WO2009119690A1 - Composite pour l'élaboration de film hydrophile, et élément hydrophile - Google Patents

Composite pour l'élaboration de film hydrophile, et élément hydrophile Download PDF

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Publication number
WO2009119690A1
WO2009119690A1 PCT/JP2009/056006 JP2009056006W WO2009119690A1 WO 2009119690 A1 WO2009119690 A1 WO 2009119690A1 JP 2009056006 W JP2009056006 W JP 2009056006W WO 2009119690 A1 WO2009119690 A1 WO 2009119690A1
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group
hydrophilic
polymer
silane coupling
hydrophilic film
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PCT/JP2009/056006
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English (en)
Japanese (ja)
Inventor
純明 山崎
智史 田中
裕一郎 村山
義顕 近藤
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富士フイルム株式会社
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Publication of WO2009119690A1 publication Critical patent/WO2009119690A1/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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane
    • 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 film forming composition and a surface hydrophilic member. Specifically, the present invention relates to a hydrophilic film forming composition that provides a hydrophilic surface layer excellent in hydrophilicity, durability, transparency, and storage stability, and a surface hydrophilic member including the surface hydrophilic film.
  • optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc.
  • optical members when used by humans, are contaminated with fingerprints, sebum, sweat, cosmetics, etc. Since removal of dirt is complicated, it is desired to perform effective dirt prevention treatment.
  • displays are often used outdoors, but when used in an environment where external light is incident, the incident light is regularly reflected on the display surface. As a result, the reflected light is mixed with the display light, causing problems such as difficulty in viewing the display image. For this reason, an antireflection optical member is often disposed on the display surface.
  • an antireflection optical member for example, a transparent substrate with a high refractive index layer and a low refractive index layer made of a metal oxide or the like laminated thereon, an inorganic or organic fluoride compound or the like on the transparent substrate surface.
  • a low refractive index layer is formed as a single layer, or those in which a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film substrate and external light is irregularly reflected by the uneven surface.
  • These anti-reflective optical member surfaces like the above-mentioned optical members, are susceptible to dirt such as fingerprints and sebum when used by humans, but only the part where the dirt is attached becomes highly reflective and the dirt is more noticeable.
  • the surface of the antireflection film usually has fine irregularities, and there is a problem that it is difficult to remove dirt.
  • an antireflection member and an antifouling member for example, an antifouling and antifriction material (for example, an antireflection film mainly composed of silicon dioxide and an antisilicon antifouling material treated with a compound containing an organosilicon substituent (for example, , See Patent Document 1), and an antifouling and friction-resistant CRT filter (for example, see Patent Document 2) in which a substrate surface is coated with a terminal silanol organopolysiloxane has been proposed.
  • an antifouling and antifriction material for example, an antireflection film mainly composed of silicon dioxide and an antisilicon antifouling material treated with a compound containing an organosilicon substituent (for example, , See Patent Document 1)
  • an antifouling and friction-resistant CRT filter for example, see Patent Document 2 in which a substrate surface is coated with a terminal silanol organopolysiloxane has been proposed.
  • an antireflection film containing a silane compound including a silane compound containing a polyfluoroalkyl group see, for example, Patent Document 3
  • an optical thin film mainly composed of silicon dioxide, a perfluoroalkyl acrylate, and an alkoxysilane group has been proposed.
  • the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and surface energy such as fluorine and silicon is low.
  • the surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.
  • a resin film generally used on the surface of an optical member or the like, or an inorganic material such as glass or metal has a hydrophobic surface or a weak hydrophilic surface.
  • the surface of a substrate using a resin film or inorganic material is made hydrophilic, the attached water droplets spread uniformly on the surface of the substrate and form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather.
  • combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and 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 (see, for example, Non-Patent Document 1), although this coating film has a certain degree of hydrophilicity, Affinity with the substrate is not sufficient, and higher durability is required.
  • a film using titanium oxide has been conventionally known.
  • a photocatalyst-containing layer is formed on the substrate surface, and the surface is highly hydrophilized according to photoexcitation of the photocatalyst.
  • Technology has been disclosed, and it has been reported that if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, water-circulating members, etc., excellent antifouling properties can be imparted to these composite materials. (For example, refer to Patent Document 5).
  • the hydrophilic film using titanium oxide does not have sufficient film strength, and since there is a problem that the use site is limited because the hydrophilization effect is not expressed unless photoexcited, and is durable, and There is a demand for antifouling members having good wear resistance.
  • 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 6).
  • the substrate is a window glass, a mirror or the like, if dust or dirt in the air adheres, it must be wiped with a dry cloth. In this case, when static electricity is generated due to friction, further dirt adheres, the dirt accumulates, and it becomes difficult to wash away even if water is applied. For this reason, further improvement of antifouling property and film
  • the heat exchanger of the air conditioner is composed of a pipe that moves the heat medium and a fin that absorbs heat in the air or dissipates heat in the heat medium.
  • a copper pipe is used by penetrating a thin aluminum plate having a thickness of about 0.1 mm, which is a fin material.
  • the condensed water generated during cooling becomes water droplets and stays between the fins, so that a bridge of water is generated and the cooling capacity is lowered.
  • even if dust or the like adheres between the fins there is a problem that the cooling capacity is similarly reduced.
  • JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Unexamined Patent Publication No. 7-16940 International Publication No. 96/29375 Pamphlet JP 2002-361800 A Newspaper "Chemical Industry Daily” article dated January 30, 1995
  • the object of the present invention is to further advance the research on the sol-gel organic-inorganic hybrid film to develop the above-mentioned prior art, and have excellent antifouling properties, water resistance, antifogging properties and better resistance to various substrate surfaces.
  • An object of the present invention is to provide a hydrophilic film forming composition used for forming a hydrophilic film having frictional properties.
  • Another object of the present invention is to provide a surface having an excellent antifouling property, antifogging property and anti-friction property provided with a hydrophilic film formed from the hydrophilic film-forming composition on an appropriate support surface. It is in providing the hydrophilic member which has this.
  • the present inventors paid attention to zwitterionic low molecular weight compounds, particularly compounds having a betaine structure, and by adding this to the composition for forming a hydrophilic film, not only the antifouling property of the hydrophilic film but also hydrophilicity,
  • the present invention was completed by finding that the coating strength and durability were further improved. That is, the above-described problems have been solved by the following means.
  • the mass ratio of the polymer to the hydrophilic polymer having a ratio ⁇ (B-1) hydrophilic polymer having a silane coupling group at the polymer terminal / (B-2) hydrophilic polymer having a silane coupling group at the polymer side chain ⁇ is 50 /
  • the metal complex catalyst (C) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table, ⁇ -diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, and enolic active hydrogen compound.
