WO2010150868A1 - Anti-fogging sheet - Google Patents

Anti-fogging sheet Download PDF

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Publication number
WO2010150868A1
WO2010150868A1 PCT/JP2010/060813 JP2010060813W WO2010150868A1 WO 2010150868 A1 WO2010150868 A1 WO 2010150868A1 JP 2010060813 W JP2010060813 W JP 2010060813W WO 2010150868 A1 WO2010150868 A1 WO 2010150868A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
layer
antifogging
water
sheet
Prior art date
Application number
PCT/JP2010/060813
Other languages
French (fr)
Japanese (ja)
Inventor
雅文 井狩
政雄 森本
正裕 原田
晃 堀川
Original Assignee
株式会社 きもと
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 きもと filed Critical 株式会社 きもと
Priority to CN201080033803.7A priority Critical patent/CN102802933B/en
Publication of WO2010150868A1 publication Critical patent/WO2010150868A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to an antifogging sheet exhibiting antifogging properties, particularly to an antifogging sheet excellent in water resistance of a coating film.
  • the reason why the substrate such as glass and plastic becomes cloudy is that when the surface temperature falls below the dew point, moisture in the air adheres as fine water droplets, and light is irregularly reflected on the substrate surface. Therefore, clouding can be prevented by preventing generation of water droplets on the substrate surface.
  • an antifogging method for example, (A) adjustment of wetting, (B) provision of water absorption, (C) provision of water repellency, and (D) adjustment of temperature by heating have been considered. .
  • Water repellency can be imparted by applying a water repellent compound. According to this method, by applying a water-repellent compound particularly to the inside of a greenhouse or the like, fine water droplets come into contact with each other and flow down as large water droplets, thereby exhibiting antifogging properties. However, in some cases, fine water droplets are attached, resulting in cloudiness.
  • the temperature adjustment by heating is effective for anti-fogging effect with the lens of a copier, the rear window of a car, a high-end mirror stand, etc., but the application range is limited because a power supply is required.
  • an antifogging coating composition comprising an organic polymer containing a surfactant having excellent water repellency.
  • the film made hydrophilic by the polyether polyol in the presence of the surfactant absorbs moisture and exhibits antifogging properties.
  • the hydrophilic film reaches the water absorption limit point or more, it is designed so that the wetness is adjusted by the contained surfactant to maintain transparency.
  • the surfactant is easily dissolved in water and flows out, the antifogging property is remarkably lowered.
  • Patent Document 1 a composition capable of forming an antifogging coating film insoluble in water while exhibiting antifogging properties and an antifogging sheet in which the composition is applied on plastic have been proposed.
  • the coating film formed using the composition described in Patent Document 1 is insoluble in water, even if the plastic on which the coating film is formed is repeatedly used as an optical lens, glasses, a vehicle window glass, etc., it is prevented. The haze can be maintained. However, for example, in a high-humidity environment or when the plastic is wet, if the coating formed on the plastic is rubbed with a dry cloth or a finger, the coating is peeled off from the plastic. Water resistance was not demonstrated.
  • one aspect of the present invention provides an antifogging sheet that is excellent in water resistance and does not peel off the coating film in the above-described environment.
  • the inventor has a laminate structure in which two layers of an antifogging coating film are laminated on a base material, and the coating film serving as the outermost layer has a high cross-linking density.
  • the present inventors have found that the coating film is hardly peeled off even in a high-humidity environment or in a state where the substrate is wet while exhibiting antifogging properties, and that the water resistance is improved, and the present invention has been achieved.
  • the anti-fogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate, and the first layer is a heat-treated product of a first coating composition containing a water-absorbing resin. It is comprised,
  • the said 2nd layer is comprised by the heat processing thing of the 2nd coating composition containing a polyol, It is characterized by the above-mentioned.
  • an antifogging sheet that is excellent in water resistance, as well as antifogging performance, for example, in a high-humidity environment or in a state where the substrate is wet. .
  • the antifogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate.
  • stacked on a base material is a layer for mainly expressing water absorption and anti-fogging property, and is comprised with the heat-processed material of a 1st coating composition.
  • the second layer laminated on the first layer is a layer for imparting water resistance while maintaining the antifogging property expressed in the first layer, and is a heat-treated product of the second coating composition. Composed.
  • the first coating composition used in the present invention contains at least a water absorbent resin.
  • the water-absorbing resin is used to develop water absorption and anti-fogging properties for the first layer when the first coating composition is heat-treated to form a coating film.
  • water-absorbing resin examples include polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”), polyacrylic acids, polyvinyl pyrrolidone, and the like. These resins are used alone or in admixture of two or more.
  • PVA polyvinyl alcohol
  • polyacrylic acids examples include acrylic acids, polyvinyl pyrrolidone, and the like.
  • the water absorbent resin preferably includes a mixture of PVA and polyacrylic acids.
  • the ratio of polyacrylic acids to PVA is preferably 5/95 to 40/60, more preferably in terms of weight. Is 5/95 to 30/70.
  • the amount of polyacrylic acid used for PVA increases, the antifogging property tends to decrease, and as the amount decreases, the water resistance of the coating film tends to decrease.
  • PVA may also be referred to as an incomplete saponification product (“partial saponification product”) having a saponification degree of 65 to 89 mol% [that is, the number of moles of hydroxyl group ⁇ 100 / (number of moles of acetyl group + number of moles of hydroxyl group)]. Is preferred). More preferably, incompletely saponified PVA having a saponification degree of 75 to 89 mol% is used. If the degree of saponification is too high or too low, water absorption and antifogging properties may not be expressed in a balanced manner.
  • the average degree of polymerization of PVA is not particularly limited, but is preferably 300 to 3500. If the degree of polymerization is too high or too low, water absorption and antifogging properties may not be expressed in a balanced manner.
  • polyacrylic acids examples include polyacrylic acid, polymethacrylic acid, polyacrylic acid methyl ester or ethyl ester, polymethacrylic acid methyl ester or ethyl ester, and the like.
  • the methyl ester or ethyl ester of polyacrylic acid and the methyl ester or ethyl ester of polymethacrylic acid each have a saponification degree of 10 to 30 mol% [that is, the number of moles of hydrolyzed ester groups ⁇ 100 / (hydrolyzed An incomplete saponified product of the number of moles of decomposed ester groups + the number of moles of unhydrolyzed ester groups)] is preferred.
  • the amount of the water-absorbent resin used in the first coating composition is preferably 20 to 99.5% by weight, more preferably 50 to 90% by weight in terms of solid content. By using the water-absorbing resin within this range, the balance of expression of water absorption and anti-fogging properties is further achieved.
  • the amount of PVA used in the first coating composition is preferably 60 to 95% by weight in terms of solid content.
  • the amount of polyacrylic acid used in the first coating composition is preferably 5 to 50% by weight in terms of solid content.
  • the first coating composition used in the present invention contains at least one compound selected from metal alkoxides, hydrolysates of metal alkoxides, and hydrolyzed polycondensates of metal alkoxides (hereinafter also referred to as “specific compounds”). Is preferred.
  • the first coating composition preferably contains a specific compound, so that when the hydrolyzate of the metal alkoxide undergoes a polycondensation reaction in the process of forming the first coating composition into a coating film, water absorption coexisting therewith. It reacts with the resin to produce a composite polymer having an inorganic part derived from the metal alkoxide and an organic part having a hydrophilic group derived from the water-absorbent resin. It is considered that the hydrophilic group of this composite polymer is effectively oriented, can absorb a large amount of moisture from the outside, and can be quickly absorbed. As a result, it can be set as the film (1st layer) which is excellent in anti-fogging property and has the insolubility, abrasion resistance, and weather resistance required as an anti-fogging coating film.
  • the hydrolyzate of metal alkoxide and the hydrolyzed polycondensate of metal alkoxide are a so-called sol-gel reaction, and a solution obtained by subjecting a metal alkoxide to hydrolysis / polycondensation reaction in a solution. It refers to a hydrolyzate obtained by forming a sol in which fine particles of oxide or metal hydroxide are dissolved, and further proceeding the reaction to form a gel, followed by a hydrolysis polycondensate.
  • a low molecular weight polycondensate having a polystyrene-reduced weight average molecular weight (Mw) of, for example, about several hundred to several tens of thousands by GPC method is used.
  • Examples of the metal alkoxide include a compound represented by the following formula (I).
  • M is an atom selected from Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, B, and P.
  • R is an alkyl group.
  • X is an alkyl group, an alkyl group having a functional group, or halogen.
  • a is the valence of M.
  • the M is Si
  • the a is 4, and such an alkoxide is represented by Si (OR 1 ) 4 .
  • R 1 is preferably an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as a lower alkyl group).
  • alkoxysilane silicon alkoxide
  • examples of such alkoxysilane (silicon alkoxide) include tetramethoxysilane (or methyl silicate) of Si (OCH 3 ) 4 , tetraethoxysilane (or ethyl silicate) of Si (OC 2 H 5 ) 4 , and the like.
  • the amount of alkoxysilane used in the metal alkoxide is preferably 50 to 100% by weight.
  • Al (OR 2 ) 3 When M is Al, the a is 3, and such an alkoxide is represented by Al (OR 2 ) 3 .
  • R 2 is preferably a lower alkyl group.
  • Examples of such aluminum alkoxide include Al (OCH 3 ) 3 , Al (OC 2 H 5 ) 3 , Al (On-C 3 H 7 ) 3 , Al (O-iso-C 3 H 7 ) 3 , such as al (OC 4 H 9) 3 and the like. You may use the said aluminum alkoxide individually or in mixture of 2 or more types.
  • Such an aluminum alkoxide is usually used by mixing with the above alkoxysilane. By using aluminum alkoxide, the translucency and heat resistance of the resulting anti-fogging coating film are improved.
  • the amount of aluminum alkoxide used in the metal alkoxide is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of alkoxysilane.
  • the a is 4, and such an alkoxide is represented by Ti (OR 3 ) 4 .
  • R 3 is preferably a lower alkyl group.
  • examples of such a titanium alkoxide include Ti (O—CH 3 ) 4 , Ti (O—C 2 H 5 ) 4 , Ti (On—C 3 H 7 ) 4 , Ti (O—iso—C 3 H). 7 ) 4 , Ti (O—C 4 H 9 ) 4 and the like.
  • the above titanium alkoxides may be used alone or in admixture of two or more. Such a titanium alkoxide is usually used by mixing with the above alkoxysilane.
  • titanium alkoxide By using titanium alkoxide, the UV resistance of the resulting antifogging coating film is improved, and the heat resistance of the substrate is also significantly improved.
  • the amount of titanium alkoxide used in the metal alkoxide is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the alkoxysilane.
  • a is 4 and such an alkoxide is represented by Zr (OR 4 ) 4 .
  • R 4 is preferably a lower alkyl group.
  • zirconium alkoxide examples include Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (O-iso-C 3 H 7 ) 4 , Zr (Ot-C 4 H 9 ) 4 , Zr (On-C 4 H 9 ) 4 and the like.
  • the zirconium alkoxides may be used alone or in admixture of two or more. Such a zirconium alkoxide is usually used by mixing with the above alkoxysilane.
  • zirconium alkoxide By using zirconium alkoxide, the toughness and heat resistance of the resulting antifogging coating film are improved.
  • the amount of zirconium alkoxide used in the metal alkoxide is preferably in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of alkoxysilane.
  • alkoxides other than the above include Ca (OC 2 H 5 ) 2 , Fe (OC 2 H 5 ) 3 , V (O-iso-C 3 H 7 ) 4 , Sn (Ot—C 4 H 9 ) 4 , Li (OC 2 H 5 ), Be (OC 3 H 5 ) 2 , B (OC 2 H 5 ) 3 , P (OC 2 H 5 ) 2 , P (OCH 3 ) 3 and the like.
  • a compound in which X is a halogen such as Cl and Br. is there.
  • a compound in which X is a halogen is hydrolyzed in the same manner as an alkoxy group to generate an OH group and undergo a polycondensation reaction.
  • X may also be an alkyl group or an alkyl group having a functional group, and the alkyl group usually has 1 to 15 carbon atoms.
  • the functional group include a carboxyl group, a carbonyl group, an amino group, a vinyl group, and an epoxy group. Such a group is suitable for improving the antifogging property as described later.
  • Compounds of formula (I) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropylmethoxy Silane etc. are mentioned.
  • the amount of the specific compound used in the first coating composition is preferably 0.5 to 50% by weight in terms of solid content.
  • the first coating composition used in the present invention preferably contains a silane coupling agent from the viewpoint of adhesion to the substrate.
  • the silane coupling agent include vinyl silane, methacryl silane, amino silane, and epoxy silane. Among these, it is particularly preferable to use a silane coupling agent having an epoxy group.
  • the silane coupling agent having an epoxy group ⁇ -glycidoxypropyltrimethoxysilane is preferable.
  • the amount of the silane coupling agent used in the first coating composition is preferably 0.2 to 10% by weight in terms of solid content.
  • the specific compound described above is contained in the first coating composition, it is preferable to further contain a catalyst.
  • the catalyst include acid catalysts.
  • the acid catalyst is used for hydrolysis reaction of metal alkoxide. Accordingly, the metal alkoxide is previously hydrolyzed to some extent and polycondensed into a polymer having an OH group (which may be a relatively low molecular weight oligomer).
  • mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are used.
  • Mineral acid anhydrides eg, hydrogen chloride gas
  • organic acids and anhydrides thereof can be used.
  • organic acids and anhydrides include tartaric acid, phthalic acid, maleic acid, dodecyl succinic acid, hexahydrophthalic acid, methyl nadic acid, pyromellitic acid, benzophenone tetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, anhydrous
  • examples thereof include phthalic acid, maleic anhydride, dodecyl succinic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dichlorosuccinic anhydride, and chlorendic anhydride.
  • an organic acid derived from the saponified portion of the polyacrylic acid ester acts as a catalyst for the hydrolysis / polycondensation reaction of the alkoxide, preferably alkoxide and ⁇ -glycidoxypropyltrimethoxysilane.
  • the first coating composition used in the present invention contains a water-absorbing resin (PVA, polyacrylic acid, etc.), preferably further contains a specific compound, and further contains a catalyst (a metal alkoxide that can be contained in the specific compound).
  • a water-absorbing resin PVA, polyacrylic acid, etc.
  • a catalyst a metal alkoxide that can be contained in the specific compound.
