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WO2010076872A1 - Élément hydrophile et procédé pour produire un matériau mince pour échangeurs de chaleur - Google Patents

Élément hydrophile et procédé pour produire un matériau mince pour échangeurs de chaleur Download PDF

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Publication number
WO2010076872A1
WO2010076872A1 PCT/JP2009/071262 JP2009071262W WO2010076872A1 WO 2010076872 A1 WO2010076872 A1 WO 2010076872A1 JP 2009071262 W JP2009071262 W JP 2009071262W WO 2010076872 A1 WO2010076872 A1 WO 2010076872A1
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WO
WIPO (PCT)
Prior art keywords
group
hydrophilic
layer
composition
fin material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/071262
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English (en)
Japanese (ja)
Inventor
誠 福田
智史 田中
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Fujifilm Corp
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Fujifilm Corp
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Filing date
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Publication of WO2010076872A1 publication Critical patent/WO2010076872A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F1/00—Tubular elements; Assemblies of tubular elements
    • F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/04—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a surface receptive to ink or other liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/16—Antiseptic; (micro) biocidal or bactericidal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2275/00—Fastening; Joining
    • F28F2275/02—Fastening; Joining by using bonding materials; by embedding elements in particular materials
    • F28F2275/025—Fastening; Joining by using bonding materials; by embedding elements in particular materials by using adhesives

Definitions

  • the present invention is a hydrophilic member excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention, and heat exchange excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention properties.
  • the present invention relates to a method for manufacturing a device fin material.
  • optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc.
  • optical members when used by humans, are contaminated with fingerprints, sebum, sweat, cosmetics, etc. Since removal of dirt is complicated, it is desired to perform effective dirt prevention treatment.
  • displays are often used outdoors, but when used in an environment where external light is incident, the incident light is regularly reflected on the display surface. As a result, the reflected light is mixed with the display light, causing problems such as difficulty in viewing the display image. For this reason, an antireflection optical member is often disposed on the display surface.
  • an antireflection optical member for example, a transparent substrate with a high refractive index layer and a low refractive index layer made of a metal oxide or the like laminated thereon, an inorganic or organic fluoride compound or the like on the transparent substrate surface.
  • a low refractive index layer is formed as a single layer, or those in which a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film substrate and external light is irregularly reflected by the uneven surface.
  • These anti-reflective optical member surfaces like the above-mentioned optical members, are susceptible to dirt such as fingerprints and sebum when used by humans, but only the part where the dirt is attached becomes highly reflective and the dirt is more noticeable.
  • the surface of the antireflection film usually has fine irregularities, and it is difficult to remove dirt.
  • an antireflection member and an antifouling member for example, an antireflection film made mainly of silicon dioxide and an antifouling and friction resistant material treated with a compound containing an organosilicon substituent (for example, Patent Document 1), and an antifouling and friction-resistant CRT filter (for example, see Patent Document 2) in which the substrate surface is coated with a terminal silanol organopolysiloxane has been proposed.
  • an antireflection film containing a silane compound including a silane compound containing a polyfluoroalkyl group see, for example, Patent Document 3
  • an optical thin film mainly composed of silicon dioxide, a perfluoroalkyl acrylate, and an alkoxysilane group has been proposed.
  • the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and the surface energy such as fluorine and silicon is low.
  • the surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.
  • a resin film generally used on the surface of an optical member or the like, or an inorganic material such as glass or metal has a hydrophobic surface or a weak hydrophilic surface.
  • the surface of a substrate using a resin film or inorganic material is made hydrophilic, the attached water droplets spread uniformly on the surface of the substrate and form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather.
  • combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and sealant elution components are difficult to adhere. Therefore, it is useful for various applications.
  • Non-Patent Document 1 a surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (see, for example, Non-Patent Document 1), although this coating film has a certain degree of hydrophilicity, Affinity with the substrate is not sufficient, and higher durability is required.
  • a film using titanium oxide has been conventionally known.
  • a technique of forming a photocatalyst-containing layer on a substrate surface and making the surface highly hydrophilic according to photoexcitation of the photocatalyst is a technique of forming a photocatalyst-containing layer on a substrate surface and making the surface highly hydrophilic according to photoexcitation of the photocatalyst.
  • a heat exchanger of an air conditioner includes a pipe that moves a heat medium and fins that absorb heat in the air or dissipate heat in the heat medium.
  • a copper pipe is used by penetrating a thin plate aluminum of about 0.1 mm, which is a fin material.
  • the condensed water generated at the time of cooling becomes water droplets and stays between the fins, so that a bridge of water is generated and the cooling capacity is lowered.
  • the adhering of dust or the like between the fins similarly reduces the cooling capacity.
  • Patent Documents 9 to 11 As a heat exchanger treated with a hydrophilic composition, for example, Patent Document 12 is known.
  • the anti-fogging and anti-fogging properties of the hydrophilic surface with a cross-linked structure by hydrolyzing and condensation-polymerizing the hydrophilic polymer and the alkoxide are focused on the characteristics of the sol-gel organic-inorganic hybrid film. It has been found that it exhibits fouling and has good rub resistance (see Patent Document 6).
  • a hydrophilic surface layer having such a crosslinked structure can be easily obtained by combining a specific hydrophilic polymer having a reactive group at its terminal and a crosslinking agent.
  • the object of the present invention is to solve the above-mentioned problems of the prior art, hydrophilic members excellent in hydrophilicity, antifouling properties, lubricity, adhesion, and rust prevention, and hydrophilic properties, antifouling properties, lubricity, adhesion It is providing the manufacturing method of the fin material for heat exchangers excellent in property and rust prevention property.
  • the present invention is as follows.
  • the hydrophilic layer contains 50 mass of the hydrophilic polymer (I) containing the structure represented by the following general formula (I-1) and the structure represented by the following general formula (I-2) with respect to the total solid content.
  • R 101 to R 108 each independently represents a hydrogen atom or a hydrocarbon group.
  • p represents an integer of 1 to 3
  • L 101 and L 102 each independently represent a single bond or a polyvalent organic linking group.
  • x and y represent a composition ratio, x represents a number satisfying 0 ⁇ x ⁇ 100 and y represents 0 ⁇ y ⁇ 100.
  • a 101 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3 (
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • the hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (I) in an amount of 80% by mass or more based on the total solid content, and in the general formula (I-2)
  • a 101 represents —CONH 2 , —CONH (R 5 ), or —CON (R 5 ) 2 (wherein R 5 independently represents a linear, branched, or cyclic alkyl group).
  • the hydrophilic member according to [6] which is characterized.
  • [9] [1] A fin material using the hydrophilic member according to any one of [8].
  • the aluminum fin material whose fin material as described in [9] is a product made from aluminum.
  • [11] [10] A heat exchanger using the aluminum fin material according to [10].
  • [12] An air conditioner using the heat exchanger according to [11].
  • a lubricant composition is applied to the surface of a fin material for a heat exchanger having a hydrophilic layer formed by applying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group to the surface of an aluminum plate and drying.
  • a method for producing a fin material for a heat exchanger comprising applying and drying to adsorb or impregnate a lubricant composition in a hydrophilic layer to form a lubricating layer having a friction coefficient of 0.05 to 0.25 .
  • a hydrophilic member excellent in hydrophilicity, antifouling property, lubricity, adhesion, and rust prevention and a heat exchanger excellent in hydrophilicity, antifouling property, friction resistance, adhesion, and rust prevention property The manufacturing method of a fin material can be provided.
