JP2003311908A - Polycarbonate resin window glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin window glass whose surfaces are protected having an outside face with high wear resistance and an inside face with excellent adhesiveness to a printing ink, adhesion processability and wear resistance. <P>SOLUTION: The polycarbonate resin window glass is a window glass formed of a polycarbonate resin molded article. The outside face is coated with a silicone hard coat, and the inside face is coated with a melamine coating. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin window glass whose surface is protected. More specifically, the present invention relates to a polycarbonate resin window glass that is not easily scratched on the surface and has excellent long-term practicality, and particularly to a polycarbonate resin window glass for automobiles that requires decorative printing such as frame printing and dot printing on the inner surface.

[0002]

2. Description of the Related Art Polycarbonate resin has excellent mechanical strength, transparency and durability and is widely used for optical disc substrates such as compact discs and OA equipment. In particular, it is a transparent resin window glass that makes use of the characteristics of excellent transparency and impact strength that is 300 times that of glass, and is a substitute for fragile inorganic glass as window glass for transportation and public facilities such as schools. Widely used as.

In the application as a window glass, it is usually used for a long period of 10 years or more. When used as a window glass, it is essential that it does not impair its appearance such as being scratched or discolored during a long period of use. Polycarbonate resin has various advantages as described above, but on the other hand, it has a drawback that its surface is soft and easily scratched, and that it is colored yellow by sunlight when used outdoors for a long period of time.

It is a known technique to coat a polycarbonate resin molded article with a melamine resin. For example, JP-A-52-127928 discloses a coating composition comprising (A) methyl etherified methylol melamine, (B) short chain glycol, (C) long chain glycol and (D) curing agent. No. 57-143336 discloses that, in addition to the components (A) to (D), a solution prepared by dissolving a composition comprising a hydrolytic condensation product of a silicon compound in a solvent is applied to a polycarbonate resin molded article.

Further, Japanese Unexamined Patent Publication (Kokai) No. 11-35712 discloses a method for producing a polycarbonate resin sheet excellent in antistatic performance by applying a melamine resin paint containing a cationic surfactant. In addition, this polycarbonate resin sheet has been shown to be useful as a window material for automobiles and vehicles, a window material for construction, and the like.

However, when these melamine resins are used on the outer surface of the window glass, there is a problem that the hardness is insufficient and they are easily scratched, and the weather resistance is discolored after long-term use.

On the other hand, in order to overcome such drawbacks and make a useful window glass which maintains a good appearance for a long period of time, a method of coating the surface of a polycarbonate resin molded article with a scratch resistant coating or an ultraviolet resistant coating is widely used. . As a coating for the purpose of preventing scratches and at the same time preventing discoloration due to sunlight, a silicon hard coat is widely known as a coating having particularly excellent performance, and many practical products are on the market. Further, JP-A-2002-36870 and JP-A-20
No. 01-354781 discloses that certain silicon hard coats are suitable for coating automobile windows.

The polycarbonate resin molded article coated with such a silicon hard coat is an excellent resin window glass that retains practical quality for a long period of time, but a silicon hard coat paint that provides a coating that can be practically used for a long period of time is extremely expensive. Moreover, in order to manufacture a polycarbonate resin molded product coated with a silicon hard coat, complicated manufacturing equipment and advanced technology are required. For this reason, a polycarbonate resin molded product coated with a silicon hard coat on both sides is very expensive, and its field of use has been limited.

Further, in recent years, in the application of vehicle window glass, post-processing such as frame printing and dot printing for the purpose of light shielding, dimming, dimming, and decoration, and design requirements and assembly cost reduction demands for automobiles. There are increasing usages such as attaching resin window glass directly to the metal body. The silicone hard coat that is coated on the polycarbonate resin window glass and can withstand long-term use is extremely hard and chemically stable, so it is excellent in preventing scratches and yellowing, but such printing and adhesion The post-processing was extremely difficult and the improvement was demanded.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a surface having a high degree of abrasion resistance on the outer side and excellent adhesion and workability of printing ink on the inner side, and a moderate abrasion resistance. To provide a protected polycarbonate resin window glass.

Another object of the present invention is that the outer surface has a high level of abrasion resistance, and the surface is protected by a cured coating having excellent weather resistance, and the inner surface has a decorative property and a resistance suitable for decorative printing. It is intended to provide a window glass for a vehicle, which is formed from a polycarbonate resin molded article whose surface is protected by a cured coating having excellent wear resistance.

As mentioned above, the polycarbonate resin is transparent and very hard to break, so that it is safe and lightweight.
Characteristics such as the degree of freedom in design have been drawing attention, and they are beginning to be used as window glass, especially for automobiles. When a polycarbonate resin molded product is used for a window glass, a device has been devised to cover a silicon hard coat to cover the susceptibility of the plastic to scratching and the easiness of yellowing due to ultraviolet rays. Silicone hard coats that are usually used are harder to prevent scratches and have long-term practicality.
A chemically more stable structure is used.

However, when the inner surface of the window glass is coated with a silicon hard coat, when the polycarbonate resin coated with the silicon hard coat is heated when printing such as frame printing or halftone printing, the thermal expansion is made to follow the polycarbonate resin. However, cracks are likely to occur, and there is a disadvantage that the binder cannot be sufficiently heated with the thermosetting type and heat drying type printing inks, so that the inks do not adhere firmly. Further, since the silicon hard coat has a chemically stable structure, the etching action of the ink solvent hardly occurs. For this reason, the adhesiveness of the printing ink is very poor, and it has not been possible to obtain a practically printed product with a commonly used and inexpensive ordinary polycarbonate resin ink.

That is, when printing a silicone hard coat-coated polycarbonate resin molded article or adhering it to a metal body, a physical treatment such as corona discharge or a mechanical pretreatment such as scraping off the coating is performed. In practice, it has been difficult to print a silicone hard coat-covered polycarbonate resin molded article or to bond it to a metal part because a very expensive special ink or adhesive has to be used.

In addition, the inner surface of the window glass is more
The conditions of use are mild, and the high level of abrasion resistance and weather resistance required for the outer surface is not required, and it is sufficient if it has appropriate performance. In addition, the inner surface of the window glass, especially for window glass for automobiles and building materials, facilitates workability such as printability and adhesiveness in the process of weight reduction, freedom of design, and designability. In addition, it is important that the cost can be reduced.

