WO2008001665A1 - Film anti-salissures et son procédé de production - Google Patents

Film anti-salissures et son procédé de production Download PDF

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Publication number
WO2008001665A1
WO2008001665A1 PCT/JP2007/062420 JP2007062420W WO2008001665A1 WO 2008001665 A1 WO2008001665 A1 WO 2008001665A1 JP 2007062420 W JP2007062420 W JP 2007062420W WO 2008001665 A1 WO2008001665 A1 WO 2008001665A1
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Prior art keywords
group
graft polymer
antifouling film
polymer chain
producing
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PCT/JP2007/062420
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English (en)
Japanese (ja)
Inventor
Toshihide Aoshima
Koichi Kawamura
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Fujifilm Corporation
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Publication of WO2008001665A1 publication Critical patent/WO2008001665A1/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
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to an antifouling film and a method for producing the same, and more particularly to an antifouling film having an antifouling surface to which oily dirt or the like is difficult to adhere and a method for producing the same.
  • a film having water repellency and antifouling property a film having a water repellency and antifouling property by wet coating (wet film formation) with a fluorine compound layer on the outermost surface thereof has been used.
  • wet film formation wet film formation
  • fluorine compound layer on the outermost surface thereof has been used.
  • surface coating with organic materials required improvements to reduce surface hardness and durability.
  • silica layer having excellent water repellency and antifouling properties and low surface energy has the above-mentioned surface hardness and durability. Promising for improvement.
  • a silica layer having water repellency and antifouling properties is coated on the support to obtain a film having water repellency and antifouling properties, the surface energy of the silica force layer is small, which When the adhesion between the body and the body is reduced, there is a problem.
  • an adhesion silica layer having a carbon content of less than 20 atomic% as an intermediate layer between the support and the surface silica layer.
  • Patent Document 2 an adhesion silica layer having a large surface energy is provided between the surface silica layer and the support to improve the adhesion between the support and the surface silica layer.
  • this adhesion is sufficient.
  • the surface energy, water repellency, and antifouling properties vary greatly depending on the carbon content, making it difficult to prepare. There was a point.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-284102
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-113805
  • the present inventors have developed an organic-inorganic composite layer including a graft polymer chain directly bonded on a support and a crosslinked structure formed by hydrolysis and polycondensation reaction of a metal alkoxide.
  • the present invention was completed by intensive research and applying the organic-inorganic composite layer to an antifouling film.
  • the first aspect of the present invention is that the antifouling film of the present invention comprises Si, Ti, Zr, and the like in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the surface of the support.
  • An organic-inorganic composite layer comprising a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide of an element selected from Al, and the surface of the organic-inorganic composite layer is subjected to a water / oil repellent treatment.
  • the graft polymer chain is preferably formed by a polymerization reaction starting from an initiation species generated on the surface of the support.
  • the graft polymer chain strength preferably includes an alkoxide group and / or an amide group of an element selected from Si, Ti, Zr, and Al in the chain.
  • a structural unit having a graft polymer chain strength polar group, preferably an amide group, and a structural unit having an alkoxide group of an element selected from Si, Ti, Zr, and Al, such as a silane coupling group It is preferable to be a copolymer of the above.
  • a graft polymer chain directly bonded to the surface of a support is generated, and a graft polymer layer comprising the graft polymer chain is formed.
  • a method for producing an antifouling film is provided.
  • the present invention can provide an antifouling film having a water and oil repellent treatment surface excellent in adhesion to a support, having high antifouling properties and its durability, and a method for producing the same.
  • the antifouling film of the present invention comprises an alkoxide of an element selected from Si, Ti, Zr, and A1 in a graft polymer layer comprising a support and a graft polymer chain directly bonded to the surface of the support. And an organic monoinorganic composite layer comprising a cross-linked structure formed by hydrolysis and condensation polymerization of the organic monoinorganic composite layer, and the surface of the organic monoinorganic composite layer is subjected to a water / oil repellent treatment.
  • a crosslinked structure is formed using Si alkoxide because of its reactivity and availability of the compound.
  • sol-gel crosslinked structure the above-mentioned crosslinked structure formed by hydrolysis and polycondensation of an alkoxide is hereinafter referred to as "sol-gel crosslinked structure" as appropriate.
