is not limited thereto.
  • the first portion provides water repellency and preferably has a property of repelling the material to be coated on which the water repellent material is applied.
  • the first moiety a fluorine-containing group
  • the group be composed of only a group containing, or.
  • the fluorine-containing group is a linear or branched perfluoroalkyl group having at least 3 carbon atoms, preferably at least 4 carbon atoms, more preferably at least 6 carbon atoms, and most preferably at least 8 carbon atoms. Is good.
  • Applied material means the surface that appears at that time.
  • the “material to be coated” is a polymer contained in the substrate surface or the water-repellent material of the present invention.
  • the first portion is a group that provides water repellency, and is preferably a group that repels these “materials to be coated”.
  • the second portion can be selected depending on the material to be coated with the water-repellent material, specifically, the material on the substrate surface.
  • the material of the substrate surface is glass
  • a group capable of binding or adsorbing to the glass for example, alkoxysilane (_S i (OR) x , R is X represents an alkyl group, and X represents an integer of 1 to 3), or one SiC1x group or one Si (NCO) group (X represents an integer of 1 to 3).
  • the second site or the group possessed by the second site can be an anionic reactive group, and, of course, the reverse is also possible.
  • the substrate surface is a gold-plated surface
  • the second portion or the group of the second portion can be a thiol group, for example. The relationship with the group having is described below, but these and the above-mentioned second part or the group which the second part has are simply It is an indication and is not limited to these.
  • the second site or a group possessed by the second site includes a thiol group, an alkoxide group, an isocyanate group, an amine group, a cyano group, a carboxy group, an aldehyde group, an OH group, and a halogen.
  • a thiol group an alkoxide group, an isocyanate group, an amine group, a cyano group, a carboxy group, an aldehyde group, an OH group, and a halogen.
  • Group, sulfone group, -toro group and the like examples of the second portion or the group having the second portion include an amine group and a cyan group.
  • the second part or the group possessed by the second part includes an alkoxide group, an isocyanate group, an amine group, a cyanide group, a carbonyl group, an aldehyde group, an OH group, a halogen group, and a sulfone. And nitro groups.
  • the substrate surface is a material containing a benzene ring such as PET (polyethylene terephthalate) or PS (polystyrene), a benzene group or the like can be given as the second site or the group of the second site.
  • a material containing a benzene ring such as PET (polyethylene terephthalate) or PS (polystyrene)
  • PET polyethylene terephthalate
  • PS polystyrene
  • a benzene group or the like can be given as the second site or the group of the second site.
  • the substrate surface is polyacrylic acid or a derivative thereof, a polymer having a COOH group or a derivative thereof, a polymer having one COOC group or a derivative thereof, or a polymer having a COO group or a derivative thereof.
  • the second part or the group possessed by the second part include an alkaline functional group such as an amine group and an OH group.
  • the substrate surface is a polymer having an OH group or a derivative thereof, for example, PVA (polyvinyl alcohol)
  • the second site or the group of the second site may include a CO OH group.
  • the substrate surface is a polymer having an NH 2 group, an NH 3 group or an NH 4 group, or a polymer having a derivative group thereof
  • an acidic group such as a COOH group may be used as the second site or a group included in the second site. Can be mentioned.
  • the “material to be applied” can be defined in the same manner as described above. That is, the second portion is preferably capable of binding and / or adsorbing to the polymer contained in the substrate surface or the water-repellent material of the present invention. More specifically, when the second portion is derived from two or more types of monomers, for example, two types of monomers, monomer a and monomer b, monomer a can bind to the substrate surface Can be selected or designed so that the monomer b has a group that can adsorb the polymer. However, the monomers a and b are merely examples, and are not limited thereto. The second monomer corresponding to the second portion may be selected or designed in various ways, whether it is one kind or a combination of plural kinds.
  • a water-repellent material having a polymer having such first and second portions will be described with reference to FIG.
  • FIG. 1 is a diagram schematically showing a polymer contained in the material of the present invention.
  • FIG. 1A is a schematic diagram of the polymer group 1 bonded and / or adsorbed on the substrate 5.
  • FIG. 1 (b) is a diagram for taking out only one polymer from the polymer group 1 and simplifying the description.