  • the hydrophilic member of the present invention has a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate, and further has a friction coefficient of 0.05. Having a lubricating layer of ⁇ 0.25.
  • the water droplet contact angle of the hydrophilic member is preferably 20 ° or less, preferably 15 ° or less, more preferably 10 ° or less. It is preferable that the water droplet contact angle is 20 ° or less because excellent hydrophilicity can be exhibited.
  • the hydrophilic layer can be formed by applying and drying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group.
  • the hydrophilic polymer having a hydrolyzable silyl group is a hydrophilic polymer (I) having a structure represented by the following general formula (I-1) and a structure represented by the following general formula (I-2). Is preferred.
  • R 101 to R 108 each independently represents a hydrogen atom or a hydrocarbon group.
  • p represents an integer of 1 to 3
  • L 101 and L 102 each independently represent a single bond or a polyvalent organic linking group.
  • x and y represent a composition ratio, x represents a number satisfying 0 ⁇ x ⁇ 100 and y represents 0 ⁇ y ⁇ 100.
  • a 101 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3 (
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • hydrophilicity In addition to being able to maintain high hydrophilicity by using a hydrophilic polymer (I) containing an alkoxysilyl group that forms a hydrophilic structure and a crosslinked structure, such as polyacrylamide, as a composition that imparts hydrophilicity, hydrophilicity can be maintained. This is presumably because the water adhering to the hydrophilic surface does not dissolve out the hydrophilic layer and has excellent long-term water resistance.
  • R 101 to R 108 each independently represents a hydrogen atom or a hydrocarbon group.
  • p represents an integer of 1 to 3
  • L 101 and L 102 each represents a single bond or a polyvalent organic linking group.
  • x and y represent a composition ratio, x represents a number satisfying 0 ⁇ x ⁇ 100 and y represents 0 ⁇ y ⁇ 100.
  • a 101 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3 (
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • R 101 to R 108 each independently represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable.
  • R 101 to R 108 are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability.
  • hydrocarbon groups may further have a substituent.
  • the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent.
  • Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ⁇ ⁇ ⁇ -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N
  • alkyl group in these substituents are the same as those of R 1 to R 8
  • specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamo Butylphen
  • alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc.
  • alkynyl examples include ethynyl, 1-butenyl, Examples include propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
  • G 1 in the acyl group examples include hydrogen and the above alkyl groups and aryl groups.
  • halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls.
  • acyloxy group N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamo Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group
  • the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
  • it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms.
  • substituted alkyl group obtained by combining the substituent and the alkylene group are chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, hydroxymethyl group, methoxymethyl group, methoxyethoxy group.
  • Ethyl group allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonyl group Group, allyloxycarbonyl butyl group,
  • Chlorophenoxycarbonylmethyl group carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropy
  • a hydroxymethyl group is preferable from the viewpoint of hydrophilicity.
  • L 101 to L 102 each represents a single bond or an organic linking group.
  • the single bond means that the main chain of the polymer and A 101 or Si atom are directly bonded without a connecting chain.
  • L 101 to L 102 represent an organic linking group
  • L 101 to L 102 represent a polyvalent linking group composed of a nonmetallic atom, including 0 to 60 carbon atoms and 0 to 10 nitrogen atoms. It consists of atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.
  • —N ⁇ an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, —O—, —S—, —CO—, —NH—, or
  • a combination containing —O— or —S— or —CO— or —NH— is preferably a divalent linking group. More specific examples of the linking group include the following structural units or those formed by combining them.
  • L 101 is a single bond or one structure selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO 2 NH—, and —SO 3 —.
  • a linking group having the above is preferable.
  • a 101 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ).
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R d is a linear, branched or cyclic group.
  • R e and R f are each independently a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 8), an alkali metal, It represents an alkaline earth metal or onium, and R g represents a halogen ion, an inorganic anion, or an organic anion.
  • —CON (R a ) (R b ), —N (R a ) (R b ), —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) R a to R g may be bonded to each other to form a ring for (R f ), —OPO 3 (R e ) (R f ), or —PO 3 (R d ) (R e )
  • the formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom.
  • R a to R g may further have a substituent, and the substituents that can be introduced here are the same as the substituents that can be introduced when R 1 to R 8 are alkyl groups. Can be listed.
  • a 101 is preferably —CONH 2 , —CONH (R 5 ), or —CON (R 5 ) 2 .
  • R 5 represents a linear, branched or cyclic alkyl group.
  • the linear, branched or cyclic alkyl group specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • the alkali metal include lithium, sodium, and potassium
  • the alkaline earth metal includes barium
  • the onium includes ammonium, iodonium, sulfonium, and the like.
  • halogen ion examples include fluorine ion, chlorine ion, bromine ion
  • inorganic anion includes nitrate anion, sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, etc.
  • organic anion includes methanesulfonate anion
  • Preferable examples include trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, p-toluenesulfonate anion and the like.
  • the A 101 specifically, -NHCOCH 3, -CONH 2, -CON (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) n H, morpholyl group and the like are preferable. More preferred are —NHCOCH 3 , —CONH 2 , —CON (CH 3 ) 2 , —SO 3 ⁇ K + , — (CH 2 CH 2 O) n H. In the above, n preferably represents an integer of 1 to 100.
  • P represents an integer of 1 to 3, preferably 2 to 3, more preferably 3.
  • x and y are represented by the general formula (I-1) in the hydrophilic polymer (I).
  • x is 0 ⁇ x ⁇ 100
  • y is 0 ⁇ y ⁇ 100.
  • x is preferably in the range of 1 ⁇ x ⁇ 90, and more preferably in the range of 1 ⁇ x ⁇ 50.
  • y is preferably in the range of 10 ⁇ y ⁇ 99, and more preferably in the range of 50 ⁇ y ⁇ 99.
  • the copolymerization ratio of the hydrophilic polymer (I) having a structure represented by the general formulas (I-1) and (I-2) is such that the amount of the general formula (I-2) having a hydrophilic group is within the above range.
  • the mass average molecular weight of the hydrophilic polymer (I) having a structure represented by the general formulas (I-1) and (I-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.
  • hydrophilic polymer (I) containing the structures represented by the general formulas (I-1) and (I-2) are shown below together with their mass average molecular weights (MW). The invention is not limited to these examples.
  • polymer of the specific example shown below means that each structural unit described is a random copolymer or block copolymer contained in the described molar ratio.
  • Each compound for synthesizing the hydrophilic polymer (I) having a structure represented by the general formulas (I-1) and (I-2) is commercially available or can be easily synthesized.
  • general radical polymerization methods include, for example, New Polymer Experiments 3 (1996, Kyoritsu Shuppan), Polymer Synthesis and Reaction 1 (Polymer Society of Japan, 1992, Kyoritsu Shuppan), New Experiment Chemistry Course 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Course, 1995, Tokyo Denki University Press) These can be applied.
  • hydrophilic polymer (II) having a structure represented by the following general formulas (II-1) and (II-2) may be used in combination with the hydrophilic polymer (I).
  • R 201 to R 205 each independently represents a hydrogen atom or a hydrocarbon group.
  • q represents an integer of 1 to 3
  • L 201 and L 202 each represents a single bond or a polyvalent organic linking group.
  • a 201 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , -OCON (R a ) (R b ), -NHCON (R a ) (R b ), -SO 3 R e , -OSO 3 R e , -SO 2 R d , -NHSO 2 R d , -SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • the hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) has a structural unit represented by the above general formula (II-2), and has a polymer chain. It preferably has a partial structure represented by the general formula (II-1) at the end thereof.
