JP2001047584A - Coated polycarbonate plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate plate with a transparent hard coat having no yellowing and no cloudiness even if it is used outdoor for a long period, surface defogging and antifouling properties. SOLUTION: The coated polycarbonate plate is obtained by sequentially laminating a primer layer made of an organic resin containing an ultraviolet absorbent containing 20 wt.% or more of an effective volatile component, a silicone hard coating layer and a photocatalyst coating layer made of a silicone resin containing a metal oxide having a photocatalytic effect in this order.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coated polycarbonate plate. More specifically, the present invention relates to a polycarbonate plate which maintains antifogging property even when used outdoors and does not cause yellowing.

[0002]

2. Description of the Related Art JP-A-2-274736 discloses that
(A) a copolymer of a (meth) acrylic monomer having an alkoxysilyl group and an alkyl (meth) acrylate,
Improved abrasion and weather resistance comprising a cured undercoat layer of a composition containing (b) ammonium perchlorate and (c) a UV absorber and a cured overcoat layer of a composition containing an organopolysiloxane containing colloidal silica. Coated polycarbonate articles are disclosed.

Japanese Patent Application Laid-Open No. Hei 10-245521 discloses a primer composition for a silicon coating agent applied to an organic resin substrate such as polycarbonate, as a binder resin which is a (meth) acrylic resin and / or a vinyl resin. 0.1 to 30 with respect to this binder resin
By weight, formulations of inorganic compounds that absorb 320 to 400 nm of UV light are disclosed.

Japanese Patent Application Laid-Open No. 11-58654 discloses a polycarbonate resin laminate having excellent weather resistance obtained by applying and curing a primer paint on at least one surface of a polycarbonate plate, and then applying and curing a top paint thereon. A board is disclosed. The primer paint is 2,2 ',
A thermosetting acrylic resin containing a benzophenone-based ultraviolet absorber containing 4,4'-tetrahydrobenzophenone in an amount of 8 to 17 parts by weight per 100 parts by weight of the nonvolatile content of the coating material. It is composed of a polyorganosiloxane containing colloidal silica containing 1 to 4 parts by weight per 100 parts by weight.

Further, JP-A-10-195829 discloses that a surface of a base material such as polycarbonate is coated with particles of a photocatalyst such as anatase type titanium oxide, water-repellent silicone, and photoexcitation of the water-repellent silicone by the photocatalyst of the photocatalyst. A sound insulating wall having a surface layer containing a substance for preventing hydrophilization, for example, a cobalt compound, is disclosed.

JP-A-10-67873 discloses that a surface of a resin such as an acrylic resin is subjected to a hydrophilic treatment, the treated surface is coated with a layer containing a photocatalyst and a silicone resin, and bonded to a silicon atom of the silicone resin. A method for hydrophilizing the surface of a resin substrate, comprising substituting at least a part of an organic group to be formed with a hydroxyl group is disclosed.

Finally, Japanese Patent Application Laid-Open No. H11-61044 has developed a building material having on its surface a coating film containing a polyorganosiloxane and inorganic particles having a photocatalytic function.

As described above, in the configuration of the prior art, the action of the photocatalyst causes the deterioration of the silicone resin and the primer resin, which are matrix resins, and as a result, cracks or peeling can occur to hold the photocatalytic coating film. Without
The resin base material is deteriorated by ultraviolet rays, and there is no known resin material capable of exhibiting sufficient weather resistance when used outdoors.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coated polycarbonate plate provided with a coating layer having a novel structure. Another object of the present invention is to provide a coated polycarbonate plate which can maintain its anti-fogging property even when used outdoors for a long period of time and is free from yellowing and fogging. Still other objects and advantages of the present invention will become apparent from the following description.

[0010]

According to the present invention, the above objects and advantages of the present invention are as follows: a primer layer comprising an organic resin containing 20% by weight or more of an effective nonvolatile content of an ultraviolet absorbent, on a polycarbonate plate; This is achieved by a coated polycarbonate plate in which a silicon hard coat layer and a photocatalytic coating layer made of a silicon resin containing a metal oxide having a photocatalytic effect are laminated in this order.