  • Such an antifouling film of the present invention is produced by the following method for producing an antifouling film of the present invention. That is, the method for producing an antifouling film of the present invention comprises a step of forming a graft polymer chain formed of a graft polymer chain by directly forming a graft polymer chain bonded directly to the surface of the support [hereinafter referred to as “graft” as appropriate. This is referred to as “polymer layer forming step”.
  • a step of forming an organic-inorganic composite layer by carrying out a crosslinking reaction by hydrolysis and polycondensation of an alkoxide of an element whose Si, Ti, Zr, and A1 forces are also selected in the graft polymer layer [hereinafter referred to as “organic This is referred to as “inorganic composite layer forming step”.
  • organic composite layer forming step a step of subjecting the surface of the organic / inorganic composite layer to a water / oil repellent treatment [hereinafter referred to as a “water / oil repellent treatment step” as appropriate. ] And that the method that has the power S is preferred.
  • the organic / inorganic composite layer in the present invention is selected from Si, Ti, Zr, and A1 in a graft polymer chain (organic component) formed by direct bonding to the support surface and a graft polymer layer comprising the graft polymer chain. Formed by hydrolysis and condensation polymerization of alkoxides And a crosslinked structure (inorganic component). Even if such an organic-inorganic composite layer is a thin layer, the wear resistance is increased and the durability is high.
  • the graft polymer chain has a polar group
  • a polar interaction is formed with the cross-linked structure by the function of the polar group, and the organic-inorganic composite layer having excellent strength and durability is obtained.
  • the graft polymer chain strength has an alkoxide group of an element selected from Si, Ti, Zr, and A1 in the chain
  • a covalent bond is formed between the graft polymer chain and the crosslinked structure, and organic The strength and durability of one inorganic composite layer are improved.
  • the crosslinked structure in the organic-inorganic composite layer has a reactive group derived from an alkoxide of an element selected from Si, Ti, Zr, and A1, and this reactive group and the water / oil repellent treatment
  • a reactive group derived from an alkoxide of an element selected from Si, Ti, Zr, and A1 By forming a covalent bond with the compound used for the substrate, it is possible to obtain a water / oil repellent treated surface having excellent adhesion to the support.
  • an antifouling film having high antifouling properties and durability can be obtained.
  • a graft polymer chain directly bonded to the surface of the support is generated to form a graft polymer layer composed of the graph polymer chain.
  • a compound having a polymerizable double bond is surface graft polymerized from the support as a base point to form a graft polymer chain.
  • Method 1 A method of forming a graft polymer chain by chemically bonding a polymer having a functional group that reacts with the support and the surface of the support (hereinafter referred to as “method 1” as appropriate)
  • Method 2 A method of forming a graft polymer chain by chemically bonding a polymer having a functional group that reacts with the support and the surface of the support.
  • Method 1 is a method generally called surface graft polymerization.
  • the surface graft polymerization method is a polymerizable double layer disposed so as to be in contact with the support by giving an active species on the surface of the support by a method such as plasma irradiation, light irradiation, or heating, and using the active species as a base point. Have a bond
  • This is a method of polymerizing a compound. According to this method, the end of the resulting graft polymer chain is directly bonded and fixed to the support surface.
  • any known method described in literatures can be used.
  • New Polymer Experiment 10 edited by Society of Polymer Science, 1994, published by Kyoritsu Shuppan Co., Ltd., P135 describes photograft polymerization and plasma irradiation graft polymerization as surface graft polymerization methods.
  • the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, published in February 1999, p203, p695 describes the radiation-induced graft polymerization method such as ⁇ -rays and electron beams.
  • a polymer surface such as PET is treated with plasma or electron beam to generate radicals as active species on the surface, and then polymerized with a support surface having the active species.
  • a graft polymer chain can be formed by reacting with a compound having a possible double bond (eg, a monomer).
  • photograft polymerization is described in JP-A-53-17407 (Kansai Vint) and JP-A-2000-212313 (Dainippon Ink). It can also be carried out by applying a photopolymerizable composition to the surface of the film support, bringing the radical polymerization compound into contact with the film, and irradiating with light.
  • a compound useful in producing a graft polymer chain by Method 1 needs to have a polymerizable double bond.
  • a double bond that can be combined and a polar group is added. It is preferable that it is a compound which has.
  • it has a polymerizable double bond and a specific element alkoxide group. A compound is preferred.
  • the compound applied to Method 1 has a double bond in the molecule, and if necessary polar As long as it has a group and / or a specific element alkoxide group, either a polymer, an oligomer or a monomer can be used.
