WO2009119605A1 - Elément hydrophile - Google Patents

Elément hydrophile Download PDF

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Publication number
WO2009119605A1
WO2009119605A1 PCT/JP2009/055854 JP2009055854W WO2009119605A1 WO 2009119605 A1 WO2009119605 A1 WO 2009119605A1 JP 2009055854 W JP2009055854 W JP 2009055854W WO 2009119605 A1 WO2009119605 A1 WO 2009119605A1
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Prior art keywords
hydrophilic
group
layer
composition
hydrophilic polymer
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PCT/JP2009/055854
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English (en)
Japanese (ja)
Inventor
智史 田中
純明 山崎
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富士フイルム株式会社
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Publication of WO2009119605A1 publication Critical patent/WO2009119605A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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

Definitions

  • the present invention relates to a hydrophilic member having excellent antifouling properties, abrasion resistance and hydrophilic sustainability.
  • organic materials such as resin films and inorganic materials such as glass and metal having high hydrophilicity.
  • the adhered water droplets spread uniformly on the substrate surface to 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 fat 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 (Non-patent Document 1). According to this report, although this coating film has a certain degree of hydrophilicity, it cannot be said that the compatibility with the substrate is sufficient, and higher durability is required.
  • Patent Document 1 discloses that when a photocatalyst-containing layer is formed on the surface of a substrate, the surface is highly hydrophilized in response to photoexcitation of the photocatalyst. This technique is disclosed in glass, lenses, mirrors, and exterior materials. It has been reported that when applied to various composite materials such as water-circulating members, these composite materials can be provided with excellent antifogging and antifouling functions. However, a hydrophilic film using titanium oxide does not have sufficient film strength, and a hydrophilic material having better wear resistance has been demanded.
  • 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 wear resistance (see Patent Document 2).
  • 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.
  • Patent Document 3 The technique described in Patent Document 3 is known as a technique for imparting antifouling properties to the substrate surface.
  • a processing fin material is described.
  • further improvements in sustainability such as hydrophilicity and antifouling properties are desired.
  • An object of the present invention is to solve the conventional problems as described above, and to provide a hydrophilic member that is excellent in hydrophilicity, wear resistance, antifouling property, and excellent in sustainability thereof.
  • a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group, and further ( a) A hydrophilic member having a low elution layer formed from a composition for a low elution layer containing a hydrophilic polymer having a reactive group.
  • the hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group has a structural unit represented by the following general formula (a-2), and has a polymer chain terminal.
  • R 1 to R 13 each independently represents a hydrogen atom or a hydrocarbon group.
  • L 1 to L 4 each independently represents a single bond or a polyvalent organic linking group.
  • x and y represent composition ratios, where x is 0 ⁇ x ⁇ 100 and y is 0 ⁇ y ⁇ 100.
  • n and m each independently represents an integer of 1 to 3.
  • Y 1 and Y 2 are each independently —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 c ) g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (
  • R a , R b and R c each independently represent a hydrogen atom or an alkyl group
  • R d represents an alkyl group
  • R e and R f each independently represent a hydrogen atom or an alkyl group, an alkali group It represents a metal, an alkaline earth metal, or onium
  • R g represents an alkyl group, a halogen atom, an inorganic anion, or an organic anion. 5).
  • the above-mentioned 1 characterized in that the hydrophilic composition contains (B) a catalyst that promotes the reaction of the hydrophilic polymer having a silicon atom having at least one of the hydroxyl group and the hydrolyzable functional group (A). 5.
  • the hydrophilic member according to any one of 1 to 4. 6). 6. The hydrophilic member as described in 5 above, wherein the catalyst (B) contained in the hydrophilic composition is a non-volatile catalyst. 7). 7. The hydrophilic member as described in any one of 1 to 6 above, wherein the hydrophilic composition contains (C) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. 8). 8. The hydrophilic member as described in any one of 1 to 7 above, wherein an undercoat layer is provided between the substrate and the hydrophilic layer. 9. 9. The hydrophilic member as described in 8 above, wherein the undercoat layer is formed by applying a composition containing (P) a catalyst. 10. 10.
  • the hydrophilic member according to any one of 10. 12 12.
  • the hydrophilic polymer (A1) and the hydrophilic polymer (A2) are included as the hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group, and the hydrophilic polymer (A1 ) And the hydrophilic polymer (A2) in a mass ratio (hydrophilic polymer (A1) / hydrophilic polymer (A2)) in the range of 5/95 to 50/50.
  • the hydrophilic member in any one. 14 14.
  • the hydrophilic member which concerns on this invention is provided with the low elution layer which consists of hydrophilic polymers, it has the outstanding hydrophilic property and antifouling property. That is, when a dirt substance adheres to the surface, excellent antifouling properties can be expressed by flowing the low elution layer together with dirt by running water or the like. However, if the low-elution layer elutes easily, long-term antifouling properties cannot be maintained. Forming a coating made of a hydrophilic polymer as such a low-elution layer is not usually used because the degree of cross-linking is not high and there is a concern that it will easily dissolve from the surface.
  • a hydroxyl group and hydrolysis are provided under a low-elution layer obtained from a composition containing a hydrophilic polymer having a reactive group (hereinafter referred to as (a) a hydrophilic polymer).
  • the hydrophilic layer formed from the hydrophilic composition containing the hydrophilic polymer (henceforth (A) hydrophilic polymer) which has a silicon atom which has at least any one of a functional functional group is provided. For this reason, said hydrophilic property and antifouling property can be maintained over a long period of time.
  • the hydrophilic member according to the present invention is (A) a hydrophilic polymer that can form a cross-linked structure, so that it becomes a high-strength film and is excellent in wear resistance.
  • the low elution layer as used in the field of this invention means the layer from which the formed film flows out slowly with flowing water etc., and the elution degree of this low elution layer is a constant temperature of 25 degreeC and 95% RH.
  • the amount of change in the weight of the coating is 1% or more and 50% or less.
  • the elution degree of the low elution layer is 2% or more and 45% or less, more preferably 5% or more and 40% or less.
  • the amount of change in the weight of the coating is determined by the weight of the hydrophilic member provided with the hydrophilic layer and the low-elution layer on the substrate after standing in the thermostatic bath, and the hydrophilic member measured before placing in the thermostatic bath. It is obtained by calculating the difference from the weight and determining the ratio of the low-elution layer to the total weight.
  • the total weight of the low elution layer can be determined from the difference between the weight of the member before forming the low elution layer and the weight of the member after forming the low elution layer.
  • a hydrophilic polymer is dissolved in a suitable solvent and stirred, whereby hydrolysis and polycondensation proceed to obtain a sol-like hydrophilic composition.
  • An organic-inorganic composite film (hydrophilic layer) having a hydrophilic functional group may be formed on the substrate surface by applying the hydrophilic composition to the substrate surface to form a film and drying. it can.
  • the composition for low elution layers containing (a) hydrophilic polymer is apply
  • the hydrophilic composition contains (C) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter referred to as (C) an alkoxide compound).
  • C an alkoxide compound
  • crosslinking increases in hydrolysis and polycondensation, and the organic-inorganic composite membrane
  • the hydrophilic member of the present invention can provide a hydrophilic member in which the substrate surface is excellent in hydrophilicity, abrasion resistance, antifouling property and sustainability thereof.
  • the present invention has a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group on a substrate, Furthermore, the present invention relates to a hydrophilic member characterized by having a low elution layer formed from a composition for a low elution layer containing a hydrophilic polymer having a reactive group (a).