  • the polymer 1 ′ has a first portion 2 providing water repellency, and a second portion 3 capable of bonding and Z or adsorbing to the substrate surface 5.
  • Reference numeral 6 in FIG. 1 (a) indicates that the polymers are adsorbed to each other via the second site 3. That is, as described above, when the water-repellent material of the present invention is applied once or a plurality of times, the polymers are laminated. At this time, the polymers are preferably adsorbed via the second site 3.
  • the cross-linking site may be included in the first or second site or may be provided separately therefrom.
  • the cross-linking site allows the polymers to cross-link through each other.
  • the water-repellent material having a crosslinked polymer tends to be less likely to be separated or detached from the surface to be coated.
  • the cross-linking site can be cross-linked by various methods. For example, it is preferable to form by heating, by irradiating ultraviolet rays, by drying a solvent, or by using a photoacid generator. Also, for example, the cross-linking site can be thermo-responsive, thermoplastic or thermosetting.
  • the position of the cross-linking site may be a part of the first and second sites, or may be any one of the first and second sites, and c) the cross-linking site is the first and second sites. ⁇ ⁇ It may be provided separately from the second part.
  • thermo-responsiveness means a property having a reversible change in which a cross-link is formed or broken by a thermal change.
  • the polymers of the invention can be designed so that cross-links are formed at low temperatures while cross-links are broken at high temperatures.
  • the temperature range at which the reversible reaction occurs depends on the crosslinking group, but the range may be any range.
  • the temperature at which the reversible reaction occurs can be controlled by the crosslinking group used.
  • the following products can be provided by using a water-repellent material in which the temperature at which this reversible reaction occurs is controlled.
  • a roof tile coated with a water-repellent material of the present invention which is a water-repellent material cross-linked through a thermoresponsive cross-linking group
  • a super-water-repellent roof tile can be manufactured.
  • This roof tile has the effect of preventing snow from accumulating when the temperature of the roof tile is about 1 o ° c or less in winter due to the characteristics of the super water-repellent material. In other words, there is no need to remove the roof from snow even in heavy snowfall areas.
  • the cross-linking of the material is strong, and the material can be applied so as not to be easily peeled or detached. However, even when used in winter, the film of the super water-repellent material gradually deteriorates due to sunlight or the like.
  • the heat-responsive cross-linking group is selected so that the cross-linking of the superhydrophobic material is broken.
  • the bond via the cross-linking group is broken, and the material can be easily peeled or detached from the roof tile. Material exfoliation or detachment is facilitated by rain, and most films can be removed.
  • the roof having the water-repellent material of the present invention is again applied to the tile from which the film has been removed, and cross-linking is formed via a cross-linking group, so that the roof can be prepared for winter and has a snow-prevention effect in accordance with the cycle of the four seasons. Tiles can be provided.
  • the polymer having the first and second sites and, if desired, the cross-linking site of the present invention can be derived from one or more monomers. That is, even if the polymer of the present invention is a homopolymer composed of one kind of monomer having first and second sites and optionally a crosslinking site, a plurality of types of monomers having a group corresponding to the above site May be a copolymer having The form of the copolymer may be any of various copolymer forms, for example, a random copolymer, a block copolymer, a graft copolymer, and the like, and these forms are not limited.
  • the case of the polymer of the present invention particularly, the case of a copolymer will be described from the viewpoint of monomers.
  • the polymer of the present invention is a copolymer
  • a plurality of types of monomers constituting the copolymer are
  • the sites and monomers may or may not have a one-to-one correspondence.
  • the first to third monomers each have a group corresponding to the first and second sites and a desired cross-linking site.
  • the copolymer is derived from first and second monomers, ie, two types of monomers, the first monomer has a group corresponding to the first moiety and the second monomer has a first moiety.
  • the copolymer of the present invention can be designed and prepared so as to have groups corresponding to other sites.
  • one site has a one-to-many correspondence derived from a plurality of types of monomers means that, for example, the first site providing water repellency may be derived from two or more types of monomers.
  • the polymer of the present invention having various properties can be designed and prepared by variously combining the correspondence between the site and the monomer.
  • the polymer of the present invention is a copolymer
  • two or more monomers forming the copolymer have a polymerizable group.