  • One of the compounds useful in the present invention is a monomer having a polar group.
  • Monomers having a polar group useful in the present invention include positively charged monomers such as ammonium and phosphonium, and negative charges such as sulfonic acid groups, carboxyl groups, phosphoric acid groups, and phosphonic acid groups.
  • positive charged monomers such as ammonium and phosphonium
  • negative charges such as sulfonic acid groups, carboxyl groups, phosphoric acid groups, and phosphonic acid groups.
  • it has a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, or a cyano group.
  • Monomers having polar groups can also be used
  • the monomer having a particularly useful polar group include the following monomers.
  • a macromer having a polar group useful in the present invention can be obtained by a synthesis method described in "New Polymer Experiments 2, Polymer Synthesis and Reaction” edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. Can do. It is also described in detail in Yu Yamashita et al., “Macromonomer Chemistry and Industry” IPC, 1989. Specifically, using a monomer having the polar group specifically described above, such as acrylic acid, attalinoleamide, 2-atalinoleamide-2 methylpropane sulfonic acid, N vinylacetamide, etc. According to the method, a macromer having a polar group can be synthesized.
  • macromers having a polar group used in the present invention particularly useful macromers having a carboxyl group-containing monomer such as acrylic acid and methacrylic acid, 2_ acrylamide _ 2_ methylpropane sulfonic acid, Sulphonic acid-based macromers derived from monomers of styrene sulfonic acid and its salts, amide-based macromers such as acrylamide and methacrylamide, N-bulu amides such as N-buluacetoamide and N-buluformamide Monomer power derived from amide macromers derived from hydroxyl group-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene Dali Call Atarirate, It is a macromer derived from an alkoxy group or ethylenoxide group-containing monomer such as polyethylene glycol acrylate
  • a macromer having an amide group as a polar group from the viewpoint that a strong polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later is formed. .
  • the useful molecular weight is in the range of 400 to 100,000, the preferred range is 1,000 to 50,000, and the particularly preferred range is 1500 to 20,000.
  • the graft polymer chain in the present invention includes an alkoxide group of an element selected from Si, Ti, Zr, and A1 (hereinafter appropriately referred to as a specific element alkoxide group and Preferably).
  • This specific element alkoxide group is a substituent capable of forming a covalent bond through hydrolysis and polycondensation reaction with a crosslinking agent (metal alkoxide) described later.
  • the graft polymer chain has a specific element alkoxide group, so that the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer are formed.
  • a covalent bond can be formed with the remer chain.
  • the surface graft polymerization method of Method 1 it is preferable to use a monomer or macromer having a specific element alkoxide group.
  • the specific element alkoxide group will be specifically described by taking a typical silane coupling group as an example.
  • Examples of the silane coupling group suitable for the present invention include functional groups represented by the following general formula (I).
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and m represents an integer of 0 to 2.
  • Examples of the hydrocarbon group when R 1 and R 2 represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, methylol group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, sbutyl group, tbutyl group, isopentyl group, neopentyl group, Examples include 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • R 1 and R 2 are preferably a hydrogen atom, a methyl group or an ethynole group from the viewpoints of effects and availability.
  • Monomers having a functional group as shown in the general formula (I) include (3-Atalyloxypropylene) trimethoxysilane, (3-Ataryloxypropyl) dimethylmethoxysilane, (3-Atarioxypropyl) Methyldimethoxysilane, (methacryloxymethyl) dimethylethoxysilane, (methacryloxymethyl) triethoxysilane, (methacryloxymethyl) trimethoxysilane, (methacryloxypropyl) dimethylethoxysilane, (methacryloxypropyl) dimethylmethoxysilane, (Methacryloxypropyl) methyl jetoxysilane, (methacryloxypropyl) triethoxysilane, (methacryloxypropyl) triisopropyl silane, methacryloxypropi Nore (trismethoxyethoxy) silane and the like.
  • Method 1 when Method 1 is used, a monomer or macromer having a polar group and a monomer or macromer having a specific element alkoxide group such as a silane coupling group are used in combination with a surface graft weight. It is preferable to copolymerize by a combined method to form a graft polymer chain. Among them, it is more preferable to use a monomer or macromer having an amide group as a polar group.
  • a polymer having a functional group that reacts with the support at the main chain end or side chain is used, and the functional group on the surface of the support is chemically reacted to generate a graft polymer chain.
  • the functional group that reacts with the support is not particularly limited as long as it can react with the functional group on the support surface.