  • R 201 to R 205 each independently represents a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R 201 to R 205 represent a hydrocarbon group.
  • the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable.
  • L 201 and L 202 each independently represents a single bond or a polyvalent organic linking group.
  • the single bond means that the main chain of the polymer is directly bonded to the A 201 and Si atoms without a connecting chain.
  • L 201 and L 202 each represent a polyvalent organic linking group, specific examples and preferred examples thereof may be the same as those described for L 101 in the general formula (I-1).
  • a 201 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3
  • L 201 and L 202 are more preferably —CH 2 CH 2 CH 2 S—, —CH 2 S—, —CONHCH (CH 3 ) CH 2 —, —CONH—, —CO—, —CO 2 —, —CH 2 —.
  • the hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) is, for example, a chain transfer agent (radical polymerization handbook (NTS, Mikiji Tsunoike, Takeshi Endo) In the presence of Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). Can be synthesized.
  • a hydrophilic monomer eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate
  • chain transfer agents examples include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane.
  • a hydrophilic monomer eg, acrylamide
  • the hydrophilic polymer (II) having a structure represented by the general formulas (II-1) and (II-2) includes a radical polymerizable monomer represented by the following general formula (i) and a general formula (ii) ) Can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.
  • R 201 to R 205 , L 201 , L 202 , A 201 , and q have the same meanings as those in the general formula (II-1). These compounds are commercially available and can also be easily synthesized.
  • the radically polymerizable monomer represented by the general formula (i) has a hydrophilic group A201 , and this monomer becomes one structural unit in the hydrophilic polymer.
  • the number of moles of the structural unit of the general formula (II-1) having a hydrolyzable silyl group amount is preferably in the range of 1000 to 10 times, more preferably in the range of 500 to 20 times, and most preferably in the range of 200 to 30 times. If it is 30 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.
  • the mass average molecular weight of the hydrophilic polymer (II) having a structure represented by the general formulas (II-1) and (II-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.
  • hydrophilic polymer (II) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.
  • * represents a bonding position to the polymer.
  • the ratio (mass ratio) of the hydrophilic polymer (I) / hydrophilic polymer (II) is preferably 5/95. Is in the range of ⁇ 95 / 5, more preferably in the range of 40/60 to 95/5, and most preferably in the range of 60/40 to 90/10.
  • the hydrophilic polymer (I) may be a copolymer with another monomer.
  • examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.
  • acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphene Le acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate
  • methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxy Phenethyl methacrylate, dihydroxyphenethyl methacrylate
  • acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide.
  • methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.
  • vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.
  • styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.
  • the ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as the hydrophilic layer is sufficient, and the hydrophilic polymer (I) In order to sufficiently obtain the advantage of adding, it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of other monomers in the hydrophilic polymer (I) is preferably 80% by mass or less, and more preferably 50% by mass or less.
  • the measurement of the copolymerization ratio of the hydrophilic polymer (I) can be carried out by preparing a calibration curve with a nuclear magnetic resonance apparatus (NMR) or a standard substance and measuring with an infrared spectrophotometer.
  • NMR nuclear magnetic resonance apparatus
  • the hydrophilic composition in this invention can use hydrophilic polymer (I) individually or in mixture of 2 or more types. From the viewpoint of curability and hydrophilicity, the hydrophilic polymer (I) is preferably used in an amount of 20 to 99.5% by mass, preferably 30 to 99.5% by mass, based on the total solid content of the hydrophilic composition. More preferably.
  • the hydrophilic composition comprises 50% by mass or more of the hydrophilic polymer (I) containing the structure represented by the general formula (I-1) and the structure represented by the general formula (I-2) based on the total solid content. It is preferable to contain.
  • the hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (1) in an amount of 80% by mass or more based on the total solid content, and A in the general formula (I-2) 101 preferably represents —CONH 2 , —CONH (R 5 ), or —CON (R 5 ) 2 (wherein R 5 independently represents a linear, branched or cyclic alkyl group). .
  • the above-mentioned hydrophilic polymer (I) forms a crosslinked film in a state of being mixed with a hydrolyzed and polycondensed product of metal alkoxide.
  • the hydrophilic polymer (I) which is an organic component, is involved in film strength and film flexibility.
  • the viscosity of the hydrophilic polymer (I) is 0.1 to 100 mPa ⁇ s (5% aqueous solution, 20% When the temperature is in the range of 0.5 to 70 mPa ⁇ s, more preferably 1 to 50 mPa ⁇ s, good film properties can be obtained.
  • Crosslinking agent When the hydrophilic composition contains the hydrophilic polymer (II), it is preferable to contain a crosslinking agent in order to obtain good curability. In addition, in the case where the hydrophilic composition (I) is contained in the hydrophilic composition, good curability can be obtained even when the crosslinking agent is not contained, but in order to obtain a coating film having extremely excellent film strength. May contain a crosslinking agent.
  • an alkoxide compound (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al is particularly preferable.
  • a metal alkoxide is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a cross-linking agent, and has a cross-linked structure due to polycondensation of metal alkoxides.
  • a strong cross-linked film can be formed and further chemically bonded to the hydrophilic polymer.
  • the metal alkoxide can be represented by general formula (V-1) or general formula (V-2), in which R 20 represents a hydrogen atom, an alkyl group or an aryl group, and R 21 and R 22 represent an alkyl group or Represents an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0-2.
  • R 20 and R 21 represent an alkyl group
  • the carbon number is preferably 1 to 4.
  • the alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.
  • This compound is a low molecular compound and preferably has a molecular weight of 2000 or less.
  • the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ⁇ - Examples include chloropropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like.
  • trimethoxysilane particularly preferred are trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and the like.
  • Z is Ti, i.e., including titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl
  • Zr that is, the one containing zirconium can include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
  • central metal is Al
  • examples of those containing aluminum in the hydrolyzable compound include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate, and the like. be able to.
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are particularly preferable.
  • the metal alkoxide compound selected from Si, Ti, Zr, and Al is preferably used in an amount of 0 to 80% by mass based on the total solid content of the hydrophilic composition when the hydrophilic polymer (I) is used. More preferably, 0 to 70% by mass is used.
  • the hydrophilic polymer (II) is used, it is preferably used in an amount of 0 to 80% by weight, more preferably 0 to 70% by weight, based on the total solid content of the hydrophilic composition.
  • the hydrophilic polymer (I), more preferably the hydrophilic polymer (II), a crosslinking agent such as a crosslinking agent is dissolved in a solvent and stirred well, These components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, and this sol solution forms a hydrophilic film having high hydrophilicity and high film strength.
  • a catalyst in order to promote hydrolysis and polycondensation reaction. By using a catalyst, the drying temperature for forming the hydrophilic layer can be set low, and thermal deformation on the substrate can be suppressed.
  • a catalyst that promotes a reaction that causes hydrolysis and polycondensation of the crosslinking agent to cause a bond with the hydrophilic polymers (I) and (II) is selected.
  • a compound in which an acid or a basic compound is dissolved in a solvent such as water or alcohol (hereinafter collectively referred to as an acidic catalyst and a basic catalyst, respectively) is used.
  • the concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like.
  • the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase.
  • a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.
  • the type of acidic catalyst or basic catalyst is not particularly limited. However, when it is necessary to use a highly concentrated catalyst, a catalyst composed of an element that hardly remains in the coating film after drying is preferable.