  • the (B-1) hydrophilic polymer having a silane coupling group at the polymer terminal has at least a structure represented by the following general formula (II-1) and a structure represented by the following general formula (II-2). 4.
  • R 201 , R 202 , R 203 , R 204 , and R 205 each independently represent a hydrogen atom or a hydrocarbon group, and m is 0 1 or 2;
  • L 201 and L 202 each independently represent a single bond or an organic linking group;
  • Y represents —N (R 7 ) (R 8 ), —OH, —NHCOR 7 , —CONH 2 , —CON (R 7 ) (R 8 ), —COR 7 , —CO 2 M or —SO 3 M, wherein R 7 and R 8 each independently represent a hydrogen atom or an alkyl group , M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.
  • the hydrophilic polymer having a silane coupling group in the polymer side chain has at least a structure represented by the following general formula (I-1) and a structure represented by the following general formula (I-2). 5.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 are each independently a hydrogen atom or Represents a hydrocarbon group.
  • L 101 represents a single bond or a polyvalent organic linking group.
  • L 102 represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO 2 NH—, and —SO 3 —.
  • n represents an integer of 1 to 3.
  • p and q represent composition ratios, and 0 ⁇ p ⁇ 100 and 0 ⁇ q ⁇ 100.
  • X is —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e) ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e And R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a linear, branched or cyclic alkyl group, halogen, Represents an atom, an inorganic anion, or an organic anion. 6).
  • a hydrophilic member obtained by coating the hydrophilic film forming composition according to any one of 1 to 5 on a substrate. 7). 6.
  • a fin material comprising a fin body and a hydrophilic film provided on at least a part of the surface of the fin body, wherein the hydrophilic film is formed with the hydrophilic film according to any one of 1 to 5 above.
  • a heat exchanger having the fin material as described in 7 or 8 above.
  • An air conditioner having the heat exchanger as described in 9 above.
  • the zwitterionic low molecular weight compound is added to the composition for forming a hydrophilic film, dirt is less likely to adhere. This is probably because the addition of the zwitterionic low molecular weight compound lowered the electrical resistance of the hydrophilic film and made it difficult to be charged. Furthermore, since the zwitterionic low molecular weight compound has high hydrophilicity, the hydrophilic film improves not only antifouling properties but also hydrophilicity.
  • the zwitterionic low molecular weight compound has a zwitterionic part
  • the zwitterionic low molecular weight compound which is an organic component
  • the composition of the present invention is hydrolyzed and polycondensed to form an organic-inorganic composite sol solution. It becomes easy to interact with the specific alkoxide hydrolysis-condensation polycondensation product, which is an inorganic component, by ionic bonding, and after curing, a coating film in which organic and inorganic are uniformly dispersed is formed, and exhibits excellent strength and durability.
  • the composition for forming a hydrophilic film of the present invention comprises (A) a zwitterionic low molecular weight compound, (B-1) a hydrophilic polymer having a silane coupling group at the polymer terminal, and (B-2) a silane cup on the polymer side chain.
  • the weight ratio of the hydrophilic polymer having a group ⁇ is in the range of 50/50 to 5/95.
  • the zwitterionic low molecular weight compound of the present invention is not particularly limited, and examples thereof include compounds having a cation and an anion in the same molecule, and compounds having an acidic group and a basic group.
  • An example of a compound having a cation and an anion in the same molecule is a compound having a betaine structure, and an example of a compound having an acidic group and a basic group in the same molecule is an amino acid.
  • Particularly preferred in the present invention is a compound having a betaine structure having no electric charge as a whole molecule, a cation such as quaternary ammonium, sulfonium or phosphonium as a cation, and —CO 2 ⁇ or —SO 3 as an anion. It is preferably an anion such as — , —PO 3 H ⁇ , —OPO 3 ⁇ —.
  • the preferred molecular weight range of the (A) zwitterionic low molecular weight compound is 100 to 1000, particularly preferably 200 to 800.
  • the zwitterionic low molecular weight compound preferably has at least one hydroxyl group in the molecule for immobilization in the hydrophilic member, and more preferably has at least one silane coupling group in the molecule.
  • Specific examples of the zwitterionic low-molecular compound include the following compounds, but the present invention is not limited thereto.
  • the content of the zwitterionic low molecular compound is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, based on the total solid content of the hydrophilic film-forming composition. Within this range, good antistatic ability, hydrophilicity and film strength can be obtained, and there is no fear of cracks in the film, which is preferable.
  • the hydrophilic film-forming composition of the present invention comprises (B-1) a hydrophilic polymer containing a silane coupling group at the polymer terminal (hereinafter also referred to as (B-1) a specific hydrophilic polymer), and (B- 2) Containing both a hydrophilic polymer containing a silane coupling group in the polymer side chain (hereinafter also referred to as (B-2) a specific hydrophilic polymer), ⁇ (B-1) a specific hydrophilic polymer / (B- 2)
  • the mass ratio of the specific hydrophilic polymer ⁇ is in the range of 50/50 to 5/95.
  • the mass ratio in which (B-1) the specific hydrophilic polymer / (B-2) the specific hydrophilic polymer is used is in the range of 50/50 to 5/95, preferably in the range of 40/60 to 5/95. Is within. Since the (B-1) specific hydrophilic polymer and the (B-2) specific hydrophilic polymer have different solubility in a solvent, there is a concern that, depending on the ratio used, there may be a problem in solubility.
  • (B-1) a hydrophilic polymer having a polymer terminal silane coupling group and (B-2) a hydrophilic polymer having a silane coupling group in the side chain will be described.
  • the log P of the monomer as the structural unit is preferably ⁇ 3 to 2, and more preferably ⁇ 2 to 0. In this range, good hydrophilicity can be obtained.
  • logP is developed by Medicinal Chemistry Project, Pona Collage, Clarmont, California, Daylight Chemical Information Inc. It is the logarithm of the octanol / water partition coefficient (P) value of a compound calculated using the more available software PCModels.
  • (B-1) as the specific hydrophilic polymer, a structure represented by the following general formula (II-1) and the following general formula (II-2) ) Is preferred (also referred to as hydrophilic polymer (II)).