  • the at least one compound selected from the metal alkoxide, the hydrolyzate of metal alkoxide, and the polymerization condensate of the hydrolyzate constituting the specific compound includes the following four cases.
  • Metal alkoxide is used to prepare the reaction solution, and the hydrolysis reaction is generated after the reaction solution is prepared.
  • What is used to prepare the reaction solution is a hydrolyzate of a metal alkoxide that has already been subjected to a hydrolysis reaction treatment.
  • What is used for preparing the reaction solution is a low molecular weight polycondensate in which the hydrolyzate of metal alkoxide has already been partially polycondensed.
  • What is used to prepare the reaction solution is a metal alkoxide, a hydrolyzate thereof and a low molecular weight polycondensate of the hydrolyzate.
  • the first coating composition used in the present invention preferably further contains a curing agent.
  • a curing agent examples include an isocyanate curing agent, an epoxy curing agent, a carbodiimide curing agent, and a melamine curing agent.
  • isocyanate curing agent examples include polyisocyanates obtained by polymerizing or copolymerizing isocyanate monomers, and can be used without particular limitation.
  • Isocyanate monomers include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-diisocyanate cyclohexane, m- or p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12- Examples include dodecamethylene diisocyanate.
  • an isocyanate that becomes a one-component curing reaction that causes a crosslinking reaction when heated to a temperature higher than a certain temperature without reacting at room temperature.
  • a blocked isocyanate or the like using a method in which a catalyst or a functional group is blocked can be used.
  • the blocked isocyanate is the above-described polyisocyanate masked with a masking agent, does not react at room temperature at all and does not proceed with the curing reaction, and is active when heated above the temperature at which the masking agent dissociates. The group is regenerated to cause a sufficient crosslinking reaction.
  • Examples of the epoxy curing agent include ethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether.
  • Examples of the carbodiimide curing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.
  • Examples of the melamine curing agent include a fully alkyl etherified melamine resin, a methylol group type melamine resin, and an imino group type melamine resin partially having an imino group.
  • the amount of the curing agent used in the first coating composition is preferably 0.5 to 20% by weight in terms of solid content.
  • the first coating composition used in the present invention preferably further contains hydrofluoric acid.
  • the amount of silicohydrofluoric acid used in the first coating composition is preferably 0.2 to 10% by weight.
  • the first coating composition used in the present invention can also contain a benzophenone compound.
  • JP-A-11-50009 proposes to add a benzophenone compound that acts as an ultraviolet absorber and a radical scavenger in order to improve the weather resistance of the antifogging coating film. Addition of compounds has been found to be effective in the present invention.
  • This benzophenone compound is represented by the following formula (II).
  • X1 to X10 are hydrogen, hydroxyl group, sulfonic acid group, carboxyl group, acyl group, ester group, ether group, hydrocarbon group, alkoxyl group having 1 to 6 carbon atoms, amino group, hydroxylalkyl group And a group selected from hydroxylalkoxyl groups, which may be the same or different. However, at least one of X1 to X10 is a group selected from a hydroxyl group and a sulfonic acid group.
  • the amount of the benzophenone compound used in the first coating composition is, for example, 0.1 to 5.0% by weight.
  • the first coating composition used in the present invention is usually realized in the form of a coating liquid.
  • a coating liquid can be prepared by dissolving or dispersing the above-described water-absorbing resin (such as a specific compound as necessary) in an organic solvent.
  • the organic solvent that is preferably used include water-compatible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and N-methylpyrrolidone. More preferably, the organic solvent is used with water.
  • the amount of the organic solvent used in the first coating composition is preferably 0 to 60% by weight. In addition, the case where the usage-amount of an organic solvent is 0 (zero) is included because it may take the form of a coating liquid, without using an organic solvent.
  • the main composition of the first coating composition used in the present invention is obtained by causing a sol-gel reaction in the presence of a water absorbent resin, the OH group of the hydrolyzate of the metal alkoxide is deprotonated.
  • the polycondensate obtained by the occurrence of a polycondensation reaction the above-mentioned composite polymer obtained by crosslinking reaction of the water-absorbing resin to the OH group of the polycondensate, and the hydrolyzate and water absorption of the metal alkoxide
  • a reaction product with a water-soluble resin, a reaction product of three of the polycondensate, hydrolyzate, and water-absorbing resin can be considered.
  • the second coating composition used in the present invention contains at least a polyol.
  • the polyol is used for further imparting water resistance while maintaining the antifogging property developed in the first layer when the second coating composition is heat-treated to form a coating film.
  • polystyrene resin examples include polyester, acrylic, partially acetalized polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone. You may use these individually or in mixture of 2 or more types.
  • polyethylene glycol is preferably used from the viewpoint of maintaining antifogging properties.
  • the amount of polyol used in the second coating composition is preferably 10 to 80% by weight, more preferably 30 to 80% by weight in terms of solid content.
  • the 2nd coating composition used by this invention contains the specific compound similar to a 1st coating composition.
  • the amount of the specific compound used in the second coating composition is preferably 0.5 to 50% by weight in terms of solid content. It is preferable that the 2nd coating composition used by this invention contains the silane coupling agent similar to a 1st coating composition. The amount of the silane coupling agent used in the second coating composition is the same as in the first coating composition.
  • the 2nd coating composition used by this invention contains the hardening
  • the amount of the curing agent used in the second coating composition is preferably 10 to 80% by weight, more preferably 30 to 60% by weight in terms of solid content.
  • a catalyst similar to the first coating composition may be included. In this case, the amount used is the same as in the first coating composition.
  • the 2nd coating composition used by this invention contains a silicohydrofluoric acid like the 1st coating composition. The amount of silicofluoric acid used in the second coating composition is the same as in the first coating composition.
  • the 2nd coating composition used by this invention can also contain a benzophenone series compound similarly to a 1st coating composition.
  • the amount of the benzophenone-based compound used in the second coating composition is the same as in the first coating composition.
  • the second coating composition used in the present invention is usually realized in the form of a coating liquid.
  • the coating liquid can be prepared by dissolving or dispersing the above-described polyol (such as a specific compound as necessary) in an organic solvent.
  • the organic solvent that is preferably used include water-compatible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, N-methylpyrrolidone, and diacetone alcohol.
  • the amount of the organic solvent used in the second coating composition is preferably 50 to 90% by weight.
  • the second layer formed on the first layer has a high cross-linking density of the coating film. For this reason, water resistance can further be provided, maintaining the antifogging property expressed by the 1st layer. Specifically, even if the coating film (first layer and second layer) is rubbed with a dry cloth or finger in a high-humidity environment or in a state where the substrate is wet, the coating film does not peel off and is water resistant. Excellent in properties.
  • Main materials include glass or plastic film.
  • glass for example, glass made of oxide glass such as silicate glass, phosphate glass, and borate glass can be used.
  • silicate glass such as silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass is preferably used as a plate glass.
  • plastic film for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, norbornene compound and the like can be used.
  • a polyethylene terephthalate film that has been stretched, particularly biaxially stretched, is preferably used because of its excellent mechanical strength and dimensional stability.
  • a substrate that has been subjected to an easy adhesion treatment it is preferable to use a substrate that has been subjected to an easy adhesion treatment.
  • a base material that has been subjected to an easy adhesion treatment on the surface it is possible to improve the adhesion with the first layer or an adhesive layer described later, as compared with a substrate that is not subjected to this treatment.
  • the easy adhesion treatment include various surface treatments (for example, plasma treatment, corona treatment, chemical activation treatment, oxidation flame treatment, deep ultraviolet irradiation treatment, etc.) and formation of an undercoat easy adhesion layer.
  • the thickness of the substrate is preferably 12 to 188 ⁇ m.
  • binder component of the easy-to-undercoat adhesive layer examples include acrylic, polyester, silicone, urethane, styrene, cellulose, vinyl, epoxy, butyral, amino, and rubber.
  • polyesters are particularly preferably used from the viewpoints of adhesion to the substrate and the first layer and workability.
  • the thickness of the easy-to-undercoat adhesive layer is preferably 0.05 to 3 ⁇ m, more preferably 0.5 to 2 ⁇ m, from the viewpoints of adhesion to the substrate and the first layer and workability.
  • an adhesive layer may be formed on the surface opposite to the surface on which the first layer of the substrate is formed.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer commonly used synthetic resin-based pressure-sensitive adhesives such as acrylic, silicone, urethane, and rubber are used, and acrylic pressure-sensitive adhesives are used from the viewpoint of handleability. preferable.
  • the adhesive polymer as the main component of the acrylic adhesive include 1 to 10 carbon atoms of alkyl groups such as 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate, butyl methacrylate, and propyl methacrylate.
  • various additives such as an ultraviolet absorber, an infrared absorber, a curing agent, a plasticizer, and a tackifier component are provided as long as the effects of the present invention are not impaired. Can be included.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be appropriately selected according to the material of the base material. Specifically, the thickness is preferably 0.5 ⁇ m to 50 ⁇ m, preferably 5 to 30 ⁇ m. .
  • the antifogging sheet of the present invention is produced, for example, as follows. First, each component of the 1st coating composition used by this invention is mixed, and a transparent 1st coating liquid (it is synonymous with a 1st coating composition in this invention) is prepared. Moreover, each component of the 2nd coating composition used by this invention is mixed, and a transparent 2nd coating liquid (it is synonymous with a 2nd coating composition in this invention) is prepared. Next, the first coating liquid is applied to at least one surface of the substrate, and this is preferably heated and dried at a temperature of 80 ° C. or higher, more preferably in the range of 80 to 150 ° C. (heat treatment). Thereby, a 1st layer is formed on a base material. If necessary, the coating liquid may be applied several times before heat treatment.
  • the second coating liquid is applied onto the first layer formed on the substrate, and this is preferably heat-dried at a temperature of 60 ° C. or higher, more preferably in the range of 60 to 150 ° C. (Heat treatment). Thereby, the second layer is formed on the first layer. If necessary, the coating liquid may be applied several times before heat treatment.
  • an adhesive layer coating solution prepared by dissolving or dispersing the material constituting the adhesive layer with an appropriate solvent is prepared.
  • the prepared adhesive layer coating solution is applied to the surface of the substrate opposite to the surface on which the first layer is to be formed, dried by a conventionally known coating method, and cured as necessary to form an adhesive layer. To do.
  • the total thickness of the first layer (T1) and the second layer (T2) is preferably 0.01 to 1.0 ⁇ m when used for an optical lens or the like. In the case of application to window glass or the like, 1.0 to 10.0 ⁇ m is preferable.
  • the total thickness (T1 + T2) of the first layer and the second layer can be appropriately adjusted by thickly applying each coating composition in the form of a coating liquid, or by applying it several times.
  • the antifogging article thus obtained gives antifogging and dew condensation prevention properties to the surface of the substrate.
  • the formed coating film (first layer + second layer) is insoluble in water and an organic solvent and has a high surface hardness.
  • the polycondensation reaction and the crosslinking reaction proceed to form a composite polymer having a three-dimensional structure.
  • the formed composite polymer has an inorganic portion and an organic portion. That is, since this polymer has an insoluble skeleton which is an inorganic part, the antifogging coating film formed by this polymer is insoluble in water and organic solvents and has a high surface hardness. Furthermore, since this polymer has a hydrophilic part derived from a water-absorbing resin (polyacrylic acid ester, PVA, etc.) which is an organic part, the coating film formed by this polymer has the hydrophilic part on its surface part.
  • the anti-fogging sheet is formed by forming only the first layer composed of the heat-treated product of the first coating composition on the substrate, the curing reaction / crosslinking reaction of the organic matter constituting the coating film Because it is still inadequate, when the coating (first layer) is rubbed with a dry waste cloth or finger in a high humidity environment or when the substrate is wet, the organic matter easily moves and the coating peels off. Will end up.
  • seat of this invention is further equipped with the 2nd layer comprised by the heat processing thing of a 2nd coating composition on the 1st layer mentioned above. This second layer has a high crosslinking density of the coating film.
  • water resistance can further be provided, maintaining the antifogging property expressed by the 1st layer.
  • the coating film first layer and second layer
  • the coating film does not peel off and is water resistant. Excellent in properties.
  • Example 1 First, a first coating composition and a second coating composition were prepared.
  • Example 1 ⁇ Metthyl silicate (MS-56: Mitsubishi Chemical Corporation) 5.0 parts ⁇ Silane coupling agent 0.3 parts (SH6040: Toray Dow Corning) -Partially saponified PVA (Kishida Chemical Co., Ltd.) 5.0 parts (100% solid content, saponification degree 87-89 mol%, average polymerization degree 3500) ⁇ Polyacrylic acid (AC-10H: Nippon Pure Chemicals Co., Ltd.) 5.0 parts (100% solids) ⁇ Methanol 40.0 parts ⁇ H 2 O 44.5 parts
  • Example 2 ⁇ The 2nd coating composition of Example 1> ⁇ Methyl silicate (MS-56: Mitsubishi Chemical Corporation) 5.0 parts ⁇ Silane coupling agent 0.3 parts (SH6040: Toray Dow Corning) ⁇ Polyethylene glycol (Kishida Chemical Co., Ltd.) 30.0 parts ⁇ Isocyanate curing agent 20.0 parts (MF-K60X: Asahi Kasei Chemicals Corporation) ⁇ Diacetone alcohol 30.0 parts ⁇ t-Butanol 14.7 parts
  • the prepared first coating composition was applied as a substrate to a 100 ⁇ m thick plastic film (Lumirror T60: Toray Industries, Inc.) with a dip coater at a speed of 50 mm / min. Thereafter, heating and drying (heating treatment) were performed at 150 ° C. for 10 minutes. As a result, a uniform, colorless and transparent first layer having a thickness of 3 ⁇ m was formed on the substrate.
  • a 100 ⁇ m thick plastic film Limirror T60: Toray Industries, Inc.
  • the second coating composition having the above composition was pulled up and applied at a speed of 30 mm / min with a dip coater. Thereafter, drying (heat treatment) was performed in a drying furnace at 100 to 120 ° C. for 15 minutes. As a result, a transparent second layer having a thickness of about 5 ⁇ m was formed on the first layer, and a sheet sample of this example was obtained.