[0016]

The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, one surface of a polycarbonate resin molded product is coated with a silicon hard coat, and this surface is used as an outer surface of a window glass. It has a high degree of wear resistance and weather resistance by using it, and by coating the other surface with a melamine coat and using this surface as the inner surface of the window glass, practically sufficient wear resistance and weather resistance can be obtained. Having, without the occurrence of cracks by heating, also obtain a polycarbonate resin molded article having a surface protected, which has good adhesion of a printing ink for a polycarbonate resin that is usually used, and this molded article is a window glass, particularly They have found that they are useful as window glasses for automobiles and have reached the present invention.

The present invention will be described in detail below.

(Polycarbonate Resin) The polycarbonate resin used in the present invention is obtained by, for example, reacting a dihydric phenol with a carbonate precursor by an interfacial polymerization method or a melt polymerization method. Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). ) Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {( 3,5-dibromo-4-hydroxy) phenyl} propane, 2,2
-Bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-)
Phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4
-Hydroxyphenyl) -3,3-dimethylbutane,
2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-
Methyl pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester. Of these, 2,2-bis (4-hydroxyphenyl) alkanes are preferable, and bisphenol A is particularly preferable. These may be used alone or in combination of two or more.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

When a polycarbonate resin is produced by reacting the above dihydric phenol with a carbonate precursor by an interfacial polymerization method or a melt polymerization method, a catalyst, a terminal terminator, and an antioxidant for the dihydric phenol may be added, if necessary. Etc. may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid. Also, it may be a mixture of two or more kinds of the obtained polycarbonate resins.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is also possible to use a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound for accelerating the reaction. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably 10 minutes to 5 hours, and the pH during the reaction is preferably 9 or more.

In the interfacial polymerization method, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Monofunctional phenols are commonly used as molecular terminating agents for molecular weight control, and the resulting polycarbonate resins are compared to those that do not because the ends are blocked by groups based on monofunctional phenols. Excellent thermal stability.
Examples of such monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol, and among them, p-tert-butylphenol is preferable.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and an alcohol produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. Alternatively, it is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter half of the reaction, the reaction system was set at 1,300 Pa to 13 Pa.
The pressure is reduced to about (10 to 0.1 Torr) to facilitate the distillation of the produced alcohol or phenol. The reaction time is usually about 1 to 4 hours.

The viscosity average molecular weight (M) of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 15,000 to 35,000. Polycarbonate resin having such a viscosity average molecular weight,
Sufficient strength is obtained, and the melt fluidity at the time of molding is also favorable, which is preferable. The term "viscosity average molecular weight" as used in the present invention refers to 100 g of methylene chloride and 0.7 g of polycarbonate resin
The specific viscosity (η _sp ) obtained from the solution dissolved at 0 ° C. was inserted into the following equation. η _sp /c=[η]+0.45×[η] ² c (however, [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

In addition to the polycarbonate resin used in the present invention, if necessary, other resins such as styrene resins and polyester resins, or stabilizers, antioxidants, ultraviolet absorbers, etc., to the extent that the objects of the present invention are not impaired. Lubricants, flame retardants, dye pigments, antiglare agents and the like may be added.

The polycarbonate resin molded article is preferably used in the present invention by an ordinary method for producing a film or sheet, for example, a method of molding by a T-die extruder by a melt extrusion method, or a method of injection molding a polycarbonate resin pellet. It is possible to obtain a polycarbonate resin molded product having a thickness of.

In the present invention, a sheet-shaped polycarbonate resin molded article produced by using the above polycarbonate resin is preferably used. The polycarbonate resin sheet is usually produced by a melt extrusion method, but may be obtained by any method industrially practiced such as injection molding and compression molding. Also, a sheet that has been subjected to post-processing such as hot bending or cold bending after forming can be used.

The polycarbonate resin molded product used in the present invention may be subjected to various pretreatments in order to improve the adhesion of the coating film to be coated. For example, a polycarbonate resin molded article that has been subjected to a physical treatment such as corona discharge or ultraviolet irradiation or a pretreatment such as a chemical treatment using amines such as monoethanolamine can be preferably used.

(Melamine Coat) In the present invention, one side of a polycarbonate resin molded product is coated with a melamine coat and used as an inner surface of a window glass. Here, the inner surface of the window glass is a surface that is not directly exposed to sunlight, and specifically means a surface on the indoor side in the case of vehicle window glass.

The melamine resin used for the melamine coating on the inner surface of the polycarbonate resin window glass of the present invention is an etherified methylol melamine which is an alkyl etherification reaction product of methylol melamine produced by the reaction of melamine and formaldehyde. And a thermosetting melamine resin obtained by reacting a polyol with an acid catalyst in the presence of a solvent and various additives are preferably used.

As the etherified methylol melamine,
For example, a completely alkyl-type methylated melamine represented by hexamethoxymethylmelamine, a part of the methoxymethyl group of hexamethoxymethylmelamine converted to a methylol group, an imino group, a butoxymethyl group, Alternatively, a completely alkyl butylated melamine represented by hexabutoxymethyl melamine and the like can be mentioned. Specific products include Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 712, Cymel 202, Cymel 207, Cymel 212 manufactured by Mitsui Cytec Co., Ltd.

Of these etherified methylol melamines, fully alkylated methylated melamines represented by hexamethoxymethylated melamine are preferably used. Specifically, Mitsui Cytec Co., Ltd. Cymel 300 (average degree of polymerization 1.35, methoxymethyl group ratio 95% or more), Cymel 301 (average degree of polymerization 1.5, methoxymethyl group ratio 90% or more). , Cymel 303 (average degree of polymerization 1.7, methoxymethyl group ratio 90% or more), Cymel 350 (average degree of polymerization 1.6, methoxymethyl group ratio 85% or more). These are used alone or as a mixture. Particularly preferred among the etherified methylolmelamines is hexamethoxymethylolmelamine.