  • R 201 , R 202 , R 203 , R 204 , and R 205 each independently represent a hydrogen atom or a hydrocarbon group, and m is 0 1 or 2;
  • L 201 and L 202 each independently represent a single bond or an organic linking group;
  • Y represents —N (R 7 ) (R 8 ), —OH, —NHCOR 7 , —CONH 2 , —CON (R 7 ) (R 8 ), —COR 7 , —CO 2 M or —SO 3 M, wherein R 7 and R 8 each independently represent a hydrogen atom or an alkyl group , M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.
  • the hydrophilic polymer (II) has a silane coupling group represented by the general formula (II-1) at at least one terminal of the polymer unit represented by the general formula (II-2).
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 7 , R 8 , Y, L 201 , L 202 , and M they may be the same as or different from each other.
  • the hydrophilic polymer (II) only needs to have a silane coupling group represented by the general formula (II-1) at at least one terminal of the polymer unit represented by the general formula (II-2).
  • the other terminus may have the silane coupling group.
  • it may have a hydrogen atom or a functional group having a polymerization initiating ability.
  • R 201 , R 202 , R 203 , R 204 , and R 205 represent a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 8 carbon atoms.
  • hydrocarbon group examples include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable.
  • R 201 , R 202 , R 203 , R 204 , and R 205 are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.
  • hydrocarbon groups may further have a substituent.
  • the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and here, a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent.
  • Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino
  • N-arylureido group N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureate group, N ′, N′-dialkyl -N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N', N'-diaryl -N-arylureido group, N'-alkyl-N'-arylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N
  • Monoarylphosphonooxy group (—OPO 3 H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group , An alkynyl group.
  • 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, and a cumenyl group.
  • alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc.
  • alkynyl examples include ethynyl, 1-butenyl, Examples include propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
  • G 1 in the acyl group examples include hydrogen and the above alkyl groups and aryl groups.
  • halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls.
  • acyloxy group N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamo Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group
  • the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
  • 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 202 represents a single bond or an organic linking group.
  • L 202 represents an organic linking group, it preferably represents a divalent linking group composed of a nonmetallic atom, and includes 0 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 Preference is given to consisting of up to 0 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More preferably, it is selected from —O—, —S—, —CO—, —NH—, —N ⁇ , an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof.
  • the linking group is more preferably —O—, —S—, —CO—, —NH—, or a combination containing —O—, —S—, —CO—, —NH—. More specific examples of the linking group include the following linking groups or linking groups constituted by combining these.
  • L 201 represents a single bond or an organic linking group.
  • the organic linking group refers to a polyvalent linking group composed of a non-metal atom, and specific examples thereof include the same as L 202 described above.
  • a particularly preferable structure is — (CH 2 ) n —S— (n is an integer of 1 to 8).
  • Y is, -N (R 7) (R 8), - OH, -NHCOR 7, -CONH 2, -CON (R 7) (R 8), - COR 7, a -CO 2 M or -SO 3 M
  • R 7 and R 8 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms).
  • R 7 and R 8 may be bonded to each other to form a ring, and the formed ring is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a heterocycle containing an atom.
  • R 7 and R 8 may further have a substituent, and the substituent that can be introduced here is introduced when R 201 , R 202 , R 203 , R 204 , and R 205 are alkyl groups. Those mentioned as possible substituents can likewise be mentioned.
  • R 7 and R 8 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, and t-butyl.
  • Preferred examples include a group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
  • M examples include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; or an onium such as ammonium, iodonium and sulfonium.
  • the Y, -NHCOCH 3, -CONH 2, -CON (R 7) 2, -COOH, -SO 3 - NMe 4 +, and the like are preferable morpholyl group, -CONH 2, -CON (R 7 ) 2 Gayori -CONH 2 is more preferable.
  • the mass average molecular weight of the specific hydrophilic polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.
  • Hydrophilic polymer (II) is, for example, the presence of a chain transfer agent (described in radical polymerization handbook (NTS, Mikiharu Tsunoike, Takeshi Endo)) or Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)).
  • a chain transfer agent described in radical polymerization handbook (NTS, Mikiharu Tsunoike, Takeshi Endo)
  • Iniferter described in Macromolecules 1986, 19, p287- (Otsu)
  • a hydrophilic monomer eg, acrylamide, acrylic acid, potassium salt of 3-sulfopropyl methacrylate.
  • chain transfer agents examples include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane.
  • a hydrophilic monomer eg, acrylamide
  • the hydrophilic polymer (II) uses a radically polymerizable monomer represented by the following general formula (i) and a silane coupling agent having chain transfer ability in the radical polymerization represented by the following general formula (ii). It can be synthesized by radical polymerization. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization. Although this reaction mode is not particularly limited, bulk reaction, solution reaction, suspension reaction and the like may be performed in the presence of a radical polymerization initiator or irradiation with a high-pressure mercury lamp.
  • reaction ratio of the structure represented by the general formula (II-2) to the structure represented by the general formula (II-1) is not particularly limited, but the structure represented by the general formula (II-1)
  • the structure represented by the general formula (II-2) should be in the range of 0.5 to 50 mol with respect to 1 mol.
  • the range of 1 to 45 mol is preferable, the range of 5 to 40 mol is most preferable.
  • R 201 to R 205 , L 201 , L 202 , Y, m are the same as those in the above general formulas (II-1) and (II-2). These compounds are commercially available and can also be easily synthesized.
  • the radically polymerizable monomer represented by the general formula (i) has a hydrophilic group Y, and this monomer becomes one structural unit in the hydrophilic polymer.
  • hydrophilic polymer (B-2) containing silane coupling group in side chain examples include a structure represented by the following general formula (I-1) and a general formula (I-2) ) Is preferred (also referred to as hydrophilic polymer (I)).
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 are each independently a hydrogen atom or Represents a hydrocarbon group.
  • L 101 represents a single bond or a polyvalent organic linking group.
  • L 102 represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO 2 NH—, and —SO 3 —.
  • n represents an integer of 1 to 3.
  • p and q represent composition ratios, and 0 ⁇ p ⁇ 100 and 0 ⁇ q ⁇ 100.
  • X is —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e) ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group
  • R d represents a linear, branched or cyclic alkyl group
  • R e And R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium
  • R g represents a linear, branched or cyclic alkyl group, halogen, Represents an atom, an inorganic anion, or an organic anion.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 represent a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 8 carbon atoms.
  • the preferred ranges of R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 , and the substituents that may be included are R 201 , R 202 in the hydrophilic polymer (II). , R 203 , R 204 , and R 205 are the same as the substituents that may be present.
  • L 101 represents a single bond or a polyvalent organic linking group.
  • the single bond means that the polymer main chain and X are directly bonded without a linking chain.
