WO2013180106A1 - 防曇性シート - Google Patents
防曇性シート Download PDFInfo
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- WO2013180106A1 WO2013180106A1 PCT/JP2013/064727 JP2013064727W WO2013180106A1 WO 2013180106 A1 WO2013180106 A1 WO 2013180106A1 JP 2013064727 W JP2013064727 W JP 2013064727W WO 2013180106 A1 WO2013180106 A1 WO 2013180106A1
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- WIPO (PCT)
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- layer
- coating composition
- antifogging
- benzotriazole
- weight
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention is an antifogging property that maintains the antifogging property even when exposed to ultraviolet rays in a high-humidity environment or in a wet state of the coating film, while preventing the whitening of the coating film or the adhesion of the coating film from decreasing.
- the sheet Regarding the sheet.
- 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 property, an antifogging sheet (Patent Document 1) on which the composition is applied on a plastic, and a substrate, A first layer for developing water absorption and anti-fogging properties, and a layered structure in which a second layer for imparting water resistance is further laminated in order while maintaining anti-fogging properties.
- Patent Document 2 an anti-fogging sheet that does not peel off the coating film even in a high humidity environment or in a wet state is proposed (Patent Document 2).
- the anti-fogging sheet formed by laminating two layers of the above-described anti-fogging coating film is superior to the conventional anti-fogging sheet in terms of anti-fogging property and water resistance.
- the coating film was whitened or the adhesiveness of the coating film was lowered.
- Patent Document 2 describes that a benzophenone compound is added as an ultraviolet absorber to the first layer that exhibits antifogging properties in order to improve the weather resistance of the antifogging coating film. According to these studies, in this configuration, it is impossible to prevent whitening of the coating film of the second layer and deterioration of coating film adhesion between the first layer and the second layer. Further, when a benzophenone compound is added to the second layer instead of the first layer, a new problem that the antifogging property is impaired is caused.
- the present invention does not whiten the coating film or deteriorate the adhesion of the coating film while maintaining the antifogging property even when exposed to ultraviolet rays in a high humidity environment or in a wet coating condition.
- An object is to provide an antifogging sheet.
- the present inventors have added a specific amount of a benzotriazole-based ultraviolet absorber having a relatively low molecular weight among the ultraviolet absorbers to the coating film of the second layer. It is possible to obtain an antifogging sheet that does not whiten the coating film or deteriorate the adhesion of the coating film while maintaining the antifogging property even when it is exposed to ultraviolet rays under the wet condition. I found out that I can do it.
- the antifogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate, the first layer includes a water absorbent resin, and the second layer has a polyol and a molecular weight of 500 or less.
- the content of the benzotriazole-based ultraviolet absorber in the second layer is 1.5 to 8% by weight.
- a 1st layer can be comprised with the heat processing thing of the 1st coating composition containing a water absorbing resin.
- a 2nd layer can be comprised with the heat-processing thing of the 2nd coating composition containing a polyol and a benzotriazole type ultraviolet absorber.
- the antifogging sheet of the present invention preferably has a molecular weight of 350 or less of the benzotriazole ultraviolet absorber. Further, the content of the benzotriazole ultraviolet absorber is preferably 5% by weight or less.
- the antifogging sheet of the present invention is preferably characterized in that the water absorbent resin contains at least one of polyvinyl alcohol and polyacrylic acids. More preferably, the water absorbent resin includes polyvinyl alcohol and polyacrylic acids.
- At least one of the first coating composition and the second coating composition is selected from a metal alkoxide, a hydrolyzate of metal alkoxide, and a hydrolyzed polycondensate of metal alkoxide. And at least one compound.
- the antifogging sheet of the present invention is preferably characterized in that at least one of the first coating composition and the second coating composition contains a curing agent.
- a high humidity environment means an environment having a relative humidity of 70% or more.
- the anti-fogging sheet in which the first layer and the second layer are sequentially laminated on the base material contains the specific ultraviolet absorber in the second layer.
- Weather resistance can be imparted to the first layer and the second layer without hindering, especially in a high humidity environment where the antifogging sheet is exposed or under the wet condition of the coating film, which has a high UV protection function. Is granted.
- benzotriazole-based UV absorber as the UV absorber used in the second layer, it can be contained in the second layer with high cross-linking strength with good compatibility. The second layer function of maintaining and imparting water resistance can be maintained.
- Sex sheets can be provided.
- the antifogging sheet of the present invention is formed by sequentially laminating a first layer and a second layer on a substrate.