  • Example 2 The amount of “MS-56” in the second coating composition is 3.0 parts, the amount of “polyethylene glycol” is 35.0 parts, the amount of “MF-K60X” is 15.0 parts, A first layer (thickness 3 ⁇ m) is formed on the substrate under the same conditions as in Example 1 except that the amount of “alcohol” is 32.0 parts, and a second layer (thickness of about 5 ⁇ m) is formed on the first layer. A sheet sample of this example in which was formed was obtained.
  • polyacrylic acid methyl ester saponified product 20 mol% polyacrylic acid methyl ester saponified product was prepared as follows. First, methanol is added to a 25% aqueous solution of polyacrylic acid (average molecular weight: 150,000) and stirred at room temperature for 30 minutes to produce polyacrylic acid methyl ester. Thereafter, sodium hydroxide (caustic soda) is added to the solution containing polyacrylic acid methyl ester so as to be 20% saponification, and the mixture is further saponified by stirring for 30 minutes. Moreover, the aluminum isopropoxide hydrolyzate was prepared by hydrolyzing aluminum isopropoxide with an acid catalyst in ethanol.
  • Example 2 the obtained coating solution was pulled up and applied to the same substrate as in Example 1 at a speed of 50 mm / min with a dip coater. Thereafter, heating and drying were performed at 150 ° C. for 10 minutes. As a result, a uniform, colorless and transparent coating film having a thickness of 3 ⁇ m was formed on the substrate, and a sheet sample of this comparative example was obtained.
  • Example 2 Evaluation of anti-fogging property at low temperature
  • the sheet sample of Example 2 was left in a freezer (about ⁇ 25 ° C.) for 60 minutes, then removed from the freezer, and the coating surface of the sheet sample after 10 seconds was observed. did. As a result, cloudiness did not occur on the coating film surface.

Abstract

Disclosed is an anti-fogging sheet having a coating film that exhibits excellent water resistance as well as excellent anti-fogging properties. The anti-fogging sheet is constituted by laminating a first layer and a second layer on a substrate, in that order. The first layer is configured from the product obtained by heat-treating a first coating composition, which contains a water-absorbent resin. The second layer is configured from the product obtained by heat-treating a second coating composition, which contains a polyol. The water-absorbent resin preferably contains a polyvinyl alcohol and a polyacrylic acid. The polyol preferably contains polyethylene glycol. The first coating composition and/or the second coating composition preferably contain at least one compound selected from among: metal alkoxides, metal alkoxide hydrolysates, and metal alkoxide hydrolytic polycondensates.

Description

防曇性シートAnti-fogging sheet
　本発明は、防曇性を発揮する防曇性シートにおいて、特に塗膜の耐水性に優れる防曇性シートに関する。 The present invention relates to an antifogging sheet exhibiting antifogging properties, particularly to an antifogging sheet excellent in water resistance of a coating film.
　ガラス、プラスチックなどの基材が曇るのは、表面温度が露点以下に下がったときに空気中の水分が細かな水滴となって付着し、基材表面で光が乱反射するためである。従って、基材表面における水滴の生成を防止することにより、曇りを防ぐことができる。このような防曇方法においては、例えば（Ａ）濡れの調整、（Ｂ）吸水性の付与、（Ｃ）撥水性の付与、および（Ｄ）加熱による温度の調整の４要素が考慮されてきた。 The reason why the substrate such as glass and plastic becomes cloudy is that when the surface temperature falls below the dew point, moisture in the air adheres as fine water droplets, and light is irregularly reflected on the substrate surface. Therefore, clouding can be prevented by preventing generation of water droplets on the substrate surface. In such an antifogging method, for example, (A) adjustment of wetting, (B) provision of water absorption, (C) provision of water repellency, and (D) adjustment of temperature by heating have been considered. .
　（Ａ）濡れの調整としては、基材と水滴との接触角を小さくするために、曇り止めスプレー剤などが市販されているが、このようなスプレー剤は界面活性剤などを利用しているため効力の持続性が低い。 (A) In order to adjust the wetting, in order to reduce the contact angle between the substrate and water droplets, anti-fogging sprays and the like are commercially available, but such sprays use a surfactant or the like. Therefore, the durability of efficacy is low.
　（Ｂ）吸水性の付与は、例えば親水性高分子のコーティング膜を形成することにより行われる。効力の持続性は、上記の濡れを調整するための曇り止めスプレー剤と比べて多少長いが、吸水能力以上となると曇り、さらに表面が溶解し始める。 (B) The provision of water absorption is performed, for example, by forming a coating film of a hydrophilic polymer. The durability of the effect is somewhat longer than the anti-fogging spray for adjusting the above-mentioned wetting, but when the water absorption capacity is exceeded, it becomes cloudy and the surface starts to dissolve.
　（Ｃ）撥水性の付与は、撥水性化合物を塗布することにより可能である。この方法によれば、特にビニールハウスなどの内側に撥水性化合物を塗布することにより、細かい水滴が相互に接触して大きな水滴となって流れ落ち、そのことによって防曇性を発揮することができる。しかし、場合によっては、かえって細かい水滴が付き、曇りを生じる。 (C) Water repellency can be imparted by applying a water repellent compound. According to this method, by applying a water-repellent compound particularly to the inside of a greenhouse or the like, fine water droplets come into contact with each other and flow down as large water droplets, thereby exhibiting antifogging properties. However, in some cases, fine water droplets are attached, resulting in cloudiness.
　（Ｄ）加熱による温度調整は、コピー機のレンズ、自動車のリアウインドウ、高級鏡台などで防曇効果をあげているが、電源が必要であるため適用範囲が限定される。 (D) The temperature adjustment by heating is effective for anti-fogging effect with the lens of a copier, the rear window of a car, a high-end mirror stand, etc., but the application range is limited because a power supply is required.
　上記のような欠点を補うものとして、撥水性の優れた界面活性剤を含む、有機ポリマーからなる防曇性コーティング組成物が提案されている。この組成物においては、界面活性剤の存在下でポリエーテルポリオールによって親水性となった膜が水分を吸収して防曇性を発揮する。親水性となった膜が吸水限界点以上になった場合には、含有されている界面活性剤により、濡れが調整されて透明性を保つように設計されている。しかし、界面活性剤は水に溶けやすく、流出するため、防曇性が著しく低下してしまう。 In order to compensate for the above drawbacks, an antifogging coating composition comprising an organic polymer containing a surfactant having excellent water repellency has been proposed. In this composition, the film made hydrophilic by the polyether polyol in the presence of the surfactant absorbs moisture and exhibits antifogging properties. When the hydrophilic film reaches the water absorption limit point or more, it is designed so that the wetness is adjusted by the contained surfactant to maintain transparency. However, since the surfactant is easily dissolved in water and flows out, the antifogging property is remarkably lowered.
　そこで近年、防曇性を発揮しつつ水に不溶性の防曇性塗膜が形成可能な組成物及び当該組成物をプラスチック上に塗布した防曇シートが提案されている（特許文献１）。 Therefore, in recent years, a composition capable of forming an antifogging coating film insoluble in water while exhibiting antifogging properties and an antifogging sheet in which the composition is applied on plastic have been proposed (Patent Document 1).
特開平１１－６１０２９号公報Japanese Patent Laid-Open No. 11-61029
　特許文献１記載の組成物を用いて形成された塗膜は、水に不溶性であるため、その塗膜を形成したプラスチックを光学レンズや眼鏡、車両の窓ガラス等として繰り返し使用しても、防曇性は維持されうる。しかし、例えば高湿度環境下やプラスチックが濡れた状態下において、プラスチック上に形成された塗膜を乾いたウエスや指等により擦ると、当該塗膜はプラスチックから剥がれてしまい、その塗膜に十分な耐水性が発揮されているとはいえなかった。 Since the coating film formed using the composition described in Patent Document 1 is insoluble in water, even if the plastic on which the coating film is formed is repeatedly used as an optical lens, glasses, a vehicle window glass, etc., it is prevented. The haze can be maintained. However, for example, in a high-humidity environment or when the plastic is wet, if the coating formed on the plastic is rubbed with a dry cloth or a finger, the coating is peeled off from the plastic. Water resistance was not demonstrated.
　そこで本発明の一側面では、上述した環境下において塗膜が剥がれることのない耐水性にも優れる防曇性シートを提供する。 Therefore, one aspect of the present invention provides an antifogging sheet that is excellent in water resistance and does not peel off the coating film in the above-described environment.
　本発明者は、基材上に防曇性の塗膜を二層積層させてなる積層体構造とし、かつ、その最外層となる塗膜を架橋密度が高いものとすることにより、塗膜の防曇性を発揮しつつ、高湿度環境下や基材が濡れた状態下においても塗膜が剥がれにくくなり、耐水性が向上することを見出し、本発明に至ったものである。 The inventor has a laminate structure in which two layers of an antifogging coating film are laminated on a base material, and the coating film serving as the outermost layer has a high cross-linking density. The present inventors have found that the coating film is hardly peeled off even in a high-humidity environment or in a state where the substrate is wet while exhibiting antifogging properties, and that the water resistance is improved, and the present invention has been achieved.
　即ち、本発明の防曇性シートは、基材上に第１層と第２層が順に積層されてなり、前記第１層は、吸水性樹脂を含む第１コーティング組成物の加熱処理物で構成されており、前記第２層は、ポリオールを含む第２コーティング組成物の加熱処理物で構成されていることを特徴とするものである。 That is, the anti-fogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate, and the first layer is a heat-treated product of a first coating composition containing a water-absorbing resin. It is comprised, The said 2nd layer is comprised by the heat processing thing of the 2nd coating composition containing a polyol, It is characterized by the above-mentioned.
　本発明によれば、防曇性能はもとより、例えば高湿度環境下や基材が濡れた状態下においても塗膜が剥がれることのない、耐水性にも優れる防曇性シートを提供することができる。 According to the present invention, it is possible to provide an antifogging sheet that is excellent in water resistance, as well as antifogging performance, for example, in a high-humidity environment or in a state where the substrate is wet. .
　本発明の防曇性シートは、基材上に第１層と第２層が順に積層されてなる。基材上に積層される第１層は、主として吸水性と防曇性を発現させるための層であり、第１コーティング組成物の加熱処理物で構成される。第１層上に積層される第２層は、第１層で発現される防曇性を維持しつつ、さらに耐水性を付与するための層であり、第２コーティング組成物の加熱処理物で構成される。 The antifogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate. The 1st layer laminated | stacked on a base material is a layer for mainly expressing water absorption and anti-fogging property, and is comprised with the heat-processed material of a 1st coating composition. The second layer laminated on the first layer is a layer for imparting water resistance while maintaining the antifogging property expressed in the first layer, and is a heat-treated product of the second coating composition. Composed.
　本発明で用いる第１コーティング組成物は、少なくとも吸水性樹脂を含む。吸水性樹脂は、第１コーティング組成物を加熱処理し塗膜化した際に、第１層に対して吸水性と防曇性を発現させるために用いられる。 The first coating composition used in the present invention contains at least a water absorbent resin. The water-absorbing resin is used to develop water absorption and anti-fogging properties for the first layer when the first coating composition is heat-treated to form a coating film.
　吸水性樹脂としては、ポリビニルアルコール（以下「ＰＶＡ」と略記することもある。）、ポリアクリル酸類、ポリビニルピロリドン等が挙げられる。これらの樹脂は、単独でまたは２種以上を混合して用いられる。 Examples of the water-absorbing resin include polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”), polyacrylic acids, polyvinyl pyrrolidone, and the like. These resins are used alone or in admixture of two or more.
　本発明では、吸水性樹脂として、ＰＶＡ及びポリアクリル酸類の少なくとも何れかを含めることが好ましい。特に、塗膜化した際に吸水性と防曇性に優れたものとする観点からは、吸水性樹脂として、より好ましくは、ＰＶＡとポリアクリル酸類を混合したものを含める。吸水性樹脂として、ＰＶＡとポリアクリル酸類の混合物を用いる場合において、ＰＶＡに対するポリアクリル酸類の使用割合（ポリアクリル酸類／ＰＶＡ）は、重量換算で、好ましくは５／９５～４０／６０、より好ましくは５／９５～３０／７０である。ＰＶＡに対するポリアクリル酸類の使用量が増えるにつれて防曇性が低下する傾向があり、少なくなるにつれて塗膜の耐水性が低下する傾向がある。 In the present invention, it is preferable to include at least one of PVA and polyacrylic acids as the water absorbent resin. In particular, from the viewpoint of excellent water absorption and antifogging properties when formed into a coating film, the water absorbent resin preferably includes a mixture of PVA and polyacrylic acids. When a mixture of PVA and polyacrylic acids is used as the water-absorbent resin, the ratio of polyacrylic acids to PVA (polyacrylic acids / PVA) is preferably 5/95 to 40/60, more preferably in terms of weight. Is 5/95 to 30/70. As the amount of polyacrylic acid used for PVA increases, the antifogging property tends to decrease, and as the amount decreases, the water resistance of the coating film tends to decrease.
　ＰＶＡとしては、鹸化度が６５～８９モル％［即ち、水酸基のモル数×１００／（アセチル基のモル数＋水酸基のモル数）］の不完全鹸化物（「部分鹸化物」とも言うことがある。）が好ましい。さらに好ましくは、鹸化度７５～８９モル％の不完全鹸化ＰＶＡを用いる。鹸化度が高すぎたり低すぎる場合、吸水性と防曇性がバランスよく発現されないこともあり得る。 PVA may also be referred to as an incomplete saponification product (“partial saponification product”) having a saponification degree of 65 to 89 mol% [that is, the number of moles of hydroxyl group × 100 / (number of moles of acetyl group + number of moles of hydroxyl group)]. Is preferred). More preferably, incompletely saponified PVA having a saponification degree of 75 to 89 mol% is used. If the degree of saponification is too high or too low, water absorption and antifogging properties may not be expressed in a balanced manner.
　ＰＶＡの平均重合度は、特に限定されないが、好ましくは３００～３５００である。重合度が高すぎたり低すぎる場合、吸水性と防曇性がバランスよく発現されないこともあり得る。 The average degree of polymerization of PVA is not particularly limited, but is preferably 300 to 3500. If the degree of polymerization is too high or too low, water absorption and antifogging properties may not be expressed in a balanced manner.