  • a silane coupling group such as alkoxysilane, an isocyanate group, an amino group, and a hydroxyl group.
  • Particularly useful as a polymer having a functional group that reacts with the support at the main chain end or side chain is a polymer having a trialkoxysilyl group at the polymer end, a polymer having an amino group at the polymer end, a carboxylate A polymer having a group at the polymer terminal, a polymer having an epoxy group at the polymer terminal, and a polymer having an isocyanate group at the polymer terminal.
  • the polymer used at this time preferably has a polar group.
  • the polymer having a polar group include polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, Examples include 2_acrylamide_2_methylpropanesulfonic acid and salts thereof, polyacrylamide, polybuluacetamide, and the like.
  • a polymer of a monomer having a polar group used in the above-described method (1) or a copolymer containing a monomer having a polar group can also be used.
  • the polymer having a functional group that reacts with the support at the main chain end or side chain further has an alkoxide group (specific element alkoxide group) of an element selected from Si, Ti, Zr, and A1. Is preferred.
  • an alkoxide group specific element alkoxide group
  • a specific element alkoxide group can be introduced into the resulting graft polymer chain.
  • a covalent bond can be formed between the zonore gel cross-linked structure formed in the organic-inorganic composite layer forming step described later and the graft polymer chain.
  • both an amide group and a specific element alkoxide group as a polymer-polar group having a functional group that reacts with the support at the terminal or side chain of the main chain.
  • an amide group and an amide group are present in view of the formation of polar interaction with the zonoregel cross-linked structure and the formation of a covalent bond.
  • a preferable introduction amount of the amide group in the graft polymer chain in the present invention is 10 mol% to 9
  • the range is preferably 90 mol%.
  • the graft polymer chain in the present invention preferably has a polar group or a specific element alkoxide group as described above in the chain, but in addition to these groups, a crosslinkable group, a polymerizable group, etc. May be introduced and a cross-linked structure may be formed between the graft polymer chains by using these groups.
  • any support having mechanical strength and dimensional stability can be used.
  • a transparent film is used. Preferably used.
  • the film used as the support include polyester films such as polyethylene terephthalate phenol, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film; nylon 66 film, nylon 6 film Polyamide film such as polypropylene film, polyethylene film, ethylene propylene copolymer film; Polyimide film; Polyamide imide film; Polybutyl alcohol phenolic; Examples include vinylenoreconole copolymer Finorem; Polyphenylene Finolem; Polysulfone film; Polyphenylene sulfide film; and the like.
  • polyester films such as polyethylene terephthalate phenol, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film
  • nylon 66 film nylon 6 film
  • Polyamide film such as polypropylene film, polyethylene film, ethylene propylene copolymer film
  • Polyimide film Polyamide imide film
  • Polybutyl alcohol phenolic examples include vinylenoreconole cop
  • polyester films such as polyethylene terephthalate film and polyolefin films such as polyethylene film and polypropylene film are preferred from the viewpoint of cost performance and transparency. These films may be stretched or unstretched, or may be used alone or may be used by laminating films having different properties.
  • the film used as the support may contain various additives and stabilizers or may be coated as long as the effects of the present invention are not impaired.
  • additives include an antioxidant, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and a heat stabilizer.
  • the film may be subjected to surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion bombardment treatment, chemical treatment, solvent treatment, or roughening treatment.
  • the thickness of the support is not particularly limited because it can be set as appropriate in consideration of the suitability for the purpose of use, such as packaging material. From the viewpoint of general practical use, From the viewpoint of flexibility and workability that is preferably in the range of m to lmm, it is more preferably in the range of 10 ⁇ to 300 ⁇ .
  • the support itself may be used as long as it can generate active species upon application of energy. However, the purpose of the generation of the starting species for forming the graft polymer chain is more efficient.
  • a surface layer having a polymerization initiating ability may be provided on the support surface.
  • the surface layer having a polymerization initiating ability is preferably a layer containing a low-molecular or high-molecular polymerization initiator.
  • a polymer having a functional group having a polymerization initiating ability in a side chain and a polymer having a crosslinkable group are preferably used as a polymerization initiating layer in which a polymerization initiator is immobilized by a crosslinking reaction.
  • a polymerization initiation layer formed by immobilization by a crosslinking reaction is more preferable.
  • An organic-inorganic composite layer is formed by carrying out a bridge reaction by hydrolysis and condensation polymerization of an alkoxide of an element selected from Si, Ti, Zr, and A1.