The primer layer is composed of 20% by weight of effective non-volatile components.
It consists of the above ultraviolet absorber and organic resin. As the organic resin, a resin that is in close contact with the polycarbonate plate and can be bonded to the silicon hard coat is used. Such organic resins are known, for example, acrylic polymers, copolymers of acrylic monomers and methacryloxysilane, or copolymers of methacrylic monomers and acrylic monomers having a benzotriazole group or a benzophenone group may be mentioned as preferable ones. it can. Among these, a copolymer of an acrylic polymer and an acrylic monomer with methacryloxysilane is more preferred. The organic resins can be used alone or in combination of two or more.

As the ultraviolet absorber contained in the primer layer, for example, benzotriazole-based and benzophenone-based are preferred.
Of these, benzophenones are more preferred. The ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butyl. Phenyl) -benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) -benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-
Butylphenyl) -5-chloro-benzotriazole,
Alternatively, Tinuvin 328, Tinuvin 384, Tinuvin 900, Tinuvin 928, and Tinuvin 1130 of Ciba Specialty Chemicals Co., Ltd. can be mentioned.

As the benzophenone type ultraviolet absorber,
For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-hydroxy-4-methoxybenzophenone, 2,2 ′, 4,
4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone can be mentioned. In addition, a silane compound having a benzotriazole or benzophenone group can also be used as the ultraviolet absorber.

[0015] Such an ultraviolet absorber accounts for 20% by weight or more of the effective nonvolatile component in the primer layer, preferably 20 to 60%.
%, More preferably 20 to 50% by weight. The primer layer is formed by applying a solvent solution containing a predetermined amount of an ultraviolet absorber and an organic resin on a polycarbonate substrate, removing the solvent, and curing by heating.

Examples of the solvent include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoacetate. Propyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Glycols such as diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone; aliphatic cyclic ketones such as p-methylcyclohexanone; ethyl acetate n-propyl acetate;
Acetates such as butyl; alcohols such as methanol, ethanol, 1-propanol and 2-propanol, and solvent naphtha and methyl ethyl ketone;

Further, the above-mentioned solvent solution is an optional component,
It may contain a leveling agent and a lubricity imparting agent for the cured film. As such an agent, for example, a copolymer of polyoxyalkylene and polydimethylsiloxane (Paint Additive 31 manufactured by Dow Corning) and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. Such an agent is used in an amount of 0.001 to 10 with respect to the total liquid volume.
It is preferably used in% by weight. In addition, an antioxidant, a weather resistance imparting agent, an antistatic agent, a bluing agent and the like can be contained as other optional components.

The above-mentioned solvent solution has a solid concentration of, for example, 2 to 2.
It is preferably used after being adjusted to 50% by weight. Application is
For example, it can be performed by a dip method, a flow method, a spinner method, or a spray method.

The coating is preferably carried out so as to have a thickness after curing of 1 to 10 μm. If it is smaller than 1 μm, yellowing resistance and weather resistance are not sufficient, while if it is larger than 10 μm, the hardness tends to decrease after hard coating. After application, the solution coating is applied, for example, for 15 minutes to several hours.
Heat treatment at a temperature of 0 to 120 ° C. gives a primer layer.

The coated polycarbonate plate of the present invention has a silicon hard coat layer on the primer layer. Effective silicon component of the silicon hard coat layer is preferably silica and formula ^{_{R 1 d R 2 e Si (}} OR 3) 4-de wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl Group, aryl group or halogenated aryl group having 6 to 12 carbon atoms, methacryloxyalkyl group having 5 to 8 carbon atoms, ureidoalkylene group having 2 to 10 carbon atoms, aromatic ureidoalkylene group, halogenated aromatic An alkylene group or a mercaptoalkylene group, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, and R ³ is a hydrogen atom or a carbon atom having 1 carbon atom. And d is 1, 2 or 3, and e is 0, 1 or 2. Consisting of a compound to be

The silica is, for example, 10 to 50% by weight of SiO
It can be derived from colloidal silica (sol) containing ₂ as an active ingredient or composite oxide fine particles containing SiO ₂ having a particle size in the range of 1 to 100 nm.