  • the hydrophilic layer is formed from a hydrophilic composition containing at least (A) a hydrophilic polymer (that is, (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group). . More specifically, (A) the hydrophilic polymer is dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed to form a hydrophilic composition that is an organic-inorganic composite sol solution. can do. And, with this sol solution, a hydrophilic layer having high hydrophilicity and high film strength can be formed.
  • a hydrophilic polymer that is, (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group.
  • the hydrophilic polymer contains a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group. As such a structure, a silanol group or a hydrolyzable silyl group is preferable.
  • the hydrophilic polymer preferably has a silanol group or a hydrolyzable silyl group at the terminal portion and / or side chain of the polymer.
  • the hydrolyzable silyl group is a group that reacts with water to produce silanol (Si—OH). For example, one or more methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- This refers to an alkoxy group such as a butoxy group, or a combination of chlorine and the like.
  • the hydrophilic polymer is preferably the following hydrophilic polymer (A1) and / or the following hydrophilic polymer (A2).
  • a hydrophilic polymer (A1) having a structural unit represented by the following general formula (a-2) and having a partial structure represented by the following general formula (a-1) at the end of the polymer chain.
  • a hydrophilic polymer (A2) having a structural unit represented by the following general formula (a-3) and a structural unit represented by the following general formula (a-4).
  • R 1 to R 13 each independently represents a hydrogen atom or a hydrocarbon group.
  • L 1 to L 4 each independently represents a single bond or a polyvalent organic linking group.
  • x and y represent composition ratios, where x is 0 ⁇ x ⁇ 100 and y is 0 ⁇ y ⁇ 100.
  • n and m each independently represents an integer of 1 to 3.
  • Y 1 and Y 2 are each independently —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 c ) g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (
  • R a , R b and R c each independently represent a hydrogen atom or an alkyl group
  • R d represents an alkyl group
  • R e and R f each independently represent a hydrogen atom or an alkyl group, an alkali group It represents a metal, an alkaline earth metal, or onium
  • R g represents an alkyl group, a halogen atom, an inorganic anion, or an organic anion.
  • R 1 to R 13 represent a hydrocarbon group
  • the hydrocarbon group is preferably a hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include an alkyl group and an aryl group, and a straight chain having 1 to 8 carbon atoms.
  • a branched or cyclic alkyl group is preferred.
  • R 1 , R 2 , R 12 and R 13 are preferably a methyl group, an ethyl group, a propyl group or an isopropyl group from the viewpoints of effects and availability.
  • R 3 to R 5 and R 6 to R 11 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 composed of a bond between the substituent and the alkylene group.
  • the substituent a monovalent nonmetallic atomic group excluding hydrogen is used.
  • 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 include the above-described alkyl groups
  • aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl
  • 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
  • examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
  • Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.
  • Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group are chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group.
  • Chlorophenoxycarbonylmethyl group carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group , Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phos Phonophenyl) sulfamoyloctyl, phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphon
  • L 1 to L 4 each independently represents a single bond or a polyvalent organic linking group.
  • the single bond means that the main chain of the polymer and -SiR 1 3-n (OR 2 ) n , -SiR 13 3-m (OR 12 ) m , Y 1 , Y 2 are directly bonded without a linking chain.
  • the organic linking group is a linking group composed of a nonmetallic atom, preferably a divalent linking group composed of a nonmetallic atom, preferably 0 to 200 carbon atoms, 0 to 150 nitrogen atoms.
  • the linking group is selected from —O—, —S—, —CO—, —NH—, and combinations thereof. More specific examples of the linking group include the following linking groups or linking groups constituted by combining these.
  • L 1 to L 4 may be formed of a polymer or an oligomer, and specifically, preferably include polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer.
  • Other preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, etc., preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene More preferred are polyacrylates and polymethacrylates.
  • the structural unit used for these polymers and oligomers may be one type or two or more types.
  • L 1 to L 4 are polymers or oligomers, the number of constituent elements is not particularly limited, and the molecular weight is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000. 000 to 200,000 is most preferred.
  • x and y represent composition ratios, where x is 0 ⁇ x ⁇ 100 and y is 0 ⁇ y ⁇ 100.
  • x is preferably in the range of 10 ⁇ x ⁇ 99, and more preferably in the range of 50 ⁇ x ⁇ 99.
  • y is preferably in the range of 1 ⁇ y ⁇ 90, more preferably in the range of 1 ⁇ y ⁇ 50.
  • n and m each independently represents an integer of 1 to 3.
  • Y 1 and Y 2 are each independently —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 c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e
  • R a , R b and R c each independently represent a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms), and R d represents an alkyl group ( Preferably represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R e and R f each independently represents a hydrogen atom or an alkyl group (preferably a linear, branched or branched group having 1 to 8 carbon atoms).
  • R a to R g may be bonded to each other to form a ring, and the formed ring is an oxygen atom, sulfur atom, nitrogen It may be a heterocycle containing a heteroatom such as an atom.
  • R a to R g may further have a substituent, and examples of the substituent that can be introduced here include those mentioned above as the substituents that can be introduced.
  • R a , R b or R c include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, and s-butyl.
  • Preferred examples include a group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
  • R d examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, t-butyl, and isopentyl.
  • Preferred examples include a group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • R e specifically as R f, in addition to the alkyl groups mentioned R d, a hydrogen atom; lithium, sodium, alkali metals such as potassium, calcium, alkaline earth such as barium metal, or ammonium, Examples include onium such as iodonium and sulfonium.
  • R d to R f may be bonded to each other to form a ring, and the formed ring may be a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
  • R d to R f may further have a substituent, and examples of the substituent that can be introduced here include those mentioned above as the substituents that can be introduced.
  • R g include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a nitrate anion, a sulfate anion, or a tetrafluoroborate anion, in addition to the alkyl groups listed as R a to R c
  • Inorganic anions such as hexafluorophosphate anion, and organic anions such as methanesulfonic acid anion, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, and p-toluenesulfonic acid anion.
  • Y 1 and Y 2, -CO 2 - Na +, -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.
  • the molecular weight of the hydrophilic polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000.
  • the aforementioned hydrophilic polymer (A) may be used alone or in combination of two or more.
  • the mass ratio of the hydrophilic polymer (A1) and the hydrophilic polymer (A2) contained in the hydrophilic composition (hydrophilic polymer (A1 ) / Hydrophilic polymer (A2)) is preferably in the range of 5/95 to 50/50.
  • the ratio is more preferably 8/92 to 45/55, and further preferably 10/90 to 40/60.
  • hydrophilic polymer (A1) and specific examples of the hydrophilic polymer (A2) are shown below together with their mass average molecular weights (MW), but the present invention is not limited thereto.
  • polymer of the specific example shown below means that it is a random copolymer in which each structural unit described is contained by the described molar ratio.
  • radical polymerization is performed using a radical-polymerizable monomer represented by the structural unit and a compound having a chain transfer ability in radical polymerization, or a radical initiator. Can be synthesized. That is, in the latter, since the compound having a reactive group has chain transfer ability or radical initiation ability, it is possible to synthesize a polymer having a reactive group introduced at the end of the polymer main chain in radical polymerization.
  • the polymerization method of the hydrophilic polymer (A2) any of the conventionally known methods can be used as the radical polymerization method. This reaction mode is not particularly limited, but bulk reaction, solution reaction, suspension reaction, etc.
  • radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (The Chemical Society of Japan, Maruzen), Materials Engineering, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., can be applied.
  • the hydrophilic polymer may be a copolymer with another monomer.
  • examples of other monomers include known acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, and the like. These 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.
  • the total proportion of these other monomers used for the synthesis of the copolymer other than the structural unit represented by the general formula is preferably 80% by mass or less, and more preferably 50% by mass or less.