  • the organic-inorganic composite layer in the present invention is a crosslinking reaction by hydrolysis and condensation polymerization of an organic component composed of a graft polymer chain and an alkoxide of an element selected from Si, Ti, Zr, and A1. It is a layer in which an inorganic component having a cross-linked structure (sol-gel cross-linked structure) formed by performing is mixed.
  • a compound capable of forming a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide of an element whose Si, Ti, Zr, and A1 forces are also selected.
  • crosslinking agent it is preferable to form the sol-gel bridge structure in the present invention using (hereinafter, sometimes simply referred to as “crosslinking agent”).
  • crosslinking agent in the present invention for example, a compound represented by the following general formula (II) is used.
  • the compound represented by the following general formula ( ⁇ ) is hydrolyzed and polycondensed with the specific element alkoxide group, whereby the graft polymer chain and the sol-gel crosslinked A covalent bond can be formed with the structure. Thereby, a strong organic-inorganic composite layer can be formed.
  • R 6 represents a hydrogen atom, an alkyl group, or an aryl group
  • R 7 represents an alkyl group or an aryl group
  • X represents Si, Al, Ti, or Zr
  • m represents an integer of 0-2.
  • R 6 and R 7 represent an alkyl group
  • the carbon number thereof 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 hydrolyzable compound contains silicon, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane , Methyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane , dimethyldimethoxysilane, jetyljetoxysilane , ⁇
  • tetramethoxysilane tetraethoxysilane
  • methyltrimethoxysilane ethyltrimethoxysilane
  • methyltriethoxysilane methyltriethoxysilane
  • ethyltriethoxysilane dimethinolegetoxysilane
  • phenolinotrimethoxysilane phenolinotrimethoxysilane.
  • Phenoletriethoxysilane diphenyldimethoxysilane, diphenyljetoxysilane, and the like.
  • X is A1
  • that is, as the hydrolyzable compound containing aluminum for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate, etc. Can be mentioned.
  • titanium includes, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethinoretrimethoxy Titanate, methyl triethoxy titanate, etyl triethoxy titanate, dimethyl jetoxy titanate, phenyl trimethoxy titanate, phenyl triethoxy titanate Can be listed.
  • X is Zr, that is, those containing zirconium, for example, zirconates corresponding to the compounds exemplified as those containing titanium can be mentioned.
  • the crosslinking agent is dissolved in a solvent such as ethanol, and then a catalyst or the like is added as necessary.
  • a method can be used in which a composition is prepared, applied onto the graft polymer layer, heated and dried. By this method, a sol-gel crosslinked structure is formed by hydrolysis and polycondensation of the crosslinking agent.
  • the heating temperature and the heating time are not particularly limited as long as the solvent in the coating solution is removed and a strong film can be formed, but the heating temperature is 200 ° C from the viewpoint of production suitability and the like.
  • the heating time (crosslinking time) preferably below is preferably within 1 hour.
  • the content of the cross-linking agent in the coating liquid composition may be determined according to the amount of the sol-gel cross-linking structure to be formed, but the surface hardness of the formed organic-inorganic composite layer and the adhesion to the support. From the viewpoint of sex, in general, it is preferable to be in the range of 5-50% by mass, more preferably in the range of 10-40% by mass.
  • the content of the crosslinking agent in the coating solution composition is such that the crosslinking group in the crosslinking agent is relative to the specific element alkoxide group. Is preferably adjusted to an amount of 5 mol% or more, more preferably 10 mol% or more.
  • the upper limit of the content of the cross-linking agent is not particularly limited as long as it is within a range that can sufficiently cross-link with the specific element alkoxide group, but when added in a large excess, the organic agent formed by the cross-linking agent not involved in the cross-linking. Problems such as stickiness of the inorganic composite layer may occur.
  • the solvent used in preparing the coating liquid composition is not particularly limited as long as it can uniformly dissolve and disperse the crosslinking agent and other components.
  • methanol, ethanol, An aqueous solvent such as water is preferred.
  • an acidic catalyst or a basic catalyst in combination, it is preferable to use an acidic catalyst or a basic catalyst in combination.
  • a catalyst is essential when trying to obtain As this catalyst, an acid or a basic compound can be used as it is, or it can be dissolved in a solvent such as water or alcohol. (Hereinafter referred to as acidic catalyst and basic catalyst, respectively) can be used.
