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.

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