The composite oxide is a composite of SiO ₂ and a metal oxide.
1, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Examples thereof include oxides of one or more metals selected from the group consisting of Zr, In, and Ti.
Specific examples of the metal oxide include Al ₂ O ₃ , SnO ₂ , S
_{b 2 O 5, Ta 2 O} 5, CeO 2, La 2 O 3, Fe 2 O 3, Z
nO, WO ₃ , ZrO ₂ , In ₂ O ₃ and TiO ₂ can be mentioned.

The surface of the composite oxide may be modified with an organic silane compound to enhance dispersibility in a solvent. The amount of the organic silane compound used is based on the weight of the composite oxide fine particles.
It is preferably at most 20% by weight. The surface treatment may be performed while the organic silane compound used for the treatment has a hydrolyzable group or after the hydrolysis.

Examples of such an organic silane compound include, for example, the following formula: R ₃ SiX wherein R is an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group or an epoxy group, and X is a hydrolysis group. A possible group, a monofunctional silane of the formula R ₂ SiX ₂ where R and X are the same as defined above, a bifunctional silane of the formula RSiX ₃ Wherein the definitions of R and X are the same as above, and a trifunctional silane represented by the following formula: SiX ₄ wherein the definition of X is the same as above; Can be.

Examples of the monofunctional silane of the above formula include trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, Vinyldimethylmethoxysilane, vinyldimethylethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldimethylethoxysilane, N-β (aminoethyl ) Γ-Aminopropyldimethylmethoxysilane, γ-
Examples include aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane and β- (3.4-epoxycyclohexyl) ethyldimethylmethoxysilane. be able to.

Further, examples of the bifunctional silane include:
Dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-acryloxypropylmethyl Dimethoxysilane, γ-methacryloxypropyldimethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropylmethoxydiethoxysilane and β- (3.4-epoxycyclohexyl) ethylmethyldimethoxysilane can be mentioned.

Further, as the trifunctional silane, for example,
Methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane, γ Acryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl)
γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, β
-Glycidoxypropyltriethoxysilane and β-
(3.4-Epoxycyclohexyl) ethyltrimethoxysilane.

Further, tetrafunctional silanes include, for example, tetraethyl orthosilicate and tetramethyl orthosilicate. When the complex oxide is treated with such a silane compound, it is preferably carried out in, for example, water, alcohol, or another organic medium.

Examples of the alcohol include saturated aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol and 2-butanol;
Cellosolves such as methyl cellosolve, ethyl cellosolve, propyl cellosolve and butyl cellosolve; propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl acetate; esters such as methyl acetate, ethyl acetate and butyl acetate;
Ethers such as diethyl ether and methyl isobutyl ether; ketones such as acetone and methyl isobutyl ketone; aromatic hydrocarbons such as xylene and toluene;
Examples include ethylene glycol, tetrahydrofuran, N, N, -dimethylformamide, dichloroethane, and the like.

The other effective silicon component of the silicon hard coat layer is a compound represented by the above formula.

Examples of such compounds include trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, and vinyldimethylmethoxysilane. ,
Vinyldimethylethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldimethylethoxysilane, N-β (aminoethyl) γ-aminopropyl Dimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, β- (3.4-epoxycyclohexyl) Ethyldimethylmethoxysilane dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, phenylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl Methyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethoxydiethoxysilane, β- (3.4-epoxycyclohexyl) ethylmethyldimethoxysilane , Methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane, γ-
Acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-glycidoxypropyltriethoxysilane, β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethylorthosilicate, tetra Methyl orthosilicate can be mentioned.

The silicon hard coat layer is formed by applying a dispersion in a liquid medium containing a predetermined amount of the effective silicon component as described above on the primer layer, removing the liquid medium, and curing by heating.

Examples of the liquid medium include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol. Monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Glycols such as coal dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone, aliphatic cyclic ketones such as p-methylcyclohexanone; ethyl acetate n-propyl acetate;
Acetates such as n-butyl acetate; and alcohols such as methanol, ethanol, 1-propanol and 2-propanol.