　ポリアクリル酸類としては、ポリアクリル酸、ポリメタクリル酸、ポリアクリル酸のメチルエステル又はエチルエステル、ポリメタクリル酸のメチルエステル又はエチルエステルなどが挙げられる。ポリアクリル酸のメチルエステル又はエチルエステルや、ポリメタクリル酸のメチルエステル又はエチルエステルとしては、それぞれ、鹸化度が１０～３０モル％［即ち、加水分解されたエステル基のモル数×１００／（加水分解されたエステル基のモル数＋加水分解されていないエステル基のモル数）］の不完全鹸化物が好ましい。 Examples of polyacrylic acids include polyacrylic acid, polymethacrylic acid, polyacrylic acid methyl ester or ethyl ester, polymethacrylic acid methyl ester or ethyl ester, and the like. The methyl ester or ethyl ester of polyacrylic acid and the methyl ester or ethyl ester of polymethacrylic acid each have a saponification degree of 10 to 30 mol% [that is, the number of moles of hydrolyzed ester groups × 100 / (hydrolyzed An incomplete saponified product of the number of moles of decomposed ester groups + the number of moles of unhydrolyzed ester groups)] is preferred.
　第１コーティング組成物中の吸水性樹脂の使用量は、固形分換算で、好ましくは２０～９９．５重量％、より好ましくは５０～９０重量％である。この範囲で吸水性樹脂を使用することで、吸水性と防曇性の発現バランスがより図られる。 The amount of the water-absorbent resin used in the first coating composition is preferably 20 to 99.5% by weight, more preferably 50 to 90% by weight in terms of solid content. By using the water-absorbing resin within this range, the balance of expression of water absorption and anti-fogging properties is further achieved.
　吸水性樹脂としてＰＶＡを用いる場合における、第１コーティング組成物中のＰＶＡの使用量は、固形分換算で、好ましくは６０～９５重量％である。吸水性樹脂としてポリアクリル酸類を用いる場合における、第１コーティング組成物中のポリアクリル酸類の使用量は、固形分換算で、好ましくは５～５０重量％である。 When PVA is used as the water absorbent resin, the amount of PVA used in the first coating composition is preferably 60 to 95% by weight in terms of solid content. When polyacrylic acid is used as the water absorbent resin, the amount of polyacrylic acid used in the first coating composition is preferably 5 to 50% by weight in terms of solid content.
　本発明で用いる第１コーティング組成物は、金属アルコキシド、金属アルコキシドの加水分解物、及び金属アルコキシドの加水分解重縮合物から選ばれる少なくとも１つの化合物（以下「特定化合物」ともいう。）を含むことが好ましい。 The first coating composition used in the present invention contains at least one compound selected from metal alkoxides, hydrolysates of metal alkoxides, and hydrolyzed polycondensates of metal alkoxides (hereinafter also referred to as “specific compounds”). Is preferred.
　第１コーティング組成物に、好ましくは特定化合物を含ませることで、その第１コーティング組成物を塗膜化する過程で金属アルコキシドの加水分解物が重縮合反応を生ずる際、これと共存する吸水性樹脂とも反応して、金属アルコキシドに由来する無機部分と吸水性樹脂に由来する親水性基を有する有機部分を持つ複合ポリマーが生成される。この複合ポリマーの親水性基が効果的に配向し、外部からの水分を多く、且つ速やかに吸収することができるものと考えられる。その結果、防曇性に優れ、かつ、防曇性塗膜として要求される、不溶性、耐摩耗性および耐候性も兼ね備えた被膜（第１層）とすることができる。 The first coating composition preferably contains a specific compound, so that when the hydrolyzate of the metal alkoxide undergoes a polycondensation reaction in the process of forming the first coating composition into a coating film, water absorption coexisting therewith. It reacts with the resin to produce a composite polymer having an inorganic part derived from the metal alkoxide and an organic part having a hydrophilic group derived from the water-absorbent resin. It is considered that the hydrophilic group of this composite polymer is effectively oriented, can absorb a large amount of moisture from the outside, and can be quickly absorbed. As a result, it can be set as the film (1st layer) which is excellent in anti-fogging property and has the insolubility, abrasion resistance, and weather resistance required as an anti-fogging coating film.
　なお、金属アルコキシドの加水分解物及び金属アルコキシドの加水分解重縮合物とは、所謂、ゾル－ゲル法反応と呼ばれる反応により、金属アルコキシドを溶液中で加水分解・重縮合反応させた溶液を、金属酸化物または金属水酸化物の微粒子が溶解したゾルとし、さらに反応を進めてゲルとすることで得られる加水分解物及び、それに続く加水分解重縮合物をいう。金属アルコキシドの加水分解重縮合物としては、ＧＰＣ法によるポリスチレン換算の重量平均分子量（Ｍｗ）が、例えば数百～数万程度の低分子量重縮合物が用いられる。 The hydrolyzate of metal alkoxide and the hydrolyzed polycondensate of metal alkoxide are a so-called sol-gel reaction, and a solution obtained by subjecting a metal alkoxide to hydrolysis / polycondensation reaction in a solution. It refers to a hydrolyzate obtained by forming a sol in which fine particles of oxide or metal hydroxide are dissolved, and further proceeding the reaction to form a gel, followed by a hydrolysis polycondensate. As the hydrolyzed polycondensate of metal alkoxide, a low molecular weight polycondensate having a polystyrene-reduced weight average molecular weight (Mw) of, for example, about several hundred to several tens of thousands by GPC method is used.
　金属アルコキシドとしては、例えば、次式（Ｉ）で示される化合物を含む。 Examples of the metal alkoxide include a compound represented by the following formula (I).
　Ｍ（ＯＲ）ｎ　（Ｘ）ａ－ｎ　・・・（Ｉ） M (OR) n (X) a-n ··· (I)
　式（Ｉ）中、Ｍは、Ｓｉ、Ａｌ、Ｔｉ、Ｚｒ、Ｃａ、Ｆｅ、Ｖ、Ｓｎ、Ｌｉ、Ｂｅ、ＢおよびＰから選択される原子である。Ｒはアルキル基である。Ｘはアルキル基、官能基を有するアルキル基、またはハロゲンである。ａはＭの原子価である。ｎは１からａまでの整数である。式（Ｉ）の化合物のうち汎用されるのは、ｎ＝ａ、つまりＭにアルコキシ基のみが結合した化合物である。 In formula (I), M is an atom selected from Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, B, and P. R is an alkyl group. X is an alkyl group, an alkyl group having a functional group, or halogen. a is the valence of M. n is an integer from 1 to a. Of the compounds of formula (I), those generally used are n = a, that is, compounds in which only an alkoxy group is bonded to M.
　上記ＭがＳｉの場合には、上記ａは４であり、このようなアルコキシドは、Ｓｉ（ＯＲ１　）４　で表される。ここでＲ１　は、好ましくは炭素数１～４のアルキル基（以下、低級アルキル基という）である。このようなアルコキシシラン（ケイ素アルコキシド）としては、Ｓｉ（ＯＣＨ３　）４　のテトラメトキシシラン（又はメチルシリケート）、Ｓｉ（ＯＣ２　Ｈ５　）４　のテトラエトキシシラン（又はエチルシリケート）などが挙げられる。金属アルコキシド中のアルコキシシランの使用量は、好ましくは５０～１００重量％である。 When the M is Si, the a is 4, and such an alkoxide is represented by Si (OR 1 ) 4 . Here, R 1 is preferably an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as a lower alkyl group). Examples of such alkoxysilane (silicon alkoxide) include tetramethoxysilane (or methyl silicate) of Si (OCH 3 ) 4 , tetraethoxysilane (or ethyl silicate) of Si (OC 2 H 5 ) 4 , and the like. The amount of alkoxysilane used in the metal alkoxide is preferably 50 to 100% by weight.
　上記ＭがＡｌの場合には、上記ａは３であり、このようなアルコキシドは、Ａｌ（ＯＲ２　）３　で表される。ここでＲ２　は、好ましくは低級アルキル基である。このようなアルミニウムアルコキシドとしては、Ａｌ（ＯＣＨ３　）３　、Ａｌ（ＯＣ２　Ｈ５　）３　、Ａｌ（Ｏ－ｎ－Ｃ３　Ｈ７　）３　、Ａｌ（Ｏ－ｉｓｏ－Ｃ３　Ｈ７　）３　、Ａｌ（ＯＣ４　Ｈ９　）３　などが挙げられる。上記アルミニウムアルコキシドは、単独でまたは２種以上を混合して用いてもよい。このようなアルミニウムアルコキシドは、通常、上記アルコキシシランと混合して用いられる。アルミニウムアルコキシドを用いることによって、得られる防曇性塗膜の透光性や耐熱性が向上する。金属アルコキシド中のアルミニウムアルコキシドの使用量は、アルコキシシラン１００重量部に対して、好ましくは１～１０重量部の範囲である。 When M is Al, the a is 3, and such an alkoxide is represented by Al (OR 2 ) 3 . Here, R 2 is preferably a lower alkyl group. Examples of such aluminum alkoxide include Al (OCH 3 ) 3 , Al (OC 2 H 5 ) 3 , Al (On-C 3 H 7 ) 3 , Al (O-iso-C 3 H 7 ) 3 , such as al (OC 4 H 9) 3 and the like. You may use the said aluminum alkoxide individually or in mixture of 2 or more types. Such an aluminum alkoxide is usually used by mixing with the above alkoxysilane. By using aluminum alkoxide, the translucency and heat resistance of the resulting anti-fogging coating film are improved. The amount of aluminum alkoxide used in the metal alkoxide is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of alkoxysilane.
　上記ＭがＴｉの場合には、上記ａは４であり、このようなアルコキシドは、Ｔｉ（ＯＲ３　）４　で表される。ここでＲ３　は、好ましくは低級アルキル基である。このようなチタニウムアルコキシドとしては、Ｔｉ（Ｏ－ＣＨ３　）４　、Ｔｉ（Ｏ－Ｃ２　Ｈ５　）４　、Ｔｉ（Ｏ－ｎ－Ｃ３　Ｈ７　）４　、Ｔｉ（Ｏ－ｉｓｏ－Ｃ３　Ｈ７　）４　、Ｔｉ（Ｏ－Ｃ４　Ｈ９　）４　などが挙げられる。上記チタニウムアルコキシドは、単独でまた２種以上を混合して用いてもよい。このようなチタニウムアルコキシドは、通常、上記アルコキシシランと混合して用いられる。チタニウムアルコキシドを用いることによって、得られる防曇性塗膜の耐紫外線性は向上し、基材の耐熱性も著しく向上する。金属アルコキシド中のチタニウムアルコキシドの使用量は、アルコキシシラン１００重量部に対して、好ましくは０．１～３重量部の範囲である。 When M is Ti, the a is 4, and such an alkoxide is represented by Ti (OR 3 ) 4 . Here, R 3 is preferably a lower alkyl group. Examples of such a titanium alkoxide include Ti (O—CH 3 ) 4 , Ti (O—C 2 H 5 ) 4 , Ti (On—C 3 H 7 ) 4 , Ti (O—iso—C 3 H). 7 ) 4 , Ti (O—C 4 H 9 ) 4 and the like. The above titanium alkoxides may be used alone or in admixture of two or more. Such a titanium alkoxide is usually used by mixing with the above alkoxysilane. By using titanium alkoxide, the UV resistance of the resulting antifogging coating film is improved, and the heat resistance of the substrate is also significantly improved. The amount of titanium alkoxide used in the metal alkoxide is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the alkoxysilane.
　上記ＭがＺｒの場合には、上記ａは４であり、このようなアルコキシドは、Ｚｒ（ＯＲ４　）４　で表される。ここでＲ４　は、好ましくは低級アルキル基である。このようなジルコニウムアルコキシドとしては、Ｚｒ（ＯＣＨ３　）４　、Ｚｒ（ＯＣ２　Ｈ５　）４　、Ｚｒ（Ｏ－ｉｓｏ－Ｃ３　Ｈ７　）４　、Ｚｒ（Ｏ－ｔ－Ｃ４　Ｈ９　）４　、Ｚｒ（Ｏ－ｎ－Ｃ４　Ｈ９　）４　などが挙げられる。上記ジルコニウムアルコキシドは、単独でまたは２種以上を混合して用いてもよい。このようなジルコニウムアルコキシドは、通常、上記アルコキシシランと混合して用いられる。ジルコニウムアルコキシドを用いることによって、得られる防曇性塗膜の靭性や耐熱性が向上する。金属アルコキシド中のジルコニウムアルコキシドの使用量は、アルコキシシラン１００重量部に対して、好ましくは０．５～５重量部の範囲である。 When M is Zr, a is 4 and such an alkoxide is represented by Zr (OR 4 ) 4 . Here, R 4 is preferably a lower alkyl group. Examples of such zirconium alkoxide include Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (O-iso-C 3 H 7 ) 4 , Zr (Ot-C 4 H 9 ) 4 , Zr (On-C 4 H 9 ) 4 and the like. The zirconium alkoxides may be used alone or in admixture of two or more. Such a zirconium alkoxide is usually used by mixing with the above alkoxysilane. By using zirconium alkoxide, the toughness and heat resistance of the resulting antifogging coating film are improved. The amount of zirconium alkoxide used in the metal alkoxide is preferably in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of alkoxysilane.
　上記以外のアルコキシドとしては、例えば、Ｃａ（ＯＣ２　Ｈ５　）２　、Ｆｅ（ＯＣ２　Ｈ５　）３　、Ｖ（Ｏ－ｉｓｏ－Ｃ３　Ｈ７　）４　、Ｓｎ（Ｏ－ｔ－Ｃ４　Ｈ９　）４　、Ｌｉ（ＯＣ２　Ｈ５　）、Ｂｅ（ＯＣ３　Ｈ５　）２　、Ｂ（ＯＣ２　Ｈ５　）３　、Ｐ（ＯＣ２　Ｈ５　）２　、Ｐ（ＯＣＨ３　）３　などが挙げられる。 Examples of alkoxides other than the above include Ca (OC 2 H 5 ) 2 , Fe (OC 2 H 5 ) 3 , V (O-iso-C 3 H 7 ) 4 , Sn (Ot—C 4 H 9 ) 4 , Li (OC 2 H 5 ), Be (OC 3 H 5 ) 2 , B (OC 2 H 5 ) 3 , P (OC 2 H 5 ) 2 , P (OCH 3 ) 3 and the like.