  • the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH.
  • the basic catalyst include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, and the like. Etc.
  • a Lewis acid catalyst comprising a metal complex
  • metal complex catalysts metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and ⁇ -diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, enolic active hydrogen compounds It is a metal complex comprised from the oxo or hydroxy oxygen containing compound chosen from these.
  • 2A group elements such as Mg, Ca, Sr and Ba
  • 3B group elements such as Al and Ga
  • 4A group elements such as Ti and Zr
  • 5A group elements such as V, Nb and Ta are preferable.
  • the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a ⁇ -diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetate Ketoesters such as ethyl and butylacetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone , 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-heptanone, ketoalcohols such as 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl- Monoethanolamine, diethanolamine Amino alcohols such as ethanol, triethanolamine, enol active
  • a preferred ligand is acetylacetone or an acetylacetone derivative.
  • the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone.
  • Substituents for substitution on the methyl group of acetylacetone are all straight-chain or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone
  • the substituents that substitute for the methylene group are carboxyl groups, both straight-chain or branched carboxyalkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms, and the substituents that substitute for the carbonyl carbon of acetylacetone are carbon atoms.
  • acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol. Of these, acetylacetone and diacetylacetone are particularly preferred.
  • the complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which 1 to 4 molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is the coordinateable bond of the metal element.
  • ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate.
  • Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc.
  • ethyl acetoacetate aluminum diisopropylate aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.
  • the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used.
  • nitrate nitrate
  • Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used.
  • the metal complex takes a coordination structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst.
  • this metal complex has led to the improvement of coating solution aging stability and film surface quality, high hydrophilicity, and high durability.
  • the catalyst is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the total solid content in the hydrophilic composition of the present invention. Moreover, a catalyst may be used independently or may be used together 2 or more types.
  • [Other additives] In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, and tackiness within a range that does not impair hydrophilicity in order to improve adhesion to the substrate. A fire etc. can be contained.
  • the tackifier specifically, a high molecular weight adhesive polymer (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms) described in JP-A-2001-49200, 5-6p.
  • a surfactant is preferably used in order to improve the surface state of the hydrophilic composition and the undercoat layer composition.
  • the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a fluorine surfactant.
  • the nonionic surfactant used in the present invention is not particularly limited, and conventionally known nonionic surfactants can be used.
  • nonionic surfactants can be used.
  • polyoxyethylene alkyl ethers polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalky
  • the anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used.
  • anionic surfactants can be used.
  • the cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
  • the amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.
  • polyoxyethylene can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.
  • More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule.
  • fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group.
  • fluorine-based surfactants described in JP-A Nos. 62-170950, 62-226143, and 60-168144 are also preferred.
  • the surfactant is used in the hydrophilic composition of the present invention in an amount of preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content.
  • surfactant can be used individually or in combination of 2 or more types.
  • the hydrophilic composition of the present invention may contain inorganic fine particles in order to improve the cured film strength and hydrophilicity of the hydrophilic film to be formed.
  • the inorganic fine particles for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
  • the inorganic fine particles preferably have an average particle diameter of 5 nm to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m. Within the above range, it is possible to form a film that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and is excellent in hydrophilicity.
  • the inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
  • the inorganic fine particles according to the present invention are used in the hydrophilic composition of the present invention in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the total solid content.
  • the inorganic fine particles can be used alone or in combination of two or more.
  • an antioxidant can be added to the hydrophilic composition.
  • the antioxidant include European Published Patent No. 223739, No. 309401, No. 309402, No. 310551, No. 310552, No. 4594416, German Published Patent No. 3435443. JP, 54-85535, 62-262447, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
  • the addition amount is appropriately selected according to the purpose, but is preferably 0.1 to 8% by mass in terms of solid content.
  • Polymer compound In order to adjust the film properties of the hydrophilic layer, various polymer compounds can be added to the hydrophilic composition of the present invention as long as the hydrophilicity is not inhibited.
  • High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin, rubber resin Waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymers obtained by copolymerization of acrylic monomers are preferred.
  • a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.
  • the hydrophilic member in this invention has a hydrophilic layer formed with the said hydrophilic composition on the base material chosen from acrylic, polycarbonate, polyester, stainless steel, aluminum, etc., for example.
  • the hydrophilic member of the present invention has a hydrophilic layer formed by coating a hydrophilic composition on a substrate, and the hydrophilic composition is the hydrophilic composition described above. It is possible to provide a hydrophilic member that has excellent hydrophilicity, friction resistance, antifouling property, and adhesion and can maintain excellent lubricity for a long period of time.
  • the hydrophilic member of the present invention may further have an undercoat layer between the base material and the hydrophilic layer in order to improve the adhesion between the base material and the hydrophilic layer.
  • the undercoat layer is preferably formed by applying the above-described composition containing the catalyst, thereby further improving the adhesion between the substrate and the hydrophilic layer.
  • the catalyst is preferably a non-volatile catalyst as described above.
  • the catalyst is used in the composition for an undercoat layer in an amount of preferably 0 to 50% by mass, more preferably 1 to 25% by mass, based on the total solid content.
  • a catalyst may be used independently or may be used together 2 or more types.
  • the undercoat layer is preferably formed by applying a composition containing the above-described crosslinking agent, and thereby, more reliably, adhesion between the substrate and the hydrophilic layer. Can be improved.
  • the crosslinking agent is preferably used in the range of 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total solid content in the composition for the undercoat layer.
  • a crosslinking agent may be used independently or may be used together 2 or more types.
  • the hydrophilic composition and the composition for the undercoat layer may contain zirconia chloride, nitrate, alkoxide, and organic complex from the viewpoints of wear resistance, acid resistance, and alkali resistance.
  • zirconium nitrate include zirconium oxynitrate (dihydrate).
  • zirconium alkoxide examples include zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium t-butoxide and the like.
  • organic complex examples include acetylacetone derivatives.
  • the zirconium compound is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the total solid content in the hydrophilic composition and the composition for the undercoat layer of the present invention.
  • a hydrophilic layer can be formed by applying such a hydrophilic composition onto a suitable substrate and drying. That is, the hydrophilic member of the present invention has a hydrophilic layer formed by applying a hydrophilic composition on a substrate, heating and drying.
  • the hydrophilic member of the present invention comprises a hydrophilic polymer (I) having a structure in which the hydrophilic layer is represented by the general formula (I-1) and the structure represented by the general formula (I-2).
  • the drying temperature is preferably 100 to 230 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure, More preferably, the temperature is 130 to 200 ° C.
  • the drying time is preferably 5 seconds to 1 hour. More preferably, it is 10 seconds to 30 minutes. If the drying time is short, the coating strength may be lowered due to insufficient drying. If the drying time is excessively longer than necessary, the substrate may deteriorate.
  • the hydrophilic member of the present invention can be prepared by a known coating method, and is not particularly limited.
  • a spray coating method for example, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a film applicator method.
  • Methods such as screen printing, bar coater, brush coating, and sponge coating can be applied.
  • the center line average roughness Ra of the surface of the hydrophilic layer is preferably 10 nm to 100 nm.
  • the Tg of the hydrophilic layer is preferably 40 ° C. to 150 ° C. from the viewpoint of coating film strength.
  • the elastic modulus of the hydrophilic layer is preferably 1 GPa to 7 GPa.
  • the surface property of the hydrophilic layer adjusts the particle size and content of the inorganic fine particles used, the surface roughness of the substrate itself, the viscosity of the hydrophilic composition, the heating temperature of the hydrophilic layer, the speed, and the like. However, the present invention is not limited to this.