Examples of polyols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, propylene glycol and dipropylene glycol. , Tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, nonapropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol, pentabutylene glycol, hexabutylene glycol, nonabutylene glycol, neopentyl Glycol and neopentyl glycol with ethylene oxide (2-10 mol) Thing, trimethylol-les-roll propane,
Ethylene oxide of trimethylol propane (2-1
0 mol) adduct, propylene oxide (2 to 10 mol) adduct of trimethylol propane, glycerin, ethylene oxide (2 to 10 mol) adduct of glycerin, propylene oxide (2 to 10 mol) adduct of glycerin, penta Erythritol, pentaerythritol ethylene oxide (2-10 mol) adduct, pentaerythritol propylene oxide (2-10 mol) adduct, dipentaerythritol, dipentaerythritol ethylene oxide (2-10 mol) adduct, dipentaerythritol Propylene oxide (2-10 mol)
Examples thereof include adducts and sorbitol polyester polyols, which may be used alone or in combination.

Among the polyols, diols and glycols of the following formula are preferably used.

[0035]

[Chemical 3]

[Wherein, m and n are integers of 2 to 30, p
Represents an integer of 1 to 5. Among the diols, butanediol and hexanediol are preferable, and among the glycols, polyethylene glycol is preferable. In particular, those using polyethylene glycol having a molecular weight of 100 to 500 are preferable because a melamine coat having sufficient wear resistance, weather resistance and post-processability can be obtained.

The melamine coat of the present invention is applied to a polycarbonate resin molded article by using etherified methylol melamine and polyols as a normal solution. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; esters such as ethyl acetate and methoxyethyl acetate; methanol. ,ethanol,
1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,
Alcohols such as 2-methoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol; n-
Hydrocarbons such as hexane, n-heptane, isocutane, benzene, toluene, xylene, gasoline, light oil, and kerosene may be used, and these may be used alone or in combination of two or more. . The concentration of the solid content of the coating film resin in the solution is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

For condensation of melamine and polyol, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid and sulfamic acid, maleic acid, formic acid, acetic acid, propionic acid,
Organic acids such as butyric acid, oxalic acid, succinic acid, lactic acid, benzenesulfonic acid and paratoluenesulfonic acid are used as catalysts. Particularly preferred catalysts include non-volatile organic acids having sufficient acidity such as maleic acid, benzenesulfonic acid and paratoluenesulfonic acid.

It is also possible to add additives that impart various functions to the melamine coating paint consisting of melamine, polyol, acid catalyst and solvent. Leveling agents, defoamers, viscosity modifiers, and ultraviolet absorbers that improve the characteristics of paints and facilitate painting are mentioned. Among them, the ultraviolet absorber is particularly important for improving the weather resistance of the melamine coat.

Examples of such ultraviolet absorbers are 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone and 4-dotesiloxy-2-. Benzophenones such as hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and bis (5-benzoyl-4-hydroxy2-methoxyphenyl) methane, 2- (2'-hydroxy-5'-methyl) Phenyl) benzotriazole, 2- (2'-hydroxy-
5'-tert-octylphenyl) benzotriazole, 2- (3'-tert-butyl-5'-methyl-
2'-hydroxyphenyl) benzotriazole, 2-
(3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-
Di-tert-pentyl-2'-hydroxyphenyl)
Benzotriazole, 2- (3'-tert-butyl-
5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ', 5'-di-ter
t-Butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidyl) Phenol, bis (3-2
H-benzotriazol-2-yl-2-hydroxy 5
Benzotriazoles such as -tert-octylphenyl) methane, ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,
Cyanoacrylates such as 3-diphenyl acrylate, phenyl salicylates, salicylates such as p-octylphenyl salicylate, diethyl p-methoxybenzylidene malonate, benzylidene malonates such as bis (2-ethylhexyl) benzylidene malonate,
2- (4,6-diphenyl-1,3,5-triazine-
Examples include triazines such as 2-yl) -5-hexyloxyphenol. The ultraviolet absorber is preferably 0.7 to 10 relative to 100 parts by weight of the solid content of the melamine coat.
0 parts by weight, more preferably 3 to 60 parts by weight, still more preferably 5 to 50 parts by weight.

Various coating methods can be used for coating the surface of the polycarbonate resin molded article with the melamine coat coating to coat the melamine coat. Particularly suitable industrial coating methods for producing resin panes are spray coating, flow coating and dip coating.

The thickness of the melamine coat coating film coated on the polycarbonate resin window glass of the present invention is 2 μm to 20 μm.
It is preferably adjusted to be in the range of μm. Two
When the film thickness is not less than μm, abrasion resistance is sufficient, which is preferable. Further, when the coating film is 20 μm or less, post-processing such as bending is excellent, and the adhesiveness of the melamine coat coating film is good, which is preferable.

The melamine coat of the present invention can be directly coated on a polycarbonate resin molded product, but various treatments are performed in order to further strengthen the adhesion between the melamine coat and the polycarbonate resin and improve the durability. You can also For example, a polycarbonate resin molded article is subjected to physical treatment such as corona discharge or ultraviolet irradiation, or monoethanolamine, 2-aminopropan-1-ol, 1-
Aminopropan-2-ol, 3-aminopropan-1
Adhesion of the melamine coat to the polycarbonate resin molded article is improved by performing a chemical treatment with amino alcohol such as -ol, 3-aminepropan-1-ol, 1-aminobutan-2-ol.

The above melamine coat prevents the polycarbonate resin window glass from being scratched and has sufficient practicality even in long-term use. The wear resistance of melamine coat is
ΔH (%) is 0.5% to 5.0% by the following evaluation method
Within the range, it is preferable that the window glass will not be damaged even if it is wiped with a cloth or the like to remove stains. If ΔH exceeds 5.0%, scratches may be formed by rubbing with a cloth or the like. △ H is 0.5%
When it is less than the above range, the film becomes too hard and the melamine coat film becomes brittle and cracks may occur in the film. <Evaluation Method> A Taber abrasion test was performed at a load of 500 g and 100 rotations using a wear wheel of CS-10F manufactured by Taber Co., and a difference between a haze (%) after the Taber abrasion test and a haze (%) before the Taber abrasion test. ΔH (%) was measured and evaluated (A
Based on STMD1044).

(Silicon Hard Coat) In the present invention, one side of a polycarbonate resin molded product is coated with a silicon hard coat to be used as an outer surface of a window glass. Here, the outside surface of the window glass is a surface directly exposed to sunlight, and specifically means the outside surface of the window glass for vehicles.

The outside surface of the window glass is exposed to wind and rain, and is under severe operating conditions where it is directly exposed to the ultraviolet rays of sunlight. In the present invention, it is possible to obtain a useful polycarbonate resin window glass by using the silicon hard coat on the outer surface of the window glass under such severe usage conditions.

