JP2002114969A - Abrasive for moisture absorptive composite material and repair method of moisture absorptive composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an abrasive capable of removing a scar on a film without loosing transparency, while keeping moisture absorption function. SOLUTION: This abrasive for moisture absorptive composite material has on a substrate surface a transparent moisture adsorptive film containing at least an inorganic binder and a moisture absorptive organic polymer, and it contains at least an inorganic particulate having an average particle diameter of 0.2-3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to at least the appearance of a coating film obtained by a water-absorbing coating composition which absorbs the surface of a member mainly used in the vicinity of water by applying it to the coating. , Anti-fogging time, film thickness of the coating, respectively, is substantially the same state or value as before the occurrence of scratches in the coating, a method for repairing a coating obtained by the composition, and an abrasive used therefor About.

[0002]

2. Description of the Related Art With regard to mirrors used in water-filled spaces, for example, mirrors placed in washrooms are often experienced that steam from hot water supply adheres to the surface and easily fogs, and loses the visibility of reflected images. It is. In order to solve this problem, a method has been conceived in which a mirror surface is coated with a water-absorbing coating composition and a moisture-absorbing coating is provided to exhibit anti-fog performance. Japanese Patent Application Laid-Open No. 58-32664 relates to this composition. Currently open to the public. The term "hygroscopicity" or "hygroscopicity" as used herein means, for example, that even when steam or hot water condensed water or water droplets adhere to the mirror surface, they are absorbed by the coating composition and remain on the surface. The function of preventing the mirror surface from being clouded or overshadowed by condensed water or water droplets of moisture by preventing the mirror surface. By the way, JP-A-58-32664 discloses, for example, a polymer having an OH group formed by hydrolysis and polycondensation of polyvinyl alcohol, which is one of water-absorbing organic polymers, and an organosilicon compound, which is an inorganic binder. , And an average particle size of about 5
And -200 nm particulate silica, each specifying a coating composition containing the same. The coating thus formed is a coating having not only moisture absorption performance but also water resistance that does not easily cause a problem that the coating melts or is easily peeled off even when the moisture absorbing coating is saturated with moisture.

[0003]

However, a hygroscopic film coated with such a hygroscopic coating composition is usually obtained by heating and drying at a high temperature of 80 ° C to 170 ° C class. The resulting coating has a pencil hardness of only about 2H, and the composition on the mirror surface is apt to be damaged. There is a disadvantage that it is not suitable as a moisture-absorbing anti-fog coating for use.

Accordingly, in the present invention, even when the member having the hygroscopic coating, that is, the hygroscopic composite material is damaged by a hard substance used daily in mirrors such as nails and scrubbers, the composite material has at least Restoration to a state where there is no problem in appearance, that is, a state where scratches are not visible under fluorescent lamps, anti-fog time is almost the same before and after restoration, and change in film thickness before and after restoration It is an object of the present invention to provide an abrasive for repairing the composite material, which can simultaneously realize the absence of the above, and to provide a repair method for repairing the coating film using the abrasive. By the way, the term "anti-fog time" as used herein refers to the time from when the composite material is cooled to about 5 ° C. under an atmosphere of 30 ° C. and 100% RH until the surface of the coating film becomes cloudy.

[0005]

According to the present invention, there is provided a transparent substrate having at least an inorganic binder and a water-absorbing organic polymer on the surface of a mirror substrate or a transparent substrate. An abrasive for a hygroscopic composite material on which a water-soluble coating is formed, which contains at least a particulate inorganic substance having an average particle diameter of 0.2 to 3 μm, and is formed on the coating while maintaining a moisture-absorbing function. The abrasive is characterized in that the abrasive can be removed without devitrification.

In the present invention, by using the above-mentioned abrasive, the recesses caused by the scratches are flattened, and the scratches formed on the composite material are erased. In other words, the restoration was made so that no damage was visible under the fluorescent lamp, the anti-fog time was almost the same before and after the restoration, and the film thickness before and after the restoration was unchanged. Can be realized. Therefore, even when the composite material is damaged by a hard substance such as a nail, the coating can be easily repaired by polishing with the abrasive. For this reason, once the conventional hygroscopic composite material was damaged, it was necessary to discard the coating or the composite material and replace it with a new coating or the composite material. Became possible. By the way, it is presumed that, by polishing the coating or the composite material to which the coating is applied with the abrasive, the scratches generated in the composite material are erased, and the appearance, anti-fogging time, coating The following reasons can be considered as the reason why the thickness can be repaired without being changed. As a reason, it is presumed that a film mainly composed of a water-absorbing organic polymer as described above has a certain degree of flexibility. It is considered that the surface of the film was partially pressed with a hard object such as a nail, and the surface of the film was locally dented, causing small irregularities on the surface. Therefore, when the surface is polished with the above-mentioned abrasive, the particulate inorganic matter in the abrasive becomes in a state where it pushes into the convex portions of the film surface unevenness having a size of 0.2 to 3 μm in average particle diameter. It is considered that the concave portions on the surface are raised in the opposite direction, and the coating surface is flattened. As a result, it is considered that the scratches can be eliminated without changing the appearance, the anti-fog time, and the thickness of the coating as described above.

In a preferred aspect of the present invention, the abrasive contains at least a particulate inorganic substance having a Mohs hardness of 8 to 9.5.

[0008] By doing so, the appearance of the coating or the composite material, the antifogging time, and the thickness of the coating are changed by polishing the scratches generated in the composite material to which the hygroscopic coating is applied with the abrasive. It is considered that the wound can be erased without causing the damage. The reason for this is, presumably,
In the inorganic binder in the composition, a hard substance such as zirconia having a Mohs' hardness of 8 also exists. When polishing the coating, the abrasive is more suitable for the inorganic binder depending on the type of abrasive used. This is because they may be crushed by the binder and may not be able to serve as an abrasive. Conversely, some of the inorganic binders have a Mohs hardness of 7 or less, and when a film obtained using the same is polished with an alumina-containing abrasive having a Mohs hardness of 9, the coating may be damaged. is there. That is, when an abrasive containing at least a particulate inorganic substance having a Mohs 'hardness of less than 8 is used, the polishing ability as an abrasive is weakened, and the Mohs' hardness is 9.
When an abrasive containing at least 5 or more fine particles of inorganic material is used, there is a possibility that the film may be conversely damaged. Therefore, an abrasive containing at least fine particles of Mohs hardness of 8 to 9.5 is used. This is because things are preferable.

In a preferred aspect of the present invention, the particulate inorganic material is alumina. By doing so, by polishing the scratches generated on the coating with the abrasive, there is an effect that the scratches can be erased without changing the appearance of the composite material, the anti-fog time, and the thickness of the coating respectively. Conceivable. As a reason for this, it is presumed that alumina has a Mohs hardness of 9 and is a particulate inorganic substance having a Mohs hardness of 8 to 9.5 as described above. Since the effect can be expected, it is considered to be suitable for the abrasive.

In a preferred aspect of the present invention, the inorganic binder is a zirconium compound. By doing so, the above-mentioned repairing method is applied to the wound generated in the composite material to which the coating is applied, thereby eliminating the appearance of the composite material, the anti-fog time, and the thickness of the coating without changing the thickness. In addition to this, even when this operation is performed twice or more, the coating can be repaired without any problem in appearance or moisture absorption performance. The reason for this, though presumed, is as follows. The operation of polishing is an operation that requires a certain degree of water resistance in order to prevent an object to be operated such as the coating from being damaged. However, a zirconium compound is a material having the highest water resistance among inorganic binders, and a coating containing the same tends to have improved water resistance. Therefore, even when the polishing is performed a plurality of times, the coating contains a zirconium compound as a binder, so that the coating has water resistance enough to withstand the polishing, and damage due to polishing is prevented. It is thought that.

In a preferred aspect of the present invention, the zirconium compound contains at least zirconyl chelate and / or zirconia. By doing so, the above-mentioned repair method is applied to the scratches generated in the composite material to which the hygroscopic coating is applied, so that the scratches can be obtained without changing the appearance of the composite material, the anti-fog time, and the thickness of the coating. Can be erased, and even if this operation is performed twice or more, the coating can be repaired without any problem in appearance or moisture absorption performance. For this reason,
Although it is estimated, the following reasons can be considered. The operation of polishing in this case is an operation that requires a certain degree of durability in order to prevent the operation target such as the coating from being damaged. However, zirconyl chelate and / or zirconia are the highest materials among inorganic binders in terms of durability such as water resistance, chemical resistance and hardness. Therefore, the inclusion of the coating in the coating improves the durability of the coating, and even when the polishing is repeated a plurality of times, the coating can be polished without being damaged, and the coating can be repaired. It is considered that the scratches can be eliminated without changing the appearance of the composite material, the antifogging time, and the thickness of the coating.