  • An intermediate layer may be provided between the base material and the hydrophilic layer as necessary for improving adhesion.
  • an intermediate layer may be provided between the aluminum plate and the hydrophilic layer for the purpose of improving the anticorrosion property and adhesion to the substrate.
  • the intermediate layer is not particularly limited. Hydrophilic layers having different compositions may be provided, or a known anticorrosion layer represented by a chromate system may be provided.
  • the hydrophilicity of the surface of the hydrophilic layer is generally measured by the water droplet contact angle.
  • the water droplet contact angle may be 10 ° C. or less, and there is a limit to the mutual comparison of the hydrophilicity.
  • there is a measurement of surface free energy As a method for evaluating the hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method.
  • the horizontal axis indicates the surface of the aqueous solution.
  • hydrophilic composition was prepared by dissolving a hydrophilic polymer having a hydrolyzable silyl group, a crosslinking agent, a catalyst, a surfactant and a specific alkoxide in a solvent such as ethanol and then stirring. Can be implemented.
  • the reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued is preferably in the range of 1 to 72 hours.
  • a composite sol solution can be obtained.
  • the solvent used in preparing the hydrophilic composition is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, an aqueous solvent such as methanol, ethanol, water or the like is preferable.
  • the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming the hydrophilic layer from the hydrophilic composition of the present invention utilizes the sol-gel method.
  • sol-gel method Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha Co., Ltd. (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic composition in the present invention.
  • the lubricating layer in the present invention has a friction coefficient of 0.05 to 0 provided on a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate. .25 is a lubricating layer.
  • the friction coefficient of the lubricating layer is preferably 0.06 to 0.24, and more preferably 0.08 to 0.22.
  • the coefficient of friction is not particularly limited, but can be measured by a known method using a Bowden-Leven type friction tester.
  • the lubricant layer can be formed of a lubricant composition.
  • the lubricant contained in the lubricant composition includes nonionic hydrophilic properties such as polyethylene glycol (PEG) and polypropylene glycol (PPG), or copolymers thereof.
  • a polymer or a surfactant can be mentioned, and preferably polyethylene glycol (PEG) or polypropylene glycol, or a copolymer polymer thereof, more preferably polyethylene glycol or polypropylene glycol. These may be used alone or in combination.
  • polyethylene glycol or polypropylene glycol it is possible to impart lubricity without impairing the hydrophilicity of the hydrophilic layer.
  • the molecular weight of the lubricant is preferably 200 to 10,000, more preferably 400 to 6000, and still more preferably 1000 to 4000. If it exists in this range, it is preferable from the reason that the lubricity robustness and the hydrophilic property of a hydrophilic layer are not impaired.
  • a commercially available lubricant may be used, and it may be synthesized by a known method. When polyethylene glycol or polypropylene glycol is used as the lubricant, it can be obtained from a commercial product.
  • the content of the lubricant in the lubricant composition is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, and 0.5 to 10% by mass. Further preferred.
  • the lubricant composition preferably further contains a surfactant.
  • Preferred examples of the surfactant used in the lubricant composition include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorine surfactants. Is a nonionic surfactant, an anionic surfactant, or a cationic surfactant, more preferably a nonionic surfactant or an anionic surfactant. Specifically, the above-described surfactant can be used.
  • the content of the surfactant in the lubricant composition is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and more preferably 0.5 to 5% with respect to the hydrophilic polymer. More preferably, it is mass%.
  • the lubricant composition preferably further contains a solvent.
  • a solvent used in the lubricant composition, water and alcohols such as methanol, ethanol and propanol can be preferably used, and water is more preferable.
  • the content of the solvent in the lubricant composition is preferably 50 to 99.99% by mass, more preferably 80 to 99.9% by mass, and further preferably 90 to 99.5% by mass. preferable.
  • Lubricant composition can also be prepared by the same method as the above hydrophilic composition.
  • the hydrophilic member of the present invention can be obtained by applying the lubricant composition of the present invention on the hydrophilic layer and drying it. That is, the hydrophilic member of the present invention is formed by applying a hydrophilic composition on a substrate, heating and drying to form a hydrophilic layer, applying a lubricant composition thereon, heating and drying. Thus, it is obtained by forming a lubricating layer.
  • the heating and drying conditions of the lubricant composition are preferably about 5 seconds to 1 hour in the temperature range of 100 to 230 ° C., and 10 to 10 in the temperature range of 130 to 200 ° C. from the viewpoint of decomposition and evaporation. It is more preferable to dry for 2 to 30 minutes.
  • a heating means of the lubricant composition and the hydrophilic composition it is preferable to use a known means, for example, a dryer having a temperature adjusting function.
  • composition for undercoat layer can also be prepared by the same method as the above hydrophilic composition.
  • the hydrophilic member of the present invention may have an undercoat layer by applying a composition for an undercoat layer on a substrate as necessary, and heating and drying.
  • the heating and drying conditions for the undercoat layer composition are preferably about 2 minutes to 1 hour in the temperature range of 50 to 200 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure, It is more preferable to dry in the temperature range of 160 ° C. for 5 to 30 minutes.
  • a heating means of the undercoat composition it is preferable to use a known means, for example, a dryer having a temperature adjusting function.
  • the catalyst when the hydrophilic layer and the undercoat layer are applied on the substrate, the catalyst can be mixed immediately before the application to the substrate. Specifically, the coating is preferably performed immediately after mixing the catalyst to within 1 hour. When the catalyst is mixed and left to stand for a long time, the composition of the undercoat layer or the hydrophilic composition increases in viscosity, which may cause defects such as coating unevenness. Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.
  • the substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, tile, rubber, latex, combinations thereof, those Any laminate can be suitably used.
  • Particularly preferred substrates are flexible flexible substrates such as plastics and metals.
  • the plastic substrate used in the present invention is not particularly limited, but the substrate used as an optical member is selected in consideration of optical characteristics such as transparency, refractive index, dispersibility, and the like, It is selected in consideration of various physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance, and durability.
  • Plastic base materials include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, poly Examples thereof include films or sheets of sulfone, polyether ketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred.
  • the thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having a thickness of about 6 to 50 ⁇ m is used. Further, 50 to 400 ⁇ m is used for a flat surface or where strength is required.
  • one or both surfaces of the base material can be subjected to surface hydrophilization treatment by an oxidation method, a roughening method, or the like as desired.
  • the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
  • a roughening method it can also be mechanically roughened by sandblasting, brush polishing or the like.
  • the plastic substrate a material in which an inorganic compound layer described in the following description of the glass plate is formed on the plastic plate can also be used.
  • the inorganic compound layer can also act as an antireflection layer. Even when the inorganic compound layer is formed on the plastic plate, it can be formed by the same method as in the inorganic base material described above.
  • a hard coat layer may be formed between both layers.
  • the hardness of the substrate surface is improved and the substrate surface is smoothed, so the adhesion between the transparent plastic substrate and the inorganic compound layer is improved, and the scratch resistance is improved, Generation of cracks in the inorganic compound layer due to bending of the substrate can be suppressed.
  • the mechanical strength of the hydrophilic member can be improved.
  • the material of the hard coat layer is not particularly limited as long as it has transparency, appropriate strength, and mechanical strength.
  • a curable resin or a thermosetting resin by irradiation with ionizing radiation or ultraviolet rays can be used, and an ultraviolet irradiation curable acrylic resin, an organosilicon resin, or a thermosetting polysiloxane resin is particularly preferable.