- the first layer can be composed of a heat-treated product of the first coating composition containing a water-absorbing resin
- the second layer is a heat-treatment of the second coating composition containing a polyol and a benzotriazole-based ultraviolet absorber. It can consist of things.
- the amount of the benzotriazole ultraviolet absorber used in the second coating composition is 1.5 to 8% by weight in terms of solid content.
- the first coating composition constituting the first layer 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 it is preferable to use at least one of PVA and polyacrylic acids as the water absorbent resin.
- a mixture of PVA and polyacrylic acids is more preferably used as the water absorbent resin.
- the ratio of polyacrylic acids to PVA is preferably 5/95 to 50/50 in terms of weight.
- 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 can be further achieved.
- the amount of PVA used in the first coating composition is preferably 50 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 includes at least one compound selected from metal alkoxide, hydrolyzate of metal alkoxide, and hydrolyzed polycondensate of metal alkoxide (hereinafter referred to as “metal alkoxide etc.”). Preferably).
- the first coating composition preferably contains a metal alkoxide or the like
- 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 coexists therewith. It reacts with the functional 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.
- 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.
- 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.
- the metal alkoxide includes, for example, 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.
- R1 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 (OR2) 3 a in the above formula (I) is 3, and such an alkoxide is represented by Al (OR2) 3 .
- R2 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.
- 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.
- M is Ti
- a in the above formula (I) is 4, and such an alkoxide is represented by Ti (OR3) 4 .
- R3 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.
- Zr (OR4) 4 When M is Zr, a in the above formula (I) is 4, and such an alkoxide is represented by Zr (OR4) 4 .
- R4 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 metal alkoxide or the like 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 contributes to the formation of a composite polymer having a three-dimensional structure having an organic part and an inorganic part in the same manner as a metal alkoxide and the like, thereby enhancing insolubility while maintaining absorbency.
- silane coupling agent examples 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.
- a silane coupling agent having an epoxy group ⁇ -glycidoxypropyltrimethoxysilane which is also a metal alkoxide 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 metal alkoxide or the like 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 metal alkoxide, etc., and further contains a catalyst (a metal that can be contained in the specific compound).
- a reaction solution containing a polycondensation reaction of an alkoxide hydrolyzate include 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 may further contain 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.
- 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 may further contain hydrofluoric acid.
- 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.
- the first coating layer is usually used in the form of a coating solution to form the first layer.
- the coating liquid can be prepared by dissolving or dispersing the above-described water-absorbing resin (and other metal alkoxides and the like as required) 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. The reason for including the case where the amount of the organic solvent used is 0 (zero) is that there may be a case where the form of the coating liquid can be obtained without using the organic solvent.
- the main composition of the first coating composition is obtained by causing a sol-gel reaction in the presence of a water-absorbing resin, the OH group of the hydrolyzate of the metal alkoxide is deprotonated, and as a result,
- the polycondensate obtained by the polycondensation reaction, the OH group of the polycondensate obtained by crosslinking the water-absorbent resin with the above-mentioned composite polymer, the hydrolyzate of metal alkoxide and the water-absorbent resin can be considered.
- the second coating composition contains at least a polyol and a benzotriazole-based ultraviolet absorber.
- 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.
- the benzotriazole-based ultraviolet absorber maintains the antifogging property expressed in the first layer even when exposed to ultraviolet rays in a high-humidity environment or in a state where the coating film is wet. It is used to prevent the coating film of the layer from being whitened or the adhesiveness of the coating film from being lowered.
- 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.
- Available benzotriazole ultraviolet absorbers include, for example, EVERSORB (trade name) series 70-78, 80, 81, 109, etc., provided by Yongkou Chemical Industry Co., Ltd., Taiwan, provided by Sumika Chemtex Co., Ltd.
- benzotriazole ultraviolet absorber having a molecular weight of 500 or less examples include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-tertiary-butyl-2-hydroxyphenyl) benzotriazole, Examples include 2- (5-chloro-2-benzotriazolyl) -6-tertiary-butyl-p-cresol and 2- (2-hydroxy-5-tertiary-octylphenyl) benzotriazole.
- Benzotriazole UV absorbers with a molecular weight of 500 or less have good compatibility with polyols and other compositions constituting the coating film, and the coating of the first layer and the second layer is whitened without impairing the antifogging property. Can be prevented. You may use these individually or in mixture of 2 or more types.
- the amount of the benzotriazole ultraviolet absorber used in the second coating composition is 1.5 to 8% by weight, preferably 1.9 to 5% by weight, in terms of solid content.