  • all two or more monomers can have an olefin group.
  • one of two or more monomers has an alcohol group or a derivative thereof, and the other has a carboxyl group or a derivative thereof. You can also.
  • the above polymerization reaction is merely an example. That is, the polymerization reaction of the present invention includes various polymerization reactions, and is not limited to the above examples.
  • the monomer has a polymerizable group, and a 4-nomer having an olefin group represented by the following general formula I as the polymerizable group is preferable. That is, it is preferable because the characteristics of the copolymer can be designed by variously changing 1 to! ⁇ 4 .
  • one or more of RR 2 , R 3 and R 4 — may have a group corresponding to the first to third sites and the crosslinking site, as described above.
  • One or more of RR 2 , R 3 and R 4 of two or more different monomers may have a group corresponding to the first to third sites and the crosslinking site.
  • RR 2 , R 3 and R 4 may be the same or different, and each will be described in detail below.
  • the first monomer can be represented by the following general formula II.
  • R F represents a group corresponding to the first site that provides water repellency.
  • RR 2 , and R 3 may be the same or different, and include a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group , substituted or unsubstituted alkoxy group or a substituted or unsubstituted ⁇ Rukanoiruokishi group, or: F or the listed R B ⁇ Pi Z or: represents a b.
  • a combination in which R 1 and R 2 are hydrogen and R 3 is hydrogen or a methyl group is preferred.
  • R F can be represented by one X—R F , X represents a divalent group which may or may not have, and represents a group having 3 or more carbon atoms, preferably 4 or more, It preferably represents 6 or more, most preferably 8 or more linear or branched perfluoroalkyl groups.
  • the second monomer having a group corresponding to the second site capable of binding and Z or adsorbing to the material to be coated with the water repellent material will be described below.
  • the second monomer can be represented by the following general formula II.
  • R B represents a group corresponding to the binding and Roh or adsorbable second portion with the coating material for coating the water-repellent material.
  • 1 , R 2 and R 3 are defined as above, and may be R F or R B and / or R b above.
  • R B depends on the material to be coated. For example, if a like substrate surface which the coating material is made of glass, R B can be represented as one Y- R B, or one R B " ⁇ '. R B , one MR 6 a (OR 7) 3 — a, and R B ,, can be represented as one MR 6 a , (OR 7 ) 2 — a , where a is an integer from 0 to 2, and a 'is 0 to 1.
  • M represents a metal, and examples thereof include Si, Ti, Zr, etc.
  • R 6 and R 7 may be the same or different, and represent a hydrogen atom or a carbon atom. Represents a substituted or unsubstituted alkyl group of 1 to 6.
  • Y represents a divalent group which may or may not be present, and Y and are defined similarly to 1 to! ⁇ 3 .
  • the alkoxy group of R B acts as a silanol group after hydrolysis, and acts as a group that bonds to or adsorbs to the glass surface.
  • Y one (CH 2 ) b- (b is an integer of 1 or more) can be mentioned, but it is not limited thereto.
  • the second monomer having the second portion a monomer having a property of binding and / or adsorbing to the polymer contained in the water-repellent material of the present invention can be used.
  • the second monomer (second monomer b) having such a property is used together with the second monomer a having the property of binding, binding, or adsorbing to the surface of the substrate, but is separated from the polymer substrate.
  • the second monomer b can be represented by the following general formula IV.
  • R 1 ! ⁇ 3 can be defined in the same manner as described above.
  • Rb represents a group capable of bonding and Z or adsorbing, particularly adsorbing with the polymer contained in the water-repellent material of the present invention.
  • R b can be defined similarly as 1 to! ⁇ 3 .
  • R b can be selected depending on the polymer.
  • R b a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alcohol group, a substituted or unsubstituted ether group, a substituted or unsubstituted ester group, a substituted or unsubstituted group But not limited thereto.
  • the second monomer b represented by the general formula IV together with the second monomer a, the bonding to the substrate and Z or adsorption can be strengthened by the second monomer a, and the polymer It can promote binding and Z or adsorption.
  • MMA C ( CH 3) C OOCH 3) ( hereinafter sometimes abbreviated as "MMA")
  • MMA ternary copolymer
  • the cross-linking site can be represented as a group corresponding to the site, that is, a cross-linking group (R c group).