　式（Ｉ）で示されるアルコキシドのうちｎ＝ａ－１以下の場合、つまりＭにアルコキシド以外の基Ｘが結合している化合物としては、例えばＸがＣｌ、Ｂｒのようなハロゲンである化合物がある。Ｘがハロゲンである化合物には、後述のように、アルコキシ基と同様に加水分解されてＯＨ基を生じ重縮合反応が起こる。Ｘはまた、アルキル基や官能基を有するアルキル基であり得、このアルキル基の炭素数は通常１～１５である。このような基は、加水分解されずに得られるポリマー中に有機部分として残留する。上記官能基としては、カルボキシル基、カルボニル基、アミノ基、ビニル基、エポキシ基などがある。このような基は、後述のように防曇性を高める上で好適である。 Among the alkoxides represented by formula (I), when n = a-1 or less, that is, the compound in which a group X other than alkoxide is bonded to M, for example, a compound in which X is a halogen such as Cl and Br. is there. As described later, a compound in which X is a halogen is hydrolyzed in the same manner as an alkoxy group to generate an OH group and undergo a polycondensation reaction. X may also be an alkyl group or an alkyl group having a functional group, and the alkyl group usually has 1 to 15 carbon atoms. Such groups remain as organic moieties in the polymer obtained without hydrolysis. Examples of the functional group include a carboxyl group, a carbonyl group, an amino group, a vinyl group, and an epoxy group. Such a group is suitable for improving the antifogging property as described later.
　Ｘを有する式（Ｉ）の化合物としては、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－アミノプロピルメトキシシランなどが挙げられる。 Compounds of formula (I) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropylmethoxy Silane etc. are mentioned.
　第１コーティング組成物中に特定化合物を含める場合における、第１コーティング組成物中の特定化合物の使用量は、固形分換算で、好ましくは０．５～５０重量％である。 When the specific compound is included in the first coating composition, the amount of the specific compound used in the first coating composition is preferably 0.5 to 50% by weight in terms of solid content.
　本発明で用いる第１コーティング組成物は、基材への密着の観点から、シランカップリング剤を含むことが好ましい。シランカップリング剤としては、ビニルシラン、メタクリルシラン、アミノシラン、エポキシシランが挙げられる。この中でも特に、エポキシ基を有するシランカップリング剤を用いることが好ましい。エポキシ基を有するシランカップリング剤としては、γ－グリシドキシプロピルトリメトキシシランが好ましい。第１コーティング組成物中にシランカップリング剤を含める場合における、第１コーティング組成物中のシランカップリング剤の使用量は、固形分換算で、好ましくは０．２～１０重量％である。 The first coating composition used in the present invention preferably contains a silane coupling agent from the viewpoint of adhesion to the substrate. Examples of the silane coupling agent include vinyl silane, methacryl silane, amino silane, and epoxy silane. Among these, it is particularly preferable to use a silane coupling agent having an epoxy group. As the silane coupling agent having an epoxy group, γ-glycidoxypropyltrimethoxysilane is preferable. When the silane coupling agent is included in the first coating composition, the amount of the silane coupling agent used in the first coating composition is preferably 0.2 to 10% by weight in terms of solid content.
　第１コーティング組成物に上述した特定化合物を含有させる場合、さらに触媒を含有させることが好ましい。触媒としては、酸触媒が挙げられる。酸触媒は金属アルコキシドの加水分解反応に用いられる。従って、予め金属アルコキシドがある程度加水分解されて、重縮合し、ＯＨ基を有するポリマー（比較的低分子量のオリゴマーであり得る）となる。 When the specific compound described above is contained in the first coating composition, it is preferable to further contain a catalyst. Examples of the catalyst include acid catalysts. The acid catalyst is used for hydrolysis reaction of metal alkoxide. Accordingly, the metal alkoxide is previously hydrolyzed to some extent and polycondensed into a polymer having an OH group (which may be a relatively low molecular weight oligomer).
　酸触媒としては、塩酸、硫酸、硝酸などの鉱酸などが用いられる。鉱酸の無水物（例えば塩化水素ガス）も用いられ得る。この他に有機酸やその無水物も利用され得る。有機酸やその無水物としては、例えば、酒石酸、フタル酸、マレイン酸、ドデシルコハク酸、ヘキサヒドロフタル酸、メチルナジック酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ジクロルコハク酸、クロレンディック酸、無水フタル酸、無水マレイン酸、無水ドデシルコハク酸、無水ヘキサヒドロフタル酸、無水メチルナジック酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、無水ジクロルコハク酸、無水クロレンディック酸などが挙げられる。第１コーティング組成物中に酸触媒を含める場合における、酸触媒の使用量は、金属アルコキシド１００重量部に対して、好ましくは０．０１～０．５重量部、さらに好ましくは０．０１５～０．３重量部である。 As the acid catalyst, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are used. Mineral acid anhydrides (eg, hydrogen chloride gas) may also be used. In addition, organic acids and anhydrides thereof can be used. Examples of organic acids and anhydrides include tartaric acid, phthalic acid, maleic acid, dodecyl succinic acid, hexahydrophthalic acid, methyl nadic acid, pyromellitic acid, benzophenone tetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, anhydrous Examples thereof include phthalic acid, maleic anhydride, dodecyl succinic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dichlorosuccinic anhydride, and chlorendic anhydride. When the acid catalyst is included in the first coating composition, the amount of the acid catalyst used is preferably 0.01 to 0.5 parts by weight, more preferably 0.015 to 0 parts per 100 parts by weight of the metal alkoxide. .3 parts by weight.
　さらに、ポリアクリル酸エステルの鹸化部分に由来する有機酸が上記アルコキシド、好ましくはアルコキシドおよびγ－グリシドキシプロピルトリメトキシシランの加水分解・重縮合反応の触媒として作用する。 Furthermore, an organic acid derived from the saponified portion of the polyacrylic acid ester acts as a catalyst for the hydrolysis / polycondensation reaction of the alkoxide, preferably alkoxide and γ-glycidoxypropyltrimethoxysilane.
　本発明で用いる第１コーティング組成物は、上述したように、吸水性樹脂（ＰＶＡ、ポリアクリル酸類など）を含み、好ましくはさらに特定化合物を含み、さらにまた触媒（特定化合物に含まれうる金属アルコキシドの加水分解物の重縮合反応を促進させるもの）を含む反応溶液で構成される。ここで、特定化合物を構成する金属アルコキシド、金属アルコキシドの加水分解物および該加水分解物の重合縮合物から選ばれる少なくとも１つの化合物とは、次の４つの場合を含む。 As described above, the first coating composition used in the present invention contains a water-absorbing resin (PVA, polyacrylic acid, etc.), preferably further contains a specific compound, and further contains a catalyst (a metal alkoxide that can be contained in the specific compound). In which the polycondensation reaction of the hydrolyzate is promoted). Here, the at least one compound selected from the metal alkoxide, the hydrolyzate of metal alkoxide, and the polymerization condensate of the hydrolyzate constituting the specific compound includes the following four cases.
（１）反応溶液を調合するのに用いるのが、金属アルコキシドであり、その加水分解反応は反応溶液の調合後に生じさせるもの。
（２）反応溶液を調合するのに用いるのが、既に加水分解反応処理が行われた金属アルコキシドの加水分解物であるもの。
（３）反応溶液を調合するのに用いるのが、金属アルコキシドの加水分解物が既に一部重縮合した低分子量重縮合物であるもの。
（４）反応溶液を調合するのに用いるのが、金属アルコキシド、その加水分解物およびその加水分解物の低分子量重縮合物の２種以上であるもの。 (1) Metal alkoxide is used to prepare the reaction solution, and the hydrolysis reaction is generated after the reaction solution is prepared.
(2) What is used to prepare the reaction solution is a hydrolyzate of a metal alkoxide that has already been subjected to a hydrolysis reaction treatment.
(3) What is used for preparing the reaction solution is a low molecular weight polycondensate in which the hydrolyzate of metal alkoxide has already been partially polycondensed.
(4) What is used to prepare the reaction solution is a metal alkoxide, a hydrolyzate thereof and a low molecular weight polycondensate of the hydrolyzate.
　本発明で用いる第１コーティング組成物は、さらに硬化剤を含むことが好ましい。硬化剤としては、イソシアネート系硬化剤、エポキシ系硬化剤、カルボジイミド系硬化剤、メラミン系硬化剤等が挙げられる。 The first coating composition used in the present invention preferably further contains a curing agent. Examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, a carbodiimide curing agent, and a melamine curing agent.
　イソシアネート系硬化剤としては、イソシアネートモノマーを重合若しくは共重合させたポリイソシアネートが主なものとして挙げられ、特に制限されること無く使用することができる。イソシアネートモノマーとしては、１，６－ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、１，３－若しくは１，４－ジイソシアネートシクロヘキサン、ｍ－若しくはｐ－テトラメチルキシレンジイソシアネート、１，４－テトラメチレンジイソシアネート、１，１２－ドデカメチレンジイソシアネートなどが挙げられる。 Examples of the isocyanate curing agent include polyisocyanates obtained by polymerizing or copolymerizing isocyanate monomers, and can be used without particular limitation. Isocyanate monomers include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-diisocyanate cyclohexane, m- or p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12- Examples include dodecamethylene diisocyanate.
　また、常温では全く反応せずにある温度以上に加熱すると架橋反応を起こすような一液型硬化反応となるイソシアネートを用いることもできる。このようなイソシアネートとしては、触媒や官能基をブロック化した手法が用いられたブロックイソシアネート等を用いることができる。 It is also possible to use an isocyanate that becomes a one-component curing reaction that causes a crosslinking reaction when heated to a temperature higher than a certain temperature without reacting at room temperature. As such an isocyanate, a blocked isocyanate or the like using a method in which a catalyst or a functional group is blocked can be used.
　ここでブロックイソシアネートとは、上述したポリイソシアネートをマスク剤でマスク化したものであり、常温では全く反応せず硬化反応を進行させることはなく、マスク剤が解離する温度以上に加熱すると活性なイソシアネート基が再生されて十分な架橋反応を起こすものである。 Here, the blocked isocyanate is the above-described polyisocyanate masked with a masking agent, does not react at room temperature at all and does not proceed with the curing reaction, and is active when heated above the temperature at which the masking agent dissociates. The group is regenerated to cause a sufficient crosslinking reaction.
　エポキシ系硬化剤としては、エチレングリコールグリシジルエーテル、ポリエチレングリコールグリシジルエーテル、グリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテルが挙げられる。カルボジイミド系硬化剤としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩が挙げられる。メラミン系硬化剤としては、完全アルキルエーテル化メラミン樹脂、メチロール基型メラミン樹脂、一部にイミノ基を有するイミノ基型メラミン樹脂などが挙げられる。 Examples of the epoxy curing agent include ethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether. Examples of the carbodiimide curing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the melamine curing agent include a fully alkyl etherified melamine resin, a methylol group type melamine resin, and an imino group type melamine resin partially having an imino group.
　第１コーティング組成物中に硬化剤を含める場合における、第１コーティング組成物中の硬化剤の使用量は、固形分換算で、好ましくは０．５～２０重量％である。 When the curing agent is included in the first coating composition, the amount of the curing agent used in the first coating composition is preferably 0.5 to 20% by weight in terms of solid content.
　本発明で用いる第１コーティング組成物は、さらにケイフッ化水素酸を含むことが好ましい。第１コーティング組成物中にケイフッ化水素酸を含める場合における、第１コーティング組成物中のケイフッ化水素酸の使用量は、好ましくは０．２～１０重量％である。 The first coating composition used in the present invention preferably further contains hydrofluoric acid. When silicohydrofluoric acid is included in the first coating composition, the amount of silicohydrofluoric acid used in the first coating composition is preferably 0.2 to 10% by weight.
　本発明で用いる第１コーティング組成物は、ベンゾフェノン系化合物を含むこともできる。特開平１１－５０００９号公報において、防曇性塗膜の耐候性の向上を図るべく、紫外線吸収剤およびラジカル捕捉剤として作用するベンゾフェノン系化合物を添加することが提案されているが、このベンゾフェノン系化合物の添加も本発明において有効であることが認められた。このベンゾフェノン系化合物は次式（ＩＩ）に示される。 The first coating composition used in the present invention can also contain a benzophenone compound. JP-A-11-50009 proposes to add a benzophenone compound that acts as an ultraviolet absorber and a radical scavenger in order to improve the weather resistance of the antifogging coating film. Addition of compounds has been found to be effective in the present invention. This benzophenone compound is represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ＩＩ）中、Ｘ１～Ｘ１０は水素、ヒドロキシル基、スルホン酸基、カルボキシル基、アシル基、エステル基、エーテル基、炭化水素基、炭素数１～６のアルコキシル基、アミノ基、ヒドロキシルアルキル基およびヒドロキシルアルコキシル基から選ばれる基であって同一でも異なるものでもよい。但し、Ｘ１～Ｘ１０の少なくとも１つはヒドロキシル基およびスルホン酸基から選ばれる基である。 In the formula (II), X1 to X10 are hydrogen, hydroxyl group, sulfonic acid group, carboxyl group, acyl group, ester group, ether group, hydrocarbon group, alkoxyl group having 1 to 6 carbon atoms, amino group, hydroxylalkyl group And a group selected from hydroxylalkoxyl groups, which may be the same or different. However, at least one of X1 to X10 is a group selected from a hydroxyl group and a sulfonic acid group.
　第１コーティング組成物中にベンゾフェノン系化合物を含める場合における、第１コーティング組成物中のベンゾフェノン系化合物の使用量は、例えば０．１～５．０重量％である。 When the benzophenone compound is included in the first coating composition, the amount of the benzophenone compound used in the first coating composition is, for example, 0.1 to 5.0% by weight.
　本発明で用いる第１コーティング組成物は、通常は塗工液の形態で実現される。例えば、上述した吸水性樹脂（必要に応じてさらに特定化合物など）を、有機溶媒に溶解または分散させることで、塗工液を調製することができる。好ましく用いられる有機溶媒としては、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブチルアルコール、Ｎ－メチルピロリドンなどの水との相溶性のある溶媒が挙げられる。さらに好ましくは、この有機溶媒は水と共に用いられる。第１コーティング組成物中の有機溶媒の使用量は、好ましくは０～６０重量％である。なお、有機溶媒の使用量が０（ゼロ）の場合を含むのは、有機溶媒を使用することなしに、塗工液の形態を取れる場合もあるからである。 The first coating composition used in the present invention is usually realized in the form of a coating liquid. For example, a coating liquid can be prepared by dissolving or dispersing the above-described water-absorbing resin (such as a specific compound as necessary) in an organic solvent. Examples of the organic solvent that is preferably used include water-compatible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and N-methylpyrrolidone. More preferably, the organic solvent is used with water. The amount of the organic solvent used in the first coating composition is preferably 0 to 60% by weight. In addition, the case where the usage-amount of an organic solvent is 0 (zero) is included because it may take the form of a coating liquid, without using an organic solvent.