- an ultraviolet absorption function sufficient to prevent whitening of the coating film can be obtained.
- it can prevent that anti-fogging property is impaired by making a usage fee into 5 weight%.
- the second coating composition contains the same metal alkoxide as the first coating composition.
- the amount of metal alkoxide used in the second coating composition is preferably 0.5 to 50% by weight in terms of solid content.
- the second coating composition contains a metal alkoxide or the like
- 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 second coating composition preferably contains the same silane coupling agent as the first 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 second coating composition 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 second coating composition is preferably 10 to 80% by weight, more preferably 30 to 60% by weight in terms of solid content.
- the second coating composition contains silicofluoric acid as in the case of the first coating composition.
- the amount of silicofluoric acid used in the second coating composition is the same as in the first coating composition.
- the second coating composition is usually used in the form of a coating solution to form the second layer.
- the coating liquid can be prepared by dissolving or dispersing the above-described polyol and benzotriazole-based ultraviolet absorber, and further, if necessary, a metal alkoxide and a curing agent 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 is a coating film in which polyol is crosslinked, the crosslinking density of the coating film is high. 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.
- the second layer contains a specific amount of a benzotriazole-based ultraviolet absorber, the anti-fogging property expressed in the first layer can be obtained even when exposed to ultraviolet light in a high humidity environment or in a wet state of the coating film. While maintaining, it can prevent that the coating film of a 1st layer or a 2nd layer whitens, or the adhesiveness of a coating film falls.
- the base material on which the first layer and the second layer are laminated mainly includes 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, potash 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 first coating composition is mixed to prepare a transparent first coating liquid (synonymous with the first coating composition in the present invention). Moreover, each component of a 2nd coating composition 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 heat-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 Since it is still insufficient, when the paint film (first layer) is rubbed with a dry cloth or finger in a high-humidity environment or when the substrate is wet, the organic matter easily moves and the paint film peels off. Will end up.
- the antifogging sheet of the present invention further comprises a second layer composed of the heat-treated product of the second coating composition on the first layer described above. Since the second layer has a high cross-linking density of the coating film, it is possible to further impart water resistance while maintaining the antifogging property developed in the first 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.
- the second layer contains a specific amount of a benzotriazole-based ultraviolet absorber, the anti-fogging property that is manifested in the first layer even when exposed to ultraviolet rays in a high-humidity environment or in a wet state of the coating film. While maintaining, it can prevent that the coating film of a 1st layer or a 2nd layer whitens, or the adhesiveness of a coating film falls.
- the addition of a benzophenone-based UV absorber instead of a benzotriazole-based UV absorber to the second layer coating can suppress the above-described whitening of the coating film and a decrease in the adhesion of the coating film. It hinders cloudiness. This is because when the second layer is a coating film having a high crosslinking density, the addition of a benzophenone-based UV absorber to an extent that suppresses whitening of the coating film or a decrease in adhesion of the coating film results in the addition of the benzophenone-based UV absorber and the second layer. It is considered that the compatibility with the two-layer coating film is poor and the antifogging property expressed in the first layer is inhibited.
- the benzotriazole-based UV absorber when a specific amount of a benzotriazole-based UV absorber is added to the second layer coating film that is directly irradiated with UV rays, the benzotriazole-based UV absorber has a good compatibility with the second layer coating film. Even if it is exposed to ultraviolet rays in a humid environment or in a state where the coating film is wet, the coating of the first layer or the second layer is whitened while maintaining the antifogging property expressed in the first layer. It can prevent that adhesiveness falls.
- 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 ⁇ Water 44.5 parts
- Benzotriazole ultraviolet absorber 1.1 parts (ADK STAB LA-32: ADEKA, chemical name: 2- (2-hydroxy-5-methylphenyl) benzotriazole, molecular weight 225) ⁇ 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
- 1.1 parts of usage-amount of the benzotriazole type ultraviolet absorber "Adekastab LA-32" of Example 1 is 1.95 weight% in conversion of solid content in a 2nd coating composition.
- 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 the antifogging sheet of this example was obtained.
- Example 2 The amount of the benzotriazole ultraviolet absorber “ADK STAB LA-32” in the second coating composition of Example 1 was 2.77 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 1. In addition, this usage-amount in a 2nd coating composition is 4.8 weight% in conversion of solid content.
- Example 3 The amount of the benzotriazole ultraviolet absorber “ADK STAB LA-32” in the second coating composition of Example 1 was 3.87 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 1. In addition, this usage-amount in a 2nd coating composition is 6.5 weight% in conversion of solid content.