In a preferred aspect of the present invention, the water-absorbing organic polymer is polyvinyl alcohol. By doing so, the above-mentioned repair method is applied to the scratches generated in the composite material to which the hygroscopic coating is applied, so that the scratches can be obtained without changing the appearance of the composite material, the anti-fog time, and the thickness of the coating. Can be erased, and even if this operation is performed twice or more, the coating can be repaired without any problem in appearance or moisture absorption performance. The reason for this, though presumed, is as follows. The operation of polishing in this case is to prevent the operation target such as the coating from being damaged.
This is an operation that requires some durability.
However, polyvinyl alcohol is the highest material among the above-mentioned water-absorbing organic polymers in terms of durability such as water resistance and the strength of a film obtained thereby, as compared with other polymers. Therefore, including the film in the film improves the durability of the film, and the film can be polished without being damaged and the film can be repaired even when the polishing is repeated a plurality of times. Therefore, the use of a polymer as the water-absorbing organic polymer can reduce the appearance of the composite material,
This is considered to be an effective method for eliminating the flaw without changing the anti-fogging time and the thickness of the coating.

[0013] In a preferred aspect of the present invention, the transparent hygroscopic film comprises a composition containing at least an inorganic binder, a water-absorbing organic polymer, and a water-containing organic solvent. It is formed by applying to the material surface. The solvent is a water-containing organic solvent.
By performing the above-mentioned repair method, the scratch can be erased without changing the appearance of the composite material, the anti-fogging time, and the thickness of the coating, respectively. Without any problem in moisture absorption performance,
Can be repaired. The reason for this, though presumed, is as follows. The operation of polishing in this case is an operation that requires a certain degree of durability in order to prevent the operation target such as the coating from being damaged. However, the inclusion of a water-containing organic solvent in the composition promotes a dehydration-condensation reaction between the water-absorbing organic polymer and the inorganic binder as compared with a solvent containing only water, and tends to enhance the film strength. is there. Therefore, the incorporation of the water-containing organic solvent in the composition improves the film strength or durability of the film, and the polishing is performed without damaging the film even when the polishing is repeated a plurality of times. And the coating can be repaired. Therefore, a water-containing organic solvent is used as such a solvent,
It is considered that the flaw can be eliminated without changing the anti-fogging time and the thickness of the coating.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The water-absorbing coating composition of the present invention comprises at least (a) an inorganic binder, (b) a water-absorbing organic polymer, and (c) a solvent. It is a coating composition. As the inorganic binder, boric acid, borax, ammonium borate,
Examples thereof include various divalent and trivalent iron salts, zirconium compounds, aluminum salts, and permanganates.
Other examples include an inorganic alkoxide and a polymer having an OH group formed by hydrolysis and polycondensation of the alkoxide. The inorganic alkoxide is, for example, at least one compound represented by the following formula (1). M (OR) _n (X) _an (1) where M is Si, Al, Ti, Zr, Ca, Fe,
V is an inorganic atom selected from the group consisting of Sn, Li, Be, B, and P, R is an alkyl group, X
Is an alkyl group, an alkyl group having a functional group, or a halogen, a is a valence of M, and n is 1
To a. Among the compounds of the formula (1), n
= A, that is, a compound in which only an alkoxy group is bonded to M is widely used.

When M is Si, the alkoxide is
It is represented by Si (OR1) ₄ . Here, R1 is preferably a lower alkyl group having 1 to 4 carbon atoms. Such alkoxysilanes include Si (OCH ₃ ) ₄ , Si (OC
₂ H ₅ ) _{4 and the} like. When M is Al, the alkoxide is represented by Al (OR2) ₃ . Where R2
Is preferably a lower alkyl group. Such aluminum alkoxides include Al (OCH ₃ ) ₄ , A
l (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. The aluminum alkoxide may be used as a mixture of two or more kinds. Such an aluminum alkoxide is usually used as a mixture with the alkoxysilane. The amount of the aluminum alkoxide to be used is preferably 10 to 100 parts by weight of the alkoxysilane.
It is in the range of not more than 5 parts by weight, more preferably about 5 parts by weight. If the amount is more than 10 parts by weight, the formed polymer tends to gel, and the resulting coating film may be cracked. When M is Ti, the alkoxide is represented by Ti (OR3) ₄ . Here, R3 is preferably a lower alkyl group. Such titanium _{alkoxide, Ti (O-CH 3)} 4, Ti (O
_{-C 2 H 5) 4, Ti} (O-n-C 3 H 7) 4, Ti (O-
_{iso-C 3 H 7) 4} , Ti (O-C 4 H 9) 4 and the like. The titanium alkoxides may be used as a mixture of two or more kinds. Such a titanium alkoxide is usually used as a mixture with the alkoxysilane. The amount of the titanium alkoxide to be used is within a range of 3 parts by weight or less, preferably about 1 part by weight, based on 100 parts by weight of the alkoxysilane.

When M is Zr, the alkoxide is represented by Zr (OR ₄ ) ₄ . Here, R4 is preferably a lower alkyl group. Such zirconium alkoxides include Zr (OCH ₃ ) ₄ and Zr (OC _{2
H 5) 4, Zr (O} -iso-C 3 H 7) 4, Zr (O-t-C
_{4 H 9) 4, Zr (} O-n-C 4 H 9) 4 and the like.
The zirconium alkoxides may be used as a mixture of two or more kinds. Such a zirconium alkoxide is usually used as a mixture with the alkoxysilane. The amount of the zirconium alkoxide used is within a range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of the alkoxysilane.

Other alkoxides include, for example, Ca (OC ₃ 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 (O
C ₂ H ₅ ), Be (OC ₃ H ₅ ) ₂ , B (OC ₂ H ₅ ) ₃ , P
(OC ₂ H ₅ ) ₂ and P (OCH ₃ ) ₃ . Among the inorganic alkoxides represented by the formula (1), when n = a-1 or less, that is, as a compound in which a group X other than alkoxy is bonded to M, for example, X is a halogen such as Cl or Br. There are compounds. A compound in which X is a halogen is hydrolyzed in the same manner as an alkoxy group to generate an OH group, and a polycondensation reaction occurs. X may also be an alkyl group or an alkyl group having a functional group, and the alkyl group usually has 1 to 15 carbon atoms. Such groups remain as organic moieties in the resulting polymer without hydrolysis.
As the functional group, a carboxyl group, a carbonyl group,
Examples include an amino group, a vinyl group, and an epoxy group. Compounds of the formula (1) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Aminopropylmethoxysilane and the like.

In the water-absorbing coating composition of the present invention, the inorganic alkoxide is hydrolyzed by the action of a hydrolysis catalyst, and the alkoxy group and halogen (X) are changed to OH groups. Furthermore, the OH group is deprotonated by the action of the curing catalyst, and as a result, the hydrolyzate starts polycondensation to form a polymer or oligomer having an OH group in the molecule. At the same time, the OH group portion of the water-absorbing organic polymer present in the composition by the curing catalyst or the like,
Reacts with the above-mentioned hydrolyzed alkoxide or a polymer or oligomer having an OH group, and
A composite polymer having an inorganic moiety such as i and an organic moiety derived from a water-absorbing organic polymer is formed. When the respective components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above, so that the inorganic alkoxide, its hydrolyzate, the polycondensation oligomer or polymer of the hydrolyzate, hydrolysis, Product, a polycondensation oligomer or polymer of the hydrolyzate, a water-absorbing organic polymer thereof, a hydrolyzate derived from the alkoxide, and a polycondensation or cross-linking reaction product of the water-absorbing organic polymer are mixed, and a state of a colloidal sol is obtained. Become. (1) When X in the formula has a specific functional group, the functional group may further react. For example, when X is a group having an epoxy group, the epoxy group is opened by a base catalyst to generate an OH group, and the reaction with an alkoxide or a water-absorbing organic polymer proceeds. When X is a group having a vinyl group, a reactive monomer can be bonded to the vinyl group. When a coating composition containing an inorganic binder such as an inorganic alkoxide is applied to a substrate, and dried, and then subjected to a heat treatment at 80 ° C. or higher, the medium condensation reaction and the crosslinking reaction proceed, and the three-dimensional A composite polymer having a structure is formed. This polymer is a polymer having an inorganic part and an organic part. That is, since this polymer has an insoluble skeleton which is an inorganic portion, a film formed by this polymer is insoluble in water and an organic solvent and has high surface hardness. Furthermore, since this polymer has a water-absorbing organic polymer that is an organic portion, a hydrophilic portion derived from the water-absorbing organic polymer is present on the surface of the formed film, and moisture is adsorbed to that portion. Further, when a carbonyl group, a carboxyl group, an amino group, a vinyl group, an amino group, an epoxy group, or the like is present at the terminal of the group (1) of formula X, moisture is further adsorbed to the group.

Other inorganic binders include:
Titanium-based coupling agents, melamine-based coupling agents,
Epoxy-based coupling agents, isocyanate-based coupling agents, copper compounds, SiO, TiO, C
Fine inorganic compounds of 5 to 200 nm such as eO2, SiO2, TiO2, ZrO2, Ta2O5 and MgF2 can also be used. In addition, Cu, B, Sn, V,
Cr compounds can also be used. The zirconium compound is particularly preferably used from the viewpoint of improving water resistance. Specific examples of the zirconium compound include, for example, zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, and zirconium bromide; zirconium sulfate, basic zirconium sulfate,
Zirconium salts of mineral acids such as zirconium oxynitrate and zirconium nitrate; zirconium formate, zirconium acetate,
Zirconium propionate, zirconium caprylate,
Zirconium salts of organic acids such as zirconium stearate; zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, zirconium ammonium acetate, sodium zirconium oxalate, sodium zirconium citrate and zirconium ammonium citrate; The amount of the inorganic binder as a crosslinking agent to be added is not particularly limited, but the number of moles (A1) of the functional group that controls the crosslinking of the inorganic binder and the number of moles (B1) of the hydrophilic functional group of the water-absorbing organic polymer. Ratio (K
(A = A1 / B1) is preferably used in a range of 0.001 or more and 10 or less. Ratio KA of this number of moles
Is more preferably in the range of 0.01 or more and 1 or less.