The silicon hard coat used on the outer surface of the polycarbonate resin window glass of the present invention comprises, as the first layer, a silicon primer coat containing an acrylic resin as a main component and a second layer of an organopolysiloxane resin as a main component. A silicon top coat made of a thermosetting film is preferable.

(Silicon primer coat) The first layer of silicon primer coat is formed from a composition in which the resin component is a resin containing an acrylic resin as a main component alone and an additive such as an ultraviolet absorber. The primer coat is interposed between the polycarbonate resin molded product and the silicone top coat (sometimes referred to as the coating layer (II)) to firmly bond the two and prevent yellowing and deterioration of the polycarbonate resin molded product. Play a protective role.

The main component of this first layer of silicon primer coat (sometimes referred to as coating layer (I)) is an acrylic resin. The acrylic resin is a polymer obtained by polymerizing 50 mol% or more of an alkyl methacrylate monomer and 50 mol% or less of a vinyl-based monomer. Specific examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate,
These may be used alone or in combination of two or more. Methyl methacrylate and ethyl methacrylate are particularly preferred.

The vinyl-based monomer optionally used is a monomer copolymerizable with an alkyl methacrylate monomer, and acrylic acid, methacrylic acid or derivatives thereof are preferably used. Specifically, acrylic acid,
Methacrylic acid, acrylic acid amide, methacrylic acid amide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N , N-diethylaminoethyl methacrylate, glycidyl methacrylate and the like.

It is also possible to use an acrylate (or methacrylate) monomer having an alkoxysilyl group. Specifically, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane,
Examples thereof include 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are preferable. In particular, 3-methacryloxypropyltrimethoxysilane is preferably used.

Further, as the acrylic resin of the present invention, an acrylic resin obtained by copolymerizing an acrylate (or a methacrylate) having an ultraviolet absorbing residue can be used. That is, the ultraviolet absorber residue here means a derivative group having a function as an ultraviolet absorber, and means a group of an ultraviolet absorber ester-bonded with a carboxyl group of acrylate (or methacrylate). Specific examples of the acrylate (or methacrylate) monomer having an ultraviolet absorbent residue include 2- (2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole and 2- (2'-hydroxy-5 '). -Methacryloxymethoxyphenyl) benzotriazole, 2-
(2'-Hydroxy-5'-methacryloxypropylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxypropoxyphenyl) -benzotriazole, 2- (2'-hydroxy-5'-methacryloxy) Ethylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-methacryloxyethyl-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methacryloxyethyl -5'-tert-butylphenyl) -5-
Chlorobenzotriazole, 2-hydroxy-4- (methacryloxymethoxy) benzophenone, 2-hydroxy-4- (methacryloxypropoxy) benzophenone, 2,2'-dihydroxy-4- (methacryloxymethoxy) benzophenone, 2-hydroxy- 4- (methacryloyloxyethyl) benzophenone etc. are mentioned. These can be used alone or in combination of two or more kinds of monomers forming the acrylic resin.

The above monomers can be polymerized by a known method. For example, there are a method of polymerizing using a catalyst, polymerization using ultraviolet rays and electron beams, and the like. The weight average molecular weight of the acrylic resin is 20,000 to 600,000.
0 is preferable and 50,000 to 400,000 is more preferable. The acrylic resin having such a molecular weight range is
Performance such as adhesion and strength as a layer is sufficiently exhibited, which is preferable.

Further, as the primer coat that can be used in the present invention, an acrylic resin obtained by crosslinking and curing the above acrylic resin can be used. That is, a polymer obtained by copolymerizing an acrylic monomer having a hydroxy group is cross-linked with a monomer having a hydroxy group and a polycondensable alkoxysilane group, an isocyanate group, a melamine group or the like.

Specific examples of the acrylate (or methacrylate) monomer having a hydroxy group suitable for cross-linking include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and vinyltriacrylate. Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like can be mentioned, among which 2-
Hydroxyethyl methacrylate is preferably adopted.

Examples of the crosslinkable alkoxysilanes include tetramethoxysilane, tetramethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, and methyl. Trimethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) -γ-aminopropyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane and the like. Of these, alkyltrialkoxysilanes are preferable, and methyltrimethoxysilane and methyltrimethoxysilane are particularly preferable. These can be used alone or in combination.

The above-mentioned crosslinkable isocyanate is diisocyanate or blocked diisocyanate.
Specific examples thereof include isophorone diisocyanate.

Melamine resin can be used as a crosslinking agent in the above-mentioned crosslinking primer coat. As the melamine resin, for example, a completely alkyl-type methylated melamine represented by hexamethoxymethylolmelamine, a part of the methoxymethylol group of hexamethoxymethylolmelamine becomes a methyl group, an imino group, a butoxymethyl group. Or a completely alkyl butylated melamine typified by hexabutoxymethylol melamine. These melamine resins are used alone or as a mixture.

The acrylic resin primer coat used in the present invention may contain an ultraviolet absorber and / or a light stabilizer for the purpose of increasing the weather resistance and stabilizing the light resistance of the polycarbonate resin. Such ultraviolet absorbers and light stabilizers may be those normally used for polycarbonate resins.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone and 4-dotesiloxy-2. -Hydroxybenzophenone, 2-2'-dihydroxy-4,4'-dimethoxybenzophenone, benzophenones such as bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy-5 ' -Methylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-tert-octylphenyl) benzotriazole, 2- (3'-tert-butyl-5'-methyl-
2'-hydroxyphenyl) benzotriazole, 2-
(3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-
Di-tert-pentyl-2'-hydroxyphenyl)
Benzotriazole, 2- (3'-tert-butyl-
5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ', 5'-di-ter
t-Butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6-3,4,5,6-tetrahydrophthalimidyl) phenol , Bis (3-2H
-Benzotriazol-2-yl-2-hydroxy-5
Benzotriazoles such as -tert-octylphenyl) methane, ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,
Cyanoacrylates such as 3-diphenyl acrylate, phenyl salicylate, salicylates such as p-octylphenyl salicylate, diethyl-p-methoxybenzylidene malonate, bis (2-ethylhexyl)
Examples thereof include benzylidene malonate such as benzylidene malonate and triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol. These agents may be used alone or in combination of two or more kinds.