The above-mentioned dispersion liquid usually contains a curing catalyst for the hard coat layer. Examples of the curing catalyst include alkali metal salts and ammonium salts of carboxylic acids, metal salts and ammonium salts of acetylacetone, metal salts of ethyl acetoacetate, and metal salts in which acetylacetone and ethyl acetoacetate are coordinated. Secondary amine, polyalkyleneamine, sulfonate, magnesium perchlorate, ammonium perchlorate and the like. These compounds can be used in combination with an organic mercaptan or a mercaptoalkylenesilane.

Specific examples of the above-mentioned metal salts include chelate compounds containing the following central metals or salts with aliphatic acids. Al, Zr, Co, Zn, Sn, M
central metals such as n, V, Cu, Ce, Cr, Ru, Ga, Cd, Fe; acetylacetone, di-n-butoxide-mono-ethyl acetate, di-n-butoxide-mono-methyl acetate, methyl ethyl ketoxime;
Chelating compounds such as 2,4-hexanedione, 3,5-heptanedione, acetoxime; and 2-ethyl-
Hexyl acid, stearic acid, lauric acid, oleic acid,
Aliphatic acid compounds such as acetic acid, sebacic acid, dodecanedioic acid, propionic acid, brassic acid, isobutylic acid and citraconic acid;

As specific examples of the primary to tertiary amines, aliphatic amines, aromatic amines, aminosilanes and the like are preferable. For example, polymethylenediamine, polyetherdiamine, diethylenetriamine, iminobispropylamine, bishexamethylene Triamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, pentaethylenehexamine, dimethylaminopropylamine, aminoethylethanolamine, methyliminobispropylamine, menthanediamine, N-aminomethylbiperazine, 1,3-diamino Cyclohexane, isophoronediamine, metaxylenediamine, tetrachloroparaxylenediamine, metaphenylenediamine, 4,4′-methylenedianiline, diaminodiphenylsulfone, Njijin, toluidine, diaminodiphenyl ether, 4,4'-thiodianiline, 4,4'-bis (o-toluidine) dianisidine,
o-phenylenediamine, 2,4-toluenediamine,
Methylenebis (o-chloroaniline), diaminiditolylsulfone, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, 4-chloro-o-
Phenylenediamine, 4-methoxy-6-methyl-m-
Phenylenediamine, m-aminobenzylamine, N,
N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-p-phenylenediamine, tetramethylguanidine, triethanolamine, 2-dimethylamino-2 -Hydroxypropane,
N, N'-dimethylpiperazine, N, N'-bis [(2-
Hydroxy) propyl] piperazine, N-methylformoline, hexamethylenetetramine, pyridine, pyrazine, quinoline, benzyldimethylamine, α-methylbenzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris ( Dimethylaminomethylol) phenol, N-methylpiperazine, pyrrolidine,
Formolin, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N
-Β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane.

The curing catalyst as described above can be added at the time of preparing the dispersion or immediately before coating. The ratio of the curing catalyst is preferably 0.001 to 10% by weight based on the effective solid component in the dispersion.

In the present invention, the above-mentioned dispersion liquid for the silicon hard coat layer is used in order to avoid the action of accelerating the deterioration of the resin due to the propagation of the extra active energy of the photocatalyst coating layer described later. It is preferable to contain a compound having an action of relaxing energy.

As such a compound, for example, a metal chelate compound having an aliphatic chelate structure or a compound of a metal salt of an aliphatic acid is preferable, and a compound having compatibility with the matrix resin of the hard coat layer is more preferable.

As the central metal of such a compound, for example, Co, Mn, V, Cu, Ce, Cr, Ru, Ga,
Cd and Fe can be mentioned. Examples of the chelating compound include acetylacetone, di-n-butoxide-mono-ethyl acetate, di-n-butoxide-mono-methyl acetate, methyl ethyl ketoxime, 2,4-hexanedione, 3,5-heptanedione and Acetoxime can be mentioned. further,
Examples of the aliphatic acid compound include 2-ethyl-hexylic acid, stearic acid, lauric acid, oleic acid, acetic acid,
Sebacic acid, dodecanedioic acid, propionic acid, brassic acid, isobutyric acid, citraconic acid. Among these compounds, those having an absorption peak at 400 to 550 nm and exhibiting a blue to magenta color in a solution containing the absorption peak are preferred.