  • the hydrophilic polymer is preferably 5 to 95% by mass, more preferably 15 to 90% by mass, and most preferably 20% from the viewpoint of curability and hydrophilicity with respect to the non-volatile component of the hydrophilic composition. It is contained in the range of ⁇ 85% by mass.
  • a hydrophilic polymer may be used by 1 type, or may be used together 2 or more types. *
  • the hydrophilic composition preferably contains (B) a catalyst that promotes the reaction of the hydrophilic polymer (A).
  • B) a catalyst By containing a catalyst, in preparation of the above-mentioned organic-inorganic composite sol liquid, a hydrolysis and a polycondensation reaction are accelerated
  • the catalyst is preferably a non-volatile catalyst.
  • the non-volatile catalyst means a catalyst having a boiling point other than 125 ° C., in other words, a catalyst having a boiling point of 125 ° C. or higher, or a catalyst having no boiling point in the first place (such as thermal decomposition, phase change). Including things that do not wake up).
  • the (B) catalyst uses an acidic catalyst or a basic catalyst that promotes a reaction that hydrolyzes and polycondenses the (C) alkoxide compound described later, and (A) causes a bond with the hydrophilic polymer. it can.
  • the acidic catalyst or basic catalyst is an acid compound or basic compound used as it is, or in a state where the acidic compound or basic compound is dissolved in a solvent such as water or alcohol (hereinafter, these are all included, respectively)
  • An acidic catalyst or a basic catalyst may also be used.
  • the concentration at which the acidic compound or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acidic compound or basic compound used, the desired content of the catalyst, and the like.
  • the concentration of the acidic compound or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase.
  • a basic catalyst having 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 kind of the acidic catalyst and the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of elements that hardly remain in the coating film after drying is preferable.
  • the acidic 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. Examples thereof include substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, and sulfonic acids such as benzenesulfonic acid.
  • the basic catalyst include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline.
  • a Lewis acid catalyst comprising a metal complex can also be preferably used.
  • Particularly preferred catalysts are metal complex catalysts, metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and ⁇ -diketones, ketoesters, hydroxycarboxylic acids or their esters, 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 above metal complex includes ⁇ diketones such as acetylacetone (2,4-pentanedione) and 2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate
  • ketoesters such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and the like
  • 4-hydroxy-4-methyl-2-pentanone 4-hydroxy- Ketoalcohols such as 2-pentanone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-monoethanolamine, diethanolamine , Trietano Amino alcohols such as amines, methylol melamine, methylol urea
  • a preferred ligand is an acetylacetone derivative.
  • An 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.
  • 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 it is possible to satisfy the improvement of coating solution aging stability and film surface quality, and high hydrophilicity and high durability.
  • the above-mentioned metal complex catalyst can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with alcohol.
  • 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 non-volatile component in the hydrophilic composition. Moreover, (B) catalyst may be used independently or may be used together 2 or more types.
  • the hydrophilic composition preferably contains (C) an alkoxide compound (that is, (C) an alkoxide compound of an element selected from Si, Ti, Zr, and Al).
  • the alkoxide compound is preferably a hydrolytic polymerizable compound having a polymerizable functional group in its structure and functioning as a crosslinking agent.
  • a (C) alkoxide compound is contained in the hydrophilic composition together with the (A) hydrophilic polymer, when the hydrophilic composition is applied to the substrate surface and heated and dried, (A) hydrophilic The polymerizable polymer and the (C) alkoxide compound can be polycondensed to form a firm film having a crosslinked structure.
  • the alkoxide compound is preferably a compound represented by the following general formula (3) or (4).
  • R 20 represents a hydrogen atom, an alkyl group or an aryl group
  • R 21 represents an alkyl group or an aryl group
  • Z represents Si, Ti or Zr
  • k represents 0 to Represents an integer of 2.
  • the number of carbon atoms when R 20 and R 21 represent an alkyl group 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 1000 or less.
  • the specific alkoxide containing silicon includes, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, Ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, ⁇ -chloropropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -a
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable.
  • Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
  • Z is Ti
  • those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate.
  • the one containing zirconium can include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
  • zirconates corresponding to the compounds exemplified as those containing titanium examples include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.
  • alkoxides in which Z is Si are preferable from the viewpoint of film properties.
  • the (C) alkoxide compound is used in the hydrophilic composition in an amount of preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the nonvolatile component.
  • An alkoxide compound may be used independently or may be used together 2 or more types.
  • the alkoxide compound can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.
  • hydrophilic composition various compounds can be used in combination with the essential components as long as the effects of the present invention are not impaired in addition to the essential components.
  • components that can be used in combination will be described.
  • surfactant It is preferable to use a surfactant in order to improve the surface state of the hydrophilic composition.
  • the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.
  • 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 acid 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 surfact
  • the surfactant is preferably used in the hydrophilic film forming composition in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component. Moreover, surfactant can be used individually or in combination of 2 or more types.
  • an antibacterial agent can be contained in the hydrophilic composition.
  • a hydrophilic / water-soluble antibacterial agent By including a hydrophilic / water-soluble antibacterial agent, a hydrophilic member having excellent antibacterial, antifungal and antialgal properties can be obtained without impairing surface hydrophilicity.
  • the antibacterial agent it is preferable to use a compound that does not lower the hydrophilicity of the hydrophilic member. Examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents.
  • antibacterial agent those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, fungi such as fungi and yeast, and the like are used.
  • organic antibacterial agents include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium salts, pyridines, triazines, benzoisothiazolines, and isothiazolines. It is done.
  • organic antibacterial agents can be appropriately selected and used in consideration of hydrophilicity, water resistance, sublimation property, safety and the like.
  • organic antibacterial agents 2-bromo-2-nitro-1,3-propanediol, TBZ, BCM, OBPA, and ZPT are preferable from the viewpoint of hydrophilicity, antibacterial effect, and cost.
  • inorganic antibacterial agents include mercury, silver, copper, zinc, iron, lead, bismuth and the like in descending order of bactericidal action.
  • supported metals and metal ions such as silver, copper, zinc, nickel, on the silicate type
  • Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells. Also, Nikko's “trade name Holon Killer Bees Sera” made of amino metal in which metal is compounded on both sides of amino acid is preferable. These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably dispersed in a molecule or solid, and the antibacterial agent is easily exposed effectively on the hydrophilic layer surface. And even if it splashes with water, it does not elute, can maintain the effect for a long time, and does not affect the human body.
  • silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects.
  • silver zeolite with silver supported on zeolite silicate carrier, antibacterial agent with silver supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred.
  • Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” by Shinagawa Fuel, “Sylwell” by Fuji Silysia Chemical, and “Bactenone” by JEOL.
  • Novalon manufactured by Toa Gosei, in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” manufactured by Catalytic Chemical Industry, and “Sun Eyebac P” (manufactured by Sanai Oil), a triazine antibacterial agent are also preferable.
  • the content of the antibacterial agent is generally 0.001 to 10% by mass, preferably 0.005 to 5% by mass, based on the non-volatile component in the hydrophilic composition. Is more preferably from 3 to 3% by weight, particularly preferably from 0.02 to 1.5% by weight, most preferably from 0.05 to 1% by weight. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Further, if the content is 10% by mass or less, the hydrophilicity is not lowered, the aging is not deteriorated, and the antifouling property and the antifogging property are not adversely affected.
  • the hydrophilic composition may contain inorganic fine particles for the purpose of improving the cured film strength and hydrophilicity of the hydrophilic film to be formed.
  • 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 are used in the hydrophilic composition in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components.
  • the inorganic fine particles can be used alone or in combination of two or more.