The ultraviolet absorbent is preferably 0.7 to 100 parts by weight of the acrylic resin of the coating layer (I).
100 parts by weight, more preferably 3 to 60 parts by weight, particularly preferably 5 to 50 parts by weight.

Examples of the light stabilizer include bis (2,2
2,6,6-Tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4
-Octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4
-Piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetra) Hindered amines such as methyl-4-piperidyl) phenylphosphite, nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate and other nickel A complex is mentioned. These light stabilizers may be used alone or in combination of two or more, and preferably 0.1 to 50 parts by weight, more preferably 0.5 to 100 parts by weight of the acrylic resin of the coating layer (I).
-10 parts by weight are used.

In the present invention, the method of forming a silicone primer coat on the surface of a polycarbonate resin molded article is carried out by adding the acrylic resin to a suitable solvent, and further adding a leveling agent, a defoaming agent, a viscosity adjusting agent, etc., if desired. A method in which a solvent is added to adjust the viscosity, the solid content ratio, etc., is applied by a means suitable for a polycarbonate resin molded article such as a spray coating method, a dip coating method, a flow coating method, the solvent is removed, and heat drying is preferably used. .

Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; esters such as ethyl acetate and methoxyethyl acetate. Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl 1-
Propanol, 2-methoxyethanol, 4-methyl 2
Alcohols such as pentanol and 2-butoxyethanol; hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, gas oil, kerosene; acetonitrile, nitromethane, water, etc. These may be used alone or in combination of two or more. The concentration of the solid content of the coating resin in the solution is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

The thickness of the coating layer (I) of the first layer is such that the polycarbonate resin molded article and the second layer are sufficiently adhered, and
The film thickness may be any thickness required to maintain the required amount of the various additives, and is preferably 0.1 to 10 μm, more preferably 2 to 5 μm. (Silicon Top Coat) The coating layer (II), which is a silicon top coat laminated on the silicon primer coat of the silicon hard coat used in the present invention, contains a thermosetting organopolysiloxane resin as a main component. . Silicone topcoat is a very hard resin, and by being coated on the outside of the window glass it imparts abrasion resistance to prevent scratching of the polycarbonate resin, and together with the silicone primer coat it also protects against ultraviolet rays and water in sunlight. It plays the role of preventing the deterioration of polycarbonate resin molded products.

The above silicon top coat is (A)
The main component is an organopolysiloxane resin obtained by applying a coating material comprising an alkoxysilane, (B) colloidal silica, (C) curing catalyst, (D) solvent and optionally (E) additive, and curing. preferable.

The (A) alkoxysilane compound is, for example, methyltrimethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ
-Trifunctional alkoxysilane such as aminopropyltrimethoxysilane, tetraethoxysilane, tetra-n-
One or a mixture of two or more tetrafunctional alkoxysilanes such as propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane, which are partially or entirely hydrolyzed, and the hydrolyzate thereof. It is a condensate obtained by subjecting part or all of the condensation reaction. In particular, in order to obtain a composition that forms a silicon top coat having excellent wear resistance, a coat in which 70% by weight or more of all alkoxysilane is methyltrimethoxysilane is preferable.

As the colloidal silica (B), silica fine particles having a particle size of 5 to 200 nm, preferably 5 to 40 nm, are colloidally dispersed in water or an organic solvent. The colloidal silica may be used in either a water dispersion type or an organic solvent dispersion type, but it is preferable to use a water dispersion type. A fine particle sol other than silica such as alumina sol or titanium sol can be mixed with the colloidal silica.

As the colloidal silica, specifically, Snowtex O manufactured by Nissan Kagaku Kogyo Co., Ltd. as a product dispersed in an acidic aqueous solution, and manufactured by Nissan Kagaku Kogyo Co., Ltd. as a product dispersed in a basic aqueous solution. Snowtex 30, Snowtex 40, Cataloid S30 manufactured by Catalyst Kasei Kogyo Co., Ltd., Cataloid S40, MA-ST, IPA-S manufactured by Nissan Chemical Industries, Ltd. as a product dispersed in an organic solvent.
T, NBA-ST, IBA-ST, EG-ST, XBA
-ST, NPC-ST, DMAC-ST, etc. are mentioned.

The coating material used for forming the silicon top coat is usually a colloidal silica solution and a dilute acidic aqueous solution of a hydrolysis catalyst are dropped into alkoxysilane to obtain a silane hydrolysis solution. , A leveling agent, a viscosity modifier, and a curing catalyst may be appropriately added.

(C) As a curing catalyst, formic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid and other aliphatic carboxylic acid lithium salts, sodium salts, potassium salts and other alkali metal salts or benzyltrimethylammonium salts,
Examples thereof include quaternary ammonium salts such as tetramethylammonium salt and tetraethylammonium salt. Among them, sodium acetate, potassium acetate and benzyltrimethylammonium acetate are preferably used. Further, ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and salts thereof, perchlorates such as ammonium trifluoromethylsulfonate and bis (tolufluoromethylsulfonyl) bromomethylammonium, hydrochlorides, nitrates, Carboxylates, amines and salts thereof, high fluoroaliphatic sulfonates, high fluoroaliphatic sulfonyl salts and the like can be used.

Further, as the solvent (D), it is necessary that the solid content of the organosiloxane resin is stably dissolved, and for that purpose, at least 20% by weight or more of the solvent,
It is desirable that 50% by weight or more is alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1.
-Propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol and the like can be mentioned, and a low-boiling alcohol having 1 to 4 carbon atoms is preferable, and in view of solubility, stability and coatability. 2-Propanol is particularly preferred.

When water in the water-dispersed colloidal silica is used as the solvent, water which does not participate in the hydrolysis reaction, a lower alcohol generated by the hydrolysis of the alkoxysilane, and an organic solvent-dispersed colloidal silica are used. Includes an organic solvent for the dispersion medium and an acid added to adjust the pH of the coating material for coating. Acids used for pH adjustment include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid and other inorganic acids or formic acid, acetic acid,
Organic acids such as propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid and paratoluenesulfonic acid can be mentioned. Among these, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable from the viewpoint of easy control of pH. Other solvents must be miscible with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; Examples thereof include esters such as ethyl acetate and ethoxyethyl acetate.