The water-absorbing organic polymer used in the present invention is not particularly limited, but it is preferable that the water-absorbing organic polymer is at least partially dissolved or uniformly dispersed in a solvent forming an aqueous solution. As the water-absorbing organic polymer, polyvinyl alcohol, polyacrylic acids or polyalkylene oxide can be suitably used. The polyvinyl alcohol generally has an average degree of polymerization of 100 to 15,000, preferably 30.
Those having a saponification value of 0 to 5,000 and a saponification value of 60 to 100%, preferably 70 to 99% are used. In the present invention, polyvinyl alcohol is a polymer having a monomer unit of vinyl alcohol as a main component. As such polyvinyl alcohol, for example, those obtained as a copolymer of vinyl alcohol and vinyl acetate, vinyl trifluoroacetate polymer, vinyl formate polymer, vinyl pivalate polymer, t-butyl vinyl ether polymer, A polymer obtained by saponifying a trimethylsilyl vinyl ether polymer or the like is included. In addition, a polyvinyl alcohol derivative can also be used, and as a functional group other than a hydroxyl group, for example, an amino group, a thiol group, a carboxyl group, a sulfone group, a phosphate group, a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, a phosphonium group ,
It may have a part of silyl group, siloxane group, alkyl group, allyl group, fluoroalkyl group, alkoxy group, carbonyl group, halogen and the like. Examples of the polyacrylic acids include polyacrylic acid, sodium polyacrylate, poly-2-hydroxyethyl acrylate, poly-
It may be at least one selected from polyacrylic acid such as 2-hydroxyethyl methacrylate and polyacrylamide, polymethacrylic acid, and salts thereof. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene glycol, polyethylene glycol, and polypropylene oxide, and polyethylene oxide is particularly preferable.
Usually, a weight average molecular weight of 1,000 to 1,500,00
0, preferably 50,000 to 750,000 polyalkylene oxides are used.

Other water-absorbing organic polymers include 2-hydroxyethyl methacrylate monomers,
Polyoxazoline, vinyl alcohol fraction 41% by mole
Vinyl alcohol resins such as the above ethylene-vinyl alcohol copolymers, isobutylene maleic anhydride copolymers, polyacrylamides, polyoxyethylenes, and polysaccharides can be suitably used. Examples of the polysaccharide include biopolymers synthesized in a biological system by polycondensation of various monosaccharides, and those obtained by chemically modifying them. Specific examples of such “polysaccharides and derivatives thereof” include, for example, viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose,
Hydroxypropyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, soluble starch, carboxymethyl starch, dialdehyde starch and the like. In addition to the water-absorbing organic polymer, sepiolite, silica gel, dextran, alginic acid, sodium alginate, carrageenan, agarose, kaolin and the like can also be used. further,
Polyethylene amide resins such as diethylene triamine-adipic acid polycondensate, polystyrene sulfonic acid, sodium polystyrene sulfonate, polyvinyl pyridine and its salts, polyethylene imine and its salts, polyallylamine and its salts, polyvinyl pyrrolidone, polyvinyl sulfonic acid and its salts, Resins having hydrophilic functional groups in the molecule, such as polyvinyl thiol and polyglycerin, may be mentioned. Here, the “hydrophilic functional group” means, for example, at least hydrogen directly bonded to an atom (hetero atom) other than carbon, such as a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfone group, and a phosphate group. Hydrogen-bonding group having one group and localized to the extent that water molecules can be hydrated in water, such as carboxylate group, sulfonate group, phosphate group, ammonium group, phosphonium group, etc. And ionic substances having at least one of positive and negative charges. Further, it may have some other functional groups such as a silyl group, a siloxane group, an alkyl group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen. In addition, polyvinylidene chloride-based emulsions, polyvinyl acetate-based emulsions, polyurethane-based emulsions, polyester-based emulsions, and acrylic-based resin emulsions that are not water-soluble but form an aqueous emulsion can be suitably used.

The solvent used in the present invention is not limited except that it contains water as one component.
% Is preferable. There is no particular limitation on the solvent used by mixing with water other than water,
The water-containing organic solvent is preferably capable of forming a homogeneous phase in a mixed state with water. There is no particular limitation on the type of solvent to be added and the mixing ratio as long as a homogeneous phase can be formed with water. Solvents that can be mixed with water include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, ethylene glycol, alkyl cellosolve, dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, formic acid, acetic acid, and propion. Polar solvents such as acids; and mixtures of two or more of these solvents.
In particular, it is preferable to use alcohols having a relatively low boiling point, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, and ethylene glycol.

The solvent used in the present invention includes water or toluene, which is generally referred to as an organic solvent,
Aromatic solvents such as xylene and aliphatic solvents such as glycerin are also used. The amount of the solvent used is preferably from 100 to 500 parts by weight based on 100 parts by weight of the inorganic binder, the water-absorbing organic polymer and the curing catalyst in total.
00 parts by weight, more preferably about 3000 parts by weight. The water-absorbing coating composition further comprises:
At least one water-absorbing inorganic composition may be contained. Examples of the water-absorbing inorganic composition include sepiolite and silica gel. Further, the water absorbing coating composition may further contain at least one kind of polyacrylic acid. Examples of the polyacrylic acids include polyacrylic acid, polymethacrylic acid, and salts thereof. The amount of the polyacrylic acid to be used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the water-absorbing coating composition.

In the present invention, the water-absorbent coating composition may further contain a fluorine-containing surfactant containing a hydrophilic group, and the fluorine-containing surfactant containing a hydrophilic group may be used. Examples thereof include perfluoroalkyl carboxylate, perfluoroalkyl ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl group-containing oligomer, trifluoropropyl trichlorosilane, trifluoropropyl bromosilane, Fluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, heptadecafluorooctyltriethoxysilane, and the like can be suitably used.

In the present invention, the water absorbing coating composition may further contain a heat ray absorbing material. If a material containing this is used for a transparent material such as glass, it is possible to suppress an increase in the room temperature due to radiation such as sunlight, and to increase the temperature of the glass surface to make it difficult for water droplets to adhere. Silver ions can be suitably used as the heat ray absorbing material.

In the present invention, the water-absorbing coating composition may further contain a heat storage material. Those containing this can accumulate radiant heat such as sunlight, keep the temperature of the glass surface high, and make it difficult for water droplets to adhere. As the heat storage material, high-density polyethylene, paraffin, or the like can be suitably used.

In the present invention, the water-absorbing coating composition may contain an ultraviolet absorbent. If a material containing this is used for a transparent material such as glass, it can block short-wavelength sunlight harmful to the human body. Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylate, cyanoacrylate, oganilide and Ce.

In the present invention, the water absorbing coating composition may contain an antimicrobial agent. Those containing this can prevent the occurrence and reproduction of mold and bacteria. Examples of the antibacterial agent include sodium sulfonate, isothiazoline, benzoic acid, and 10,10-
Oxybisphenoxyarsine, 2- (4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) -phthalimide, 2-methylcarbonylaminobenzimidazole, silver, copper, zeolite, silver zirconium phosphate, silver hydroapatite, Silver phosphate glass, silver phosphate ceramic, and the like.

In addition, the above-mentioned hygroscopic coating composition comprises silicone or silica forming an inorganic skeleton,
Mixing with a zirconium compound or zirconia, or
A photocatalyst particle-containing water-absorbing coating composition in which each of them alone and a photocatalyst particle is dispersed may be used. In such a composition, since the photocatalyst is photoexcited, the surface of silicone or silica is highly hydrophilized, and moisture in the air is chemically adsorbed on the surface of the member in the form of hydroxyl groups. The condensed water and water droplets thus adhered are quickly turned into a water film and spread uniformly on the surface, so that the surface exhibits a high degree of anti-fogging property. The silicone and silica mentioned here are not particularly limited, and any commonly used silicone and silica may be used. In addition, hydrophobic contaminants and the like are difficult to adhere to the surface of a member having the composition, and even if it adheres, the adhesion is unstable. Deposits are decomposed and desorbed, and the member surface can be maintained in a clean state. The following photocatalyst particles can be used. When the photocatalyst particles are anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, or strontium titanate, the light to be irradiated may be sunlight, indoor lighting, a fluorescent lamp, a mercury lamp, an incandescent lamp, a xenon lamp, or a high-pressure lamp. Light from a sodium lamp, a metal halide lamp, or a BLB lamp is preferred. When the photocatalyst particles are tin oxide, light from a solar germicidal lamp, a BLB lamp, or the like is preferable. Further, the illuminance of the irradiated light may be appropriately determined in consideration of the composition of the member, its use, and the like. And the illuminance of the excitation light is 0.001.
is preferably mW / cm ² or more, more preferably 0.01 mW / cm ² or more, most preferably 0.1 mW / cm ² or more. Further, according to a preferred embodiment of the present invention, the photocatalytic particle-containing water-absorbent coating composition layer may be formed by adding a metal such as Ag, Cu, or Zn.