Such a compound is preferably used at 0.001 to 5% by weight based on the solid content of the dispersion. 0.001
If the amount is less than 5% by weight, the effect of using such a compound is hardly obtained. If the amount is more than 5% by weight, the hardness of the hard coat layer tends to deteriorate.

Further, the above-mentioned dispersion liquid may contain a leveling agent for a cured film and a lubricity imparting agent as optional components. As such an agent, for example, a copolymer of polyoxyalkylene and polydimethylsiloxane (Paint Additive 31 manufactured by Dow Corning) and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. Such an agent is preferably used at 0.001 to 10% by weight based on the total amount of the solution. In addition, an antioxidant, a weather resistance imparting agent, an antistatic agent, a bluing agent and the like can be contained as other optional components.

The dispersion has a solid concentration of, for example, 2 to 5
It is preferably used after being adjusted to 0% by weight. The coating can be performed by, for example, a dip method, a flow method, a spinner method, or a spray method.

The coating is preferably carried out so as to have a thickness after curing of 2 to 7 μm. If it is smaller than 2 μm, the hardness is not sufficient, while if it is larger than 7 μm, cracks are easily generated in the hard coat layer. After the application, the dispersion coating film is subjected to heat treatment at a temperature of 100 to 130 ° C. for, for example, 1 to 24 hours to give a silicon hard coat layer.

The coated polycarbonate plate of the present invention further has a photocatalytic coating layer on the silicon hard coat layer. Such a layer is made of a silicon resin containing a metal oxide having a photocatalytic effect. As the metal oxide having a photocatalytic effect, metal oxide fine particles that generate a band gap that exhibits the photocatalytic effect by irradiation with ultraviolet rays are preferable. Such fine particles include, for example, TiO ₂ , TiO ₃ , Sr
TiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , I
n ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, Cd
S, CdSe, GaP, GaAs, CdFeO ₃ , Mo
S ₂ and LaRhO ₃ can be exemplified. Preferred are TiO ₂ and ZnO, and particularly preferred is anatase TiO ₂ .

As the silicone resin, the following formula described for the silicon hard coat layer: R ¹ _d R ² _e Si (OR ³ ) _4-de where R ¹ , R ² , R ³ , d and e A cured product of the compound represented by the same definition as described above can be mentioned as a preferable example.

The same curing catalyst and liquid medium as those described for the hard coat and the like can be used. Here, 1-propanol is particularly preferred as the liquid medium. The coating liquid for the photocatalyst coating layer preferably has a solid content concentration of 1 to 10% by weight.

The coating can be performed by, for example, a dip method, a flow method, a spinner method, or a spray method. The coating is preferably performed in a thickness such that the film thickness after curing is 5 to 50 nm. If it is larger than 50 nm, the film becomes cloudy and interference colors become undesirably visible. After application,
The solution coating is subjected to a heat treatment at a temperature of 100 to 130 ° C. for, for example, 1 to 5 hours to give a photocatalyst coating layer.

The photocatalyst coating layer is preferably provided on a corona-treated silicon hard coat layer. Thereby,
The photocatalyst coating layer is strongly bonded to the silicon hard coat layer. In addition, the photocatalytic coating layer has an action of relaxing the active energy in order to avoid the action described in the hard coat layer, that is, the excess active energy of the photocatalytic layer from propagating and promoting the deterioration of the resin. Can be contained.

The coated polycarbonate plate of the present invention can be used, for example, for soundproof walls, glazing applications, and indoor applications.

[0051]

As described above, according to the present invention, there is provided a polycarbonate plate with a transparent hard coat having a surface antifogging property and an antifouling property which does not cause yellowing even when used outdoors for a long period of time. Can be provided.