  • the concentration at which the catalyst is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, etc. Hydrolysis and polycondensation rates tend to increase. However, if a basic catalyst with a high concentration is used, precipitates may be generated in the coating liquid composition. Therefore, when a basic catalyst is used, the concentration should be 1 N or less in terms of concentration in an aqueous solution. Is desirable.
  • the type of the acidic catalyst or basic catalyst is not particularly limited, but if it is necessary to use a highly concentrated catalyst, the catalyst is composed of an element that hardly remains in the coating film after drying. Is good.
  • the acid catalyst includes hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic acid, acetic acid and other rubonic acids, and their RCOOH.
  • Examples thereof include substituted carboxylic acids obtained by substituting R in the structural formula with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and the like, and basic catalysts include ammoniacal bases such as aqueous ammonia, ethylamine Amines such as diphosphorus are listed.
  • various additives can be used in this coating solution composition depending on the purpose as long as the effects of the present invention are not impaired.
  • a surfactant or the like can be added to improve the uniformity of the coating solution.
  • the graft polymer layer and the organic-inorganic composite layer may be formed by the following method. That is, for example, in addition to the polar group and the specific element alkoxide group as described above, a coating liquid composition containing a polymer having a functional group that reacts with the support at the main chain terminal or side chain, a crosslinking agent, and a catalyst. There is a method in which a product is prepared, treated with plasma, electron beam or the like, coated on a support on which radicals as active species are generated on the surface, heated and dried.
  • the functional group that reacts with the support of the polymer reacts with the support, whereby a graft polymer directly bonded to the support is formed, and a graft polymer layer is formed.
  • the coating liquid composition is heated and dried, hydrolysis and polycondensation reaction of the crosslinking agent occurs, and a crosslinked structure can be formed in the graft polymer layer.
  • a coating liquid composition is prepared and applied, heated and dried, Through a series of steps, the graft polymer layer and the organic-inorganic composite layer can be formed at a time.
  • a hydrophilic polymer may be included separately.
  • the hydrophilic polymer can be obtained by polymerizing a monomer having a polar group useful for forming the graft polymer chain mentioned above.
  • the content of the hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content is 50% by mass or more, the film strength tends to decrease. When the content is less than 10% by mass, the film characteristics are decreased, and the possibility of cracks in the film increases. Absent.
  • the formation of the organic-inorganic composite layer in the present invention uses the sol-gel method.
  • the Zonoregel method Sakuo Sakuo "Sol-Gel Science", Agne Jofusha (published) (1988), Satoshi Hirashima "Functional Thin Film Making Technology Using the Latest Zonole-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the formation of the organic-inorganic composite layer in the present invention.
  • the film thickness of the organic-inorganic composite layer can be selected depending on the application of the antifouling film, but generally the range of 0.1 / 1 111 to 10/1 111 is preferred 0.5. The range of / 1 111 to 10/1 111 is even better. Within this film thickness range, an antifouling film excellent in adhesion and flexibility to the support is obtained, and curling is not likely to occur, and flexibility is less likely to cause a decrease in bending resistance. Good.
  • the surface of the organic / inorganic composite layer obtained in the organic / inorganic composite layer forming step is subjected to water / oil repellent treatment.
  • the compound (water repellent) and the treatment method used in the water / oil repellent treatment in the present invention are no particular limitations on the compound (water repellent) and the treatment method used in the water / oil repellent treatment in the present invention, but it is preferable that a fluorine or alkyl group is imparted to the surface of the organic-inorganic composite layer.
  • Masle for the water / oil repellent treatment, for example, an organometallic compound such as a silylating agent, a titanate coupling agent, or alkylaluminum is preferably used.
  • the silylating agent is a compound in which an alkyl group, aryl group, fluorine-containing fluoroalkyl group, or the like is bonded to a hydrolyzable silyl group having affinity or reactivity for the sol-gel crosslinked structure in the present invention.
  • the hydrolyzable group bonded to silicon include an alkoxy group, a halogen atom, an acetoxy group, and a silazane. Specifically, it is preferable to use a perfluoroalkylsilane compound or an alkylsilane compound.
  • a polydimethylsiloxane compound may be used as a water-repellent agent.
  • the critical inclination angle of the water / oil repellent treatment surface is the inclination angle of the plate where a certain amount of water drops placed on the surface of the antifouling film start rolling.