According to another preferred embodiment of the present invention,
The photocatalytic particle-containing water-absorbing coating composition layer contains P
A material to which a platinum group metal such as t, Pd, Ru, Rh, Ir, and Os is added may be used. The surface layer to which such a metal is added can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.

The zirconium compound used in the present invention may contain at least one of zirconyl chelate and zirconia in the zirconium compound and / or may further contain any of the zirconium compounds. . Among them, zirconium oxynitrate and zirconia derived from zirconium oxynitrate are preferably used.

Examples of the zirconium chelate include zirconium oxynitrate, zirconium oxychloride, zirconium oxysulfate, and one of zirconium nitrates, Zr (OH) ₂ (NO ₃ ) ₂ .4H ₂ O, ZrO (N
_{O 3) 2, Zr 2 O} 3 (NO 3) 2, Zr 4 O 7 (NO 3) and ₂ or the like,
Zirconium acetate, zirconium fluoride, zirconium bromide, zirconium iodide, zirconium oxychloride hydroxide, zirconyl carbonate (zirconium oxycarbonate), zirconyl hydroxide, zirconyl acetate, zirconyl ammonium carbonate, zirconyl stearate, zirconyl octylate Is used.

The method of producing the zirconia is not particularly limited, but the zirconia may be obtained by performing an operation such as heating or pressurizing the aqueous solution of the zirconia chelate, or may be reacted by adding a catalyst or the like. A zirconia solution derived from the zirconyl chelate obtained by the operation can be used. The form of the zirconia solution derived from the zirconyl chelate is not particularly limited, but preferably has an average particle diameter of 0.1 to 100 nm, more preferably 1 to 40 nm. Is preferred. Further, with respect to the method for producing the same, it is preferable that the reaction is performed for 3 hours to 18 hours while stirring under a heating condition of 90 ° C. or more, and more preferable that the reaction is performed for 4 hours to 9 hours at the same temperature condition. Is desirable. Then, the zirconium chelate or the zirconia obtained by these methods reacts with the water-absorbing organic polymer,
A composite polymer having an inorganic portion of Zr and an organic portion derived from a water-absorbing organic polymer is formed. When the components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above, and thus the polycondensation of the hydrolyzate such as a zirconium compound, a hydrolyzate thereof, and zirconia is performed. A colloidal sol is obtained by mixing a polymer, a water-absorbing organic polymer, and a polycondensation or cross-linking reaction product of the hydrolyzate derived from the zirconium compound and the water-absorbing organic polymer. As the water-absorbing organic polymer used at this time, the above-mentioned polyvinyl alcohol or a derivative thereof is desirable. When preparing such a colloidal sol, a zirconia solution derived from the zirconyl chelate and an anion which causes a problem such as discoloration of the coating in the formation of a coating such as nitrate ion or sulfate ion present in the composition. May be present.
However, for these, the anions are removed in advance with an anion-sympathetic resin or the like and then mixed to prepare the composition, or the anion is applied by directly applying an anion-sympathetic resin or the like to the composition. By removing, when coating the composition, there is a high possibility that a film with high transparency is obtained, and a film with high quality in appearance is obtained.

The mixing amount of the water-absorbing organic polymer to be mixed with the zirconium chelate and the zirconia, such as the zirconia solution derived from the zirconyl chelate, alone or mixed with each other is determined by the amount of the inorganic binder as described above. The ratio (K) between the number of moles (A1) of the functional group that controls crosslinking and the number of moles (B1) of the hydrophilic functional group of the water-absorbing organic polymer.
A = A1 / B1) is preferably used in a range of 0.001 or more and 10 or less, more preferably,
The ratio KA of the number of moles is in the range of 0.01 or more and 1 or less. However, when the water-absorbing organic polymer is the polyvinyl alcohol or a derivative thereof, the number of moles of the zirconyl chelate and the functional group (A2) that controls crosslinking such as a hydroxyl group in the zirconia, as shown in FIG. It is preferable that the ratio (K2 = A2 / B2) of the polyvinyl alcohol or the derivative thereof to the mole number of the vinyl alcohol unit (B2) be in the range of 0.001 or more and 10 or less. More preferably, it is in the range of 1 or less.

The anion exchange resin used at this time is not particularly limited as long as it can exchange anions such as nitrate ions. As the functional group of the ion exchange resin, an amine type such as dimethylethanolamine and trimethylamine, and a quaternary ammonium type can be used. There are various ion exchange methods, such as putting a zirconium oxynitrate solution in a reaction tank, filling an anion exchange resin in a cylindrical column, and flowing the solution into the column to react. It can be taken, but the method is not particularly limited. The shape of the obtained zirconia may be any of a granular shape and a chain shape, and is not particularly limited.

As the inorganic binder, a yttrium salt or a magnesium salt which can increase the strength of the produced zirconia itself and which has been heated beforehand may be used as the inorganic binder. The use amount of this reagent is preferably 5 to 100 parts by weight of the zirconium compound.
80 parts by weight, more preferably 30 to 60 parts by weight. As the yttrium salt, yttrium salts such as yttrium chloride, yttrium nitrate, yttrium sulfate, yttrium acetate and yttrium carbonate can be suitably used, and other yttrium salts can also be used. Further, as the magnesium salt, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium salts such as magnesium carbonate can be suitably used,
Others can also be used.

Further, zirconyl acetate, which can suppress the reaction speed of the dehydration condensation reaction from zirconyl chelate to zirconia, may be added in advance and then heated to be used as the inorganic binder. Thereby, a sharp increase in the viscosity of the composition can be suppressed. The amount of the reagent used is preferably 5 to 15 parts by weight, more preferably about 8 parts by weight, per 100 parts by weight of the zirconium compound. Further, the same effect can be exerted even when the zirconyl acetate is directly added to the composition. However, if it is added too much, it becomes easy for bubbles to be entangled in the composition, which may impair the appearance of the coating. Therefore, the amount of addition is preferably 1 to 10 g, more preferably 4 to 8 g, per 100 parts by weight of the composition.

Further, the composition may contain a catalyst. The catalyst includes a hydrolysis catalyst such as hydrochloric acid or acetic acid for giving a hydroxide ion to a zirconium compound or zirconyl chelate to form zirconyl hydroxide, or a dehydration polymerization for converting zirconyl hydroxide to zirconia. There are curing catalysts such as ammonia and hydrogen peroxide that promote.

The catalyst includes a hydrolysis catalyst and a curing catalyst. The hydrolysis catalyst is used for a hydrolysis reaction of the inorganic binder such as a zirconium compound or the inorganic alkoxide. Therefore, when a zirconium compound is previously hydrolyzed to some extent and polycondensed to use a polymer having an OH group, a hydrolysis catalyst may be unnecessary.

As the hydrolysis catalyst, hydrochloric acid, sulfuric acid,
A mineral acid such as nitric acid is used. Anhydrides of mineral acids, such as hydrogen chloride gas, may also be used. In addition, organic acids and their anhydrides can also be used. For example, tartaric acid, phthalic acid, maleic acid, dodecyl succinic acid, hexahydrophthalic acid, methyl nadic acid, pyromellitic acid, benzophenone tetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, Examples include dodecylsuccinic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dichlorosuccinic anhydride, chlorendic anhydride, and the like. These hydrolysis catalysts are used in an amount of 0.1 to 100 parts by weight of the inorganic binder.
The amount is from 0.01 to 0.5 part by weight, preferably from 0.015 to 0.3 part by weight. If the amount is less than 0.01 part by weight, the hydrolysis may be insufficient. If the amount is more than 0.5 part by weight, the polycondensation reaction may proceed and the viscosity may increase.

As the curing catalyst, an inorganic base such as sodium hydroxide, potassium hydroxide, ammonia or the like is also used as a catalyst. These polymerization catalysts, 0.01 to 0.5 parts by weight based on 100 parts by weight of the inorganic binder,
It is preferably 0.015 to 0.3 parts by weight. 0.01
If the amount is less than 0.5 parts by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 parts by weight, the polycondensation reaction may proceed, and the viscosity may increase.

The curing catalyst is mainly used as a catalyst for a polycondensation reaction of a zirconium compound or the above-mentioned inorganic alkoxide, and as a catalyst for a crosslinking reaction of a water-absorbing organic polymer.
And it is used as a catalyst for a polycondensation reaction and / or a cross-linking reaction among the hydrolyzate, the polymer having an OH group, the zirconium compound, and the water-absorbing organic polymer. Examples of such curing catalysts include 1,8-diazabicyclo [5.4.0] undecene-7, quaternary phosphonium salts, organic amines, amino acids, metal acetylacetonates, metal salts of organic acids, Lewis acids, and peroxides. At least one of an oxo acid such as a substance and perchloric oxide or an oxo acid salt can be suitably used.