  • the refractive index of these resins is more preferably equal to or close to the refractive index of the transparent plastic substrate.
  • Such a coating method of the hard coat layer is not particularly limited, and any method can be adopted as long as it is uniformly applied.
  • the hard coat layer having a thickness of 3 ⁇ m or more has sufficient strength, but is preferably in the range of 5 to 7 ⁇ m from the viewpoint of transparency, coating accuracy, and handling.
  • a light diffusing treatment generally called anti-glare can be performed. These particles are not particularly limited as long as they are transparent, but a low refractive index material is preferable, and silicon oxide and magnesium fluoride are particularly preferable in terms of stability, heat resistance, and the like.
  • the light diffusing treatment can also be achieved by providing irregularities on the surface of the hard coat layer.
  • an aluminum plate is particularly preferable.
  • the aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of different elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy.
  • foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.
  • the content of foreign elements in the alloy is preferably 10% by mass or less.
  • a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element.
  • the composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.
  • the thickness of the base material is preferably 0.05 to 0.6 mm, and more preferably 0.08 to 0.2 mm.
  • a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.
  • the processing method of an aluminum base material can be performed by a well-known method.
  • the base material used in the present invention may be a base material that has been surface-treated as described above and has an anodized film as it is.
  • the micropore enlargement treatment or sealing treatment of the anodized film and the surface hydrophilization treatment soaked in an aqueous solution containing a hydrophilic compound described in Japanese Patent No. 253181 and Japanese Patent Application Laid-Open No. 2001-322365 are appropriately selected. It can be carried out.
  • the enlargement process and the sealing process are not limited to those described above, and any conventionally known method can be performed.
  • the sealing treatment in addition to the vapor sealing, a single treatment with fluorinated zirconic acid, a treatment with sodium fluoride, or a vapor sealing with addition of lithium chloride is possible.
  • the sealing treatment used in the present invention is not particularly limited, and a conventionally known method can be used. Among them, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and heat Sealing with water is preferred. Each will be described below.
  • the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound include metal fluorides.
  • metal fluorides Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluorinated titanate, fluorinated zirconic acid, fluorinated titanic acid, hexafluorosilicic acid, nickel fluoride, iron fluoride, fluorinated phosphoric acid, and ammonium fluorinated phosphate.
  • sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.
  • the concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.
  • the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound.
  • Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals. Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphate
  • sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
  • the combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.
  • the concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving stain resistance, In this respect, it is preferably 20% by mass or less, and more preferably 5% by mass or less.
  • the ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
  • the temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • the aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
  • the method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more. Of these, the dipping method is preferred.
  • the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, and preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.
  • the sealing treatment with water vapor includes, for example, a method in which pressurized or normal pressure water vapor is brought into contact with the anodized film continuously or discontinuously.
  • the temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
  • the pressure of water vapor is preferably in the range (1.00 ⁇ 10 5 to 1.043 ⁇ 10 5 Pa) from (atmospheric pressure ⁇ 50 mmAq) to (atmospheric pressure + 300 mmAq).
  • the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.
  • sealing treatment with hot water examples include a method of immersing an aluminum plate on which an anodized film is formed in hot water.
  • the hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
  • the temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
  • the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.
  • hydrophilization treatment As the hydrophilization treatment, U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734 are used. There are alkali metal silicate methods as described. In this method, the substrate is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.
  • the substrate preferably has a center line average roughness of 0.10 to 1.2 ⁇ m. Within this range, good adhesion to the undercoat layer and good stain resistance can be obtained.
  • glass plate used in the present invention examples include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO Metal oxides such as (Indium Tin Oxide); Inorganic compound layers formed of metal halides such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; Glass plates can be mentioned.
  • the undercoat layer and the overcoat layer can be coated with the base glass as it is, but if necessary, for the purpose of improving the adhesion of the undercoat layer and the overcoat layer, on one side or both sides by an oxidation method or a roughening method, etc. Surface hydrophilization treatment can be performed.
  • Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
  • a roughening method it can also be mechanically roughened by sandblasting, brush polishing or the like.
  • the inorganic compound layer can have a single layer structure or a multilayer structure. Depending on the thickness of the inorganic compound layer, the light transmittance can be maintained, and the inorganic compound layer can also function as an antireflection layer.
  • the inorganic compound layer forming method include dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method, etc., vacuum deposition method, reactive deposition method, ion beam
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition method
  • hydrophilic resins include polyvinyl alcohol (PVA), cellulose resins [methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins, chitosans, starch, and ether bonds.
  • PVA polyvinyl alcohol
  • cellulose resins [methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.
  • chitins chitosans, starch, and ether bonds.
  • examples thereof include resins [polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), etc.], and the like.
  • PAAM polyacrylamide
  • PVP polyvinyl pyrrolidone
  • the polyacrylic acid salt which has a carboxyl group, maleic
  • At least one selected from a polyvinyl alcohol resin, a cellulose resin, a resin having an ether bond, a resin having a carbamoyl group, a resin having a carboxyl group, and gelatin is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.
  • PVA polyvinyl alcohol
  • water-dispersible latex examples include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
  • the above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
  • a cross-linking agent applicable to the present invention a cross-linking agent that forms a cross-link by known heat can be used.
  • General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981).
  • the number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex.
  • thermal crosslinking agent examples include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene ethylene glycol diglycidyl ether, polyethylene or Polyepoxy compounds such as polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal, terephthalaldehyde, Range isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate Polyisocyanate compounds such as cyanate, polymethylene polyphenyl
  • a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
  • the total amount of the hydrophilic resin and / or water-dispersible latex in the undercoat layer is preferably 0.01 to 20 g / m 2 and more preferably 0.1 to 10 g / m 2 .
  • Layer structure when using hydrophilic member When the hydrophilic member of the present invention is used in anticipation of the appearance of antifouling properties and / or antifogging effects, another layer is appropriately formed according to the purpose, form and place of use. Can be used. The layer structure added as needed is described below.
  • a pressure-sensitive adhesive that is a pressure-sensitive adhesive is preferably used as an adhesive layer on the back surface of the substrate.
  • an adhesive what is generally used for an adhesive sheet, such as a rubber adhesive, an acrylic adhesive, a silicone adhesive, a vinyl ether adhesive, and a styrene adhesive, can be used.
  • an adhesive for optical use is selected.
  • a pattern such as coloring, semi-transparency, or matte is required, in addition to the patterning on the substrate, a dye, organic or inorganic fine particles can be added to the adhesive to produce an effect.
  • a resin for example, a rosin-based resin, a terpene-based resin, a petroleum-based resin, a styrene-based resin, or an adhesion-imparting resin such as a hydrogenated product thereof can be used alone or in combination.
  • the adhesive strength of the pressure-sensitive adhesive used in the present invention is generally called strong adhesion, and is 200 g / 25 mm or more, preferably 300 g / 25 mm or more, more preferably 400 g / 25 mm or more.
  • the adhesive force here is based on JIS Z 0237 and is a value measured by a 180 degree peel test.
  • a release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. In order to give mold release properties to the mold release layer, it is preferable to contain a mold release agent.
  • a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used.
  • various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other acrylic-silicone copolymer Resin, acrylic-fluorine-based copolymer resin, and copolymer-based resin such as urethane-silicone-fluorine-based copolymer resin, resin blend of silicone-based resin and acrylic resin, and fluorine-based resin and acrylic-based resin A resin blend is used.