  • the cross-linking group may be contained in the first monomer and / or the second monomer (and optionally the third monomer if necessary) or may be derived from a new monomer having a new cross-linking group. .
  • the cross-linking group may be cross-linked by the same type of group, or may be cross-linked by two or more types of groups.
  • the third monomer can be represented by the following general formula V.
  • Ri R 3 can be defined as above.
  • R c represents a group having a crosslinking group, as described above.
  • the cross-linking groups allow the polymers to cross-link with each other.
  • the water-repellent material having a crosslinked polymer tends to be less likely to be peeled or detached from the surface to be applied.
  • the crosslinking group can be, for example, thermoresponsive, thermoset, or thermoplastic.
  • a thermo-responsive cross-linking group a cross-link is formed at low temperatures, while a cross-link is formed at high temperatures.
  • a so-called reversible reaction can be performed. By this reversible reaction, it is possible to provide a roof tile having a snow prevention effect adapted to the above-described four seasons cycle.
  • cross-linking group examples include, but are not limited to, the following.
  • epoxy groups, phenol, urea, melamine and the like can be mentioned as thermosetting crosslinking groups.
  • (GMA) represented by the following formula a.
  • (GMA) represented by the following formula a.
  • thermoresponsive crosslinking group examples include monomers each having a group represented by a combination of the following formulas b and b ′. maleiini ⁇ le-m difie d polymer
  • the first monomer having a group corresponding to the site providing water repellency and the other monomer
  • the first monomer when the total amount of monomers and 1 0 0 mol%, the first monomer is 5 mole 0/0 or more, preferably 1 0 mol% or more, more favorable More preferably, it is at least 20 mol%.
  • the first monomer is 5 0 mole 0/0 or less, preferably 4 0 mol% or less, more preferably good not less 3 0 mol% or less Re. Even if the mole% of the first monomer is high, the value of the water repellency of the obtained polymer is saturated, so that the above upper limit tends to give sufficient water repellency.
  • the selection range of the solvent in which the monomer is dissolved tends to be limited.
  • the mole% of the first monomer is too low, the desired water repellency tends not to be obtained.
  • the polymer of the present invention can be prepared by variously combining the first and second monomers described above, and optionally the third monomer, and selecting a polymerization method depending on the polymerizable group contained in the monomer.
  • a polymer having properties can be prepared. Further, by using a water-repellent material having the polymer, the above object can be achieved.
  • the water-repellent surface of the present invention is adjusted through various steps after preparing the polymer.
  • the method for preparing the polymer of the present invention includes a step of mixing one or more monomers and a polymerization initiator to carry out a polymerization reaction. Thereby, the polymer of the present invention can be obtained. Thereafter, a step of diluting the obtained polymer and a step of applying a diluting liquid to the substrate surface can prepare a surface having water repellency.
  • the solvent used in the step of diluting the polymer of the present invention, preferably the copolymer, is not particularly limited as long as it dissolves the polymer of the present invention. That is, it is not particularly limited as long as it is a better solvent than the so-called ⁇ -solvent.
  • concentration of the polymer of the present invention in, 1 0 0 g Z dm 3 or less, preferably not less 3 0 g Z dm 3 or less.
  • a polymer is cross-linked using a cross-linking group
  • a step of adding a crosslinking reaction initiator to the diluent is provided.
  • a coating step may be performed to start a crosslinking reaction after the application.
  • crosslinking group and the crosslinking reaction conditions should be designed so that the crosslinking reaction is effective after the application.
  • the polymer of the present invention can be obtained.
  • the water-repellent film of the present invention has any one of the following features a) to c), preferably at least two of them, and more preferably a) to c). It has all the features.
  • A) The water contact angle on the surface is 110 ° or more; b) Transparent in the visible region; and c) The water contact angle is 100 ° after 3000 slidings with a dry cloth under a load of 100 g. That is the feature of the above.
  • AIBN 2,2′-azobisisobutymouth-tolyl
  • Example 8 8. Fixing the MPTMS of Example 1 to 8.70 g (25 mol%), and setting the amount of FMA to x mol 0 / o and the amount of MMA to (75-x) mol%, A / MP TMS / MMA copolymer was obtained.