The quaternary phosphonium salts include tetrabis (hydroxymethyl) phosphonium chloride,
Tetrabutylphosphonium bromide and the like.
Examples of the organic amine include ethylamine, dimethylamine, N, N-dimethylamine, tributylamine, tri-n-propylamine, tripentylamine, tripropargylamine, N, N, N-trimethylethylenediamine, n-hexylamine and the like. Is mentioned.

The amino acids include glycine and the like.

As the metal acetylacetonate,
Examples include aluminum acetylacetonate, indium acetylacetonate, chromium acetylacetonate, titanium acetylacetonate, and cobalt acetylacetonate.

Examples of the organic acid metal salts include sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate and tin octylate.

Examples of the Lewis acid include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, antimony chloride and the like.

The peroxide includes hydrogen peroxide.

Examples of the above-mentioned perchloric oxide include lithium perchlorate.

The oxo acids and salts thereof include, in addition to the peroxides and perchloric oxides, orthoboric acid, metaboric acid, trimetaboric acid, hypoboric acid, carbonic acid, cyanic acid, isocyanic acid, thunderic acid , Orthosilicic acid, metasilicic acid, peroxonitrate, nitrous acid, peroxonitrite, nitroxylic acid, hyponitrite, phosphoric acid, diphosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, polyphosphoric acid, metaphosphoric acid, trimetaphosphoric acid , Tetrametaphosphoric acid, peroxophosphoric acid, peroxoniric acid, hypophosphoric acid, diphosphoric acid, phosphite, diphosphorous acid, hypophosphorous acid, arsenic acid, arsenous acid, hexahydroantimonic acid, disulfuric acid , Peroxosulfuric acid, peroxoniline sulfuric acid, thiosulfuric acid, dithiosulfuric acid, sulfite, bisulfite, thiosulfite, nitrous acid,
Sulfoxylic acid, polythionic acid, selenic acid, selenous acid, telluric acid, chromic acid, dichromic acid, chloric acid, chlorite, hypochlorous acid, bromate, bromate, hypobromite, periodate, Examples thereof include iodic acid, hypoiodic acid, permanganic acid, manganic acid, pertechnetic acid, technetic acid, perrhenic acid, rhenic acid, and the like, and salts thereof.

The amount of the curing catalyst used is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the total of the inorganic binder and the water absorbing organic polymer in the water absorbing coating composition. , More preferably 0.0
5 parts by weight. If the amount is more than 2 parts by weight, the polycondensation proceeds rapidly, so that it is difficult to dissolve in the organic solvent, and the resulting coating becomes non-uniform, so that the strength may be reduced.

In the present invention, there is provided a composite material having a member surface coated with the transparent water-absorbing coating composition comprising a composite polymer having an inorganic skeleton crosslinked with organic molecules. The water-absorbing coating composition is composed of an inorganic polymer and an organic polymer cross-linked to each other, and the surface layer of the composite material is covered with a highly durable film insoluble in water and an organic solvent. . for that reason,
The composite material coated with this composition has antifogging properties, antifouling properties, dewproofing properties and humidity control properties.

As described above, the anti-fogging property means that, for example, in the case of a mirror, when minute water droplets such as steam come into contact with the film surface of the composite material, moisture is not condensed on the surface and the surface layer is not condensed. Means that it reaches the water-absorbing organic polymer in the water-absorbing coating composition and is absorbed, so that clouding can be prevented and the visibility of the reflected image can be maintained.

As described above, the anti-dew property means that the surface layer of the member has a function of preventing the following phenomena. The phenomenon is that when small water droplets such as steam come into contact with the surface of the composite material, they are rapidly cooled due to the difference in temperature between the air and the surface layer, causing water droplets to condense, and the size that can be visually determined This is a phenomenon that water droplets are formed on the surface layer of the member. The antifouling property is not only that the film itself has a structure that does not easily become dirty, but that it can be easily removed even if it becomes dirty, and that there is no problem that the film will be damaged even if washed with detergent etc. Means

As described above, the humidity control means a function of keeping the humidity around the member constant.

The composition may contain a particulate inorganic oxide added thereto. Examples of the particulate inorganic oxide include titania, silica, alumina, zirconia, yttrium oxide, niobium oxide, cerium oxide and the like. Can be used. The particulate inorganic oxide mixed into the composition preferably has an average particle size in the range of 5 nm to 200 nm, and more preferably 40 nm to 10 nm.
It preferably has an average particle size in the range of 0 nm. Also, as its shape, a chain is better than a granular one,
A chain is preferred because the resulting coating film is good in terms of transparency. These particulate inorganic oxides are used in an amount of 1 to 50 parts by weight, preferably 20 to 40 parts by weight, based on a total of 100 parts by weight of the inorganic binder and the water-absorbing organic polymer.

Among the finely divided inorganic oxides, silica is the best in terms of alkali resistance and water resistance as compared with alumina and titania. Examples of the finely divided silica include silica sol. It is a colloidal dispersion of high molecular weight silicic anhydride in an organic solvent such as water and / or alcohol. In the present invention, those having an average particle diameter of 5 to 200 nm are used.
If the dispersion state is poor, and if it exceeds 200 nm, the transparency of the resulting coating film will be poor.

The above-mentioned composition may contain fine zirconia particles. The average particle diameter of the fine zirconia particles is preferably in the range of 0.5 nm to 40 nm. More preferably, the range is 0.5 nm to 5 nm. When the average particle diameter is less than 0.5 nm, the film strength is reduced, and at the same time, the appearance during film formation is deteriorated,
For example, when zirconium nitrate or the like is used, coloring becomes easy. In addition, the viscosity change of the composition is sharp. In addition, zirconia having an average particle diameter of more than 40 nm causes deterioration of the transparency of the formed coating film.

The composition may contain formaldehyde. The addition of formaldehyde has a merit that it is less susceptible to strong alkaline chemicals because polyvinyl alcohol is formalized. In addition, chemical resistance is improved by acetalization, benzalization, butyralization with an aldehyde compound such as acetaldehyde, and the like. These aldehyde compounds contain a total of 10 parts of the inorganic binder and the water-absorbing organic polymer.
1 to 50 parts by weight, preferably 15 to 3 parts by weight per 0 parts by weight
0 parts by weight.

According to the present invention, the composite material is formed, for example, as follows. First, the components of the water-absorbing coating composition are mixed to obtain a transparent to translucent coating solution. Next, this coating liquid is coated on at least one surface of the member, and is heated and dried at a temperature of 80 ° C. or more, preferably in a range of 120 ° C. to 200 ° C., thereby obtaining the water-absorbing coating composition of the present invention. A coating or a covering member, ie a composite material, is obtained. If necessary, the heat treatment may be performed after coating the coating liquid several times.

The coating method is not particularly limited, and any coating method such as a bar coat, a die coat, a curtain flow coat, and a roll coat can be used. Since the composition can be coated by curtain flow coating even on a veneer such as a mirror, coating can be quickly carried out even on a veneer such as a considerably large mirror. Therefore, in the case of a single plate such as a mirror, a curtain flow coat is preferable. The thickness of the film obtained in this way is not particularly limited, but when performing only one coating, 2
To 20 μm, more preferably 8 to 12 μm.
m.

When the composition is applied to the surface of a member and the composition is dried or cured, the composition is heated from 80 ° C. to 17 ° C.
At the stage of drying or curing at the set temperature of 0 ° C,
The temperature may be once returned to the normal temperature, and after the member has reached the normal temperature, the member may be heated again at the original set temperature to be completely cured and dried or cured. What has been dried or cured by such a method can prevent discoloration of the coating. In this case, for example, 8
When forming a μm class coating film, a completely cured coating film without discoloration can be obtained by a heating operation such as drying at 150 ° C. for 10 minutes, natural cooling at room temperature and drying for 20 minutes. That is, 1
Such an effect can be obtained by heating the coat 2 bake or 2 bake or more. In this case, this time distribution
There is no particular limitation. The effect of preventing the discoloration of the coating can be obtained by providing a temporal change in the set temperature such as lowering the set temperature by 10 ° C. or more for a certain period of time during the heating operation. Such a method is particularly effective for a composition in which the inorganic binder is a zirconium compound.

When the composition is applied to the surface of a member and the composition is dried or cured, the composition is dried or cured at a low temperature, washed with water and / or an organic solvent, and then heated again at a high temperature. May be dried or cured.
What has been dried or cured by such a method can prevent discoloration of the coating. In the present invention, as the organic solvent, aromatic solvents such as toluene and xylene, which are generally referred to as organic solvents, and aliphatic solvents such as glycerin are used. Organic solvents that are compatible with water, such as ethyl alcohol, isopropyl alcohol, and butyl alcohol, are preferred.
This organic solvent is often used with water. The low temperature is not particularly limited as long as the composition does not flow out with water and does not color, and is preferably 50 to 100 ° C, more preferably 80 to 100 ° C. 100 ° C. The high temperature is not particularly limited as long as the composition can maintain the desired anti-fog performance and durability.
To 180 ° C, more preferably 130 to 150 ° C. Further, the method of washing with water and / or an organic solvent is not particularly limited as long as a sufficient washing effect can be obtained. For example, water is directly discharged onto the surface of the composition by a tube hose. I can deal with that.
Such a method is particularly effective for a composition in which the inorganic binder is a zirconium compound.