  • an ultraviolet absorber can be added to the hydrophilic composition.
  • the ultraviolet absorber are described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-197075, JP-A-9-34057, and the like.
  • Benzotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No.
  • JP-B-48-30492 JP-A-56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP
  • the addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by mass in terms of solid content.
  • an antioxidant can be added to the hydrophilic composition.
  • the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443.
  • the addition amount is appropriately selected according to the purpose, but is preferably 0.1 to 8% by mass in terms of solid content.
  • solvent examples include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride.
  • ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone
  • alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol
  • chlorine such as chloroform and methylene chloride.
  • Solvents aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
  • VOC volatile organic solvent
  • Polymer compound In order to adjust the film properties of the hydrophilic layer, various polymer compounds can be added to the hydrophilic composition as long as the hydrophilicity is not inhibited.
  • High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester” or “acrylic acid alkyl ester” as a structural unit is also preferably used.
  • 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.
  • the hydrophilic composition can contain zirconia chlorides, nitrates, alkoxides and organic complexes 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, specifically tetrakis (acetylacetonato) zirconium, bis (acetylacetonato) zirconium dibutoxide, bis (acetylacetonato) zirconium dichloride.
  • the zirconium compound is preferably used in the hydrophilic composition as a non-volatile component in the range of 0 to 50% by mass, more preferably 5 to 25% by mass.
  • the hydrophilic composition can be prepared by dissolving (A) a hydrophilic polymer (preferably (B) a catalyst and (C) an alkoxide compound) in a solvent such as ethanol and stirring.
  • 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 each component can be uniformly dissolved and dispersed, but for example, an aqueous solvent such as methanol, ethanol, water and the like is preferable.
  • the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming the hydrophilic layer can utilize a 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 Using the Latest Sol-Gel Method” It is described in detail in a book such as the Technical Center (published) (1992), and the methods described therein can be applied.
  • a hydrophilic layer can be formed by coating a hydrophilic composition on a suitable substrate and heating or drying.
  • the coating method can be a known method, and is not particularly limited. For example, spray coating, dip coating, flow coating, spin coating, roll coating, film applicator, screen printing, bar printing Methods such as a coater method, brush coating, and sponge coating can be applied.
  • the heating and drying conditions after coating with the hydrophilic composition are from 2 minutes in the temperature range of 50 to 200 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure. It is preferably performed for about 1 hour, and more preferably dried at a temperature range of 80 to 160 ° C. for 5 to 30 minutes.
  • a heating means it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.
  • the catalyst when the substrate is coated with a hydrophilic composition, can be mixed immediately before the coating. 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 hydrophilic composition increases in viscosity, and defects such as coating unevenness may occur. Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.
  • the thickness of the hydrophilic layer is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.02 ⁇ m to 80 ⁇ m, and most preferably 0.05 ⁇ m to 50 ⁇ 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 2. with m 2, it is possible to obtain a film thickness of the.
  • the low elution layer is formed from a composition for a low elution layer containing (a) a hydrophilic polymer (that is, (a) a hydrophilic polymer having a reactive group).
  • a hydrophilic polymer that is, (a) a hydrophilic polymer having a reactive group.
  • the reactive group include a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a phosphoric acid group, and a phosphonic acid group. Is preferred.
  • a hydrophilic polymer a known polymer can be used.
  • hydrophilic polymer (a) examples include polyethylene glycol and polypropylene glycol.
  • Anionic polymers such as acids, polymaleic acid, polyitaconic acid, poly (meth) acrylates containing phosphoric acid groups and their salts, polyallylamine, polydimethylallylamine, poly ((meth) acryloylpropyltrimethylammonium chloride), poly (chlorinated) Cationic polymers such as (meth) acrylamidopropyltrimethylammonium), poly (4-vinylpyridine), poly (2-vinylpyridine), poly (2-vinylpyridine), poly (2-
  • hydrophilic polymers (a) from the viewpoint of interaction with the hydrophilic layer, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, carboxydimethyl cellulose, and carboxymethyl cellulose are preferable, and polyethylene glycol, carboxydimethyl cellulose, and polyvinyl alcohol are more preferable. . (A) As long as the hydrophilicity of the hydrophilic polymer is not lowered, copolymers with other monomer components can also be used.
  • the hydrophilic polymer is preferably a copolymer with a monomer having a hydroxyl group.
  • the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, hydroxyphenyl Acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, ⁇ -hydroxymethylmethyl acrylate, ⁇ -hydroxymethylethyl acrylate, ⁇ -hydroxymethyl n-propyl acrylate, ⁇ -hydroxymethylisopropyl acrylate, ⁇ -hydroxymethyl (n- I-, sec- or t-) butyl
  • 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ⁇ -hydroxymethyl Methyl acrylate, N-hydroxyethyl acrylamide, and ⁇ -hydroxymethyl acrylamide are preferable, and 2-hydroxyethyl acrylate and N-hydroxyethyl acrylamide are more preferable.
  • the total proportion of monomers having a hydroxyl group is preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the mass average molecular weight of the hydrophilic polymer is preferably 500 or more and 100,000 or less, more preferably 500 to 80,000, and most preferably 1,000 to 50,000. By being 500 or more, elution of the (a) hydrophilic polymer from the low elution layer can be delayed.
  • the hydrophilic polymer is preferably used in the low-elution layer composition in the range of 5 to 99% by mass, more preferably 10 to 98% by mass with respect to the nonvolatile component.
  • the composition for low elution layers contains (b) a crosslinking agent.
  • a crosslinking agent By containing a crosslinking agent, the effect which suppresses that (a) hydrophilic polymer elutes early is acquired.
  • a well-known thing can be used for a crosslinking agent. Specific examples of (b) the crosslinking agent are listed below, but are not limited thereto.
  • the organic crosslinking agent an isocyanate crosslinking agent or an epoxy crosslinking agent can be suitably used.
  • Isocyanate-based crosslinking agents include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,5-pentamethylene diisocyanate, ethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, 1, 3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1-isocyanato-2-isocyanatomethylcyclopentane, bis- (4-isocyanato Hexyl) -methane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclo
  • diisocyanate-based crosslinking agents preferably, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate are preferable. 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate.
  • epoxy-based crosslinking agent examples include polyethylene glycol diglycidyl ether, ethylene-polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, propylene-polypropylene glycol diglycidyl ether, sorbitol-polyglycidyl ether, and preferably polyethylene glycol diglycidyl ether.
  • Ether and ethylene-polyethylene glycol diglycidyl ether are preferable, and polyethylene glycol diglycidyl ether is more preferable.
  • a compound having an alkoxysilyl group can be suitably used as the inorganic crosslinking agent.
  • the compound having an alkoxysilyl group include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, propylmethyldimethoxysilane, dimethyldiethoxysilane, diethyldisilane.
  • Methoxysilane and ethyltrimethoxysilane are preferable, and tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane can be more preferably used.
  • the content of the crosslinking agent in the composition for low elution layer is preferably in the range of 0.01 to 15% by mass, more preferably 0.02%, based on the hydrophilic polymer (a). It is in the range of ⁇ 10% by mass, more preferably 0.05 to 8% by mass.
  • a catalyst is preferably used.
  • the same catalyst as the above-mentioned (B) catalyst can be exemplified.
  • the catalyst is used in the low-elution layer composition in an amount of preferably 0.1 to 50% by mass, more preferably 1 to 25% by mass, based on the nonvolatile components.
  • the low elution layer is formed by dissolving and stirring at least the (a) hydrophilic polymer in an appropriate solvent to form a composition for the low elution layer.