The solvent is preferably used in an amount of 50 to 900 parts by weight, more preferably 150 to 700 parts by weight, based on 100 parts by weight of the solid content of the coating resin.

Examples of the (E) additive which is optionally used include a leveling agent, a defoaming agent and a viscosity adjusting material.

The silicone top coat of the present invention can be applied by any industrially suitable coating method such as a spray coating method, a flow coating method and a roll coating method on the polycarbonate resin molded article coated with the above silicon primer coating. The flow coating method and the dip coating method are particularly preferable as the coating method when used for vehicle window glass applications because they give good appearance products, but the spray coating method is also an excellent coating method for coating molded products with curved surfaces. Is.

The thickness of the silicon top coat is preferably in the range of 1 to 20 μm, more preferably 3 to 10 μm. A film thickness within this range is preferred because cracks are less likely to occur and the hardness inherent in the silicon coat can be exhibited.

(Resin Window Glass) The polycarbonate resin window glass obtained in the present invention is suitable as a window glass for a vehicle attached to an automobile or various transportations, or a building glass attached to a building such as a house or a building. used.

When a transparent plastic sheet is applied to a window glass for an automobile, for example, it is necessary to prevent the occurrence of scratches on the windshield when the wiper is activated, and it is necessary to prevent the occurrence of scratches on the side window when the window is moved up and down. There is. In such applications, a particularly high level of abrasion resistance equivalent to that of glass is required. Further, automobile window glass is exposed to various outdoor environments for a long period of time. The outer surface of such a window glass is required to have a high level of abrasion resistance at the same time as glass and a high degree of weather resistance, and the polycarbonate resin molded article having the outer surface coated with the silicon hard coat of the present invention is the most suitable material. Can be said.

The abrasion resistance of the window glass for automobiles is determined by the Taber abrasion test (CS-10F abrasion) according to ASTM D1044 on the outer surface of the window glass in the driving field such as the windshield, the side window of the driver's seat and the side window of the passenger's seat. As a result of a wear test by using a wheel and measuring 1,000 rotations under a load of 500 g), a change in haze value (ΔH) of 2% or less, a side window of the rear seat, a window outside the driving field of view such as a rear window As a result of the abrasion test by the above Taber abrasion test (measured at 100 rotations), the haze value change (ΔH)
It can be said that a resin window glass for automobiles having a value of 5% or less is a resin window glass for automobiles, which is not practically damaged and is sufficiently practical.

In the sunshine weather test (temperature 63 ° C., rain condition for 18 minutes in 120 minutes and temperature 83 ° C., no rain condition), the weather resistance was 5000 hours for the outside surface of the window glass and 1000 hours for the inside surface. No peeling or cracking of the coating film, no further deterioration of wear resistance, Δhaze before and after the test of 3.0% or less, preferably 2.0% or less, and hue change (ΔYI) of 3 or less. As long as it has durability, it can be practically used.

The polycarbonate resin window glass of the present invention satisfies these conditions and has sufficient performance as an automobile window glass. (Printing of Polycarbonate Resin Molded Article) Various printing inks such as a heat-drying type and an ultraviolet curing type are available from each printing ink manufacturer as a printing ink used for the polycarbonate resin molded article. For example, Toyo Ink Co., Ltd. SS-8000, SS83000, Teikoku Ink Co., Ltd. Sericol VG, Sericol B, Seiko Advance Co., Ltd. # 2500, Jujo Processing Co., Ltd. # 800.
0PC, # 8100 SNP and the like. By using these printing inks, a polycarbonate resin molded product can be subjected to printing such as frame printing and dot printing by screen printing or the like.

[0083]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The coated transparent polycarbonate resin molded product was evaluated by the following method. In addition, parts and% in the examples mean parts by weight and% by weight.

(1) Appearance evaluation: The appearance of the coat layer of the test piece (peeling of the film) and the presence or absence of cracks (cracks) were visually confirmed.

(2) Adhesion: Nine-ban adhesive tape (product name "Cellotape") was pressure-bonded to the coat layer with a cutter knife to make 100 squares with a cutter knife, and strongly peeled off vertically onto the substrate. It was evaluated by the number of remaining grids (J
According to IS K5400). 2 tape pressing and peeling operations
After repeating the number of times, the number of crosses left on the substrate was evaluated.

(3) Abrasion resistance: CS-10 manufactured by Taber
Using a wear wheel of F, a Taber abrasion test was performed under a load of 500 g, and a difference ΔH (%) between the haze (%) after the Taber abrasion test and the haze (%) before the Taber abrasion test was measured and evaluated ( According to ASTM D1044). The rotation speed of the Taber abrasion test was performed according to the following criteria. Rotation speed: 100 rotations of melamine coat side Silicon coating side (for outside window of automobile driving view) 100 rotations Silicon coating side (for inside window of automobile driving view) 1000 rotations Haze = Td / Tt × 100 (Td: scattered light transmittance,
Tt: total light transmittance) Haze measurement is made by Nippon Denshoku Co., Ltd. haze meter 1001.
Performed using DP.

(4) Weather resistance test I Using a Sunshine Weather Meter-WEL-SUN-HCH-B manufactured by Suga Test Instruments Co., Ltd. as a test piece (black panel temperature: 63 ° C., 18 minutes in 120 minutes under rain conditions). ) After exposure test, appearance, adhesion and yellowness change before and after the test (△
YI) was evaluated by the C light source reflection method. The yellowness (YI) was measured using a spectroscopic colorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd.

(5) Weather resistance test II The same evaluation as the weather resistance test I was carried out except that the exposure test of the test piece was conducted under the conditions of black panel temperature: 83 ° C. and no rainfall.

[Reference Example] (Coating used in the present invention) (1) Melamine-coated top coating (I) Hexamethoxymethylol melamine (Mitsui Cyanamid Cymel 350) 100 parts, polyethylene glycol (molecular weight 200) 25 parts, 45 parts of 1,4-butanediol, 118 parts of isopropyl alcohol, 244 parts of isobutanol, 7 parts of maleic acid, and 6 parts of 2,4-dihydroxybenzophenone were mixed to obtain a melamine coat paint (I).

(2) Melamine-coated primer paint (I) Monoethanolamine 0.5 part, isobutanol 99.
5 parts were mixed to obtain a melamine coat primer coating (I).