  • the embodiment 2 x 20 mol 0/0
  • x 10 mol%
  • X was 0 mol%.
  • a copolymer coating solution in which the obtained copolymer was adjusted to a concentration of 12.5 g / 1 with a solvent 2-butanone was prepared.
  • the copolymer solution was spin-coated on a substrate having a smooth surface, that is, 5 cm X 5 cm Pyrex glass, at 150 Orm for 10 seconds. Then, it was dried at 120 ° C. for 1 hour to form a water-repellent surface.
  • the contact angle of the obtained water repellent surface was measured.
  • the values of X (mol%), the obtained water repellent surface, and the contact angle of Comparative Examples 1 to 3 are shown in Table 1 and FIG. '' In Examples 1 to 3 and Comparative Example 1,
  • the amount of the first monomer used (X mole 0 / o) and
  • F3 of Example 3 has a high water repellency with a contact angle exceeding 100 °. Further, F1 in Example 1 has a contact angle of 115. It is. This value is the calculated value obtained when forming a homopolymer of FMA.
  • Example 1 can provide a material having higher water repellency.
  • the raw material cost is high for FMA, even if the amount of FMA with high raw material cost is suppressed from the value of the contact angle in Example 1, almost the same water repellency can be obtained.
  • the present invention can provide a water-repellent material with reduced raw material costs.
  • Example 11-A is the same as Example 1 above. It is a manufacturing method.
  • Example 3 has the same manufacturing method as in Example 1 described above.
  • Examples 1-A to 1-F and Examples 3-A to 3-F The film thickness and the contact angle of the water-repellent surfaces obtained by the methods were measured. The value of these X (mol. / 0), water-repellent surface obtained, the film thickness and the contact angle to Table 2 and Table 3, and summarized in FIGS. Table 2.
  • 12.5 g / 1 copolymer coating liquid was obtained from the obtained copolymer using 2-butanone as a solvent. After adding 0.5 g of maleic anhydride to this copolymer coating solution, spin coating was performed at 1500 rpm for 10 seconds on a substrate having a smooth surface, that is, 5 cm ⁇ 5 cm Pyrex glass. Then, it was dried at 120 ° C. for 1 hour, and subjected to a thermosetting reaction for 7 days to form a water-repellent surface F15.
  • the contact angle of the obtained water repellent surface F15 was measured.
  • the abrasion resistance was evaluated. The results are shown in Table 4 and FIG.
  • the wear resistance was measured using a traverse sliding tester. In the measurement, the following conditions were used: load: 0.1 kg / crn 2 ; sliding speed: 30 reciprocations / minute.
  • the contact angle after repeating the sliding X times with the testing machine was used to evaluate the deterioration.
  • the same abrasion resistance test as F15 was performed on F1 of Example 1 prepared without containing GMA. In Table 4 below, X times are described as the number of repetitions (one round trip is assumed). Table 4. Examples 1 and 4
  • Example 4 113.0 110.0 109.0 81.5
  • the surface F15 prepared using the monomer having a thermosetting crosslinking group has higher durability than the surface F1 of Example 1. You can see this.
  • MP TMS-NCO was used instead of MP TMS used in Example 4. In this method, all the methoxy groups (one OCH 3 group) of MPTMS were replaced with isocyanate groups (one NCO group). Its structural formula was the following formula A.
  • a CO-based copolymer was prepared. This copolymer was applied on Pyrex glass in the same manner as in Example 5 (immersion method) to form a water-repellent surface F 17 (copolymer film thickness: about 350 nm).
  • FAS—NCO structural formula CF 3 (CF 2 ) 9 (CH 2 ) 2 -S i (NCO) 3
  • a water-repellent surface F 18 polymer film thickness: about 300 nm
  • the contact angles of the obtained water repellent surfaces F16 to F18 were measured.
  • the wear resistance was evaluated. These results are shown in FIGS. 6 and 7.
  • the abrasion resistance was measured using a trappersliding tester, and the measuring method was the same as that described above, that is, the method used for the water-repellent surface F15 in Example 4.
  • the water-repellent surface F1 prepared in Example 1 is also shown in FIG. 6 (in FIG. 6, denoted by “rFMA / MMA / MP TMS”).