　本発明で用いる第１コーティング組成物の主な組成は、吸水性樹脂の存在下でゾル－ゲル反応を生じさせて得られるものであるから、金属アルコキシドの加水分解物のＯＨ基が脱プロトン化し、その結果、重縮合反応が生じて得られる重縮合物や、重縮合物が有するＯＨ基に吸水性樹脂が架橋反応して得られる、前述の複合ポリマーや、金属アルコキシドの加水分解物と吸水性樹脂との反応物や、上記重縮合物、加水分解物および吸水性樹脂の三者の反応物などが考えられる。 Since the main composition of the first coating composition used in the present invention is obtained by causing a sol-gel reaction in the presence of a water absorbent resin, the OH group of the hydrolyzate of the metal alkoxide is deprotonated. As a result, the polycondensate obtained by the occurrence of a polycondensation reaction, the above-mentioned composite polymer obtained by crosslinking reaction of the water-absorbing resin to the OH group of the polycondensate, and the hydrolyzate and water absorption of the metal alkoxide A reaction product with a water-soluble resin, a reaction product of three of the polycondensate, hydrolyzate, and water-absorbing resin can be considered.
　本発明で用いる第２コーティング組成物は、少なくともポリオールを含む。ポリオールは、第２コーティング組成物を加熱処理し塗膜化した際に、第１層で発現される防曇性を維持しつつ、さらに耐水性を付与するために用いられる。 The second coating composition used in the present invention contains at least a polyol. The polyol is used for further imparting water resistance while maintaining the antifogging property developed in the first layer when the second coating composition is heat-treated to form a coating film.
　ポリオールとしては、ポリエステル、アクリル、部分アセタール化ポリビニルアルコール、ポリエチレングリコール、ポリビニルピロリドンが挙げられる。これらは、単独でまたは２種以上を混合して用いてもよい。特に防曇性を維持する観点からは、ポリエチレングリコールを用いることが好ましい。第２コーティング組成物中のポリオールの使用量は、固形分換算で、好ましくは１０～８０重量％、より好ましくは３０～８０重量％である。 Examples of the polyol include polyester, acrylic, partially acetalized polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone. You may use these individually or in mixture of 2 or more types. In particular, polyethylene glycol is preferably used from the viewpoint of maintaining antifogging properties. The amount of polyol used in the second coating composition is preferably 10 to 80% by weight, more preferably 30 to 80% by weight in terms of solid content.
　本発明で用いる第２コーティング組成物は、第１コーティング組成物と同様の特定化合物を含むことが好ましい。第２コーティング組成物中の特定化合物の使用量は、固形分換算で、好ましくは０．５～５０重量％である。
　本発明で用いる第２コーティング組成物は、第１コーティング組成物と同様のシランカップリング剤を含むことが好ましい。第２コーティング組成物中のシランカップリング剤の使用量は、第１コーティング組成物における場合と同じである。 It is preferable that the 2nd coating composition used by this invention contains the specific compound similar to a 1st coating composition. The amount of the specific compound used in the second coating composition is preferably 0.5 to 50% by weight in terms of solid content.
It is preferable that the 2nd coating composition used by this invention contains the silane coupling agent similar to a 1st coating composition. The amount of the silane coupling agent used in the second coating composition is the same as in the first coating composition.
　本発明で用いる第２コーティング組成物は、さらに第１コーティング組成物と同様の硬化剤を含むことが好ましい。第２コーティング組成物中の硬化剤の使用量は、固形分換算で、好ましくは１０～８０重量％、より好ましくは３０～６０重量％である。
　第２コーティング組成物に特定化合物を含有させる場合、第１コーティング組成物と同様の触媒を含めてもよい。この場合、使用量は、第１コーティング組成物における場合と同様とする。
　本発明で用いる第２コーティング組成物は、第１コーティング組成物と同様に、ケイフッ化水素酸を含むことが好ましい。第２コーティング組成物中のケイフッ化水素酸の使用量は、第１コーティング組成物における場合と同じである。 It is preferable that the 2nd coating composition used by this invention contains the hardening | curing agent similar to a 1st coating composition further. The amount of the curing agent used in the second coating composition is preferably 10 to 80% by weight, more preferably 30 to 60% by weight in terms of solid content.
When a specific compound is contained in the second coating composition, a catalyst similar to the first coating composition may be included. In this case, the amount used is the same as in the first coating composition.
It is preferable that the 2nd coating composition used by this invention contains a silicohydrofluoric acid like the 1st coating composition. The amount of silicofluoric acid used in the second coating composition is the same as in the first coating composition.
　本発明で用いる第２コーティング組成物は、第１コーティング組成物と同様に、ベンゾフェノン系化合物を含むこともできる。第２コーティング組成物中のベンゾフェノン系化合物の使用量は、第１コーティング組成物における場合と同じである。 The 2nd coating composition used by this invention can also contain a benzophenone series compound similarly to a 1st coating composition. The amount of the benzophenone-based compound used in the second coating composition is the same as in the first coating composition.
　本発明で用いる第２コーティング組成物も、第１コーティング組成物の場合と同様、通常は塗工液の形態で実現される。例えば、上述したポリオール（必要に応じてさらに特定化合物など）を、有機溶媒に溶解または分散させることで、塗工液を調製することができる。好ましく用いられる有機溶媒としては、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブチルアルコール、Ｎ－メチルピロリドン、ジアセトンアルコールなどの水との相溶性のある溶媒が挙げられる。第２コーティング組成物中の有機溶媒の使用量は、好ましくは５０～９０重量％である。 As in the case of the first coating composition, the second coating composition used in the present invention is usually realized in the form of a coating liquid. For example, the coating liquid can be prepared by dissolving or dispersing the above-described polyol (such as a specific compound as necessary) in an organic solvent. Examples of the organic solvent that is preferably used include water-compatible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, N-methylpyrrolidone, and diacetone alcohol. The amount of the organic solvent used in the second coating composition is preferably 50 to 90% by weight.
　第１層上に形成される第２層は、塗膜の架橋密度が高い。このため、第１層で発現される防曇性を維持しつつ、さらに耐水性を付与することができる。具体的には、高湿度環境下や基材が濡れた状態下において、塗膜（第１層及び第２層）が乾いたウエスや指等により擦られても、塗膜が剥がれることなく耐水性に優れたものとなる。 The second layer formed on the first layer has a high cross-linking density of the coating film. For this reason, water resistance can further be provided, maintaining the antifogging property expressed by the 1st layer. Specifically, even if the coating film (first layer and second layer) is rubbed with a dry cloth or finger in a high-humidity environment or in a state where the substrate is wet, the coating film does not peel off and is water resistant. Excellent in properties.
　基材としては、主にガラス又はプラスチックフィルムが挙げられる。ガラスとしては、例えばケイ酸塩ガラス、リン酸塩ガラス、ホウ酸塩ガラス等の酸化ガラスを板ガラス化したものを使用することができる。特にケイ酸ガラス、ケイ酸アルカリガラス、ソーダ石灰ガラス、カリ石灰ガラス、鉛ガラス、バリウムガラス、ホウケイ酸ガラス等のケイ酸塩ガラスを板ガラス化したものが好ましい。プラスチックフィルムとしては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリエチレン、ポリプロピレン、ポリスチレン、トリアセチルセルロース、アクリル、ポリ塩化ビニル、ノルボルネン化合物等が使用できる。特に、延伸加工、特に二軸延伸されたポリエチレンテレフタレートフィルムが機械的強度、寸法安定性に優れているために好適に使用される。 基材 Main materials include glass or plastic film. As the glass, for example, glass made of oxide glass such as silicate glass, phosphate glass, and borate glass can be used. In particular, silicate glass such as silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass is preferably used as a plate glass. As the plastic film, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, norbornene compound and the like can be used. In particular, a polyethylene terephthalate film that has been stretched, particularly biaxially stretched, is preferably used because of its excellent mechanical strength and dimensional stability.
　本発明では、基材として、易接着処理が施されたものを用いることが好ましい。表面に易接着処理が施された基材を用いることで、これを施さないものと比較して、第１層や後述する粘着層との密着性の向上を図ることができる。易接着処理としては、各種表面処理（例えばプラズマ処理、コロナ処理、ケミカル・アクチベーション処理、酸化炎処理、遠紫外線照射処理など）の他、下引き易接着層の形成などが挙げられる。基材の厚みは、１２～１８８μｍであることが好ましい。
　下引き易接着層のバインダー成分としては、アクリル系、ポリエステル系、シリコーン系、ウレタン系、スチレン系、セルロース系、ビニル系、エポキシ系、ブチラール系、アミノ系、ゴム系等が挙げられる。これらの中でも基材や第１層との接着性や作業性の観点から、ポリエステル系が特に好ましく用いられる。
　下引き易接着層の厚みは、基材や第１層との接着性や作業性の観点から、０．０５～３μｍが好ましく、０．５～２μｍがより好ましい。 In the present invention, it is preferable to use a substrate that has been subjected to an easy adhesion treatment. By using a base material that has been subjected to an easy adhesion treatment on the surface, it is possible to improve the adhesion with the first layer or an adhesive layer described later, as compared with a substrate that is not subjected to this treatment. Examples of the easy adhesion treatment include various surface treatments (for example, plasma treatment, corona treatment, chemical activation treatment, oxidation flame treatment, deep ultraviolet irradiation treatment, etc.) and formation of an undercoat easy adhesion layer. The thickness of the substrate is preferably 12 to 188 μm.
Examples of the binder component of the easy-to-undercoat adhesive layer include acrylic, polyester, silicone, urethane, styrene, cellulose, vinyl, epoxy, butyral, amino, and rubber. Among these, polyesters are particularly preferably used from the viewpoints of adhesion to the substrate and the first layer and workability.
The thickness of the easy-to-undercoat adhesive layer is preferably 0.05 to 3 μm, more preferably 0.5 to 2 μm, from the viewpoints of adhesion to the substrate and the first layer and workability.
　本発明の防曇性シートは、基材の第１層が形成されている面とは反対面に、粘着層が形成されていてもよい。粘着層に用いられる粘着剤としては、一般に使用されるアクリル系、シリコーン系、ウレタン系、ゴム系などの合成樹脂系粘着剤が用いられ、取り扱い性等の観点からアクリル系粘着剤を用いることが好ましい。このようなアクリル系粘着剤の主成分である粘着性ポリマーとしては、アクリル酸２－エチルヘキシル、アクリル酸ブチル、アクリル酸イソオクチル、メタクリル酸ブチル、メタクリル酸プロピルなどのアルキル基の炭素数が１～１０の（メタ）アクリル酸アルキルエステルと、アクリル酸、メタクリル酸、マレイン酸、フマル酸、アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチルなどの官能基含有不飽和単量体とを主成分として含む単量体混合物を共重合させてなるものが好ましく用いられる。これら粘着層中には、上記粘着性ポリマー成分のほか、本発明の効果を阻害しない範囲であれば、紫外線吸収剤、赤外線吸収剤、硬化剤、可塑剤、粘着付与成分などの種々の添加剤を含ませることができる。 In the antifogging sheet of the present invention, an adhesive layer may be formed on the surface opposite to the surface on which the first layer of the substrate is formed. As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, commonly used synthetic resin-based pressure-sensitive adhesives such as acrylic, silicone, urethane, and rubber are used, and acrylic pressure-sensitive adhesives are used from the viewpoint of handleability. preferable. Examples of the adhesive polymer as the main component of the acrylic adhesive include 1 to 10 carbon atoms of alkyl groups such as 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate, butyl methacrylate, and propyl methacrylate. (Meth) acrylic acid alkyl ester and a functional group-containing unsaturated monomer such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, hydroxyethyl acrylate, hydroxyethyl methacrylate and the like as main components Those obtained by copolymerizing a mixture are preferably used. In these adhesive layers, in addition to the above-mentioned adhesive polymer component, various additives such as an ultraviolet absorber, an infrared absorber, a curing agent, a plasticizer, and a tackifier component are provided as long as the effects of the present invention are not impaired. Can be included.
　粘着層の厚みは、特に限定されるものではなく、基材の材料に応じた厚みを適宜選択すればよく、具体的には０．５μｍ～５０μｍ、好適には５～３０μｍとすることが好ましい。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be appropriately selected according to the material of the base material. Specifically, the thickness is preferably 0.5 μm to 50 μm, preferably 5 to 30 μm. .
　本発明の防曇性シートは、例えば、以下のようにして製造される。まず、本発明で用いる第１コーティング組成物の各成分を混合し、透明の第１塗工液（本発明では第１コーティング組成物と同義）を準備する。また、本発明で用いる第２コーティング組成物の各成分を混合し、透明の第２塗工液（本発明では第２コーティング組成物と同義）を準備する。次に、第１塗工液を基材の少なくとも片面に塗布し、これを好ましくは８０℃以上の温度、さらに好ましくは８０～１５０℃の範囲内で加熱乾燥させる（加熱処理）。これにより基材上に第１層が形成される。必要に応じて、塗工液を数回重ねて塗工した後、加熱処理を行ってもよい。 The antifogging sheet of the present invention is produced, for example, as follows. First, each component of the 1st coating composition used by this invention is mixed, and a transparent 1st coating liquid (it is synonymous with a 1st coating composition in this invention) is prepared. Moreover, each component of the 2nd coating composition used by this invention is mixed, and a transparent 2nd coating liquid (it is synonymous with a 2nd coating composition in this invention) is prepared. Next, the first coating liquid is applied to at least one surface of the substrate, and this is preferably heated and dried at a temperature of 80 ° C. or higher, more preferably in the range of 80 to 150 ° C. (heat treatment). Thereby, a 1st layer is formed on a base material. If necessary, the coating liquid may be applied several times before heat treatment.