  • the hydrophilic layer is formed from the low elution layer composition. It can be formed by coating and drying on the coated substrate. If necessary, the (b) crosslinking agent and the catalyst can be added to the composition for a low-elution layer.
  • the reaction temperature is room temperature to 80 ° C.
  • the reaction time that is, the time for continuing the stirring is preferably in the range of 1 to 72 hours.
  • the solvent used in preparing the composition for low elution layer is not particularly limited as long as each component can be uniformly dissolved and dispersed.
  • each component can be uniformly dissolved and dispersed.
  • the hydrophilic solvent is preferred.
  • the heating and drying conditions after coating the composition for the low-elution layer are from 50 to 200 ° C. from the viewpoint of efficiently evaporating the solvent and forming a crosslinked structure.
  • the drying is preferably performed for about 2 minutes to 1 hour, and more preferably for 5 to 30 minutes in the temperature range of 80 to 160 ° C.
  • a heating means it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.
  • the thickness of the low elution layer is preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.02 ⁇ m to 20 ⁇ m, and most preferably 0.05 ⁇ m to 10 ⁇ m.
  • the dry coating amount of the low-elution layer is preferably 0.01 g / m 2 to 50 g / m 2 , more preferably 0.02 g / m 2 to 20 g / m 2 , and particularly preferably 0.05 g / m 2 to 10 g / m 2. with m 2, it is possible to obtain a film thickness of the.
  • the undercoat layer preferably contains (P) a catalyst, and the (P) catalyst is preferably a non-volatile catalyst.
  • the cross-linking reaction can be further advanced over time, and the coating film has a very high strength. Furthermore, since the non-volatile catalyst exists at the interface with the substrate without losing activity, the reaction between the substrate and the hydrophilic layer proceeds with time, and high adhesion can be realized.
  • the nonvolatile catalyst include metal chelate compounds and silane coupling agents.
  • the metal chelate compound (hereinafter also referred to as a metal complex) is not particularly limited, but a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and ⁇ -diketone, ketoester, hydroxycarboxylic acid or the like
  • metal complexes composed of oxo or hydroxy oxygen-containing compounds selected from esters, amino alcohols, and enolic active hydrogen compounds.
  • 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.
  • complexes obtained from Zr, Al and Ti are excellent and preferred. Specific examples thereof include those similar to those shown for the metal complex described in the hydrophilic layer.
  • silane coupling agent Although it does not specifically limit as a silane coupling agent, What has the functional group which shows acidity or alkalinity is mentioned, More specifically, peroxo acid, carboxylic acid, carbohydrazone acid, carboxymidic acid, sulfonic acid, sulfinic acid , Silane coupling agents having a functional group showing acidity such as sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid, and the above alkali metal salts, or a basic functional group such as an amino group It is done.
  • the non-volatile catalyst is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the non-volatile component in the undercoat layer forming composition. Moreover, a non-volatile catalyst may be used independently or may be used together 2 or more types.
  • the undercoat layer preferably contains (Q) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.
  • Examples of the alkoxide compound of an element selected from Si, Ti, Zr, and Al include the same alkoxide compounds as those described above.
  • the alkoxide compound of an element selected from Si, Ti, Zr, and Al is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the nonvolatile component in the undercoat layer forming composition. Used in the range of%.
  • the alkoxide compound of an element selected from Si, Ti, Zr, and Al may be used alone or in combination of two or more.
  • Such an undercoat layer is present in which a non-volatile catalyst is contained without losing its activity, especially when the hydrophilic layer is further provided on the undercoat layer due to its presence on the surface. Therefore, the adhesiveness at the interface between the undercoat layer and the hydrophilic layer is extremely high.
  • the undercoat layer can be further improved in adhesion at the interface between the undercoat layer and the hydrophilic layer by providing fine irregularities by mixing plasma etching or metal particles.
  • hydrophilic resins include polyvinyl alcohol (PVA), cellulosic resins (methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, chitosans, starch, and ether bonds.
  • PVA polyvinyl alcohol
  • MC methyl cellulose
  • HEC hydroxyethyl cellulose
  • CMC carboxymethyl cellulose
  • chitins chitosans, starch, and ether bonds.
  • examples 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.
  • the polyacrylic acid salt which has a carboxyl group, maleic acid resin, alginate, gelatins etc. can also be mentioned.
  • at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.
  • 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 crosslinking agent the crosslinking agent which forms bridge
  • 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 Polyisocyanate compounds such as isocyanate, polymethylene polyphenyl isocyanate,
  • 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 hydrophilic resin and / or water-dispersible latex total amount of the undercoat layer is preferably from 0.01 ⁇ 20 g / m 2, more preferably 0.1 ⁇ 10g / m 2.
  • the undercoat layer composition can also be adjusted by the same method as that for the hydrophilic composition.
  • a plurality of undercoat layers may be provided.
  • the thickness of the undercoat layer is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.02 ⁇ m to 80 ⁇ m, and most 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 , and particularly preferably 0.05 g / m 2 to By setting it to 50 g / m 2 , the above film thickness can be obtained.
  • the hydrophilic member of the present invention can be used by appropriately adding another layer depending on the purpose, form, and place of use.
  • 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 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, and an adhesion-imparting resin such as a hydrogenated product thereof can be used alone or in combination.
  • the adhesive strength of the adhesive is generally called strong adhesion, and is 200 g / 25 mm or more, preferably 300 g / 25 mm or more, and 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.
  • the release layer preferably contains a release agent in order to give release properties.
  • 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 substrate is not particularly limited, but any of glass, plastic, metal, tile, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, a combination thereof, and a laminate thereof can be suitably used. .
  • a substrate formed of glass, metal, ceramics or plastic is preferred. Particularly preferred substrates are glass substrates, plastic substrates, and aluminum substrates.
  • a metal plate such as magnesium oxide, magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride, etc .; be able to.
  • float plate glass, mold plate glass, ground plate glass, mesh-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do.
  • the hydrophilic layer can be applied as it is with the base glass, but if necessary, surface hydrophilic treatment is performed on one or both sides by an oxidation method, a roughening method or the like for the purpose of improving the adhesion of the hydrophilic layer.
  • an 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.
  • the surface roughening method the surface can 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 Known methods such as a physical vapor deposition method (PVD) such as an assist method, a sputtering method, and an ion plating method, and a vapor phase method such as a chemical vapor deposition method (CVD) can be applied.
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition method
  • the plastic substrate is not particularly limited, but a substrate used as an optical member is selected in consideration of optical characteristics such as transparency, refractive index, and dispersibility, and various physical properties such as resistance It is selected in consideration of physical properties such as strength such as impact and flexibility, heat resistance, weather resistance and durability.
  • Plastic substrates include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone.
  • polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use.
  • the thickness of the plastic substrate varies depending on the mating partner. 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.
  • the inorganic compound layer described in description of the glass plate on the plastic plate can also be used.
  • the inorganic compound layer can also act as an antireflection layer.
  • a cycle of aeration with palmitic acid for 1 hour, washing with water for 30 minutes, drying for 30 minutes is one cycle, and the water contact angle after repeating the cycle for 5 cycles is 40 ° or less.
  • hydrophilic member according to the present invention is not particularly limited, and is not limited to building materials, building exteriors such as outer walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, bicycles.
  • Exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and equipment, dust covers and paintings, signboards, traffic signs, various display devices, advertising towers, sound barriers for roads, sound barriers for railways, bridges, guard rails And painting, tunnel interior and painting, insulator, solar battery cover, solar water heater heat collection cover, plastic house, tent material, vehicle lighting cover, vending machine, housing equipment, veranda, air conditioner indoor unit, air conditioner outdoor unit , Radiating fins for heat exchangers, outdoor benches, shutters, toilet bowls, bathtubs, bathroom mirrors, washstands, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers, dish drying , Sinks, kitchen ranges, kitchen hoods, ventilation fans, (including film to be attached to and the surface of the above articles.) Window sash, and the like. Further, in the case of having a drying process in the process of manufacturing products used for these applications, the drying time can be shortened and the productivity can be expected to be improved.