[0052]

The present invention will be described in more detail with reference to the following examples. The various substances used in the examples are as follows. Polycarbonate plate: Polyca Ace (made by Tsutsuna Plastics Co., Ltd.) 5 mm thick plate (1 m × 30 cm × 5 mm)
Was used.

Primer 1: Copolymer of methyl methacrylate and methacryloxypropyltrimethoxysilane in a molar ratio of 4: 1 (Mn = 10000, Mw = 4000)
100 g), 50 g of 2,4-dihydroxybenzophenone and 8 g of propylene glycol monomethyl ether.
A solution consisting of 50 g and 0.1 g of Dow Corning Paint Additive 31.

Primer 2: Acryloid A-10S
(Rohm & Haas acrylic resin) 100g and 2,
2 ', 4,4'-tetrahydroxybenzophenone 40
g, propylene glycol monomethyl ether to 860
g and Dow Corning Paint Additive 31
A solution consisting of 0.1 g.

Hard coat 1: Snowtex 0-40
(Nissan Chemical: colloidal silica, water dispersion, nonvolatile content 4
0%) 150 g and methyltrimethoxysilane 200 g
A solution obtained by adding 648 g of isopropyl alcohol, 2 g of sodium acetate, and 0.1 g of Dow Corning paint additive 31 after the reaction.

Hard coat 2: Snowtex 0-40
(Nissan Chemical: colloidal silica, water dispersion, nonvolatile content 4
0%) 150 g and methyltrimethoxysilane 200 g
After reacting, a solution consisting of 20 g of 2,4-dihydroxybenzophenone, 628 g of isopropyl alcohol, 2 g of sodium acetate, and 0.1 g of Dow Corning Paint Additive 31.

Hard coat 3: Snowtex 0-40
(Nissan Chemical: colloidal silica, water dispersion, nonvolatile content 4
0%) 150 g and methyltrimethoxysilane 200 g
After the reaction, 647 g of isopropyl alcohol, C
o (II) A solution in which 0.1 g of acetylacetone dihydrate, 2 g of sodium acetate, and 0.1 g of Dow Corning paint additive 31 are added.

A solution containing TiO ₂ : a solution comprising 50 wt% of ST-K03 (manufactured by Ishihara Sangyo, nonvolatile content: 10%) and 50 wt% of 1-propyl alcohol.

The conditions such as the coating method and the various test methods used in the examples are as follows.

Coating method: flow coating or dip coating. Corona treatment conditions: output 500 W, irradiation distance 5 mm, treatment for 3 minutes. Hard coat curing condition: 120 ° C. for 60 minutes. Curing conditions for solution containing TiO ₂ : 30-60 at 120 ° C
Minutes.

Adhesion: Go board test JIS K5400. Yellowness: Measured according to JIS K7103. Hardness: In a Taber abrasion test based on JIS K7204, the turbidity around 500 rotations was compared with an excess of 500 g. Turbidity: Based on JIS K7105. Initial contact angle: 3 light sources with an ultraviolet intensity of 0.5 mW / cm ²
After irradiation for an hour, the contact angle with a 0.1 cc water drop was measured. Contact angle after weathering test: The contact angle with a 0.1 cc water drop was measured.

Weatherability 1: The appearance and adhesion after 3000 hours were evaluated using a sunshine carbon arc weatherometer meter weathering tester (black panel temperature: 63 ° C., water spray: 12 minutes per hour).

Example 1 Primer 1 was applied to a polycarbonate plate by flow coating.
After the cloth is cured (thickness of primer layer after curing is 1.8 to 3.5μ)
m), hard coat 1 is applied and cured by flow coating (hard
Hard coat layer thickness 2-5 μm)
TiO after treatment _TwoApply and cure a solution containing
The thickness of the photocatalyst coating layer was set to 20 to 40 nm.

Example 2 After the primer 2 was applied and cured by a flow coat (thickness after curing is 1 to 2 μm), the hard coat 2 was applied and cured by a flow coat (thickness of the hard coat layer after curing was 2 to 5. 5μ
m) After the corona treatment, a solution containing TiO ₂ was applied and cured, so that the thickness of the cured photocatalytic coating layer was 20 to 40 nm.