When the composition is applied to the surface of a member and the composition is dried or cured, the heat source may be located on the side opposite to the painted surface of the member. This makes it possible to shorten the heating time. The type of heat source at this time is not particularly limited, such as the far-infrared lamp, the near-infrared lamp, the electric heater, and the heat capacity, and the installation position. Condition. In addition, a near-infrared lamp is considered to be more advantageous as a heat source because it does not require much circulation of air around the member, and is also advantageous in terms of dust prevention.

The composition may be applied to the surface of a member, and after the composition is dried or cured, the member may be submerged in water for a certain period of time. By performing such an operation, the anti-fog performance can be improved. By performing this operation, it is intended that the film be swollen with water so that moisture can be easily taken into the film. The longer the immersion time is, the better, but at least 10 minutes is required. As a method for completing this operation in a short time, there is a steam cleaning operation. In this operation, the steam generated by the boiler is uniformly applied to the composite material surface.
It is intended that the same effect as the water immersion operation can be obtained by applying for 0 second or more. There is no particular limitation on the operation method at this time, but it is necessary to change the operation method according to the members so that the vapor is uniformly applied to the entire surface of the composite material.

The member may be provided with a dryer including a heater and a blower. In this case, by providing a dryer in the vicinity of the member, the water absorbing ability of the water-absorbing coating composition can be remarkably improved, and higher dew-proofing and anti-fog effects can be obtained. In addition, by controlling the water absorption rate of the water absorbing coating composition, the humidity of the atmosphere can be adjusted.

In the present invention, when the surface of the member is coated with the water-absorbing coating composition, the surface of the member may be previously washed with a detergent. By performing such an operation, impurities on the member surface can be removed, and the hydrophilicity of the member can be enhanced. And thereby, there is no air bubble between the member and the coating, and a coating with high adhesiveness is obtained,
In addition, the alkali resistance of the coating is improved.

The term “washing” as used herein refers to degreasing for removing foreign substances adhering to members, such as cleaning with freon, isopropanol, ethanol, sodium hydroxide, a neutral detergent, or the like, or polishing members with sandpaper or the like. Means a physical treatment for the purpose of increasing the smoothness of the member surface and reducing the surface tension. For example, in the case of coating the mirror with the water-absorbing coating composition, the washing is preferably washing with ceria polishing. This is to make a detergent by dissolving particles mainly composed of ceria in a neutral detergent, etc.
By washing the member surface with it, the improvement of hydrophilicity by degreasing and smoothing of the member surface can be achieved.

In the present invention, as described above, by pre-hydrophilizing, the wettability of the member is improved, a clean film can be formed, and a film having high adhesion can be obtained.

The hydrophilization includes chemicals, ultraviolet rays, radiation,
The oxidation of the surface of the member by electric discharge or the like is considered as a method. Among them, in particular, after the member is subjected to corona discharge treatment, when the coating liquid is coated, the hydrophilic performance of the member is further improved than in other cases. As a result, a clean film can be formed, and a highly adherent film can be obtained. Particularly effective when used in combination with ceria polishing.

This is because, by corona discharge on the surface of the base material, high-speed and low-speed electrons in the air gap collide with oxygen atoms to generate excited oxygen molecules. To change. The active species can oxidize the surface of the member and improve the wettability of the coating liquid. In this way, by modifying the surface of the base material, the adhesion between the coating composition, which is another polar molecule, and the base material can be promoted, and as a result, the adhesion can be improved. .

In the moisture absorbing film, the moisture absorbing function allows, for example, an anti-fogging function and water condensed water and / or water droplets adhering to the surface to be absorbed on the surface of the film, so that the fogging or the fogging on the surface of the film is prevented. It has the function of preventing shadowing. When preparing the composite material, the substrate on which the composition can be coated is not particularly limited, and includes, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, and a combination thereof. In addition, those laminates can be suitably used. The members serving as the base material for these coatings may be determined in consideration of the use of the members. When an anti-fog function is expected, as a substrate, for example, a mirror, a transparent plate-like member, a transparent lens, and a transparent film can be suitably used. The mirror as the base material is a mirror made of a glass base material provided with a reflective coat on the back surface, a mirror made of a transparent plastic provided with a reflective coat on the back surface, plastic,
Glass, a mirror provided with a reflective coat on the surface of a base material such as metal, plastic, glass, a mirror provided with a reflective coat on the surface of a member such as a metal, and a mirror further provided with a transparent hard coat thereon,
A mirror made of a mirror-polished metal base, a mirror provided with a transparent hard coat on the surface of a mirror made of a mirror-polished metal base,
A mirror or the like having a transparent hard coat provided on a transparent plastic substrate having a reflective coat provided on the back surface can be suitably used.
As the transparent plate-shaped member as the base material, a plastic base material such as polyethylene terephthalate, polyvinyl chloride, and methacrylic resin, and a glass plate such as soda-lime glass, borosilicate glass, and aluminosilicate glass are preferably used. it can. The transparent lens as the base material, polyethylene terephthalate, polyvinyl chloride,
A plastic base material such as methacrylic resin, glass such as soda-lime glass, borosilicate glass, and aluminosilicate glass can be suitably used. As the transparent film as the base material, a plastic base material such as polyethylene terephthalate, polyvinyl chloride, and methacrylic resin can be suitably used. The substrate is not limited to the above substrate. A transparent intermediate layer may be provided between the substrate and the surface layer for the purpose of improving the adhesion to the member.

Further, the surface layer may be further covered with a porous hard coat film, whereby the abrasion resistance and the weather resistance can be improved and the reflected light can be reduced.
The surface of the hygroscopic mirror according to the present invention has a hard film having a pencil hardness of about H to 4H or more.

The mirror as the member according to the present invention can be used for an automobile side mirror, an automobile interior mirror, a mirror installed in a bathroom or a washroom, and the like. In particular, considering the water absorption capacity of the anti-fog mirror of the present invention, very large water droplets do not adhere, but the steam of hot water adheres to the surface and is easily clouded, so that it can be suitably used in a washroom.

As the transparent plate-like member as the member, it can be used for window glass for houses, glass for furniture, window glass for automobiles, instrument glass for automobiles and the like. Further, as the transparent lens as the member, it can be used for glasses, goggles, lenses for cameras, lenses for portable video cameras, lenses for astronomical telescopes, and the like.

Further, as the transparent film as the member, it can be used for food wrapping paper, car side mirrors, car room mirrors, anti-fog films to be attached to mirrors installed in bathrooms and toilets, and the like. In addition, the member is suitable for any of a ceiling material for a bathroom having antifouling property and anti-dew property, a pipe for a toilet, a pipe for water supply, a urinal, a toilet, a trap for a toilet, a wash bowl, and a wash trap. Available to Further, the member is a stain-resistant, dew-proof bathtub, bathroom wall material, bathroom flooring, bathroom grating, shower hook, bathtub handgrip, bathtub apron section,
Bathtub drain plugs, bathroom windows, bathroom window frames, bathroom window floorboards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, floorboards, mats, Soap rest, pail, bathroom mirror, bath chair, transfer box
, Water heaters, bathroom storage shelves, bathroom handrails, bath lids, bathroom towel rails, shower chairs, basins, etc., bathroom components, kitchen kitchen bags, kitchen flooring, sinks, kitchen counters , Drain basket, dish dryer, dish washer, stove, range hood, ventilation fan, stove ignition, floor material for toilet, wall material for toilet, ceiling for toilet, ball tap, water tap, cigarette roll, toilet seat , Elevator seat, toilet door,
Toilet members such as toilet bus keys, toilet towel rails, toilet lids, toilet handrails, toilet counters, flush valves, tanks, flushing nozzles for toilet seats with cleaning functions,
Wash basin, lavatory mirror, lavatory shelves, drain plug, toothbrush stand, lavatory mirror lighting fixture, lavatory counter, water soap dispenser, basin, mouth washer, hand dryer, washing tub, washing machine lid, Suitable for washing machine pan, dewatering tub, air conditioner filter, touch panel, faucet fitting, cover of human body detection sensor, shower hose, shower head, shower water discharge section, sealant, joint Available to

As described above, the water-absorbing coating composition which can be repaired by the above-mentioned repairing method and the application member thereof have been presented in the above-described form. However, as the water-absorbing coating composition and the application member thereof, However, the present invention is not limited to these forms, and any type of water-absorbing coating composition and a member to which the composition is applied can be applied as long as the film has both moisture absorption and water resistance.

Hereinafter, a method for repairing a flaw generated in the coating film obtained from the above water-absorbing coating composition will be described.

Here, the coating was repaired with the water-absorbing coating composition coated on the mirror surface. The coating used here is a coating obtained from a water-absorbing coating composition comprising a water-absorbing organic polymer of polyvinyl alcohol and an inorganic binder of zirconia and zirconyl chelate as a basic composition. Has excellent features.