　次に、第２塗工液を、基材上に形成された第１層の上に塗布し、これを好ましくは６０℃以上の温度、さらに好ましくは６０～１５０℃の範囲内で加熱乾燥させる（加熱処理）。これにより第１層上に第２層が形成される。必要に応じて、塗工液を数回重ねて塗工した後、加熱処理を行ってもよい。 Next, the second coating liquid is applied onto the first layer formed on the substrate, and this is preferably heat-dried at a temperature of 60 ° C. or higher, more preferably in the range of 60 to 150 ° C. (Heat treatment). Thereby, the second layer is formed on the first layer. If necessary, the coating liquid may be applied several times before heat treatment.
　なお、本発明の防曇性シートが粘着層を備える場合、粘着層を構成する材料を適当な溶媒によって溶解または分散して調整した粘着層用塗布液を準備する。次に、基材の、第１層が形成される面とは反対面に、準備した粘着層用塗布液を、従来公知のコーティング方法で塗布、乾燥し、必要により硬化させて粘着層を形成する。 When the antifogging sheet of the present invention includes an adhesive layer, an adhesive layer coating solution prepared by dissolving or dispersing the material constituting the adhesive layer with an appropriate solvent is prepared. Next, the prepared adhesive layer coating solution is applied to the surface of the substrate opposite to the surface on which the first layer is to be formed, dried by a conventionally known coating method, and cured as necessary to form an adhesive layer. To do.
　本発明の防曇性シートにおいて、第１層の厚み（Ｔ１）と第２層の厚み（Ｔ２）の合計は、光学レンズなどに用いる場合には、０．０１～１．０μｍが好ましい。窓ガラスなどに塗布する場合には、１．０～１０．０μｍが好ましい。第１層と第２層の合計厚み（Ｔ１＋Ｔ２）は、各コーティング組成物を塗工液の形態で厚く塗布することにより、あるいは数回重ねて塗布することにより、適宜、調節し得る。このようにして得られる防曇性の物品は、基材の表面に防曇性および結露防止性を与える。形成された塗膜（第１層＋第２層）は、水および有機溶剤に不溶であり、且つ高い表面硬度を有する。 In the antifogging sheet of the present invention, the total thickness of the first layer (T1) and the second layer (T2) is preferably 0.01 to 1.0 μm when used for an optical lens or the like. In the case of application to window glass or the like, 1.0 to 10.0 μm is preferable. The total thickness (T1 + T2) of the first layer and the second layer can be appropriately adjusted by thickly applying each coating composition in the form of a coating liquid, or by applying it several times. The antifogging article thus obtained gives antifogging and dew condensation prevention properties to the surface of the substrate. The formed coating film (first layer + second layer) is insoluble in water and an organic solvent and has a high surface hardness.
　本発明では、第１コーティング組成物を基材に塗工し、加熱乾燥（加熱処理）を行うと、上記重縮合反応および架橋反応が進行し、三次元構造を有する複合ポリマーが形成される。形成される複合ポリマーは、無機部分と有機部分とを有する。すなわち、このポリマーは無機部分である不溶性骨格を有しているため、このポリマーにより形成される防曇性の塗膜は、水および有機溶剤に不溶であり、高い表面硬度を有する。さらに、このポリマーは、有機部分である吸水性樹脂（ポリアクリル酸エステルやＰＶＡ等）に由来する親水部分を有しているため、このポリマーにより形成される塗膜は、その表面部分に当該親水部分が存在し、その部分に水分が吸着する。さらに、上記式（Ｉ）のＸ基の端末にカルボキシル基、カルボニル基、アミノ基、ビニル基、エポキシ基などを有する場合には、さらにその基にも水分が吸着する。 In the present invention, when the first coating composition is applied to a substrate and heat-dried (heat treatment), the polycondensation reaction and the crosslinking reaction proceed to form a composite polymer having a three-dimensional structure. The formed composite polymer has an inorganic portion and an organic portion. That is, since this polymer has an insoluble skeleton which is an inorganic part, the antifogging coating film formed by this polymer is insoluble in water and organic solvents and has a high surface hardness. Furthermore, since this polymer has a hydrophilic part derived from a water-absorbing resin (polyacrylic acid ester, PVA, etc.) which is an organic part, the coating film formed by this polymer has the hydrophilic part on its surface part. There is a part, and moisture is adsorbed on the part. Further, when the terminal of the X group of the above formula (I) has a carboxyl group, a carbonyl group, an amino group, a vinyl group, an epoxy group or the like, moisture is further adsorbed on the group.
　ただし、防曇性シートが、基材上に第１コーティング組成物の加熱処理物で構成される第１層のみを形成したものであると、塗膜を構成する有機物の硬化反応・架橋反応が未だ不十分なため、高湿度環境下や、基材が濡れた状態下において、塗膜（第１層）を乾いたウエスや指等で擦ると、有機物が容易に移動し、塗膜が剥がれてしまうこととなる。
　これに対し、本発明の防曇性シートは、上述した第１層上に、さらに第２コーティング組成物の加熱処理物で構成される第２層を備える。この第２層は、塗膜の架橋密度の高い。このため、第１層で発現される防曇性を維持しつつ、さらに耐水性を付与することができる。具体的には、高湿度環境下や基材が濡れた状態下において、塗膜（第１層及び第２層）が乾いたウエスや指等により擦られても、塗膜が剥がれることなく耐水性に優れたものとなる。 However, if the anti-fogging sheet is formed by forming only the first layer composed of the heat-treated product of the first coating composition on the substrate, the curing reaction / crosslinking reaction of the organic matter constituting the coating film Because it is still inadequate, when the coating (first layer) is rubbed with a dry waste cloth or finger in a high humidity environment or when the substrate is wet, the organic matter easily moves and the coating peels off. Will end up.
On the other hand, the antifogging sheet | seat of this invention is further equipped with the 2nd layer comprised by the heat processing thing of a 2nd coating composition on the 1st layer mentioned above. This second layer has a high crosslinking density of the coating film. For this reason, water resistance can further be provided, maintaining the antifogging property expressed by the 1st layer. Specifically, even if the coating film (first layer and second layer) is rubbed with a dry cloth or finger in a high-humidity environment or in a state where the substrate is wet, the coating film does not peel off and is water resistant. Excellent in properties.
　以下、本発明を実施例に基づいて説明する。なお、「部」、「％」は特に示さない限り、重量基準とする。 Hereinafter, the present invention will be described based on examples. “Parts” and “%” are based on weight unless otherwise specified.
［実施例１］
　まず、第１コーティング組成物と第２コーティング組成物を調製した。 [Example 1]
First, a first coating composition and a second coating composition were prepared.
＜実施例１の第１コーティング組成物＞
・メチルシリケート（ＭＳ－５６：三菱化学社）　　　　　　　５．０部
・シランカップリング剤　　　　　　　　　　　　　　　　　　０．３部
（ＳＨ６０４０：東レ・ダウコーニング社）
・部分鹸化ＰＶＡ（キシダ化学社）　　　　　　　　　　　　　５．０部
（固形分１００％、鹸化度８７～８９モル％、平均重合度３５００）
・ポリアクリル酸（ＡＣ－１０Ｈ：日本純薬社）　　　　　　　５．０部
（固形分１００％）
・メタノール　　　　　　　　　　　　　　　　　　　　　　４０．０部
・Ｈ２　Ｏ　　　　　　　　　　　　　　　　　　　　　　　　４４．５部 <First Coating Composition of Example 1>
・ Methyl silicate (MS-56: Mitsubishi Chemical Corporation) 5.0 parts ・ Silane coupling agent 0.3 parts (SH6040: Toray Dow Corning)
-Partially saponified PVA (Kishida Chemical Co., Ltd.) 5.0 parts (100% solid content, saponification degree 87-89 mol%, average polymerization degree 3500)
・ Polyacrylic acid (AC-10H: Nippon Pure Chemicals Co., Ltd.) 5.0 parts (100% solids)
・ Methanol 40.0 parts ・ H 2 O 44.5 parts
＜実施例１の第２コーティング組成物＞
・メチルシリケート（ＭＳ－５６：三菱化学社）　　　　　　　５．０部
・シランカップリング剤　　　　　　　　　　　　　　　　　　０．３部
（ＳＨ６０４０：東レ・ダウコーニング社）
・ポリエチレングリコール（キシダ化学社）　　　　　　　　３０．０部
・イソシアネート系硬化剤　　　　　　　　　　　　　　　　２０．０部
（ＭＦ－Ｋ６０Ｘ：旭化成ケミカルズ社）
・ジアセトンアルコール　　　　　　　　　　　　　　　　　３０．０部
・ｔ－ブタノール　　　　　　　　　　　　　　　　　　　　１４．７部 <The 2nd coating composition of Example 1>
・ Methyl silicate (MS-56: Mitsubishi Chemical Corporation) 5.0 parts ・ Silane coupling agent 0.3 parts (SH6040: Toray Dow Corning)
・ Polyethylene glycol (Kishida Chemical Co., Ltd.) 30.0 parts ・ Isocyanate curing agent 20.0 parts (MF-K60X: Asahi Kasei Chemicals Corporation)
・ Diacetone alcohol 30.0 parts ・ t-Butanol 14.7 parts
　次に、調製した第１コーティング組成物を、基材として厚み１００μｍのプラスチックフィルム（ルミラーＴ６０：東レ社）へディップコート装置にて５０ｍｍ／ｍｉｎの速度で引き上げ塗布した。その後、１５０℃で１０分間加熱・乾燥（加熱処理）を行った。その結果、基材上に、厚みが３μｍで、均一且つ無色透明な第１層が形成された。 Next, the prepared first coating composition was applied as a substrate to a 100 μm thick plastic film (Lumirror T60: Toray Industries, Inc.) with a dip coater at a speed of 50 mm / min. Thereafter, heating and drying (heating treatment) were performed at 150 ° C. for 10 minutes. As a result, a uniform, colorless and transparent first layer having a thickness of 3 μm was formed on the substrate.
　次に、形成した第１層上に、前記組成の第２コーティング組成物をディップコート装置にて３０ｍｍ／ｍｉｎの速度で引き上げ塗布した。その後、１００～１２０℃の乾燥炉で１５分間乾燥（加熱処理）を行った。その結果、第１層上に、厚みが約５μｍの透明な第２層が形成され、本実施例のシートサンプルを得た。 Next, on the formed first layer, the second coating composition having the above composition was pulled up and applied at a speed of 30 mm / min with a dip coater. Thereafter, drying (heat treatment) was performed in a drying furnace at 100 to 120 ° C. for 15 minutes. As a result, a transparent second layer having a thickness of about 5 μm was formed on the first layer, and a sheet sample of this example was obtained.
［実施例２］
　第２コーティング組成物の「ＭＳ－５６」の量を３．０部とし、「ポリエチレングリコール」の量を３５．０部とし、「ＭＦ－Ｋ６０Ｘ」の量を１５．０部とし、「ジアセトンアルコール」の量を３２．０部とした以外は、実施例１と同じ条件で、基材上に第１層（厚み３μｍ）が形成され、第１層上に第２層（厚み約５μｍ）が形成された、本実施例のシートサンプルを得た。 [Example 2]
The amount of “MS-56” in the second coating composition is 3.0 parts, the amount of “polyethylene glycol” is 35.0 parts, the amount of “MF-K60X” is 15.0 parts, A first layer (thickness 3 μm) is formed on the substrate under the same conditions as in Example 1 except that the amount of “alcohol” is 32.0 parts, and a second layer (thickness of about 5 μm) is formed on the first layer. A sheet sample of this example in which was formed was obtained.
［比較例１］
　下記のコーティング組成物に示す成分（各々、重量部）に従って、まず、γ－グリシドキシプロピルトリメトキシシランと、アルミニウムイソプロポキシド加水分解液と、ケイフッ化水素酸の０．４７％メタノール溶液（溶液の％は重量％、以下同じ）を混合させた第１の溶液を調製した。
　次に、ポリアクリル酸メチルエステル２０モル％鹸化物の、２．５％の水－メタノール溶液に、ＰＶＡの１０％水溶液を加え、常温（２５℃）で１０分間撹拌して第２の溶液を調製した。その後、第２の溶液に第１の溶液を加え、常温で１５分間撹拌して、コーティング組成物（塗布液）を調製した。得られた塗布液は、無色透明であった。 [Comparative Example 1]
According to the components shown in the following coating composition (each by weight), first, γ-glycidoxypropyltrimethoxysilane, aluminum isopropoxide hydrolyzate, and 0.47% methanol solution of hydrofluoric acid ( A first solution was prepared in which% of the solution was mixed by weight, and the same applies hereinafter.
Next, a 10% aqueous solution of PVA was added to a 2.5% water-methanol solution of 20 mol% polyacrylic acid methyl ester, and the mixture was stirred for 10 minutes at room temperature (25 ° C.). Prepared. Then, the 1st solution was added to the 2nd solution, and it stirred for 15 minutes at normal temperature, and prepared the coating composition (coating liquid). The obtained coating liquid was colorless and transparent.
　なお、ポリアクリル酸メチルエステル２０モル％鹸化物は、次のようにして調製した。まず、ポリアクリル酸（平均分子量：１５０，０００）の２５％水溶液にメタノールを加え、常温で３０分間撹拌してポリアクリル酸メチルエステルを生成させる。その後、ポリアクリル酸メチルエステルを含む溶液に水酸化ナトリウム（苛性ソーダ）を、２０％鹸化となるように加え、さらに３０分間撹拌して鹸化させる。
　また、アルミニウムイソプロポキシド加水分解液は、エタノール中で、アルミニウムイソプロポキシドを酸触媒により加水分解させることにより調製した。 In addition, 20 mol% polyacrylic acid methyl ester saponified product was prepared as follows. First, methanol is added to a 25% aqueous solution of polyacrylic acid (average molecular weight: 150,000) and stirred at room temperature for 30 minutes to produce polyacrylic acid methyl ester. Thereafter, sodium hydroxide (caustic soda) is added to the solution containing polyacrylic acid methyl ester so as to be 20% saponification, and the mixture is further saponified by stirring for 30 minutes.
Moreover, the aluminum isopropoxide hydrolyzate was prepared by hydrolyzing aluminum isopropoxide with an acid catalyst in ethanol.