  • the water repellent is hydrolyzed as necessary before being used for coating the water repellent layer.
  • the surface treatment with the water repellent as described above is performed by spraying, flow coating, spin coating, dipping and lifting, or surface adsorption by liquid phase adsorption.
  • the surface treated with the water repellent is dried and then at a temperature of 300 ° C or lower, preferably 100 ° C to 250 ° C.
  • the water-repellent agent forms a monomolecular layer on the surface of the organic-inorganic composite layer, it exhibits water-repellent performance.
  • the preferred thickness of the water / oil repellent treated layer after the heat treatment is lnm ⁇ :! Onm.
  • the antifouling film of the present invention is excellent in the adhesion between the water / oil repellent treated surface and the organic / inorganic composite layer, and the adhesion between the organic / inorganic composite layer and the support, As a result, the water and oil repellent surface is excellent in adhesion to the support. Therefore, the antifouling film of the present invention is excellent in antifouling property and excellent in its sustainability.
  • Biaxially stretched polyethylene terephthalate film with a film thickness of 188 / im (A4100, Toyobo Co., Ltd.)
  • a lithographic magnetron sputtering device (CFS-10-EP70, manufactured by Shibaura ELECTRIC CO., LTD.)
  • a glow treatment device an oxygen glow treatment was performed under the following conditions to obtain a PET support.
  • the PET support was immersed in this mixed solution at 70 ° C for 7 hours. After the immersion, the PET support is thoroughly washed with ethanol, and the graft polymer layer is formed by directly bonding the graft polymer chain having the silane coupling group and amide group, which are specific element alkoxide groups, in the structure to the support surface. Formed.
  • the PET support having this graft polymer layer was designated as support A.
  • a coating solution composition 1 containing ethanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred on a support for 24 hours at room temperature, and heated at 100 ° C for 10 minutes.
  • An organic / inorganic hybrid film A was obtained by drying to form an organic / inorganic composite layer.
  • the obtained organic-inorganic hybrid film A was mixed with 0.1% by mass of 1H, 1H, 2H, 2H
  • An antifouling film A was obtained by dipping in a solution of monofluorodecyltrichlorosilane / hexane for 10 minutes, pulling up, and drying by heating (100 ° C., 30 min).
  • the total thickness of the formed water / oil repellent layer and organic / inorganic composite layer was 500 nm.
  • Example 1 ⁇ Formation of graft polymer layer 1> was changed to ⁇ Formation of graft polymer layer 2> below to prepare support B, and further used in ⁇ Formation of organic-inorganic composite layer 1>
  • An antifouling film E was obtained in the same manner as in Example 1 except that the support A was changed to the support B to produce an organic-inorganic hybrid film B.
  • Example 2 An aqueous acrylamide solution (concentration: 50% by mass) was subjected to nitrogen publishing.
  • the PET support used in Example 1 was immersed in this aqueous solution at 70 ° C for 7 hours.
  • the immersed PET support was thoroughly washed with distilled water to form a graft polymer layer in which a graft polymer chain having an amide group in the structure was directly bonded to the support surface.
  • the PET support having this graft polymer layer was designated as support B.
  • graft polymer layer 3 Methacryloxypropyl triethoxysilane ethanol solution (concentration: 50 mass 0/0) were nitrogen Paburingu.
  • the PET support used in Example 1 was immersed in this solution at 70 ° C. for 7 hours. After the immersion, the PET support is thoroughly washed with distilled water, and a graft polymer layer having a structure in which a graft polymer chain having a silane coupling group which is a specific element alkoxide group is directly bonded to the support surface is formed. Formed.
  • the PET support having this graft polymer layer was designated as support C.
  • a coating solution composition 2 containing 2_propanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred at room temperature for 5 hours, and then coated at 100 ° C., 10
  • Organic-inorganic hybrid film C was obtained by heating and drying for a minute to form an organic-inorganic hybrid layer.
  • the obtained organic / inorganic hybrid film C was treated in the same manner as the water / oil repellent treatment> in Example 1 to obtain an antifouling film F.
  • the total thickness of the formed water / oil repellent layer and the organic / inorganic composite layer was 1.2 ⁇ m.
  • Example 2_ perfluorobutyl) ethyl acrylate (manufactured by Azmax Co., Ltd.) 0.5 g, 1-methoxy-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 g, Mix to make a homogeneous solution.