  • a protective layer may be provided on the hydrophilic layer.
  • the protective layer has a function of preventing damage to the hydrophilic surface during handling, transportation, storage, and the like, and deterioration of hydrophilicity due to adhesion of dirt substances.
  • the hydrophilic polymer layer used in the release layer can be used as the protective layer.
  • the protective layer is peeled off after the hydrophilic member is attached to an appropriate substrate.
  • the hydrophilic member having the hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll or a ribbon, and may be cut in advance to be attached to an appropriate substrate. It can also be supplied.
  • the hydrophilic layer of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired and compatibility with durability is possible.
  • the thickness of the hydrophilic layer of the present invention is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, and most preferably 0.1 ⁇ m to 20 ⁇ m.
  • the dry coating amount of the hydrophilic layer is preferably 0.01 g / m 2 to 100 g / m 2 , more preferably 0.02 g / m 2 to 80 g / m 2 , particularly preferably 0.05 g / m 2 to 50 g / m.
  • the thickness of the lubricating layer is preferably 0.001 ⁇ m to 1 ⁇ m, more preferably 0.005 ⁇ m to 0.5 ⁇ m, and most preferably 0.1 ⁇ m to 0.3 ⁇ m.
  • the film thickness is 0.001 ⁇ m or more, sufficient hydrophilicity and durability can be obtained, and when the film thickness is 1 ⁇ m or less, there is no problem in film forming properties such as cracking, which is preferable.
  • the dry coating amount of the lubricating layer is 0.001g / m 2 ⁇ 1g / m 2, more preferably 0.005g / m 2 ⁇ 0.5g / m 2, and most preferably 0.01g / m 2 ⁇ 0.
  • the thickness of the undercoat layer is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.02 ⁇ m to 80 ⁇ m, and particularly preferably 0.05 ⁇ m to 50 ⁇ m.
  • the dry coating amount of the undercoat layer composition is preferably 0.01 g / m 2 to 100 g / m 2 , more preferably 0.02 g / m 2 to 80 g / m 2 , particularly preferably 0.05 g / m 2 to 50 g / m 2. with m 2, it is possible to obtain a film thickness of the.
  • Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer.
  • the light transmittance is preferably from 100% to 70%, more preferably from 95% to 75%, and most preferably from 95% to 80%.
  • the hydrophilic member provided with a hydrophilic layer can be applied to various applications without obstructing the field of view.
  • the hydrophilic member of the present invention applies the hydrophilic composition and, if necessary, the composition for the undercoat layer onto an appropriate substrate, and is heated and dried to form a hydrophilic layer.
  • the lubricant composition is applied thereon, heated and dried to form a lubricating layer having a friction coefficient of 0.05 to 0.25.
  • a known coating method can be employed as a method for applying the undercoat layer composition, the hydrophilic composition, and the lubricant composition.
  • a known coating method can be employed as a known coating method. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film Applicator methods, screen printing methods, bar coater methods, brush coating, sponge coating, and the like can be applied.
  • the hydrophilic member of the present invention can be applied, for example, in the case of expecting an antifogging effect, such as a transparent glass substrate or a transparent plastic substrate, a lens, a prism, a mirror, etc. is there.
  • a transparent glass substrate or a transparent plastic substrate such as soda glass, lead glass and borosilicate glass
  • any glass such as soda glass, lead glass and borosilicate glass may be used.
  • float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, crime prevention glass, high heat insulation Low-E double-glazed glass should be used. Can do.
  • Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; other glass for building materials; Ropeway gondola, amusement park gondola, various vehicle windows; automobiles, rail cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, various vehicle windshields Glass; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Las; cover glass measuring instruments, and films to be attached to the article surface. The most preferred application is glass for automobiles and building materials.
  • the base material is, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, in addition to glass and plastic, Any of paper, combinations thereof, and laminates thereof can be suitably used.
  • Applications with antifouling components include building materials, building exteriors such as exterior walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, bicycles, motorcycles Exterior and painting of such vehicles, machinery and equipment exteriors, dust covers and coatings, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and coatings, tunnel interiors And paint, insulators, solar battery covers, solar water heater heat collector covers, greenhouses, vehicle lighting cover, housing equipment, toilets, bathtubs, sinks, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers A dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film to be attached to the surface of the article.
  • the base material may be, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric in addition to glass and plastic.
  • Paper, combinations thereof, and laminates thereof can be suitably used.
  • Applications that can be applied to members that have a quick-drying effect such as water include building materials, building exteriors such as outer walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, and bicycles.
  • Exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and equipment, dustproof covers and paintings, traffic signs, various display devices, advertising towers, soundproof walls for roads, soundproof walls for railways, bridges, guardrails and paints , Tunnel interior and painting, insulator, solar battery cover, solar water heater heat collection cover, plastic house, vehicle lighting cover, housing equipment, toilet, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, It includes a dishwasher, a dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film for application to the surface of the article.
  • the hydrophilic member according to the present invention is preferably a fin material, and is preferably a fin material having an aluminum fin main body. That is, the fin material of the present invention is a fin material comprising a fin main body (preferably an aluminum fin main body) and a hydrophilic layer provided on at least a part of the surface of the fin main body. Is formed by coating the hydrophilic composition according to the present invention.
  • Aluminum fin material (aluminum fin body itself) used in heat exchangers such as indoor air conditioners and automobile air conditioners causes water droplets to form as water droplets and stay between the fins, resulting in water bridges. Ability is reduced.
  • the adhering of dust or the like between the fins similarly reduces the cooling capacity.
  • the fin material in which the composition for forming a hydrophilic film of the present invention is applied to the fin body provides a fin material excellent in hydrophilicity, antifouling property, and sustainability thereof. It is done.
  • the fin material according to the present invention preferably has a water contact angle of 40 ° or less after 5 cycles of 1-hour aeration, 30-minute water washing, and 30-minute drying of palmitic acid.
  • Examples of the aluminum used for the fin body of the fin material include those having a degreased surface and, if necessary, a chemically treated aluminum plate. It is preferable that the surface of the fin body made of aluminum is subjected to a chemical conversion treatment in terms of adhesion of the hydrophilic treatment film, corrosion resistance, and the like.
  • Examples of the chemical conversion treatment include chromate treatment, and typical examples thereof include alkali salt-chromate method (BV method, MBV method, EW method, Al And a treatment method such as a chromic acid method, a chromate method, and a chromic phosphate method, and an anhydrous washing coating type treatment with a composition mainly composed of chromium chromate.
  • pure aluminum plate such as 1100, 1050, 1200, 1N30, Al—Cu based alloy plate such as 2017, 2014, 3003, Any of Al-Mn alloy plates such as 3004, Al-Mg alloy plates such as 5052 and 5083, and Al-Mg-Si alloy plates such as 6061 may be used. Any of the coils may be used.
  • the fin material which concerns on this invention for a heat exchanger. Since the heat exchanger using the fin material according to the present invention has excellent hydrophilicity, antifouling property and durability thereof, it is possible to prevent water droplets and dust from adhering between the fins. it can.
  • the heat exchanger include heat exchangers used for indoor coolers, air conditioners, construction machine oil coolers, automobile radiators, capacitors, and the like.
  • the heat exchanger using the fin material according to the present invention for an air conditioner Since the fin material according to the present invention has excellent hydrophilicity, antifouling property and sustainability thereof, it is possible to provide an air conditioner in which problems such as a decrease in cooling capacity as described above are improved.