- Example 4 The amount of the benzotriazole ultraviolet absorber “ADK STAB LA-32” in the second coating composition of Example 1 was 4.42 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 1. In addition, this usage-amount in a 2nd coating composition is 7.4 weight% in conversion of solid content.
- Example 5 The benzotriazole ultraviolet absorber “Adekastab LA-32” of the second coating composition of Example 1 was changed to a benzotriazole ultraviolet absorber (Sumisorb 300: Sumika Chemtex Co., Ltd., chemical name: 2- (5-chloro-2- Benzotriazolyl) -6-tertiary-butyl-p-cresol, molecular weight 315) 1.1 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 1. In addition, this usage-amount in a 2nd coating composition is 1.95 weight% in conversion of solid content.
- Example 6 The amount of the benzotriazole ultraviolet absorber “Sumisorb 300” in the second coating composition of Example 5 was 2.77 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 5. In addition, this usage-amount in a 2nd coating composition is 4.8 weight% in conversion of solid content.
- Example 7 The amount of the benzotriazole ultraviolet absorber “Sumisorb 300” in the second coating composition of Example 5 was 3.87 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 5. In addition, this usage-amount in a 2nd coating composition is 6.5 weight% in conversion of solid content.
- Example 8 The amount of the benzotriazole ultraviolet absorber “Sumisorb 300” in the second coating composition of Example 5 was 4.42 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 5. In addition, this usage-amount in a 2nd coating composition is 7.4 weight% in conversion of solid content.
- Example 9 The benzotriazole ultraviolet absorber “Adekastab LA-32” of the second coating composition of Example 1 was changed to a benzotriazole ultraviolet absorber (Sumisorb 250: Sumika Chemtex Co., Ltd., chemical name: N- [3- (2H-benzo Triazol-2-yl) -2-hydroxy-5-methylbenzyl] -3,4,5,6-tetrahydrophthalimide, molecular weight 388) changed to 1.1 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 1. In addition, this usage-amount in a 2nd coating composition is 1.95 weight% in conversion of solid content.
- Example 10 The amount of the benzotriazole ultraviolet absorber “Sumisorb 250” in the second coating composition of Example 9 was 2.77 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 9. In addition, this usage-amount in a 2nd coating composition is 4.8 weight% in conversion of solid content.
- Example 11 The amount of the benzotriazole ultraviolet absorber “Sumisorb 250” in the second coating composition of Example 9 was 3.87 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 9. In addition, this usage-amount in a 2nd coating composition is 6.5 weight% in conversion of solid content.
- Example 12 The amount of the benzotriazole ultraviolet absorber “Sumisorb 250” in the second coating composition of Example 9 was 4.42 parts. Otherwise, the antifogging sheet of this example was obtained under the same conditions as in Example 9. In addition, this usage-amount in a 2nd coating composition is 7.4 weight% in conversion of solid content.
- the anti-fogging sheet subjected to the weather resistance promotion test was stored in a refrigerator (about 0 ° C.) for 5 minutes, and then left in an atmosphere of 23 ° C. and 55% RH.
- the coating film surface of the anti-fogging sheet was “ ⁇ ” when no fogging occurred, “ ⁇ ” when slight fogging occurred, and “ ⁇ ” when fogging occurred. did.
- the results of Table 1 are summarized as follows.
- the first layer and the second layer are sequentially laminated on the base material, the first layer contains a water-absorbing resin, and the second layer is a polyol and a benzotriazole-based ultraviolet absorber.
- the amount of the benzotriazole ultraviolet absorber used in the second layer is 1.9 to 5% by weight in terms of solid content.
- the evaluation of the property was good without any fogging, and the evaluation of the whitening of the coating and the adhesion of the coating were also good. Further, the evaluation of antifogging properties tends to decrease as the amount of the benzotriazole ultraviolet absorber used increases. In Examples 9 to 12 using the benzotriazole ultraviolet absorber having a molecular weight of 350 or more, the amount used was 2 The antifogging property was maintained up to the weight percent, but the antifogging property was slightly lowered when the amount exceeded 4 wt%.
- the antifogging sheet of Comparative Example 1 does not contain a benzotriazole ultraviolet absorber in the second layer, the antifogging evaluation is good without any fogging, but the whitening of the coating film and the adhesion of the coating film are good. Evaluation of was bad.