  • the hydrophilic member according to the present invention is preferably applied to a fin material, and is preferably applied to an aluminum fin material.
  • Aluminum fin materials used for heat exchangers such as indoor air conditioners and automobile air conditioners have water droplets formed by condensed water generated during cooling and staying between the fins.
  • the adhering dust between the fins similarly reduces the cooling capacity.
  • 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 for palmitic acid.
  • Examples of the aluminum used for the fin material include a degreased surface and an aluminum plate subjected to chemical conversion treatment as necessary. It is preferable that the fin material made of aluminum has a surface subjected to chemical conversion treatment from the viewpoint 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.
  • aluminum thin plates used for fin materials for heat exchangers are JIS standards such as pure aluminum plates such as 1100, 1050, 1200 and 1N30, Al—Cu alloy plates such as 2017 and 2014, 3003 and 3004, etc. Any of Al—Mn alloy plates, Al—Mg alloy plates such as 5052 and 5083, and Al—Mg—Si alloy plates such as 6061 may be used. But it ’s okay.
  • 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 properties 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, oil coolers for construction machines, automobile radiators, capacitors, and the like.
  • 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 any of room air conditioner, packaged air conditioner, car air conditioner, etc. may be used.
  • 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 obtained solid was washed with acetone to obtain the hydrophilic polymer (I-1) as the exemplified compound (I-1).
  • the mass after drying was 21.7 g. It was a polymer having a weight average molecular weight of 9,000 according to GPC (polyethylene oxide standard).
  • hydrophilic polymer (II-1) which is the exemplified compound (II-1).
  • the mass after drying was 65.6 g. It was a polymer having a mass average molecular weight of 22,000 according to GPC (polyethylene oxide standard).
  • Example 1 [Hydrophilic sol-gel solution] In 100 g of purified water, 10 g of hydrophilic polymer (I-1) as (A) hydrophilic polymer was mixed and stirred at room temperature for 2 hours to prepare. [Hydrophilic composition] A hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by weight aqueous solution of the following anionic surfactant.
  • composition for low elution layer In 100 g of dimethylacetamide, (a) 10 g of polyethylene glycol (PEG, mass average molecular weight 20,000) as a hydrophilic polymer was mixed and stirred at room temperature for 1 hour to obtain a composition for a low elution layer. [Coating method] An alkali-degreased aluminum substrate (thickness: about 100 ⁇ m) is prepared, and the hydrophilic composition is bar-coated on the aluminum substrate and oven-dried at 150 ° C. for 30 minutes to obtain a dry coating amount of 0.7 g / m 2 . A hydrophilic layer was formed.
  • PEG polyethylene glycol
  • composition for a low elution layer was coated on the bar, and oven-dried at 150 ° C. for 30 minutes to form a low elution layer having a coating dry amount of 0.2 g / m 2.
  • the hydrophilic member was obtained.
  • the thickness of the hydrophilic layer was 0.7 ⁇ m, and the thickness of the low elution layer was 0.2 ⁇ m.
  • Example 2 A hydrophilic member of Example 2 was prepared in the same manner as in Example 1 except that the hydrophilic polymer (a) of Example 1 was changed to polyvinyl alcohol (PVA, mass average molecular weight 50,000, saponification degree 99%).
  • PVA polyvinyl alcohol
  • Example 3 The hydrophilic member of Example 3 was prepared in the same manner as in Example 1 except that 0.5 g of 1,4-tetramethylene diisocyanate was added as the crosslinking agent (b) to the composition for the low elution layer of Example 1. .
  • Example 4 In Example 3, a hydrophilic member was produced in the same manner as in Example 3 except that 0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were added as the (B) catalyst to the hydrophilic sol-gel solution.
  • Example 5 A hydrophilic member of Example 5 was produced in the same manner as in Example 4 except that the composition for the low elution layer of Example 4 was changed to the following composition.
  • dimethylacetamide and 20 g of purified water (a) 10 g of polyethylene glycol (mass average molecular weight 20,000) as a hydrophilic polymer, (b) 0.5 g of tetramethoxysilane (TMOS) as a crosslinking agent, (c) as a catalyst 0.05 g of acetylacetone and 0.05 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 1 hour to obtain a composition for a low elution layer.
  • TMOS tetramethoxysilane
  • Example 6 A hydrophilic member of Example 6 was produced in the same manner as in Example 4 except that (a) the hydrophilic polymer of Example 4 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 7 A hydrophilic member of Example 7 was produced in the same manner as in Example 5 except that (a) the hydrophilic polymer of Example 5 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 8 The hydrophilic members of Examples 8 and 9 were prepared in the same manner as in Example 4 except that the (B) catalyst in the hydrophilic sol-gel solution of Example 4 was changed to the following.
  • Example 8 2 g of ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH)
  • Example 9 Zirconium chelate compound 2g The zirconium chelate compound was obtained by adding 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate to a reactor equipped with a stirrer and stirring at room temperature for 1 hour.
  • Example 10 The hydrophilic members of Examples 10 and 11 were produced in the same manner as in Example 4 except that the hydrophilic polymer (I-1) in the hydrophilic sol-gel solution of Example 4 was changed to the following.
  • Example 10 Hydrophilic polymer (I-2) (: Using Exemplified Compound (I-2))
  • Example 11 Hydrophilic polymer (I-11) (: Using exemplified compound (I-11))
  • Example 12 [Hydrophilic sol-gel solution] Prepared by mixing 12 g of tetramethoxysilane as (C) alkoxide compound and 4 g of hydrophilic polymer (I-1) as (A) hydrophilic polymer in 20 g of ethyl alcohol and 100 g of purified water, and stirring at room temperature for 2 hours. did. [Hydrophilic composition] The hydrophilic sol-gel solution was mixed with 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 60 g of purified water to obtain a hydrophilic composition.
  • Example 13 A hydrophilic member of Example 13 was prepared in the same manner as in Example 12 except that 1.0 g of acetylacetone and 1.0 g of tetraethyl orthotitanate were added as the (B) catalyst to the hydrophilic sol-gel solution of Example 12.
  • Example 14 [Sol-gel solution for undercoat] Into 200 g of ethyl alcohol, 10 g of acetylacetone as the (P) catalyst, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane as the (Q) alkoxide compound were mixed and stirred at room temperature for 2 hours to prepare. [Composition for undercoat layer] 30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
  • Example 15 A hydrophilic member of Example 15 was obtained in the same manner as Example 14 except that the hydrophilic layer of Example 14 was changed to the hydrophilic layer of Example 12.
  • Example 16 A hydrophilic member of Example 16 was obtained in the same manner as Example 14 except that the hydrophilic layer of Example 14 was changed to the hydrophilic layer of Example 13.
  • Comparative Example 1 In Example 4, a member of Comparative Example 1 was obtained in the same manner as in Example 4 except that the low-elution layer was not formed.
  • Comparative Example 2 In Example 3, a member of Comparative Example 2 was obtained in the same manner as Example 3 except that the hydrophilic layer was not formed.
  • Example 17 [Hydrophilic sol-gel solution]
  • 10 g of hydrophilic polymer (II-1) as (A) hydrophilic polymer was mixed and stirred at room temperature for 2 hours to prepare.
  • a hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by weight aqueous solution of the anionic surfactant of Example 1.