  • the air conditioner may be any one of a room air conditioner, a packaged air conditioner, a car air conditioner, and the like.
  • publicly known techniques for example, JP 2002-106882 A, JP 2002-156135 A, etc.
  • JP 2002-106882 A, JP 2002-156135 A, etc. can be used for the heat exchanger and the air conditioner of the present invention, and are not particularly limited.
  • the heat exchanger fin material has a hydrophilic layer formed by applying and drying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on the surface of an aluminum plate. And applying a lubricant composition containing at least one substance selected from the group consisting of polyethylene glycol and polypropylene glycol, and drying to adsorb or impregnate the lubricant composition in the hydrophilic layer.
  • the drying temperature of the hydrophilic composition and the lubricant composition is preferably 130 to 230 ° C.
  • ⁇ Aluminum base degreasing treatment> An aluminum plate (A1200, thickness 0.1 mm) was immersed in an alkaline cleaning liquid (Yokohama Yushi Co., Ltd., Semi-clean A 5 mass% aqueous solution) for 10 minutes, and washing with water was repeated three times.
  • an alkaline cleaning liquid Yokohama Yushi Co., Ltd., Semi-clean A 5 mass% aqueous solution
  • the mass average molecular weight of the polymer B determined by GPC was 11,000. Thereafter, the polymers B-2 to B-3 used in the examples were synthesized by the same method as described above. The structures of the polymers B-1 to B-3 are shown below.
  • Examples 1 to 42 and Comparative Examples 1 to 11 ⁇ Hydrophilic composition> As shown in Tables 1 to 3 below, a hydrophilic polymer was dissolved in pure water, a catalyst solution was added and stirred for 2 hours, and an aqueous surfactant solution was added and stirred. In Tables 1 to 3, the amounts of the surfactant and the catalyst are the amounts excluding the solvent.
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PPG polyacrylamide
  • a hydrophilic composition was applied to a degreased aluminum plate with a # 8 bar, and heated and dried at the temperatures shown in Tables 1 to 3 for 15 seconds to form a hydrophilic layer. Further, the lubricant composition was applied thereon with a # 3 bar and heated and dried at the temperatures shown in Tables 1 to 3 for 15 seconds to form a lubricating layer, which was used as a test piece.
  • the drying temperatures in Tables 1 to 3 are the drying temperatures of both the hydrophilic layer and the lubricating layer, and when there is no lubricating layer, the drying temperature of only the hydrophilic layer.
  • the film thicknesses in Tables 1 to 3 were calculated by cutting the test piece and observing the cross section with SEM. [Evaluation] The obtained test piece was evaluated as follows. The evaluation results are shown in Tables 4 to 6 below. ⁇ Surface shape> Since there was no problem in any of the hydrophilic layers, the coated surface shape of only the lubricating layer was confirmed by visual observation.
  • hydrophilic polymers A-6 to A-8 used in Comparative Examples and the catalyst solutions and surfactant aqueous solutions used in Examples and Comparative Examples are shown in Tables 1 to 3.
  • Catalyst 1 1.8 g of ethanol, 0.1 g of acetylacetone, 0.1 g of tetraethoxytitanium and 0.015 g of distilled water were mixed and prepared by stirring for 1 hour.
  • Catalyst 2 Zircozole ZA-30 (ZrO (C 2 H 3 O 2 ) 2 aqueous solution, manufactured by Daiichi Rare Elemental Chemical Co., Ltd.)
  • Catalyst 3 Orgatechs TC-310 ((OH) 2 Ti [OCH (CH 3 ) COOH] 2 aqueous solution, manufactured by Matsumoto Kosho Co., Ltd.)
  • hydrophilic member of the present invention is excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention properties.
  • a hydrophilic member excellent in hydrophilicity, antifouling property, lubricity, adhesion, and rust prevention property and heat excellent in hydrophilicity, antifouling property, friction resistance, adhesion property, and rust prevention property The manufacturing method of the fin material for exchangers can be provided.

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Abstract

L'invention porte sur un élément hydrophile présentant une excellente hydrophilie, d'excellentes propriétés anti-salissures, une excellente capacité de lubrification, une excellente adhérence et d'excellentes propriétés d'anti-oxydation. L'invention porte également sur un procédé pour produire un matériau mince pour échangeurs de chaleur présentant une excellente hydrophilie, d'excellentes propriétés anti-salissures, une excellente capacité de lubrification, une excellente adhérence et d'excellentes propriétés d'anti-oxydation. L'élément hydrophile est caractérisé en ce qu'une couche hydrophile, qui est formée à partir d'une composition hydrophile contenant un polymère hydrophile possédant un groupe silyle hydrolysable, est disposée sur une base, et en ce qu'une couche lubrifiante présentant un coefficient de frottement de 0,05 à 0,25 est disposée sur la couche hydrophile. Le procédé pour produire un matériau mince pour échangeurs de chaleur est caractérisé en ce que la surface d'un matériau mince pour échangeurs de chaleur, qui comprend une couche hydrophile qui est formée par revêtement d'une surface de plaque d'aluminium avec une composition hydrophile contenant un polymère hydrophile possédant un groupe silyle hydrolysable, puis séchage du revêtement sur celle-ci, est revêtue par une composition lubrifiante, après quoi le revêtement est séché sur celle-ci de telle sorte que la composition lubrifiante est adsorbée sur la couche hydrophile ou imprègne l'intérieur de celle-ci, de façon à former ainsi une couche lubrifiante présentant un coefficient de frottement de 0,05 à 0,25.
PCT/JP2009/071262 2009-01-05 2009-12-21 Élément hydrophile et procédé pour produire un matériau mince pour échangeurs de chaleur Ceased WO2010076872A1 (fr)

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JP6374219B2 (ja) * 2014-05-23 2018-08-15 三菱アルミニウム株式会社 熱交換器用フィン材及びその製造方法
KR101528708B1 (ko) * 2014-09-02 2015-06-16 한양대학교 산학협력단 초발수 특성을 갖는 열교환기 및 그 제조방법
US10503063B2 (en) 2014-09-01 2019-12-10 Industry-University Cooperation Foundation Hanyang University Super water repellent polymer hierarchical structure, heat exchanger having super water repellency, and manufacturing method therefor
JP6717659B2 (ja) * 2015-07-06 2020-07-01 株式会社神戸製鋼所 樹脂被覆金属板、樹脂組成物、熱交換器用フィン材及び空調機
WO2017006878A1 (fr) * 2015-07-06 2017-01-12 株式会社神戸製鋼所 Plaque de métal revêtue de résine, composition de résine, matériau d'ailette pour échangeur de chaleur, et conditionneur d'air
JP6558337B2 (ja) 2016-09-30 2019-08-14 ブラザー工業株式会社 オーバーコート剤及び画像形成方法
JP6555536B2 (ja) 2016-09-30 2019-08-07 ブラザー工業株式会社 オーバーコート剤及び画像形成方法
JP7108925B2 (ja) * 2018-08-29 2022-07-29 パナソニックＩｐマネジメント株式会社 防汚被覆膜が形成された熱交換器
JP7651361B2 (ja) 2021-04-09 2025-03-26 株式会社神戸製鋼所 アルミニウム製フィン材

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JPH0639347A (ja) * 1992-07-24 1994-02-15 Showa Alum Corp 熱交換器用プレコート・フィン材の製造法
JPH0914888A (ja) * 1995-06-30 1997-01-17 Kobe Steel Ltd アルミニウムフィン及びその製造方法
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