  • L 101 represents an organic linking group, it preferably represents a divalent linking group composed of a nonmetallic atom, and includes 0 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 atoms. Preferred are those consisting of up to oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More preferably, it is selected from —O—, —S—, —CO—, —NH—, —N ⁇ , an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof.
  • the linking group is more preferably —O—, —S—, —CO—, —NH—, or a combination containing —O—, —S—, —CO—, —NH—. More specific examples of the linking group include the following linking groups or linking groups constituted by combining these.
  • L 101 may be formed of a polymer or an oligomer, and specifically includes polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer.
  • Preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, and the like, and preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, and 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.
  • 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, and more preferably 1,000 to 200,000 is most preferred.
  • L 102 represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO 2 NH—, and —SO 3 —.
  • the single bond means that the polymer main chain and the Si atom are directly bonded without a linking group.
  • the structure may be present two or more, in this case, be the same as each other, may be different. If the structure than including one or more, other structures may have the same structure as those listed in L 101.
  • X is a hydrophilic group, and is —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), — NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , — NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ) ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (
  • R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R d is linear, branched or Represents a cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), an alkali metal Represents an alkaline earth metal or onium, and R g represents a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), a halogen atom, an inorganic anion, or an organic anion.
  • 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 substitution that can be introduced when R 203 to R 205 in formula (II-2) are alkyl groups. Those mentioned as groups can be mentioned as well.
  • 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 a ⁇ R d, a hydrogen atom; lithium, sodium, alkali metals such as potassium, calcium, alkaline earth such as barium metal, or, , Ammonium, iodonium, sulfonium and the like.
  • R g include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a nitrate anion, a sulfate anion, and a tetrafluoroborate anion, in addition to the alkyl groups listed as R a to R d
  • inorganic anions such as hexafluorophosphate anion, and organic anions such as methanesulfonate anion, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, and p-toluenesulfonate anion.
  • X -CO 2 - Na +, -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.
  • composition ratios p and q represent the composition ratio of the structure represented by the general formula (I-1) and the structure represented by the general formula (I-2) in the hydrophilic polymer (I), and 0 ⁇ p ⁇ 100, 0 ⁇ Q ⁇ 100.
  • the composition ratios p and q are preferably 30 ⁇ p ⁇ 100 and 0 ⁇ q ⁇ 70.
  • the structure represented by the general formula (I-1) and the structure represented by the general formula (I-2) which are structural units constituting the polymer chain are all the same, It may contain a plurality of different structural units, in which case the composition ratio of the structure represented by the general formula (I-1) and the structure represented by the general formula (I-2) is in the above range. It is preferable.
  • the weight average molecular weight of the hydrophilic polymer containing a silane coupling group in the side chain is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, 000 to 200,000 is most preferred.
  • hydrophilic polymer containing a silane coupling group in the side chain B-2
  • M.W. mass average molecular weight
  • the 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 method for synthesizing the (B-1) specific hydrophilic polymer and (B-2) the specific hydrophilic polymer any of conventionally known methods can be used.
  • general 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 (B-1) specific hydrophilic polymer and (B-2) specific hydrophilic polymer may be a copolymer with other monomers.
  • Other monomers include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyls or hydrolysates thereof, vinyl esters, styrenes, acrylic acid or salts thereof, methacrylic acid or its Known monomers such as salts, acrylonitrile, maleic anhydride, maleic imide and the like are also included.
  • various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.
  • monomers having an amino group, an ammonium group, a hydroxyl group, a sulfonamide group, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an ether group, particularly an ethyleneoxy group are preferable.
  • hydrophilic polymers having a urethane bond, an amide bond, or a urea bond in the main chain can also be used.
  • acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxy Phenethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl
  • methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxy Phenethyl methacrylate, dihydroxyphenethyl methacrylate
  • acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide.
  • methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.
  • vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.
  • styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.
  • the ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but it has a sufficient function as a hydrophilic film, and (B-1) and In order to sufficiently obtain the advantage of adding the hydrophilic polymer (B-2), the ratio is preferably not too large. Therefore, the preferred total proportion of structural units derived from other monomers in the total hydrophilic polymer of (B-1) specific hydrophilic polymer and (B-2) specific hydrophilic polymer is preferably 80% by mass or less, More preferably, it is 50 mass% or less.
  • the total amount of (B-1) specific hydrophilic polymer and (B-2) specific hydrophilic polymer according to the present invention is curable and hydrophilic with respect to the non-volatile components of the hydrophilic film-forming composition of the present invention.
  • the content is preferably 5 to 95% by mass, more preferably 15 to 90% by mass, and most preferably 20 to 85% by mass.
  • the non-volatile component refers to a component excluding a volatile solvent.
  • composition for forming a hydrophilic film of the present invention (A) a zwitterionic low-molecular compound, (B-1) a specific hydrophilic polymer, and (B-2) a specific hydrophilic polymer are dissolved in a solvent and stirred well. Thus, these components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, and a hydrophilic film having high hydrophilicity and high film strength is formed by this sol solution.
  • a metal complex catalyst is used to promote hydrolysis and polycondensation reactions.
  • Examples of the (C) metal complex catalyst used in the present invention include hydrolysis and polycondensation of the silane coupling group in the hydrophilic polymer (B-1) and (B-2), and (B-1), (B B-2)
  • a catalyst that promotes a reaction that causes a bond between hydrophilic polymers to occur is selected.
  • a Lewis acid catalyst composed of a metal complex can also be preferably used.
  • Particularly preferred catalysts are metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and ⁇ -diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and oxo compounds selected from enolic active hydrogen compounds.
  • it is a metal complex comprised from a hydroxy oxygen containing compound.
  • 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, and 5A group elements such as V, Nb and Ta are preferable.
  • 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.
  • the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a ⁇ -diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butyl acetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone, Keto alcohols such as 4-hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-mono Ethanolamine, diethanol Aminoalcohols such as ethanol and triethanolamine
  • a preferred ligand is acetylacetone or an acetylacetone derivative.
  • the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone.
  • Substituents for substitution on the methyl group of acetylacetone are all straight-chain or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone
  • the substituents that substitute for the methylene group are carboxyl groups, both straight-chain or branched carboxyalkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms, and the substituents that substitute for the carbonyl carbon of acetylacetone are carbon atoms.
  • acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol.
  • 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, A salt form such as a halogenate salt, a sulfate salt, a phosphate salt, etc., that ensures stoichiometric neutrality is used.
  • a salt form such as a halogenate salt, a sulfate salt, a phosphate salt, etc., that ensures stoichiometric neutrality is used.
  • the metal complex takes a coordination structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst.