＜比較例１のコーティング組成物＞
・ポリアクリル酸メチルエステル２０モル％鹸化物　　　　５９．５０部
（２．５％の水－メタノール溶液）
・ＰＶＡの１０％水溶液　　　　　　　　　　　　　　　　３７．５０部
（ＰＶＡの鹸化度：約８２モル％、ＰＶＡの平均重合度：２０００）
・γ－グリシドキシプロピルトリメトキシシラン　　　　　　０．１４部
・アルミニウムイソプロポキシド加水分解液　　　　　　　　０．２８部
（Ａｌの含有量：Ａｌ２　Ｏ３　換算で５％）
・ケイフッ化水素酸の０．４７％メタノール溶液　　　　　　２．５８部 <Coating composition of Comparative Example 1>
-Polyacrylic acid methyl ester 20 mol% saponified product 59.50 parts (2.5% water-methanol solution)
37% of PVA in 10% aqueous solution (degree of saponification of PVA: about 82 mol%, average degree of polymerization of PVA: 2000)
・ Γ-glycidoxypropyltrimethoxysilane 0.14 parts ・ Aluminum isopropoxide hydrolyzed solution 0.28 parts (Al content: 5% in terms of Al 2 O 3 )
-0.47% methanol solution of hydrofluoric acid 2.58 parts
　次に、得られた塗布液を、実施例１と同様の基材へディップコート装置にて５０ｍｍ／ｍｉｎの速度で引き上げ塗布した。その後、１５０℃で１０分間加熱・乾燥を行った。その結果、基材上に、厚みが３μｍで、均一且つ無色透明な塗膜が形成され、本比較例のシートサンプルを得た。 Next, the obtained coating solution was pulled up and applied to the same substrate as in Example 1 at a speed of 50 mm / min with a dip coater. Thereafter, heating and drying were performed at 150 ° C. for 10 minutes. As a result, a uniform, colorless and transparent coating film having a thickness of 3 μm was formed on the substrate, and a sheet sample of this comparative example was obtained.
［比較例２］
　第２層を形成しなかった以外は、実施例１と同様に、基材上に第１層（厚み３μｍ）を形成し、得られた２層構造のシートを本比較例のシートサンプルとした。 [Comparative Example 2]
Except that the second layer was not formed, the first layer (thickness 3 μm) was formed on the base material in the same manner as in Example 1, and the obtained two-layer structure sheet was used as a sheet sample of this comparative example. .
［比較例３］
　第１層を形成しなかった以外は、実施例１と同様に、基材上に第２層（厚み３μｍ）を形成し、得られた２層構造のシートを本比較例のシートサンプルとした。 [Comparative Example 3]
Except that the first layer was not formed, the second layer (thickness 3 μm) was formed on the substrate in the same manner as in Example 1, and the obtained sheet having the two-layer structure was used as a sheet sample of this comparative example. .
　各例で得られたシートサンプルに対して、下記の評価を行なった。 The following evaluation was performed on the sheet samples obtained in each example.
（１）防曇性の評価
　すべてのシートサンプルを冷蔵庫（約０℃）に５分間収納し、その後、２５℃、８１％ＲＨの雰囲気下に放置した。実施例１，２及び比較例１，２の各サンプルに形成された塗膜表面には、曇りがまったく発生していなかった。一方、比較例３のサンプルに形成された塗膜表面には、曇りが発生していた。 (1) Evaluation of antifogging property All sheet samples were stored in a refrigerator (about 0 ° C.) for 5 minutes, and then left in an atmosphere of 25 ° C. and 81% RH. Haze did not occur at all on the coating film surfaces formed on the samples of Examples 1 and 2 and Comparative Examples 1 and 2. On the other hand, fogging occurred on the surface of the coating film formed on the sample of Comparative Example 3.
（２）低温下における防曇性の評価
　実施例２のシートサンプルを冷凍庫（約－２５℃）に６０分間放置し、その後、冷凍庫から取り出し、１０秒経過後のシートサンプルの塗膜表面を観察した。その結果、塗膜表面には、曇りは発生していなかった。 (2) Evaluation of anti-fogging property at low temperature The sheet sample of Example 2 was left in a freezer (about −25 ° C.) for 60 minutes, then removed from the freezer, and the coating surface of the sheet sample after 10 seconds was observed. did. As a result, cloudiness did not occur on the coating film surface.
（３）防曇持続性の評価
　（１）の評価により曇りが発生していなかったシートサンプル（実施例１，２及び比較例１，２）に対し、更に、４０℃、９５％ＲＨの恒温恒湿条件下で、一週間放置した。その後、各サンプルに形成された塗膜表面を観察した。その結果、いずれのサンプルにも曇りは発生しておらず、防曇性は低下していなかった。 (3) Evaluation of anti-fogging durability The sheet samples (Examples 1 and 2 and Comparative Examples 1 and 2) in which fogging did not occur according to the evaluation of (1) were further maintained at 40 ° C. and 95% RH. It was left for one week under constant humidity. Thereafter, the surface of the coating film formed on each sample was observed. As a result, no fogging occurred in any sample, and the antifogging property was not lowered.
（４）耐水性の評価
　すべてのシートサンプルの塗膜が形成された面に対し、約６０℃の湯気を５分間当てた。その後、塗膜が形成された面を乾いたウエスで３回擦り、塗膜表面を目視にて観察した。実施例１，２及び比較例３のサンプルについては、塗膜が剥がれてはいなかった。一方、比較例１，２のサンプルについては、塗膜が剥がれてしまっていた。 (4) Evaluation of water resistance Steam of about 60 ° C. was applied for 5 minutes to the surface on which the coating film of all the sheet samples was formed. Thereafter, the surface on which the coating film was formed was rubbed with a dry waste three times, and the coating film surface was visually observed. For the samples of Examples 1 and 2 and Comparative Example 3, the coating film was not peeled off. On the other hand, about the sample of Comparative Examples 1 and 2, the coating film had peeled off.
（５）塗膜の耐摩擦性の評価
　すべてのシートサンプルの塗膜が形成された面に対し、スチールウールを用いて５００ｇの荷重を掛けながら１０往復擦り、塗膜が形成された面（塗膜表面）の傷付き度合いを目視にて評価した。実施例１，２及び比較例３のサンプルの塗膜表面には、目視にて確認できる傷が存在しかなかった。一方、比較例１，２のサンプルの塗膜表面には、目視にて確認できる傷が無数に存在していた。 (5) Evaluation of friction resistance of coating film The surface on which the coating film of all the sheet samples was formed was rubbed 10 times while applying a load of 500 g using steel wool, and the surface on which the coating film was formed (coating The degree of scratching on the film surface was visually evaluated. There were only scratches that could be visually confirmed on the coating film surfaces of the samples of Examples 1 and 2 and Comparative Example 3. On the other hand, the surface of the coating film of the samples of Comparative Examples 1 and 2 had numerous scratches that could be visually confirmed.
（６）まとめ
　防曇性については、比較例３に対し、実施例１，２及び比較例１、２のシートサンプルが優れていた。これら４つのサンプルは、いずれも防曇持続性に優れていた。実施例２のシートサンプルは、低温下における防曇性に優れていた。
　耐水性については、比較例１，２に対し、実施例１，２及び比較例３のシートサンプルが優れていた。塗膜の耐摩擦性についても同様に、実施例１，２及び比較例３のシートサンプルが優れていた。
　以上より、実施例１，２のシートサンプルのみが、（２）の評価を除くすべての性能を持ち合わせていることが確認できた。特に実施例２のシートサンプルは、低温下においても防曇性に優れていることが確認できた。 (6) Summary Regarding antifogging properties, the sheet samples of Examples 1 and 2 and Comparative Examples 1 and 2 were superior to Comparative Example 3. All of these four samples were excellent in antifogging durability. The sheet sample of Example 2 was excellent in antifogging properties at low temperatures.
Regarding the water resistance, the sheet samples of Examples 1 and 2 and Comparative Example 3 were superior to Comparative Examples 1 and 2. Similarly, the sheet samples of Examples 1 and 2 and Comparative Example 3 were excellent in terms of the friction resistance of the coating film.
From the above, it was confirmed that only the sheet samples of Examples 1 and 2 had all the performance except the evaluation of (2). In particular, it was confirmed that the sheet sample of Example 2 was excellent in antifogging property even at low temperatures.

Claims (9)

  1. 　基材上に第１層と第２層が順に積層されてなる防曇性シートであって、
    　前記第１層は、吸水性樹脂を含む第１コーティング組成物の加熱処理物で構成されており、前記第２層は、ポリオールを含む第２コーティング組成物の加熱処理物で構成されていることを特徴とする防曇性シート。     An antifogging sheet in which a first layer and a second layer are sequentially laminated on a substrate,
    The first layer is composed of a heat-treated product of a first coating composition containing a water-absorbing resin, and the second layer is composed of a heat-treated product of a second coating composition containing a polyol. Anti-fogging sheet characterized by
  2. 　請求項１記載の防曇性シートにおいて、
    　前記吸水性樹脂は、ポリビニルアルコール及びポリアクリル酸類の少なくとも何れかを含むことを特徴とする防曇性シート。     In the antifogging sheet according to claim 1,
    The anti-fogging sheet, wherein the water-absorbent resin contains at least one of polyvinyl alcohol and polyacrylic acids.
  3. 　請求項１又は２記載の防曇性シートにおいて、
    　前記第１コーティング組成物中の前記吸水性樹脂の使用量は、固形分換算で、２０～９９．５重量％であることを特徴とする防曇性シート。     In the antifogging sheet according to claim 1 or 2,
    The antifogging sheet, wherein the water-absorbent resin is used in the first coating composition in an amount of 20 to 99.5% by weight in terms of solid content.
  4. 　請求項１～３の何れか一項記載の防曇性シートにおいて、
    　前記第１コーティング組成物及び前記第２コーティング組成物の少なくとも何れかが、金属アルコキシド、金属アルコキシドの加水分解物及び金属アルコキシドの加水分解重縮合物から選ばれる少なくとも１つの化合物を含むことを特徴とする防曇性シート。     In the antifogging sheet according to any one of claims 1 to 3,
    At least one of the first coating composition and the second coating composition contains at least one compound selected from a metal alkoxide, a hydrolyzate of metal alkoxide, and a hydrolyzed polycondensate of metal alkoxide, Anti-fogging sheet.
  5. 　請求項４記載の防曇性シートにおいて、
    　前記第１コーティング組成物及び前記第２コーティング組成物の少なくとも何れかが、硬化剤を含むことを特徴とする防曇性シート。     In the anti-fogging sheet according to claim 4,
    At least one of the first coating composition and the second coating composition contains a curing agent.
  6. 　請求項１～５の何れか一項記載の防曇性シートにおいて、
    　前記ポリオールは、ポリエチレングリコールを含むことを特徴とする防曇性シート。     In the antifogging sheet according to any one of claims 1 to 5,
    The said anti-fogging sheet | seat characterized by the above-mentioned polyol containing polyethyleneglycol.
  7. 　請求項１～６の何れか一項記載の防曇性シートにおいて、
    　前記第２コーティング組成物中の前記ポリオールの使用量は、固形分換算で、１０～８０重量％であることを特徴とする防曇性シート。     In the antifogging sheet according to any one of claims 1 to 6,
    The anti-fogging sheet, wherein the amount of the polyol used in the second coating composition is 10 to 80% by weight in terms of solid content.
  8. 　請求項１～７の何れか一項記載の防曇性シートにおいて、
    　前記基材は、少なくとも前記第１層が積層される面に易接着処理が施されていることを特徴とする防曇性シート。     In the antifogging sheet according to any one of claims 1 to 7,
    The anti-fogging sheet, wherein the base material is subjected to an easy adhesion treatment on at least a surface on which the first layer is laminated.
  9. 　請求項１～８の何れか一項記載の防曇性シートにおいて、
    　前記基材の、前記第１層が積層されている面とは反対面に、粘着層が積層されていることを特徴とする防曇性シート。     In the antifogging sheet according to any one of claims 1 to 8,
    An anti-fogging sheet, wherein an adhesive layer is laminated on a surface of the substrate opposite to a surface on which the first layer is laminated.
PCT/JP2010/060813 2009-06-25 2010-06-25 Anti-fogging sheet WO2010150868A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022014204A1 (en) * 2020-07-15 2022-01-20 恵和株式会社 Protection sheet and laminate body

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6152100B6 (en) * 2012-05-29 2018-06-27 株式会社きもと Anti-fogging sheet
CN104045229B (en) * 2014-07-01 2016-06-22 福建省港达玻璃制品有限公司 A kind of preparation technology of safety glass
US20180201796A1 (en) * 2015-07-16 2018-07-19 Lintec Corporation Antifouling composition, antifouling sheet, and process for producing antifouling sheet
CN112280335B (en) * 2020-10-24 2022-03-15 杭州临安绿源助剂有限公司 PO (polyolefin) membrane coating liquid and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09174750A (en) * 1995-10-27 1997-07-08 Sumitomo Chem Co Ltd Defogging film
JPH11109105A (en) * 1997-08-07 1999-04-23 Canon Inc Fogging preventive and reflection preventive optical article
JP2005278560A (en) * 2004-03-30 2005-10-13 Mitsubishi Chem Mkv Co Agricultural anti-frost film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2898589B2 (en) * 1994-12-08 1999-06-02 株式会社中戸研究所 Antifogging coating composition and coated substrate using the same
JP2000309068A (en) * 1999-02-23 2000-11-07 Toto Ltd Film equipped with hydrophilic property, stream droplet property, anti-cloudiness and anti-fouling property, manufacture of the film, method for imparting hydrophilic property, steam droplet property, anti- cloudiness and anti-fouling property to base material by the film, base material to which the film is affixed, coating composition for manufacturing the film, preparation of the coating composition
JP2001145982A (en) * 1999-09-08 2001-05-29 Toto Ltd Hygroscopic anti-fogging film and method of manufacturing the same
JP2005314495A (en) * 2004-04-27 2005-11-10 Dainichiseika Color & Chem Mfg Co Ltd Antifog coating material, antifog film and method for producing the same
CN1303137C (en) * 2005-04-19 2007-03-07 华东理工大学 Exterior coating antifogging film and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09174750A (en) * 1995-10-27 1997-07-08 Sumitomo Chem Co Ltd Defogging film
JPH11109105A (en) * 1997-08-07 1999-04-23 Canon Inc Fogging preventive and reflection preventive optical article
JP2005278560A (en) * 2004-03-30 2005-10-13 Mitsubishi Chem Mkv Co Agricultural anti-frost film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022014204A1 (en) * 2020-07-15 2022-01-20 恵和株式会社 Protection sheet and laminate body

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