  • Figure 7 shows the following. That is, it can be seen that the F'MAZMMAZMP TMS-NCO / GMA-based copolymer has higher durability than FAS-NCO which is considered to have high durability against dynamic friction.
  • Example 4 0.1 g of the FMA / MP TMS // MMAZGMA-based copolymer obtained in Example 4 was dissolved in a solvent 2-ptanone to obtain a 12.5 gZ1 copolymer coating solution. To 6.52 g of this copolymer coating solution was added 0.1 g (0.211111101) or 0.2 ⁇ (0.4 mmo 1) of xafluorophosphoric acid to difluoromethane as a photoacid generator, and the mixture was smoothed. Spin coating was performed on a substrate having a surface, that is, 5 cm ⁇ 5 cm Pyrex glass at 1,500 rpm for 10 seconds.
  • the coated surface is irradiated with ultraviolet rays (Hg—Xe lamp) for 30 minutes or 60 minutes, and then heated at 120 ° C. for 1 hour as a bostochyur to obtain a water-repellent surface F 19 to F 21 Was formed.
  • Table 5 shows the preparation conditions for the water-repellent surfaces F19 to F21. Table 5. Preparation conditions of water-repellent surface F19 to F21
  • F21 with a large amount of the photoacid generator and a long ultraviolet irradiation time exhibits high water repellency (high contact angle value) and also has excellent durability. Understand. Industrial applicability
  • the water repellent material of the present invention has various applications due to its properties.
  • the water-repellent material of the present invention can prevent water droplets from adhering and can easily remove water droplets by wind, vibration, or the like. Therefore, it can be applied to the following members.
  • the water-repellent material of the present invention can prevent oil from adhering and can easily remove oil by wind or vibration. Therefore, it can be applied to the following members.
  • the water repellent material of the present invention can prevent permeation of water. Therefore, it can be applied to the following members. That is, shoes, cloth, clothing, carpets, curtains, flooring, gloves, hats, umbrellas, bicycles, pikes, paper, chairs, sofas, wallpapers, tatami, cushions, futons, sheets, beds, pillows, blankets, tents, sleeping bags , Rucksacks, school bags, cardboard, envelopes, cement bags, postcards, silk cups, books, pools, artificial ponds, bathrooms, bathtubs, paper bags, newspapers, magazines, wrapping paper, etc.
  • the water repellent material of the present invention can prevent fingerprint adhesion. Therefore, it can be applied to the following members. That is, video cameras, cameras, mobile phones, glasses, mirrors, goggles, glasses, sunglasses, car bodies, signboards, signals, washrooms, bathrooms, medical tools, kitchen surroundings, dishes, indoor and outdoor lighting, walls, tables, and washbasins It can be applied to bowls, doors, railings, televisions, personal computers, telephones, photo stands, hanging leather, polymer film, anorepam, photographs, etc.
  • the water repellent material of the present invention can prevent strong adhesion of snow and ice. Therefore, it can be applied to the following members. That is, it can be applied to various outdoor structures in cold regions.
  • vending machines glass, mirrors, goggles, glasses, sunglasses, helmets, car bodies, signboards, signals, washrooms, bathrooms, pools, medical equipment, cooking utensils, kitchen surroundings, bicycles, clothing, speakers , Antennas, tableware, dishwashers, indoor and outdoor lighting, roofs, walls, gates, piers, outdoor fans, aircons, washing machines, benches, tanks, cylinders, bosts, pikes, umbrellas, bags, shoes, gloves, Applicable to hats, sashes, sofas, carpets, sheets, tables, desks, chairs, floors, curtains, bathtubs, washbasins, storerooms, under viaducts, ceilings, tombstones, etc.
  • vending machines glass, mirrors, goggles, glasses, sunglasses, helmets, car bodies, signboards, signals, washrooms, baths Places, swimming pools, medical equipment, cooking utensils, kitchen surroundings, bicycles, clothing, speakers, antennas, tableware, dishwashers, indoor and outdoor lighting, roofs, walls, gates, piers, outdoor fans, air conditioners, washing machines, Benches, tanks, cylinders, posts, motorcycles, umbrellas, bags, shoes, gloves, hats, sashes, sofas, carpets, sheets, tables, desks, chairs, floors, pots, bathtubs, basins, washrooms, sheds, viaducts Applicable to lower, ceiling, tombstone, etc.