  • this metal complex has led to the improvement of coating solution aging stability and film surface quality, high hydrophilicity, and high durability.
  • the (C) metal complex catalyst according to the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 25%, based on the nonvolatile components in the hydrophilic film-forming composition of the present invention. Used in the mass% range. Moreover, (C) a catalyst may be used independently or may be used together 2 or more types.
  • composition for forming a hydrophilic film of the present invention includes (A) an amphoteric ionic low molecular weight compound, (B-1) a specific hydrophilic polymer, (B-2) a specific hydrophilic polymer and (C) which are the essential components.
  • B-1 amphoteric ionic low molecular weight compound
  • B-2 a specific hydrophilic polymer
  • C specific hydrophilic polymer
  • various compounds can be used in combination as long as the effects of the present invention are not impaired.
  • components that can be used in combination will be described.
  • the (D) alkoxide compound of an element selected from Si, Ti, Zr, and Al (also referred to as a specific alkoxide) used in the present invention has a polymerizable functional group in its structure and functions as a crosslinking agent. It is a hydrolyzable polymerizable compound that performs condensation polymerization with (B-1) a specific hydrophilic polymer and (B-2) a specific hydrophilic polymer to form a strong film having a crosslinked structure.
  • the specific alkoxide is preferably a compound represented by the following general formula (3) or (4).
  • (B-1 A specific hydrophilic polymer, (B-2) a specific hydrophilic polymer, and (D) a specific alkoxide represented by the general formula (3) or (4) are mixed, coated on the surface of the support, heated and dried.
  • 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 an integer of 0 to 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 represented by (D) the general formula (3) or (4) are shown below, but the present invention is not limited thereto.
  • 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,
  • 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.
  • the specific alkoxide include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.
  • the alkoxide whose Z is Si is preferable from a viewpoint of film property.
  • the (D) specific alkoxide according to the present invention may be used alone or in combination of two or more.
  • the specific alkoxide is preferably used in the range of 0 to 80% by mass, more preferably 10 to 70% by mass with respect to the nonvolatile component in the hydrophilic film forming composition of the present invention.
  • the specific alkoxide 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.
  • surfactant in the present invention, it is preferable to use a surfactant in order to improve the coating surface of the hydrophilic film forming 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.
  • those having “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.
  • the composition for forming a hydrophilic film of the present invention may contain inorganic fine particles in order to improve the cured film strength and hydrophilicity of the hydrophilic film to be formed.
  • the inorganic fine particles for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
  • the inorganic fine particles preferably have an average particle diameter of 5 nm to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m. Within the above range, it is possible to form a film that is stably dispersed in the hydrophilic film, sufficiently retains the film strength of the hydrophilic film, and is excellent in hydrophilicity.
  • the inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
  • the inorganic fine particles according to the present invention are used in the hydrophilic film-forming composition of the present invention as a non-volatile component, preferably 20% by mass or less, more preferably 10% by mass or less.
  • the inorganic fine particles can be used alone or in combination of two or more.
  • an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the hydrophilic member.
  • Examples of 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 film-forming coating solution.
  • the antioxidant include European Published Patent Nos. 223739, 309401, 309402, 310551, 310552, 457416, and German Patent No. 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.
  • Polymer compound In order to adjust the film properties of the hydrophilic film, various polymer compounds can be added to the coating liquid for forming a hydrophilic film of the hydrophilic member of the present invention as long as the hydrophilicity is not impaired.
  • 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.
  • leveling additives for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers to the extent that hydrophilicity is not impaired in order to improve adhesion to the substrate, etc.
  • 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.
  • Preparation of hydrophilic film-forming composition comprises (A) a zwitterionic low molecular weight compound, (B-1) a specific hydrophilic polymer, (B-2) a specific hydrophilic polymer, and (C) a metal complex catalyst, If necessary, (D) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al is dissolved in a solvent such as ethanol and then stirred.
  • the reaction temperature is from room temperature to 80 ° C.
  • 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.
  • a hydrophilic film-forming composition containing the (A) zwitterionic low molecular weight compound, (B-1) a specific hydrophilic polymer, (B-2) a specific hydrophilic polymer, and (C) a metal complex catalyst is prepared.
  • the solvent used at the time is not particularly limited as long as these 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 solution (hydrophilic film-forming composition) for forming the hydrophilic film by the hydrophilic film-forming composition of the present invention uses the sol-gel method.
  • sol-gel method Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha Co., Ltd. (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of a hydrophilic film-forming composition in the present invention.
  • the hydrophilic member of the present invention can be obtained by coating a solution containing such a composition for forming a hydrophilic film of the present invention on an appropriate substrate and drying. That is, the hydrophilic member of the present invention has a hydrophilic film formed by applying the hydrophilic film forming composition of the present invention on a substrate.
  • the heating and drying conditions after coating the solution containing the hydrophilic film-forming composition are 50 to 200 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure. In the range, it is preferable to carry out for about 2 minutes to 1 hour, and more preferably in the 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 application of the hydrophilic film-forming composition to the substrate can employ a known application method, and is not particularly limited. For example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, A roll coating method, a film applicator method, a screen printing method, a bar coater method, a brush coating, a sponge coating or the like can be applied.
  • the material contains glass or an inorganic compound layer.
  • a substrate capable of transmitting visible light such as an inorganic substrate such as glass, a metal substrate such as stainless steel or aluminum, a transparent plastic, or a transparent plastic layer containing an inorganic compound layer, can be suitably used.
  • the details of the inorganic substrate include a normal glass plate, a laminated glass plate including a resin layer, a gas layer, and a vacuum layer, and various glass plates including a reinforcing component and a colorant.
  • the glass plate containing the inorganic compound layer include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide,
  • ITO Indium Tin Oxide
  • a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride
  • 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
  • examples of the transparent plastic substrate include substrates made of various plastic materials having visible light permeability.
  • a substrate used as an optical member is selected in consideration of optical properties such as transparency, refractive index, and dispersibility, and has various physical properties such as impact resistance and flexibility depending on the purpose of use. It is selected in consideration of physical properties including heat resistance, weather resistance, durability and the like.
  • polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins, or polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polyethylene vinyl alcohol, and acrylic resins.
  • Preferred examples include resins, cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellophane. 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 plastic substrate a substrate in which an inorganic compound layer described in the description of the glass plate is formed on the plastic plate can be used.
  • the inorganic compound layer can also act as an antireflection layer. Even when the inorganic compound layer is formed on the plastic plate, it can be formed by the same method as in the inorganic substrate described above.