Specifically, first, a washbasin mirror KJ003 (manufactured by Aisen Kogyo) was applied to a mirror for a vanity table having a coating coated with the water-absorbing coating composition. It was wiped dry with human hands with force to produce small scratches on the coating.

Here, when the surface of this mirror was observed,
As shown in FIG. 2, a concave portion due to a scratch was formed on the coating. In addition, the surface of the concave portion was rough.

Thereafter, dust and foreign matter on the mirror surface are removed with a clean towel, and then 1 ml of an abrasive containing ultra-fine abrasive particles (for ultra-fine compound Metallic Pearl dark car; Wilson) is dropped on the towel. Then, the vicinity of the concave portion was polished. Although it depends on the degree of scratches, it is preferable to use an abrasive containing medium-sized abrasive particles at first, and to use an abrasive containing fine abrasive particles for finishing. The polishing was performed from the inner peripheral side to the outer peripheral side so that no excessive force was applied.

The polishing was finished at a time when the light from the fluorescent lamp was obliquely applied to the concave portion so that the difference from the surroundings was hardly recognized.

By the above polishing, the surface of the concave portion in the mirror became smooth.

Thereafter, excess abrasive was wiped off or washed with water, the surface was wiped with a towel, and further cleaned with pure water.

Then, when the mirror in which the flaw was repaired in this manner was observed again, it was found that the appearance of the mirror was unchanged from that before the flaw was generated, and the film returned to the same anti-fog performance.

Although the method for repairing a film with the water-absorbing coating composition coated on the mirror surface according to the present invention has been described above, the present invention is not limited to the above-described embodiment, and various modifications and changes can be made. Is possible. For example, the type of polishing agent used for polishing the vanity mirror and the polishing method can be changed as appropriate. Further, the present invention is not limited to the vanity mirror, and may be applied to any of the above-mentioned transparent plate-like members and transparent films.

The type of the abrasive in the present invention is not particularly limited as described above, but fine particles of inorganic substances such as diatomaceous earth, celite, zeolite, and zircon are mainly used as the abrasive. Can be. The amount is not particularly limited.

The finely divided inorganic substance is required to form a uniform film regardless of whether it is inorganic or organic as long as it is a fine particle. Examples of such powders include kaolin, talc, silica, pearlite, silica, calcium carbonate, alumina, aluminum hydroxide, chromium oxide, titanium oxide, zinc oxide, cerium oxide, zirconium silicate,
Examples include diamond powder, glass powder, PTFE resin powder, silicone powder, and nylon powder. These can be used alone or in combination of two or more.

The particle size of these fine particles is 0.5 to 10 μm
Must be. If it is less than 0.5 μm, there will be no cleaner effect. Conversely, if it is more than 10 μm, fine particles will remain during polishing and will appear white on the painted surface, or the painted surface will be damaged by polishing. 0.05 ~
It is preferably 3% by weight, particularly preferably 0.2% to 3.0% by weight. If the amount is less than 0.05% by weight, there is no cleaner effect or no effect for forming a uniform film. Conversely, if it exceeds 3% by weight, fine particles will remain during polishing and will appear white on the painted surface, making it impossible to form a uniform coating. In addition, the abrasive may contain, in addition to the abrasive, mainly an auxiliary solvent, a surfactant, an organic acid, and water.

Aromatic, naphthenic, n-paraffinic, isoparaffinic or other hydrocarbon solvents or mixed solvents thereof can be used in combination as the auxiliary solvent to facilitate the dispersion of each component. The amount of the hydrocarbon solvent is usually up to 20 parts by weight, based on 100 parts by weight of the whole abrasive.

The above-mentioned surfactants include polyoxyethylene alkylphenyl ether ammonium sulfonate, sodium polyoxyethylene alkylphenyl ether sodium sulfonate, sodium soap fatty acid, fatty acid soap, sodium dioctisulfosuccinate, and alkyl sulfonate. Peat, alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate soda salt,
Polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate TEA
Salts, sodium 2-ethylhexyl alkyl sulfate, sodium acylmethyltaurate, sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, disodium lauryl sulfosuccinate,
Polyoxyethylene lauryl disodium succinate disodium, polycarboxylic acid, oleoyl sarcosine, amido ether sulphate, lauroyl sarcosine, sulfo FA ester sodium salt and other anionic surfactants; polyoxyethylene lauryl ether Ter, polyoxyethylene tridecyl ether, polyoxyethylene steatyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylphenyl ether, Polyoxyethylene laurate,
Polyoxyethylene stearate, polyoxyethylene oleate, sorbitan stearate, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, polyether-modified silicone, polyester-modified silicone, sorbitan laura Sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethylene sorbitan laurate,
Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate,
Nonionic surfactants such as polyglycerin fatty acid ester, alkyl alcohol amide, lauric acid diethanolamide, oleic acid diethanolamide, polyoxyethylene alkylamine, polyoxyethylene stearate, polyoxyethylene alkylpropylenediamine, etc. Alkyl dimethyl benzyl ammonium chloride, 1-hydroxyethyl 2-alkyl imidazoline 4
Grade salt, alkyl isoquinolinium bromide, polymer amine, alkyl trimethyl ammonium chloride, alkyl imidazoline quaternary salt, dialkyl dimethyl ammonium chloride, octadecyl amine acetate, alkyl propylene diamine acetate, tetradecyl amine acetate, dioleyl dimethyl Cationic surfactants such as benzylammonium chloride; and other surfactants such as amphoteric surfactants such as dimethylalkylbetaine, alkylglycine, amidobetaine, and imidazoline can be appropriately selected. The compounding amount is 10% for the whole abrasive.
When the weight is 0, it is in the range of 0.5 to 90.0 parts by weight.

The organic acid is malic acid, glycolic acid,
Any compound capable of performing a chelate reaction with calcium such as sulfamic acid, tartaric acid, gluconic acid, ascorbic acid, lactic acid, and malonic acid can be used. And the compounding quantity is 0.1 when the whole abrasive is 100 weight.
~ 2.0 parts by weight.

Abrasives can also be prepared by adding a predetermined amount of water or hot water heated to an appropriate temperature while stirring to prepare an abrasive. It is selected from the range of 0 to 80.0 parts by weight.

As described above, the type of the abrasive in the present invention is not particularly limited, but silicone oil can be blended. Examples of the silicone oil include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, alkyl-modified silicone oils, silicone polyether copolymers (copolymers with polyoxyalkylenes), amino-modified silicone oils, and fatty acid-modified silicone oils. Modified silicone oils such as silicone oil and epoxy-modified silicone oil are exemplified. Preferably, it is dimethyl silicone oil or modified silicone oil. The mixing amount of these silicone oils is in the range of 1.0 to 30.0 parts by weight when the total amount of the abrasive is 100 parts by weight.

As one example, the abrasive used in the present invention is, as described above, 10 to 95.0 parts by weight of an abrasive and 0.5 to 90 to 90 parts by weight of a surfactant in 100 parts by weight of the composition. 0 parts by weight and water in the range of 10.0 to 80.0 parts by weight. Here, it is possible to use an abrasive prepared by mixing the above components, melting or dissolving by heating, adding a surfactant, and then adding a predetermined amount of water or hot water with stirring.

[0097]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The evaluation methods used in the examples and comparative examples are as follows.

[0098] Antifogging performance evaluation method: A member coated with a coating is placed in an atmosphere of 30 ° C and 100% humidity, and the time required for fogging to cover half of the entire film surface is measured. At this time, the sample is allowed to stand in a refrigerator at 5 ° C. for 30 minutes and then measured. This measurement is performed on the coating before and after the repair work. A: Time until fogging is less than 2 minutes and 1 minute 30 seconds or more. ；: The time until fogging is from 1 minute to 1 minute 30 seconds. Δ: Time until clouding is 30 seconds or more and 1 minute or less. ×: Time until clouding is 30 seconds or less.

Evaluation of Appearance The coating before and after the repair work is visually evaluated for appearance. A: No scratch is seen on the film surface. ；: The surface of the film has only such a degree that scratches are not noticeable when viewed. Δ: Some scratches are seen on the film surface. ×: A scratch is conspicuous on the film surface.

Evaluation of Water Resistance After the member coated with the coating was immersed in water at room temperature for 30 seconds, the surface of the coating was scratched with a pencil having a pencil hardness of 2H.
After drying, the scratch marks are observed and evaluated. Perform on the coating before repair work. A: No scar is seen on the film surface. ○: No scar is seen on the film surface, but immediately after scratching,
Depressions are seen in the coating. However, those that cannot be seen when dried. Δ: No scar is seen on the film surface, but immediately after scratching,
Depressions are seen in the coating. In addition, those in which the depression of the coating does not heal even after drying. ×: A scar is seen on the film surface.

Measurement of Film Thickness of Coating As a method of measuring the film thickness of the coating film, the film to be measured is damaged by a corner of another glass, and the depth of the damage is measured by a measuring instrument. The measurement is performed on the coating before and after the repair work.