(3) Silicon Coat Primer Paint (a) Preparation of Silicon Coat Primer Paint (I) Methyl methacrylate (hereinafter abbreviated as MMA) was provided in a flask equipped with a reflux condenser and a stirrer and replaced with nitrogen.
65 parts, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) benzotriazole (hereinafter abbreviated as MEBT) 25 parts, 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as MPTMS) 10 parts, azo 0.16 parts of bisisobutyronitrile and 200 parts of 1,2-dimethoxyethane were added and mixed and dissolved. Then, the mixture was reacted in a nitrogen stream at 70 ° C. for 6 hours with stirring.
N-Hexane was added to the obtained reaction solution for reprecipitation purification,
The composition ratio of MMA / MEBT / MPTMS is 65 by weight.
Thus, 86 parts of a copolymer acrylic resin having a molar ratio of / 25/10 (85/10/5 in molar ratio) was obtained. The weight average molecular weight of the copolymer was 90,000. Obtained copolymer acrylic resin 9
Parts were dissolved in 60 parts of 4-methyl-2-pentanone and 30 parts of 2-butanol to obtain 99 parts of silicone coat primer coating (I).

(B) Silicone coat primer coating (I
Preparation of I) 470 parts of polymethylmethacrylate was added with ethyl acetate 28
It was dissolved in 00 parts and 3800 parts of diacetone alcohol, 2800 parts of isobutanol and 120 parts of 2-hydroxy-4-octoxybenzophenone were added to obtain a silicone-coated primer coating (II).

(C) Silicone coat primer coating (II
Preparation of I) 400 parts of ethyl cellosolve, 19 methyl methacrylate
While maintaining a mixture of 0 parts and 10 parts of γ-methacryloxypropyltrimethoxysilane at 75 ° C. under a nitrogen atmosphere, 1.0 part of benzoyl peroxide was added to ethyl cellosolve 20.
The solution dissolved in 0 part was added over 2 hours and kept at the same temperature for 6 hours. Then, ethyl cellosolve 1500
Parts, aluminum acetylacetonate 2 parts, 1,6-
2.4 parts of hexanediol and 20 parts of 2,4-dihydroxybenzophenone were added to obtain a silicone-coated primer coating (III). (4) Silicone coat top coating (a) Preparation of silicone coat top coating (I) 60 parts of γ-glycidoxypropyltrimethoxysilane,
80-85 by mixing 173 parts of methyltrimethoxysilane, 71 parts of colloidal silica (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.) and 190 parts of 0.1N acetic acid aqueous solution.
The mixture was refluxed at 0 ° C. for 2 hours for hydrolysis to obtain a ternary cohydrolyzate solution. To 450 parts of this solution, 42 parts of ethyl cellosolve, 0.8 part of ammonium perchlorate, 0.5 part of ammonium chloride
Parts were added to obtain a silicone coat top coating (I).

(B) Preparation of Silicone Coat Top Paint (II) While maintaining a mixed solution of 136 parts of methyltrimethoxysilane, 105 parts of isopropanol and 30 parts of isobutanol at 20 ° C., 44 parts of 0.1N hydrochloric acid was added in 1 hour. Dropped. Then, a leveling agent (SH-1 manufactured by Toray Silicone Co., Ltd.)
90) 1 part and a catalyst (a mixed solution of 20.7 parts of acetic acid and 1.08 parts of a 50% aqueous solution of choline) were added to obtain a silicone-coated top coating (II).

(C) Silicone coat top coating (III)
Methyltrimethoxysilane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) 12 in a 3 L three-necked flask equipped with a controlled reflux condenser.
70 parts and 100 parts of tetraethoxysilane (KBE-06 manufactured by Shin-Etsu Chemical Co., Ltd.) were added and colloidal silica (Cataloid S3 manufactured by Catalysts & Chemicals Co., Ltd.) was maintained at 20 ° C.
(0) Solid content concentration 30% by weight) A liquid obtained by mixing 240 parts of acetic acid with 800 parts was added dropwise over 7 minutes, and the temperature inside the flask was adjusted to 2
The temperature was kept at 7 ° C. and stirring was continued for 90 minutes. After further raising the temperature to 68 ° C. and stirring for 120 minutes, 1740 parts of isopropyl alcohol was added, and then the temperature inside the flask was 83 ° C.
Up to 200 with water and isopropanol mixture.
Silicone coating top coating (III) 215
I got 0 copies.

Example 1 (Melamine Coat) The melamine coat primer coating (I) obtained in Reference Example was used as a polycarbonate resin sheet (Panlite sheet PC-1111 manufactured by Teijin Chemicals Ltd .; thickness 5 mm × length 600 mm ×). Width 600mm, viscosity average molecular weight 25,000) coated on one side by spray method at 110 ℃
Was heated and dried in a hot air circulation type drying oven for 25 minutes to obtain a primer-treated polycarbonate resin sheet for melamine coat. The primer-treated polycarbonate resin sheet was coated with the melamine-coated top coating (I) obtained in Reference Example by a flow coating method, dried at room temperature for 15 minutes, and then hung in a hot air circulation oven at 130 ° C. for 60 minutes to be dried by heating. A melamine-coated polycarbonate resin sheet on one side was obtained. The abrasion resistance of the obtained melamine coat was ΔH = 2.5% at 100 rotations.

(Silicone coating) The silicone coating primer coating composition (I) obtained in Reference Example was applied to the surface not coated with melamine of the melamine-coated polycarbonate resin sheet obtained by the above method by a flow coating method, After drying at room temperature for 30 minutes, it was dried by heating in a hot air circulation type oven at 95 ° C. for 30 minutes to obtain a polycarbonate resin sheet coated with a silicon primer coat.

On the silicon primer coating layer of the obtained sheet, the silicon coat top coating material (I) obtained in Reference Example was applied by the flow coating method and dried at room temperature for 10 minutes.
Heat and dry for 60 minutes in a hot air circulation oven at 20 ° C,
A polycarbonate resin sheet having a melamine hard coat on one side and a silicon hard coat on the other side was obtained. The abrasion resistance of the silicon hard coat surface of this polycarbonate resin sheet is ΔH = 1.0% at 100 rotations and ΔH at 1000 rotations.
H = 3.5%.

To examine the weather resistance of the obtained polycarbonate resin sheet, the silicone hard coat side was 5000
Table 1 shows the results of the weather resistance test I for 1000 hours on the melamine-coated side.