  • a hard coat layer may be formed between the two layers.
  • the hardness of the substrate surface is improved and the substrate surface is smoothed, so that the adhesion between the transparent plastic substrate and the inorganic compound layer is improved, the scratch resistance is improved, and the substrate is bent. It is possible to suppress the occurrence of cracks in the inorganic compound layer due to the above.
  • the mechanical strength of the hydrophilic member can be improved.
  • the material of the hard coat layer is not particularly limited as long as it has transparency, appropriate strength, and mechanical strength.
  • a curable resin or a thermosetting resin by irradiation with ionizing radiation or ultraviolet rays can be used, and an ultraviolet irradiation curable acrylic resin, an organosilicon resin, or a thermosetting polysiloxane resin is particularly preferable.
  • the refractive index of these resins is more preferably equal to or close to the refractive index of the transparent plastic substrate.
  • Such a coating method of the hard coat layer is not particularly limited, and any method can be adopted as long as it is uniformly applied.
  • the hard coat layer having a thickness of 3 ⁇ m or more has sufficient strength, but is preferably in the range of 5 to 7 ⁇ m from the viewpoint of transparency, coating accuracy, and handling.
  • a light diffusing treatment generally called anti-glare can be performed. These particles are not particularly limited as long as they are transparent, but a low refractive index material is preferable, and silicon oxide and magnesium fluoride are particularly preferable in terms of stability, heat resistance, and the like.
  • the light diffusing treatment can also be achieved by providing irregularities on the surface of the hard coat layer.
  • the hydrophilic member of the present invention can be obtained by using a glass plate or plastic plate having an inorganic compound layer as a substrate and forming a hydrophilic surface. Since the hydrophilic member has a hydrophilic film excellent in hydrophilicity and durability on the surface, it is excellent in antifouling property on the surface of the support (substrate), in particular, antifouling property against oil and fat stains, antifogging property or Both can be granted.
  • the antireflection layer applicable to the surface of the hydrophilic member of the present invention is not limited to the above-described inorganic compound layer. For example, an antireflection effect is obtained by laminating a plurality of thin layers having different reflectivities and refractive indexes.
  • a known antireflection layer or the like can also be used as appropriate, and the material can be either an inorganic compound or an organic compound.
  • the substrate on which the inorganic compound layer as the antireflection film is formed on the surface is applied with the hydrophilic polymer chain according to the present invention on the surface on the side where the antireflection film is formed.
  • the antifouling and / or antifogging member of the present invention having excellent antifogging function and antireflection properties can be obtained.
  • the hydrophilic member of the present invention can be used in various ways by bonding a functional optical member such as a polarizing plate to a member having the above-described structure by a bonding technique typified by a laminate. An antireflection / optical functional member having functions and characteristics can also be obtained.
  • anti-reflective members and anti-reflective / optical functional members can be used for the front plate of display devices of various displays (liquid crystal displays, CRT displays, projection displays, plasma displays, EL displays, etc.) using adhesives, adhesives, etc. By applying it to a glass plate, a plastic plate, a polarizing plate or the like, this antireflection member can be applied to a display device.
  • hydrophilic member of the present invention can be applied to various uses requiring antifouling and / or antifogging effects in addition to the display device described above.
  • the antifouling and / or antifogging member when trying to apply the antifouling and / or antifogging member to a substrate that does not require transparency, in addition to the above transparent substrate, for example, metal, ceramics, wood, stone, cement, concrete, Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used as the support substrate.
  • one or more undercoat layers can be provided between the substrate and the hydrophilic film.
  • the undercoat layer is preferably obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr and Al and a nonvolatile catalyst.
  • An undercoat layer obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst has a crosslinked structure.
  • a crosslinked structure formed by hydrolysis and condensation polymerization of a compound is appropriately referred to as a sol-gel crosslinked structure.
  • alkoxide compound containing an element selected from Si, Ti, Zr and Al examples include those described above.
  • Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.
  • Nonvolatile catalysts used in the undercoat layer are those other than those having a boiling point of less than 20 ° C., in other words, those having a boiling point of 20 ° C. or higher, or those having no boiling point in the first place (such as thermal decomposition, Including those that do not cause changes).
  • a metal complex it is also called a metal chelate compound
  • silane coupling agent are mentioned.
  • an acid or an alkali is suitably used as a catalyst in the industry, any of those having a boiling point of 20 ° C. or higher can be applied without particular limitation.
  • nitric acid having a boiling point of 121 ° C. and phosphoric acid having a decomposition temperature of 213 ° C. are applied as a nonvolatile catalyst in the present invention.
  • the metal complex include those described above.
  • the silane coupling agent used as the non-volatile catalyst is not particularly limited, and examples thereof include those having a functional group showing acidity or alkalinity, and more specifically, peroxo acid, carboxylic acid, carbohydrazone acid, carboxymid A functional group showing acidity such as acid, sulfonic acid, sulfinic acid, sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid and the above alkali metal salts, or a basic functional group showing amino group, etc.
  • the silane coupling agent which has is mentioned.
  • the undercoat layer is formed by applying a composition having at least the alkoxide compound and the non-volatile catalyst on the base material, heating and drying the base composition, thereby hydrolyzing and polycondensing the composition. Can be formed.
  • the heating temperature and heating time for forming the undercoat layer are not particularly limited as long as the solvent in the sol solution is removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.
  • the undercoat layer can be prepared by a known coating method, and is not particularly limited. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing Methods such as coating, bar coating, brush coating, and sponge coating are applicable.
  • the subbing layer thus obtained contains a non-volatile catalyst without losing its activity, and in particular also on the surface thereof, the subbing layer and the hydrophilic film The adhesion at the interface is extremely high.
  • the undercoat layer can be further improved in adhesion at the interface between the undercoat layer and the hydrophilic film 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 cross-linking agent applicable to the present invention a cross-linking agent that forms a cross-link by known heat can be used.
  • General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981).
  • the number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex.
  • thermal crosslinking agents include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, polyethylene or polypropylene Polyepoxy compounds such as glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tolylene diene Isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diiso Polyisocyanate compounds such as anate, polymethylene polyphenyl iso
  • a water-soluble crosslinking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic film.
  • the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 ⁇ 20 g / m 2, more preferably 0.1 ⁇ 10g / m 2.
  • the hydrophilic member may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a material that has been cut in advance so as to be attached to an appropriate substrate.
  • the hydrophilic member When the hydrophilic member is applied (used or pasted) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer.
  • the light transmittance is preferably from 100% to 70%, more preferably from 95% to 75%, and most preferably from 95% to 80%. By being in this range, the hydrophilic member can be applied to various uses without obstructing the field of view.