(Example 1) 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water were added, and the mixture was stirred for 5 minutes, and then ion-exchange resin WA-20 (manufactured by Mitsubishi Kasei); 60 g And stir until the solution is at pH 3.0. Thereafter, the solution and the ion exchange resin were separated by decantation, the separated solution was transferred to a sealed glass bottle, and the transferred solution was placed in a 95 ° C. oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) with a magnetic stirrer while stirring for 5 hours. Then, it is left at room temperature (25 ° C.) for one month. (Hereinafter referred to as M1 solution.) Then, the ion exchange resin WA-20 was added to this solution.
(Manufactured by Mitsubishi Chemical); 20 g was mixed again and the solution was adjusted to pH
The mixture was stirred until reaching 4.0, the solution and the ion exchange resin were separated by decantation, and allowed to stand at room temperature (25 ° C.) for 1 hour. (Hereinafter referred to as M2 liquid) On the other hand, PVA-1
05 (average degree of polymerization: 500, complete saponification type; saponification value:
(98-99%) (manufactured by Kuraray); 10 g of water; 90 g are added, and the mixture is stirred at 90 ° C for 5 hours to dissolve polyvinyl alcohol. (Hereinafter referred to as C1 liquid).
A4 solution: 80 g, C1 solution: 100 g, water: 56 g, ethanol: 56 g, and mixed at room temperature (25 ° C.)
For 30 minutes to obtain a coating solution. This coating solution is coated on one side of the mirror once with an applicator and coated, and then oven (DK-400, manufactured by Yamato Scientific Co., Ltd.)
After heating and drying at 150 ° C. for 10 minutes, the film was naturally dried until the film reached room temperature.
After heating and drying at for 30 minutes, a transparent coating film (film thickness: 8 μm) was obtained. The coated surface of this coated mirror is
J003 (made by Aisen Kogyo)
It is slid 3650 times in a dry wiping state while applying a load of 70 g / cm 2. (Sliding operation) This sliding is performed with a washability tester (manufactured by Toyo Seiki). Thereafter, the following procedure is used as a restoration method. Abrasive 1 (for Wilson ultrafine compound metallic pearl dark colored car; average particle diameter 0.5 μm containing alumina) 1 m on coated surface
1 was dropped, and the coated surface of the dropped mirror was coated with a jersey cotton cloth under a load of 70 g / cm 2 under a load of 50 g / cm 2.
Slide it twice. Further, the abrasive 1 is rinsed with water to clean it off. (Repair operation) The sliding operation and the repair operation are two
Repeat before and after each evaluation before and after the restoration.

(Example 2) Ethyl silicate 40 (manufactured by Colcoat); 0.3 g and silane coupling agent SH6
040 (manufactured by Toray Dow Corning); 0.46 g, 2N
-HCl; 0.01 g, aluminum isopropoxide; 0.05 g, 35% HCl; 0.04 g, water 0.0
A solution obtained by adding 9 g, ethanol; 0.40 g, N, N-dimethylbenzylamine; 0.01 g and stirring at 25 ° C. for 10 minutes was added to a 25% aqueous solution of polyacrylic acid (number average molecular weight: 130,000). ); 20.04 g of methanol and 178.60 g of methanol were added, and the mixture was stirred at 25 ° C. for 2 minutes to obtain a transparent coating solution. This coating solution is coated once on one side of a mirror with an applicator, and then coated in an oven (DK-400,
(Yamato Scientific Co., Ltd.) and dried at 150 ° C. for 25 minutes to obtain a transparent coating film (film thickness: 8 μm). The coated surface of this coated mirror is slid 3650 times with a load of 70 g / cm 2 with a glass washing scrubber of Biosil Salan Cleaner KJ003 (manufactured by Aisen Industry) under a load of 70 g / cm 2. (Sliding operation) This sliding is performed with a washability tester (manufactured by Toyo Seiki). After that, the abrasive 1
1 ml (for Wilson ultra-fine particle compound metallic pearl dark-colored car; average particle size 0.5 μm alumina)
Is dropped, and the coated surface of the dropped mirror is slid 50 times with a load of 70 g / cm 2 using a jersey cotton cloth. Further, the abrasive 1 is rinsed with water to clean it off. (Repair operation) The sliding operation and the repair operation are repeatedly performed twice, and the evaluation before and after the repair is performed each time.

Example 3 25% aqueous solution of polyacrylic acid of Example 2 (number average molecular weight: 130,000); 20.0
PVA-105 (average degree of polymerization: 500, complete saponification type; saponification value: 98-99%) where a solution obtained by mixing 4 g and methanol; 178.60 g is added.
(Manufactured by Kuraray); same as Example 2 except that 90 g of water was added to 10 g, and the mixture was stirred at 90 ° C. for 5 hours and a solution in which polyvinyl alcohol was dissolved was added.

(Example 4) Abrasive 1 described in Example 1
(Wilson ultrafine compound Metallic Pearl for dark-colored cars; average particle diameter 0.5 μm containing alumina) Same as Example 1.

(Example 5) Abrasive 1 described in Example 1
(Wilson ultrafine compound Metallic Pearl for dark-colored cars; average particle size 0.5 μm containing alumina)
0; average particle diameter 0.3 μm).

(Comparative Example 1) Abrasive 1 described in Example 1
Same as Example 1 except that (Ulson ultra-fine particle compound metallic pearl for dark-colored vehicles; average particle diameter 0.5 μm containing alumina) was replaced with a cleanser (manufactured by Kao).

(Comparative Example 2) Abrasive 1 described in Example 1
The same as Example 1 except that the neutral detergent Mama Lemon (made by Kao) was used instead of Wilson's ultra-fine particle compound metallic pearl for dark-colored cars; containing an average particle size of 0.5 μm alumina.

(Comparative Example 3) Abrasive 1 described in Example 1
(Wilson ultrafine compound Metallic Pearl for dark-colored cars; average particle size 0.5 μm containing alumina) was replaced with abrasive 4 (Wilson Hunelli Compound;
The same as Example 1 except that the average particle diameter was 7 μm.

[0110]

[Table 1]

[0111]

[Table 2]

The results shown in Tables 1 and 2 show that in the film obtained from the water-absorbent coating composition, the scratches formed on the film were polished with the above-mentioned abrasive to obtain the anti-fog performance and the film thickness. It can be seen that the measured values are the same before and after the first and second repair operations. Besides, 1,
It can be seen that the appearance after the second restoration operation is also improved. From this fact, even in the case where the coating is damaged by the sliding operation of the scourer as described above, by performing the polishing as described above, it is possible to restore the coating to almost the same as the coating before the sliding operation. It can be seen that is possible.

[0113]

By performing the repairing operation in the above-described manner, the coating obtained by the water-absorbing coating composition can be used to erase the scratches formed on the coating, to prevent the coating from becoming fogged, and to improve the thickness of the coating. It is possible to restore the coating to the same condition as before the scratching without damaging the appearance.

[Brief description of the drawings]

FIG. 1 is a diagram showing a molecular formula of a vinyl alcohol unit.

FIG. 2 is a diagram showing scratches on a hygroscopic film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 29/04 C08L 29/04 Z C09D 7/12 C09D 7/12 129/04 129/04 185/00 185 / 00 201/00 201/00 C09K 3/18 C09K 3/18 F term (reference) 4F071 AA29 AB18 AC18 AF30 AF56 AH03 DA17 4H020 AA01 AA04 AA05 AB02 4J002 BE021 DD076 DE096 DE147 EC076 EG006 GC00 GH00 GL00 GN00 PG1 4J038 BA01 CC091 CE021 CG031 CG141 CG171 CH121 CK001 CK031 CK041 CR071 DF021 DH001 DJ011 DL022 DL032 DM022 HA216 HA246 HA476 KA07 NA06 NA09 PB02 PB05 PB07 PB08 PB12 PC03

Claims (8)

[Claims] 1. A polishing agent for a hygroscopic composite material having a transparent hygroscopic film containing at least an inorganic binder and a water-absorbing organic polymer formed on a surface of a base material, wherein the abrasive has an average particle size. A polishing agent comprising at least a particulate inorganic substance having a diameter of 0.2 to 3 [mu] m, and capable of removing a flaw generated in the film without devitrifying while maintaining a moisture absorbing function. 2. The fine particle inorganic substance has a Mohs hardness of 8 to 8.
The abrasive according to claim 1, wherein the abrasive is 9.5. 3. The particulate inorganic material is alumina,
The abrasive according to claim 1. 4. The abrasive according to claim 1, wherein the inorganic binder is a zirconium compound. 5. The polishing agent according to claim 4, wherein the zirconium compound contains at least a zirconyl chelate and / or zirconia. 6. The polishing agent according to claim 1, wherein the water-absorbing organic polymer is polyvinyl alcohol. 7. The transparent hygroscopic film is obtained by applying a composition containing at least an inorganic binder, a water-absorbing organic polymer, and a water-containing organic solvent to a mirror substrate or a transparent substrate surface. The abrasive according to claim 1, which is formed by: 8. A flaw generated in a composite material in which a transparent hygroscopic film containing at least an inorganic binder and a water-absorbing organic polymer is formed on a mirror substrate or a transparent substrate surface, A hygroscopic composite material which is polished with the abrasive according to any one of claims 1 to 7, thereby removing a flaw generated in the film without devitrification while maintaining a hygroscopic function. How to repair.