  • the texture when touched becomes smooth. Therefore, it can be applied to the following members. That is, it can be applied to clothing, leather products (bags, shoes, gloves, hats), curtains, sofas, chairs, mouse pads, mats, cushions, slippers, carpets, and the like.
  • the water repellent material of the present invention When the water repellent material of the present invention is applied, electric leakage hardly occurs. Therefore, it can be applied to the following members. That is, it can be applied to various electric products, electronic circuits, electronic parts, cords, switches, switchboards, batteries, cables, and the like.
  • water repellent material of the present invention can prevent mold, algae and moss from being generated and firmly adhered to them. Therefore, it can be applied to the following members. That is, it can be applied to kitchen surroundings, bathrooms, toilets, washrooms, entrances, pools, roofs, under floors, temples, shoes, sashes, closets, packings, rain gutters, shutters, walls, closets, ceilings, sheds, shelves, etc. .
  • the water repellent material of the present invention When the water repellent material of the present invention is applied, the resistance to water supply can be reduced, and the pool can be reduced. Therefore, it can be applied to the following members. That is, it can be applied to hoses, tubes, pulp, piping, ships, and the like.
  • the water repellent material of the present invention When the water repellent material of the present invention is applied, the degree of corrosion can be reduced or reduced. Therefore, it can be applied to the following members. That is, it can be applied to metal parts and the like.
  • the water repellent material of the present invention When the water repellent material of the present invention is applied, a high degree of vacuum can be easily obtained. Therefore, it can be applied to the following members. That is, vacuum vessels, vacuum pumps, vacuum tubes, vacuum hoses, vacuum pipes, and vacuum pulp water repellency can be applied to hydrophilicity, heat resistance, lubricity, and the like.

Abstract

L'invention concerne un produit hydrophobe, particulièrement un produit hydrophobe durable, pouvant être appliqué sur des articles utilisés à l'extérieur. Ce produit hydrophobe contient un polymère constitué d'un ensemble de premières parties qui lui confèrent son caractère hydrophobe, ainsi que d'un ensemble de secondes parties qui peuvent se lier et/ou être absorbées par la surface sur laquelle le produit hydrophobe est appliqué. Ce polymère peut éventuellement comporter des parties réticulables. On confère sa durabilité au produit en soumettant les parties réticulables du polymère à une réticulation.
PCT/JP2002/002168 2001-03-19 2002-03-08 Produit hydrophobe WO2002074878A1 (fr)

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JP2001-078233 2001-03-19
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0348946A1 (fr) * 1988-06-28 1990-01-03 Kansai Paint Co., Ltd. Composition filmogène et hydrophobe
JPH02145665A (ja) * 1988-11-28 1990-06-05 Shin Etsu Chem Co Ltd 室温硬化性塗料組成物
JPH02228352A (ja) * 1989-03-01 1990-09-11 Kansai Paint Co Ltd 樹脂組成物、硬化性組成物及び塗料組成物
JPH10120941A (ja) * 1996-10-21 1998-05-12 Shin Etsu Chem Co Ltd 撥水性塗料組成物
EP0953584A1 (fr) * 1998-04-30 1999-11-03 JSR Corporation Polymére d'olefin, procédé pour sa fabrication, composition de résine durcissable et revêtement anti-réfléchissant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0348946A1 (fr) * 1988-06-28 1990-01-03 Kansai Paint Co., Ltd. Composition filmogène et hydrophobe
JPH02145665A (ja) * 1988-11-28 1990-06-05 Shin Etsu Chem Co Ltd 室温硬化性塗料組成物
JPH02228352A (ja) * 1989-03-01 1990-09-11 Kansai Paint Co Ltd 樹脂組成物、硬化性組成物及び塗料組成物
JPH10120941A (ja) * 1996-10-21 1998-05-12 Shin Etsu Chem Co Ltd 撥水性塗料組成物
EP0953584A1 (fr) * 1998-04-30 1999-11-03 JSR Corporation Polymére d'olefin, procédé pour sa fabrication, composition de résine durcissable et revêtement anti-réfléchissant

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