  • the hydrophilicity of the hydrophilic film surface is generally measured by the water droplet contact angle.
  • a method for evaluating the hydrophilicity of the solid surface in more detail there is a measurement of surface free energy.
  • the surface free energy can be measured by using a 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. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution.
  • Vehicle rearview mirrors bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, lighting lenses, semiconductor lenses, and copying machines Lenses such as lenses; prisms; window glass for buildings and surveillance towers; glass for other building materials; various vehicles such as automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, etc.
  • Windshields Windshields; Windshields for various vehicles such as automobiles, railway cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, protective goggles, sports goggles, protective Mask shield, sports mask shield, helmet shield, frozen food display case glass; measuring instrument cover glass, building materials, exterior wall Building exteriors such as roofs, building interiors, window frames, window glass, structural members, automobiles, rail cars, aircraft, ships, bicycles, exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and equipment, dust covers and Paint, traffic signs, various display devices, advertising towers, sound barriers for roads, sound barriers for railways, bridges, guardrail exteriors and paints, tunnel interiors and paints, insulators, solar cell covers, solar water heater heat collection covers, greenhouses , Cover for vehicle lighting, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range, kitchen
  • the hydrophilic member according to the present invention is preferably a fin material, and is preferably a fin material having an aluminum fin main body. That is, the fin material of the present invention is a fin material comprising a fin main body (preferably an aluminum fin main body) and a hydrophilic film provided on at least a part of the surface of the fin main body. Is preferably coated with the hydrophilic film-forming composition according to the present invention.
  • Aluminum fin material (aluminum fin body itself) used in heat exchangers such as indoor air conditioners and automobile air conditioners causes water droplets to form as water droplets and stay between the fins. Ability is reduced.
  • the adhering dust between the fins similarly reduces the cooling capacity.
  • the fin material in which the composition for forming a hydrophilic film of the present invention is applied to the fin body provides a fin material excellent in hydrophilicity, antifouling property, and sustainability thereof. It is done.
  • Examples of the aluminum used for the fin body of the fin material include those having a degreased surface and, if necessary, a chemically treated aluminum plate. It is preferable that the surface of the fin body made of aluminum is subjected to a chemical conversion treatment in terms of adhesion of the hydrophilic treatment film, corrosion resistance, and the like.
  • Examples of the chemical conversion treatment include chromate treatment, and typical examples thereof include alkali salt-chromate method (BV method, MBV method, EW method, Al And a treatment method such as a chromic acid method, a chromate method, and a chromic phosphate method, and an anhydrous washing coating type treatment with a composition mainly composed of chromium chromate.
  • pure aluminum plate such as 1100, 1050, 1200, 1N30, Al—Cu based alloy plate such as 2017, 2014, 3003, Any of Al-Mn alloy plates such as 3004, Al-Mg alloy plates such as 5052 and 5083, and Al-Mg-Si alloy plates such as 6061 may be used. Any of the coils may be used.
  • the fin material which concerns on this invention for a heat exchanger. Since the heat exchanger having 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. .
  • the heat exchanger include heat exchangers used for indoor coolers, air conditioners, oil coolers for construction machines, automobile radiators, capacitors, and the like.
  • 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.
  • Example 1 Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by glow treatment, and then a hydrophilic film coating solution (1) having the following composition is applied to a bar at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic film with a dry coating amount of 1.0 g / m 2 to form a hydrophilic member.
  • ⁇ Sol-gel preparation liquid (1)> In 200 g of ethyl alcohol, 0.25 g of acetylacetone, 0.3 g of tetraethyl orthotitanate and 300 g of purified water, 7.5 g of the following (B-1) specific hydrophilic polymer (B-1-1), (B-2) The mixture was prepared by mixing 22.5 g of the specific hydrophilic polymer (B-2-1) and 7.5 g of the specific betaine compound (Exemplary Compound (1)) and stirring at room temperature for 2 hours.
  • the polymer (B-1-1) having a mass average molecular weight of 4000 was confirmed by GPC (polyethylene oxide standard).
  • the 5% aqueous solution viscosity was 2.5 cP, and the functional group density of the hydrophilic group was 13.4 meq / g.
  • the obtained solid was washed with acetone to obtain a specific hydrophilic polymer (B-2-1).
  • the mass after drying was 65.6 g. It was a polymer having a mass average molecular weight of 8,500 by GPC (polyethylene oxide standard).
  • Anti-fogging Applying water vapor for 1 minute under an indoor fluorescent lamp in the daytime, separating from the water vapor, placing it in an environment of 25 ° C., 10% RH, and clouding under a fluorescent lamp under the same irradiation conditions as above The condition and its change were sensory-evaluated in three stages according to the following criteria. ⁇ : No cloudiness is observed ⁇ : Cloudy, but recovers within 10 seconds, no cloudiness is seen ⁇ : Cloudy, no cloudiness recovers even after 10 seconds
  • Antifouling property Apply with air spray containing carbon black suspension (10% aqueous solution) until the surface of the hydrophilic member is uniformly concealed, dry at 60 ° C. for 1 hour, and then cool to room temperature. . Thereafter, the carbon black on the surface of the hydrophilic member was washed away under running water, dried at room temperature for 1 hour, and the water droplet contact angle of distilled water was measured with DROP MASTER 500 manufactured by Kyowa Interface Science. If the water droplet contact angle shows a low value even after the carbon black (CB) treatment (after coating, drying, washing and drying at room temperature for 1 hour), the antifouling property is considered good. .
  • carbon black suspension 10% aqueous solution
  • Water resistance A hydrophilic member having a size of 120 cm 2 was rubbed with a sponge 10 times in water, and the remaining film ratio was measured from the change in mass before and after that. The higher the remaining film ratio, the higher the water resistance.
  • Scratch test Starting from 5 g on a 0.1 mm diameter sapphire needle, applying 5 g increments to scan the hydrophilic membrane surface and evaluating the weight at which scratches occurred (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.) )did. The durability is better when there is no damage even if the load is large.
  • Storage stability 50 sheets of 5 cm square hydrophilic members are stacked, pressure-bonded using a vise with a torque of 300 kg, and evaluated for backside adhesion after aging in a 45 ° C 75% humidity environment for 1 day. did. If the back side is not bonded, it means that the storage stability is excellent.
  • Example 1 A hydrophilic member was formed in the same manner as in Example 1 except that the specific betaine compound (Exemplary Compound (1)) was not added. The results are shown in Table 1.