Example 3 Primer 1 was applied by dip coating (pulling speed: 1.5 m / min) and cured at 115 ° C. for 30 minutes (primer layer thickness after curing: 1.8 to 3.5 μm). Coating 3 is applied by dip coating (pulling speed 1.5m /
), And cured at 120 ° C for 60 minutes (hardened hard coat layer thickness 2-5 µm). After corona treatment, the solution containing TiO ₂ was applied and strengthened, and the cured photocatalytic coating layer thickness was reduced to 20. ４０40 nm.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the step after corona treatment in Example 1 was not carried out.

Comparative Example 2 The procedure of Example 1 was repeated except that the step of coating and hardening the hard coat 1 was not performed. The results are shown in Tables 1 and 2.

[0068]

[Table 1]

[0069]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/04 CFD C08J 7/04 CFDB CFDF CFDM C08K 3/22 C08K 3/22 5/07 5/07 5 / 09 5/09 (72) Inventor Hisayuki Kayagi 136 Anesaki Beach, Ichihara-shi, Chiba F-term (reference) 4F006 AA36 AB24 AB39 AB54 AB55 AB64 AB65 AB76 BA01 BA02 BA03 BA10 BA11 DA04 4F073 AA01 BA26 BA33 BA52 CA21 4F100 AA17D AH02H AH06C AH06D AK01B AK25B AK45A AK52B AK52D AL01B AR00C BA04 BA07 BA10A BA10D CA07 EH46 EH462 EJ08 EJ082 EJ55 EJ552 EJ65B JK12C JL08D JL09 JN01 4J002 BG041 BG051 CP031 CP081 CP091 CP101 CP161 DE096 DE136 DG026 DJ016 EC037 ED027 EE036 EE037 EG048 EH037 EH157 EU176 FB096 FB106 FB136 FB146 FB156 FD056 GL00

Claims (8)

[Claims] 1. A polycarbonate layer, a primer layer comprising an ultraviolet absorbent and organic resin of 20% by weight or more of an effective nonvolatile content, a silicon hard coat layer, and a photocatalyst coating comprising a silicon resin containing a metal oxide having a photocatalytic effect. A coated polycarbonate plate in which film layers are laminated in this order. 2. The coated polycarbonate plate according to claim 1, wherein the ultraviolet absorber in the primer layer is a benzophenone-based. 3. The coated polycarbonate plate according to claim 1, wherein the organic resin in the primer layer is an acrylic polymer or a copolymer of an acrylic monomer and methacryloxysilane. Wherein the effective silicon component of the silicon hard coat layer is silica and the following formula ^{_{R 1 d R 2 e Si (}} OR 3) 4-de wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, halogen Alkyl group, aryl group or halogenated aryl group having 6 to 12 carbon atoms, methacryloxyalkyl group having 5 to 8 carbon atoms, ureidoalkylene group having 2 to 10 carbon atoms, aromatic ureidoalkylene group, halogenation An aromatic alkylene group or a mercaptoalkylene group, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group; and R ³ is a hydrogen atom or a carbon atom. An alkyl group, an acyl group or an alkylacyl group of the formulas 1-4, and d is 1, 2 or 3, and e is 0, 1 or 2. Coated polycarbonate plate according to claim 1 consisting of the compound. 5. The silicon hard coat layer contains a compound having an action of relaxing the active energy of the photocatalytic coating layer in order to avoid the action of promoting the excess active energy of the photocatalyst coating layer to accelerate the deterioration of the resin. The coated polycarbonate plate according to claim 1. 6. The compound according to claim 5, wherein the compound having an action of relaxing the active energy is a metal chelate compound in which the structure of the chelate is aliphatic or a metal salt of an aliphatic acid, and is compatible with the matrix resin of the hard coat. A coated polycarbonate plate as described in the above. 7. The coated polycarbonate plate according to claim 5, wherein the compound having an action of relaxing the active energy has an absorption peak at 400 to 550 nm, and the solution containing the compound exhibits a blue to reddish purple color. 8. The coated polycarbonate plate according to claim 1, wherein the photocatalytic coating layer is provided on a corona-treated silicon hard coat layer.