- the antifogging sheet of Comparative Example 2 contained more than 8% by weight of the second layer benzotriazole-based UV absorber, the whitening of the coating and the evaluation of the adhesion of the coating were good. However, the evaluation of anti-fogging property was poor due to cloudiness.
- the second layer contains not a benzotriazole ultraviolet absorber but a benzophenone ultraviolet absorber, and when the amount used is 1.95% by weight in terms of solid content (comparison) Example 3) Although the decrease in antifogging property was small, the whitening of the coating film and the evaluation of the adhesion of the coating film were poor.
- the amount used was 4.8 wt% in terms of solid content and 6.5 wt% (Comparative Examples 4 and 5), the whitening of the coating and the evaluation of the adhesion of the coating were good, The evaluation of anti-fogging property was poor due to cloudiness.
- the second layer contains a benzotriazole-based ultraviolet absorber having a molecular weight of 500 or more, and the whitening of the coating film and the evaluation of the adhesion of the coating film were good. Even when the amount was small, the evaluation of anti-fogging property was poor due to cloudiness.
- the first layer and the second layer maintain the antifogging property even when exposed to ultraviolet rays in a high humidity environment or in a wet state of the coating film. It was confirmed that the coating film was not whitened or the adhesiveness of the coating film was not lowered.
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Abstract
Description
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することができる。また第2層は、ポリオールとベンゾトリアゾール系紫外線吸収剤とを含む第2コーティング組成物の加熱処理物で構成することができる。
(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。
[実施例1]
まず、下記処方の第1コーティング組成物及び第2コーティング組成物を調製した。
・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
・水 44.5部
・ベンゾトリアゾール系紫外線吸収剤 1.1部
(アデカスタブLA-32:ADEKA社、化学名:2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、分子量225)
・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
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」の量を2.77部とした。それ以外は、実施例1と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で4.8重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」の量を3.87部とした。それ以外は、実施例1と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で6.5重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」の量を4.42部とした。それ以外は、実施例1と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で7.4重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」をベンゾトリアゾール系紫外線吸収剤(Sumisorb 300:住化ケムテックス社、化学名:2-(5-クロロ-2-ベンゾトリアゾリル)-6-ターシャリー-ブチル-p-クレゾール、分子量315)1.1部に変更した。それ以外は、実施例1と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で1.95重量%である。
実施例5の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 300」の量を2.77部とした。それ以外は、実施例5と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で4.8重量%である。
実施例5の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 300」の量を3.87部とした。それ以外は、実施例5と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で6.5重量%である。
実施例5の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 300」の量を4.42部とした。それ以外は、実施例5と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で7.4重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」をベンゾトリアゾール系紫外線吸収剤(Sumisorb 250:住化ケムテックス社、化学名:N-[3-(2H-ベンゾトリアゾール-2-イル)-2-ヒドロキシ-5-メチルベンジル]-3,4,5,6-テトラヒドロフタルイミド、分子量388)1.1部に変更した。それ以外は、実施例1と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で1.95重量%である。
実施例9の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 250」の量を2.77部とした。それ以外は、実施例9と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で4.8重量%である。
実施例9の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 250」の量を3.87部とした。それ以外は、実施例9と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で6.5重量%である。