  • Examples 2 to 5 A hydrophilic film was formed and evaluated in the same manner as in Example 1 except that the specific betaine compound (Exemplary Compound (1)) was changed to the specific betaine compound shown in Table 2. The results are shown in Table 1.
  • Example 6 Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, the surface of the plate glass is hydrophilized by UV / O 3 treatment for 10 minutes, and then the first layer coating solution (1) having the following composition is spun. The coating was applied and oven-dried at 100 ° C. for 10 minutes to form a first layer having a dry coating amount of 1.0 g / m 2 . After sufficiently cooling at room temperature, the hydrophilic coating solution (1) used in Example 1 was applied as a second layer to the first layer coating surface by spin coating, dried in an oven at 100 ° C. for 10 minutes, and dried. A second layer of 1.0 g / m 2 was formed. The evaluation results are shown in Table 1.
  • Example 7 A polyethylene terephthalate (PET) substrate (thickness: 50 ⁇ m) whose surface has been hydrophilized by glow treatment is prepared, and the first layer coating solution (2) having the following composition is spin-coated (1000 rpm for 30 seconds) and oven-dried at 100 ° C. for 2 minutes. A first layer having a dry coating amount of 0.5 g / m 2 was formed. The water droplet contact angle of the first layer was 80 °. Subsequently, the hydrophilic film coating liquid (1) used in Example 1 was spin-coated on the first layer (100 rpm for 2 minutes, then 50 rpm for 5 minutes, 200 rpm for 2 minutes), and 100 ° C. for 10 minutes. Oven dried to form a hydrophilic film having a dry coating amount of 2.0 g / m 2 to produce a hydrophilic member. The evaluation results are shown in Table 1.
  • Example 8 The first layer described in Example 7 was provided on a SUS substrate (thickness: 1.1 mm) whose surface was hydrophilized by UV / O 3 treatment for 10 minutes, and a first layer coating liquid having the following composition was further formed on the first layer ( 3) was spin-coated (1000 rpm for 60 seconds) and oven-dried at 100 ° C. for 10 minutes to form a layer having a dry coating amount of 0.5 g / m 2 to form a first layer having a two-layer structure.
  • membrane was formed on the 1st layer of this two-layer structure using the hydrophilic film
  • the evaluation results are shown in Table 1.
  • Example 9 An aluminum plate (A1200, thickness 0.1 mm) prepared by immersing in an alkaline cleaning solution (Yokohama Yushi Co., Ltd., Semi-clean A 5% aqueous solution) for 10 minutes and repeating washing with water three times was prepared, and the first layer coating solution (4 ), And oven dried at 100 ° C. for 10 minutes to form a first layer having a dry coating amount of 0.1 g / m 2 . After sufficiently cooling at room temperature, the hydrophilic layer coating solution (2) is applied as a second layer to the first layer coating surface as a second layer, oven dried at 150 ° C. for 30 minutes, and a dry coating amount of 0.5 g / m 2 . A second layer was formed to produce a hydrophilic member and evaluated.
  • an alkaline cleaning solution Yokohama Yushi Co., Ltd., Semi-clean A 5% aqueous solution
  • the hydrophilic layer coating solution (2) is applied as a second layer to the first layer coating surface as a second layer, oven
  • ⁇ Sol-gel preparation liquid (3)> In 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water, 4 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4 g of methyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. Stir at room temperature for 2 hours to prepare.
  • Contamination resistance 0.2 g of palmitic acid in a 50 ml glass container, covered with a hydrophilic member so that the hydrophilic membrane side is exposed to palmitic acid, and after aeration at 105 ° C./1 hour, Washing with running water for 30 minutes and drying at 80 ° C./30 minutes were taken as one cycle, and the contact angle after 5 cycles was measured. The smaller the contact angle value, the better the stain resistance.
  • Example 2 A hydrophilic member was prepared and evaluated in the same manner as in Example 9 except that (B-1) the specific hydrophilic polymer in the hydrophilic film coating solution (2) was changed to polyacrylamide.
  • Example 9 except that the types and mass ratios of (B-1) specific hydrophilic polymer and (B-2) specific hydrophilic polymer in the hydrophilic film coating solution (2) were changed as shown in Table 3. A hydrophilic member was produced in the same manner and evaluated.
  • Example 14 to 16 A hydrophilic member was prepared and evaluated in the same manner as in Example 1 except that the specific betaine compound (Exemplary Compound (1)) was changed to the zwitterionic low molecular weight compound shown in Table 5. The results are shown in Table 6.
  • Example 9 except that the type and mass ratio of (B-1) specific hydrophilic polymer and (B-2) specific hydrophilic polymer in the hydrophilic film coating solution (2) were changed as shown in Table 7. A hydrophilic member was produced in the same manner and evaluated. The results are shown in Table 8.
  • Examples of applicable fields of the hydrophilic film forming composition and the hydrophilic member of the present invention include: a vehicle rearview mirror, a bathroom mirror, a washing surface, as a useable substrate that can transmit visible light.
  • Mirrors such as industrial mirrors, dental mirrors, road mirrors; glasses lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, semiconductor lenses, copier lenses; prisms; buildings and Window glass of surveillance towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondolas, vehicle windows such as spaceships; automobiles, rail vehicles, aircraft, ships, diving Windshields for boats, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, spacecraft vehicles; protective goggles, sports goggles, protective masks De, shield for sports masks, helmet shield, glass frozen food display cases; cover glass measuring instruments, and the like films for attached to the article surface and the like.

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Abstract

L'invention concerne un composite pour l'élaboration de film hydrophile, qui comprend un composé zwittérionique de faible poids moléculaire (A), un polymère hydrophile à groupe de couplage silane sur une extrémité polymère correspondante (B-1), un polymère hydrophile à groupe de couplage silane sur une chaîne latérale polymère correspondante (B-2) et un catalyseur en complexe métallique (C). Le rapport de masse entre le polymère hydrophile à groupe de couplage silane sur une extrémité polymère (B-1) et un polymère hydrophile à groupe de couplage silane sur une chaîne latérale polymère (B-2) va de 50/50 à 5/95. Le composite permet de former un film hydrophile sur divers types de surfaces, et le film hydrophile présente d'excellentes propriétés antisalissure et antibuée et il présente en outre une bonne résistance au frottement.
PCT/JP2009/056006 2008-03-25 2009-03-25 Composite pour l'élaboration de film hydrophile, et élément hydrophile WO2009119690A1 (fr)

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JP2008079325A JP2009235130A (ja) 2008-03-25 2008-03-25 親水性膜形成用組成物および親水性部材

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