  • composition for low elution layer In 100 g of dimethylacetamide, 10 g of polyethylene glycol (mass average molecular weight 20,000) (a) as a hydrophilic polymer was mixed and stirred at room temperature for 1 hour to obtain a composition for a low elution layer.
  • [Coating method] Prepare the aluminum substrate to an alkali degreasing (thickness about 100 [mu] m), the hydrophilic composition on the aluminum substrate by bar coating, 0.99 ° C., and dried in an oven at 30 minutes, the dry coating amount 0.7 g / m 2 A hydrophilic layer was formed. Further, the above composition for a low elution layer was coated on a bar and oven-dried at 150 ° C.
  • a low elution layer having a coating dry amount of 0.2 g / m 2. 1 hydrophilic member.
  • the thickness of the hydrophilic layer was 0.7 ⁇ m, and the thickness of the low elution layer was 0.2 ⁇ m.
  • Example 18 A hydrophilic member of Example 18 was produced in the same manner as in Example 17 except that the hydrophilic polymer (a) in Example 17 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 19 The hydrophilic member of Example 19 was prepared in the same manner as in Example 17 except that 0.5 g of 1,4-tetramethylene diisocyanate was added as the crosslinking agent (b) to the composition for low elution layer of Example 17. did.
  • Example 20 In Example 19, the hydrophilic member of Example 20 was produced in the same manner as in Example 19 except that 0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were added as the (B) catalyst to the hydrophilic sol-gel solution. .
  • Example 21 A hydrophilic member of Example 21 was produced in the same manner as in Example 20, except that the composition for low elution layer of Example 20 was changed to the following composition.
  • dimethylacetamide and 20 g of purified water (a) 10 g of polyethylene glycol (mass average molecular weight 20,000) as a hydrophilic polymer, (b) 0.5 g of tetramethoxysilane as a crosslinking agent, and (c) acetylacetone in an amount of 0. 05 g and 0.05 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 1 hour to obtain a composition for a low elution layer.
  • Example 22 A hydrophilic member of Example 22 was produced in the same manner as in Example 20, except that (a) the hydrophilic polymer in Example 20 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 23 A hydrophilic member of Example 23 was produced in the same manner as in Example 21 except that (a) the hydrophilic polymer of Example 21 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 24 A hydrophilic member was produced in the same manner as in Example 20 except that the catalyst (B) in the hydrophilic sol-gel solution of Example 20 was changed to the following.
  • Example 24 Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 2 g
  • Example 25 Zirconium chelate compound 2g The zirconium chelate compound was obtained by adding 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate to a reactor equipped with a stirrer and stirring at room temperature for 1 hour.
  • Example 26 A hydrophilic member was produced in the same manner as in Example 20, except that the hydrophilic polymer (II-1) in the hydrophilic sol-gel solution of Example 20 was changed to the following.
  • Example 26 Hydrophilic polymer (II-6) (: Using Exemplified Compound (II-6))
  • Example 27 Hydrophilic polymer (II-21) (: Using Exemplified Compound (II-21))
  • Example 28 A hydrophilic member of Example 26 was obtained in the same manner as in Example 18 except that the hydrophilic layer of Example 18 was changed to the following.
  • [Hydrophilic sol-gel solution] Prepared by mixing 12 g of tetramethoxysilane (C) as an alkoxide compound and 4 g of hydrophilic polymer (II-1) as a hydrophilic polymer in 20 g of ethyl alcohol and 100 g of purified water and stirring at room temperature for 2 hours. did.
  • hydrophilic composition The hydrophilic sol-gel solution was mixed with 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 60 g of purified water to obtain a hydrophilic composition.
  • Coating method An alkali degreased aluminum substrate (thickness: about 100 ⁇ m) is prepared, and the hydrophilic composition is bar-coated on the aluminum substrate and oven-dried at 150 ° C. for 30 minutes to obtain a dry coating amount of 0.1 g / m 2 . A hydrophilic layer was formed. Furthermore, the low-elution layer composition of Example 20 was bar-coated and oven-dried at 150 ° C.
  • Example 28 The hydrophilic member of Example 28 was obtained.
  • the thickness of the hydrophilic layer was 0.1 ⁇ m, and the thickness of the low elution layer was 0.2 ⁇ m.
  • Example 29 A hydrophilic member of Example 29 was produced in the same manner as in Example 28 except that 1.0 g of acetylacetone and 1.0 g of tetraethyl orthotitanate were added as the (B) catalyst to the hydrophilic sol-gel solution of Example 28.
  • Example 30 [Sol-gel solution for undercoat] Into 200 g of ethyl alcohol, 10 g of acetylacetone as the (P) catalyst, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane as the (Q) alkoxide compound was mixed and stirred at room temperature for 2 hours to prepare. [Composition for undercoat layer] 30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
  • Example 31 A hydrophilic member of Example 31 was obtained in the same manner as Example 30 except that the hydrophilic layer of Example 30 was changed to the hydrophilic layer of Example 28.
  • Example 32 A hydrophilic member of Example 32 was obtained in the same manner as Example 30 except that the hydrophilic layer of Example 30 was changed to the hydrophilic layer of Example 29.
  • Example 32 a member of Comparative Example 3 was obtained in the same manner as in Example 32 except that the low-elution layer was not formed.
  • Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 29 except that a hydrophilic polymer (comparative polymer (1)) having the following structure was used in place of (A) hydrophilic polymer (II-1) in the hydrophilic sol-gel solution. The hydrophilic member was obtained.
  • Example 5 JP, 2005-344144, paragraph 0046 (JP 2002-201289, Table 2, B1), 100 parts by weight of polyacrylic acid (average polymerization degree 400) and sodium carboxymethyl cellulose (average polymerization degree 500)
  • the low elution layer of Example 19 was formed on a mixed composition hydrophilic film (comparative hydrophilic film, film thickness 0.5 ⁇ m) consisting of 30 parts by weight to obtain a hydrophilic member of Comparative Example 5.
  • Example 33 [Hydrophilic sol-gel solution] In 100 g of purified water, (A) 2.5 g of hydrophilic polymer (I-1), 7.5 g of hydrophilic polymer (II-1) as hydrophilic polymer, (B) 0.1 g of acetylacetone as catalyst, orthotitanium The mixture was prepared by mixing 0.1 g of tetraethyl acid and stirring at room temperature for 2 hours. [Hydrophilic composition] A hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by weight aqueous solution of the following anionic surfactant.
  • composition for low elution layer In 100 g of dimethylacetamide, (a) 10 g of polyethylene glycol (PEG, mass average molecular weight 20,000) as a hydrophilic polymer and (b) 0.5 g of 1,4-tetramethylene diisocyanate as a cross-linking agent are mixed. The mixture was stirred for a time to obtain a composition for a low elution layer.
  • PEG polyethylene glycol
  • 1,4-tetramethylene diisocyanate 1,4-tetramethylene diisocyanate
  • a hydrophilic layer was formed. Further, the above composition for a low elution layer was coated on a bar and oven-dried at 150 ° C. for 30 minutes to form a low elution layer having a coating dry amount of 0.2 g / m 2. 1 hydrophilic member. The thickness of the hydrophilic layer was 0.7 ⁇ m, and the thickness of the low elution layer was 0.2 ⁇ m.
  • Example 34 A hydrophilic member of Example 34 was produced in the same manner as in Example 33 except that (a) the hydrophilic polymer of Example 33 was changed to polyvinyl alcohol (PVA, mass average molecular weight 50,000, saponification degree 99%).
  • PVA polyvinyl alcohol
  • Example 35 A hydrophilic member of Example 35 was produced in the same manner as in Example 33 except that the composition for low elution layer of Example 33 was changed to the following composition.