実施例9の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「Sumisorb 250」の量を4.42部とした。それ以外は、実施例9と同じ条件で、本実施例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で7.4重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」を添加しなかった。それ以外は、実施例1と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で0重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」の量を5.53部とした。それ以外は、実施例1と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で9.1重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」をベンゾフェノン系紫外線吸収剤(ケミソーブ11:ケミプロ化成社、化学名:2-ヒドロキシ-4-メトキシベンゾフェノン、分子量228)1.1部に変更した。それ以外は、実施例1と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で1.95重量%である。
比較例3の第2コーティング組成物のベンゾフェノン系紫外線吸収剤「ケミソーブ11」の量を2.77部とした。それ以外は、比較例3と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で4.8重量%である。
比較例3の第2コーティング組成物のベンゾフェノン系紫外線吸収剤「ケミソーブ11」の量を3.87部とした。それ以外は、比較例3と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で6.5重量%である。
実施例1の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「アデカスタブLA-32」をベンゾトリアゾール系紫外線吸収剤(EVERSORB 78:台湾永光化学工業股分有限公司社、化学名:2,2'-メチレンビス[6-(ベンゾトリアゾール-2-イル)-4-tert-オクチルフェノール]、分子量:658)1.1部に変更した。それ以外は、実施例1と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で1.95重量%である。
比較例6の第2コーティング組成物のベンゾトリアゾール系紫外線吸収剤「EVERSORB 78」の量を2.77部とした。それ以外は、比較例6と同じ条件で、本比較例の防曇性シートを得た。なお、第2コーティング組成物中の、この使用量は、固形分換算で4.8重量%である。
実施例1~12、及び比較例1~7の防曇性シートを、JIS-A5759―2008に基づいて、サンシャインカーボンアーク灯式の耐候性試験機(スガ試験機社)を用いて、防曇層側に紫外光を照射して水噴射を行なう耐候性促進試験を250時間行った。耐候性促進試験を行なった防曇性シートについて、下記項目の評価を行った。結果を表1に示す。
耐候性促進試験を行なった防曇性シートを冷蔵庫(約0℃)に5分間収納し、その後、23℃、55%RHの雰囲気下に放置した。防曇性シートの塗膜表面に、曇りがまったく発生していなかったものを「○」、わずかに曇りが発生していたものを「△」、曇りが発生していたものを「×」とした。
(2)塗膜の白化の評価
耐候性促進試験を行なった防曇性シートの外観評価を行い、防曇性シートの第1層や第2層の塗膜の白化が観察されなかったものを「○」、白化がわずかに観察されたものを「△」、白化が観察されたものを「×」とした。
(3)塗膜の接着性の評価
耐候性促進試験を行なった防曇性シートを乾燥させた後、JIS-K5400:1990における碁盤目テープ法に基づき測定して、基材と第1層との接着性を評価した。碁盤目部分の面績が10%以上剥離したものを「×」、5%以上10%未満のものを「△」、5%未満のものを「○」とした。
表1の結果をまとめると次のとおりである。
実施例1~12の防曇性シートは、基材上に第1層と第2層が順に積層し、第1層は吸水性樹脂を含み、第2層はポリオールとベンゾトリアゾール系紫外線吸収剤を固形分換算で1.5~8重量%含むので、防曇性の評価は良好であり、また塗膜の白化および塗膜の接着性の評価も良好であった。
特に、実施例1、2、5、6の防曇性シートは、第2層でのベンゾトリアゾール系紫外線吸収剤の使用量が固形分換算で1.9~5重量%であるので、防曇性の評価は曇りがまったく無く良好であり、塗膜の白化および塗膜の接着性の評価も良好であった。またベンゾトリアゾール系紫外線吸収剤の使用量が多くなるにつれて防曇性の評価は下がる傾向にあり、分子量が350以上のベンゾトリアゾール系紫外線吸収剤を用いた実施例9~12では、使用量が2重量%までは防曇性が維持されたが、4重量%を超えると防曇性がやや低下した。
Claims (11)
- 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、吸水性樹脂を含み、前記第2層はポリオールと分子量が500以下のベンゾトリアゾール系紫外線吸収剤とを含み、
前記第2層中の前記ベンゾトリアゾール系紫外線吸収剤の含有量が1.5~8重量%であることを特徴とする防曇性シート。 - 請求項1記載の防曇性シートにおいて、
前記ベンゾトリアゾール系紫外線吸収剤の分子量が350以下であることを特徴とする防曇性シート。 - 請求項1又は2記載の防曇性シートにおいて、
前記ベンゾトリアゾール系紫外線吸収剤の含有量が4重量%以下であることを特徴とする防曇性シート。 - 請求項1又は2記載の防曇性シートにおいて、
前記ベンゾトリアゾール系紫外線吸収剤の含有量が5重量%以下であることを特徴とする防曇性シート。 - 請求項1~4の何れか一項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。 - 請求項1に記載の防曇性シートにおいて、
前記第2層は、ポリオールとベンゾトリアゾール系紫外線吸収剤とを含む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。 - 請求項6記載の防曇性シートにおいて、
前記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つの化合物を含むことを特徴とする防曇性シート。 - 請求項6又は7記載の防曇性シートにおいて、
前記コーティング組成物が硬化剤を含むことを特徴とする防曇性シート。 - 請求項1に記載の防曇性シートにおいて、
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、ポリオールとベンゾトリアゾール系紫外線吸収剤とを含む第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。 - 請求項9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。 - 請求項9又は10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。
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JP2015232507A (ja) * | 2014-06-10 | 2015-12-24 | 横河電機株式会社 | 測定用窓 |
JP2016108523A (ja) * | 2014-11-28 | 2016-06-20 | 日本板硝子株式会社 | 防曇膜つき物品 |
WO2018038270A1 (ja) * | 2016-08-26 | 2018-03-01 | 三井化学株式会社 | 防曇性積層体 |
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