  • the PET support used in Example 1 was immersed in this solution at 70 ° C. for 7 hours. After the immersion, the PET support is thoroughly washed with ethanol to obtain an antifouling finalem G in which the graft polymer chain (hydrophobic graft polymer chain) containing fluorine atoms in the structure is directly bonded to the support surface. It was.
  • Example 2 The antifouling film H was obtained in the same manner as in Example 1 except that the support (PET support having a graft polymer layer) A used in Example 1 was replaced with polyethylene terephthalate. It was.
  • Anti-fouling film A to H water- and oil-repellent treated surfaces (in the antifouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded), manufactured by Kyowa Interface Science Co., Ltd., CA- After using Z, and dropping pure water, the angle after 20 seconds was measured. A with a water droplet contact angle of 150 ° or more was designated as A. The results are shown in Table 1.
  • the surface of the antifouling film A to H is a rotary cutter against the water and oil repellent treated surface (in the antifouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded).
  • a 90 ° peel test was performed 3 times at a speed of 30000 mm / min. The evaluation was performed by measuring the number of cells remaining after the peel test. The results are shown in Table 1.
  • Anti-fouling film A to H water- and oil-repellent treated surfaces in the anti-fouling film G, the surface where the graft polymer chains containing fluorine atoms are directly bonded
  • “(Registered trademark)” the number of times until the characters were wiped clean using “Bemcoton” (registered trademark) manufactured by Asahi Kasei Corporation was measured. The results are shown in Table 1.
  • the antifouling films A to F of the examples having an organic-inorganic composite layer have good water repellency and good adhesion between the support and the water / oil repellent treatment layer. I understand. Further, the antifouling films A to F of the examples are excellent in initial antifouling property and repeated antifouling property. From these facts, it can be seen that the antifouling film of the present invention is excellent in antifouling property and its sustainability.
  • the antifouling film of the present invention is suitable for a display such as CRT, LCD, PDP, and FED, touch panel, glass, table, decorative plywood, and the like, as well as a surface protective film for recording media such as CD and DVD. Can adapt.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film anti-salissures comprenant un corps de support et une couche composite organique/inorganique. Dans ce film, une structure réticulée formée par polymérisation par hydrolyse et par polymérisation par condensation d'un alkoxyde d'un élément sélectionné parmi : Si, Ti, Zr et Al est contenue dans une couche de polymères greffé constituée d'une chaîne de polymères greffés. La couche composite organique/inorganique est directement collée sur la surface du corps de support. Dans ce film, la surface de la couche composite organique/inorganique est soumise à un traitement hydrofuge/oléofuge. L'invention concerne un procédé de production d'un tel film anti-salissures.
PCT/JP2007/062420 2006-06-30 2007-06-20 Film anti-salissures et son procédé de production WO2008001665A1 (fr)

Applications Claiming Priority (2)

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JP2006182291A JP2008007729A (ja) 2006-06-30 2006-06-30 防汚性フィルム及びその製造方法
JP2006-182291 2006-06-30

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WO2008001665A1 true WO2008001665A1 (fr) 2008-01-03

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TWI774748B (zh) * 2017-04-04 2022-08-21 日商日本精化股份有限公司 含有陰離子性親水基之（甲基）丙烯醯胺化合物及含有該化合物之塗料組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361800A (ja) * 2001-06-11 2002-12-18 Fuji Photo Film Co Ltd 表面親水性部材
JP2003127268A (ja) * 2001-10-22 2003-05-08 Fuji Photo Film Co Ltd 親水性部材及びそれに用いる親水性グラフトポリマー
JP2004136638A (ja) * 2002-02-14 2004-05-13 Fuji Photo Film Co Ltd ガスバリヤーフィルム及びその製造方法
JP2006056949A (ja) * 2004-08-18 2006-03-02 Fuji Photo Film Co Ltd 表面機能性部材の製造方法及び表面機能性部材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361800A (ja) * 2001-06-11 2002-12-18 Fuji Photo Film Co Ltd 表面親水性部材
JP2003127268A (ja) * 2001-10-22 2003-05-08 Fuji Photo Film Co Ltd 親水性部材及びそれに用いる親水性グラフトポリマー
JP2004136638A (ja) * 2002-02-14 2004-05-13 Fuji Photo Film Co Ltd ガスバリヤーフィルム及びその製造方法
JP2006056949A (ja) * 2004-08-18 2006-03-02 Fuji Photo Film Co Ltd 表面機能性部材の製造方法及び表面機能性部材

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