  • dimethylacetamide and 20 g of purified water, (a) 10 g of polyethylene glycol (mass average molecular weight 20,000) as a hydrophilic polymer, (b) 0.5 g of tetramethoxysilane as a crosslinking agent, and (c) acetylacetone in an amount of 0. 05 g and 0.05 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 1 hour to obtain a composition for a low elution layer.
  • Example 36 A hydrophilic member of Example 36 was produced in the same manner as in Example 35 except that the hydrophilic polymer (a) in Example 35 was changed to polyvinyl alcohol (mass average molecular weight 50,000, saponification degree 99%).
  • Example 37 A hydrophilic member was prepared in the same manner as in Example 33 except that (A) the hydrophilic polymer (I-1) in Example 33 was changed to the following.
  • Example 37 Hydrophilic polymer (I-2)
  • Example 38 hydrophilic polymer (I-11)
  • Example 39 A hydrophilic member was prepared in the same manner as in Example 33 except that (A) the hydrophilic polymer (II-1) in Example 33 was changed to the following.
  • Example 39 hydrophilic polymer (II-6)
  • Example 40 hydrophilic polymer (II-21)
  • Example 41 A hydrophilic member was prepared in the same manner as in Example 33 except that the addition amount of the hydrophilic polymer (I-1) and the hydrophilic polymer (II-1) in the hydrophilic sol-gel solution was changed to the following.
  • Example 41 0.5 g of hydrophilic polymer (I-1), 9.5 g of hydrophilic polymer (II-1)
  • Example 42 5.0 g of hydrophilic polymer (I-1), 5.0 g of hydrophilic polymer (II-1)
  • Example 43 [Hydrophilic sol-gel solution] In 20 g of ethyl alcohol and 100 g of purified water, (C) 12 g of tetramethoxysilane as alkoxide compound, (A) 1.0 g of hydrophilic polymer (I-1) as hydrophilic polymer, hydrophilic polymer (II-1) 3. 0 g, (B) 1.0 g of acetylacetone as a catalyst and 1.0 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 2 hours to prepare.
  • hydrophilic polymer (I-1) as hydrophilic polymer
  • hydrophilic polymer (II-1) 3.0 g
  • B 1.0 g of acetylacetone as a catalyst and 1.0 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 2 hours to prepare.
  • hydrophilic composition The hydrophilic sol-gel solution was mixed with 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 60 g of purified water to obtain a hydrophilic composition.
  • Coating method An alkali degreased aluminum substrate (thickness: about 100 ⁇ m) is prepared, and the hydrophilic composition is bar-coated on the aluminum substrate and oven-dried at 150 ° C. for 30 minutes to obtain a dry coating amount of 0.1 g / m 2 . A hydrophilic layer was formed. Furthermore, the low-elution layer composition of Example 33 was bar-coated and oven-dried at 150 ° C.
  • Example 12 The hydrophilic member of Example 12 was obtained.
  • the thickness of the hydrophilic layer was 0.1 ⁇ m, and the thickness of the low elution layer was 0.2 ⁇ m.
  • Example 44 [Sol-gel solution for undercoat] Into 200 g of ethyl alcohol, 10 g of acetylacetone as the (P) catalyst, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane as the (Q) alkoxide compound were mixed and stirred at room temperature for 2 hours to prepare. [Composition for undercoat layer] 30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
  • Example 45 A hydrophilic member of Example 45 was obtained in the same manner as in Example 44 except that the hydrophilic layer of Example 44 was changed to the hydrophilic layer of Example 43.
  • the hydrophilicity of the hydrophilic layer surface is generally measured with a water droplet contact angle (Kyowa Interface Science Co., Ltd., DropMaster 500). However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and even 5 ° or less, and there is a limit to the mutual comparison of the hydrophilicity. .
  • a measurement of surface free energy 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.
  • an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration.
  • the horizontal axis indicates the surface of the aqueous solution.
  • Hydrophilic durability A hydrophilic member is immersed in ultrapure water for 5 days, taken out, air-dried, and when the contact angle is measured with pure water, the smaller the change in the contact angle, the better the hydrophilic durability.
  • the case where the change in contact angle after immersion is 2 ° or less is evaluated as ⁇
  • the case of 2 to 7 ° is evaluated as ⁇
  • the case of 7 ° or more is evaluated as ⁇ .
  • the hydrophilic member of the present invention can be used in various applications that require hydrophilicity, wear resistance, and antifouling properties, such as a fin material for a heat exchanger included in an air conditioner.
  • This application is based on a Japanese patent application (Japanese Patent Application No. 2008-79314) filed on Mar. 25, 2008, the contents of which are incorporated herein by reference.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un élément hydrophile, comprenant : un matériau de base ; une couche hydrophile agencée sur le matériau de base et formée à partir d'une composition hydrophile contenant un polymère hydrophile (A) comportant au moins un groupe hydroxy et/ou un groupe fonctionnel hydrolysable et comportant également un atome de silicium ; et une couche légèrement éluante agencée sur la couche hydrophile et comprenant un polymère hydrophile (a) comportant un groupe réactif. L'élément hydrophile présente une excellente hydrophilicité, une excellente résistance à l'usure, et d'excellentes propriétés antitache, et peut présenter ces propriétés sur une longue période.
PCT/JP2009/055854 2008-03-25 2009-03-24 Elément hydrophile WO2009119605A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-079314 2008-03-25
JP2008079314A JP2009233872A (ja) 2008-03-25 2008-03-25 親水性部材

Publications (1)

Publication Number Publication Date
WO2009119605A1 true WO2009119605A1 (fr) 2009-10-01

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JP (1) JP2009233872A (fr)
WO (1) WO2009119605A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2977417A4 (fr) * 2013-03-21 2016-11-09 Nihon Parkerizing Agent de traitement de surface hydrophile pour échangeurs thermiques métalliques contenant de l'aluminium doués d'un excellent drainage

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5654844B2 (ja) * 2010-11-11 2015-01-14 三菱アルミニウム株式会社 熱交換器用耐アルカリ性アルミニウムフィン材及び熱交換器
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
JP6887366B2 (ja) * 2017-12-07 2021-06-16 株式会社Uacj プレコートフィン材
KR102189357B1 (ko) * 2018-06-01 2020-12-11 엘지전자 주식회사 냉장고

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10323619A (ja) * 1997-03-28 1998-12-08 Jsr Corp 硬化体
JP2000336233A (ja) * 1999-05-27 2000-12-05 Hitachi Chem Co Ltd 親水性樹脂組成物及び親水性塗膜の製造法
JP2002361800A (ja) * 2001-06-11 2002-12-18 Fuji Photo Film Co Ltd 表面親水性部材
JP2005344144A (ja) * 2004-06-01 2005-12-15 Kobe Steel Ltd 熱交換器用親水性表面処理フィン材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10323619A (ja) * 1997-03-28 1998-12-08 Jsr Corp 硬化体
JP2000336233A (ja) * 1999-05-27 2000-12-05 Hitachi Chem Co Ltd 親水性樹脂組成物及び親水性塗膜の製造法
JP2002361800A (ja) * 2001-06-11 2002-12-18 Fuji Photo Film Co Ltd 表面親水性部材
JP2005344144A (ja) * 2004-06-01 2005-12-15 Kobe Steel Ltd 熱交換器用親水性表面処理フィン材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2977417A4 (fr) * 2013-03-21 2016-11-09 Nihon Parkerizing Agent de traitement de surface hydrophile pour échangeurs thermiques métalliques contenant de l'aluminium doués d'un excellent drainage

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