Further, when the obtained polycarbonate resin sheet was cut out and a window frame was attached and it was used as a fixed triangular window glass in the rear seat of an automobile, it was a window glass excellent in appearance, abrasion resistance and weather resistance.

Example 2 Instead of the silicone coat primer coating (I) and the silicone coat top coating (I) in the (silicon coat) of Example 1, the silicone coat primer coating (II) obtained in Reference Example and A polycarbonate resin sheet having a melamine hard coat on one side and a silicon hard coat on the other side was obtained in the same manner as in Example 1 except that the silicon coat top coating (II) was used. The abrasion resistance of the silicon hard coat surface of this polycarbonate resin sheet is ΔH = 1.8 at 100 rotations.
%, At 1000 rotations, ΔH = 12%.

In order to examine the weather resistance of the obtained polycarbonate resin sheet, 5 was applied to the silicone hard coat side.
The results of the weathering test I for 000 hours are shown in Table 1.

Further, when the obtained polycarbonate resin sheet was cut out and a window frame was attached and it was used as a fixed triangular window glass in the rear seat of an automobile, it was a window glass excellent in appearance, abrasion resistance and weather resistance.

Example 3 Instead of the silicone coat primer coating (I) and the silicone coat top coating (I) in the (silicon coat) of Example 1, the silicone coat primer coating (III) obtained in Reference Example and A polycarbonate resin sheet having a melamine hard coat on one side and a silicone hard coat on the other side was obtained in the same manner as in Example 1 except that the silicon coat top coating (III) was used. The abrasion resistance of the silicone hard coat surface of this polycarbonate resin sheet is ΔH = 100 rotations
ΔH = 1.8% at 0.8% and 1000 rotations.

In order to examine the weather resistance of the obtained polycarbonate resin sheet, 5 was applied to the silicone hard coat side.
The results of the weathering test I for 000 hours are shown in Table 1.

Further, when the obtained polycarbonate resin sheet was cut out and a window frame was attached and it was used as a window glass on the driver's seat side of an automobile, it was a window glass excellent in appearance, abrasion resistance and weather resistance.

Comparative Example 1 The same test as in Example 1 was conducted on the polycarbonate resin sheet which was not coated with melamine or silicone. However, the weather resistance test I is 1
It was 000 hours. The results are shown in Table 1. This polycarbonate resin sheet was inferior in abrasion resistance and weather resistance and could not be used at all as a window glass for automobiles.

[0108]

[Table 1]

Example 4 Screen printing was performed on the melamine-coated surface of the polycarbonate resin sheet of the one-sided melamine hard coat and the other-sided silicon hard coat obtained in Example 1 using Cericol VG manufactured by Teikoku Ink Co., Ltd. It was performed (see FIG. 1).

In order to check the weather resistance of the polycarbonate resin sheet after screen printing, the weather resistance test II was 100
I went for 0 hours. The abrasion resistance, haze, and yellowness were measured on the non-printed portion. The results are shown in Table 2. As a result, no abnormal appearance such as peeling of the print or peeling of the melamine film occurred. Further, after the weather resistance test, no significant decrease was observed in the wear resistance, haze, and yellowness of the melamine coat.

Further, when the obtained polycarbonate resin sheet was cut out and a window frame was attached and it was used as a fixed triangular window glass in the back seat of an automobile, it was a window glass excellent in appearance, abrasion resistance and weather resistance.

[Comparative Example 2] The same test as in Example 4 except that screen printing was performed on the silicone hard-coated surface of the polycarbonate resin sheet having the one-sided melamine hard coat and the other-sided silicon hard coat in Example 4. I went. The results are shown in Table 2. As a result, repellency was found in the print, and all the print was peeled off after the weather resistance test, and this sheet could not be used as a window glass for automobiles.

[Comparative Example 3] The same test as in Example 4 was carried out except that one side of the polycarbonate resin sheet not subjected to the melamine coating and the silicon coating was screen-printed. The results are shown in Table 2. As a result, the printed part showed the same performance as that of Example 4, but the non-printed part was inferior in abrasion resistance, haze and yellowness after the weather resistance test, and this sheet can be used as an automobile window glass. Was not.

[0114]

[Table 2]

[0115]

INDUSTRIAL APPLICABILITY The polycarbonate resin window glass of the present invention is a window glass whose outer surface has a high degree of abrasion resistance and whose inner surface has excellent adhesiveness and workability of printing ink and abrasion resistance. Especially, it is preferably used as a window glass for vehicles, and its industrial effect is remarkable.

[Brief description of drawings]

FIG. 1 is a schematic perspective view showing an example of a resin window glass of the present invention.

[Explanation of symbols]

1. Inner surface of window glass; melamine coated surface 2. Outer surface of window glass; Silicon coated surface 3. Inner surface of window glass; halftone dot printed on melamine coated surface

Claims (11)

[Claims] 1. A window glass formed from a polycarbonate resin molded article, the outside surface of which is covered with a silicon hard coat and the inside surface of which is covered with a melamine coat. 2. The coated melamine coat is a condensate of hexamethoxymethylol melamine and one or a mixture of two or more glycols represented by the following formula.
The described polycarbonate resin window glass. [Chemical 1] [In formula, m and n show the integer of 2-30, p shows the integer of 1-5. ] 3. The polycarbonate resin window glass according to claim 1, wherein the coated melamine coat is a condensate of hexamethoxymethylolmelamine and a glycol represented by the following formula. [Chemical 2] [In formula, m shows the integer of 2-30. ] 4. The polycarbonate resin window glass according to claim 1, wherein the window glass is a vehicle window glass. 5. The polycarbonate resin window glass according to claim 4, wherein the vehicle window glass is an automobile window glass. 6. The silicon hard coat is ASTM D
The polycarbonate resin window glass according to claim 1, wherein a change in haze value is 5% or less as a result of a wear test by a Taber wear test according to 1044 (using a CS-10F wear wheel and 100 rotations under a load of 500 g). 7. The polycarbonate resin window glass according to claim 6, wherein the window glass is a window glass for a vehicle outside the driving field of view. 8. The silicon hard coat is ASTM D
The polycarbonate resin window glass according to claim 1, wherein a change in haze value is 2% or less as a result of a wear test by a Taber wear test according to 1044 (using a CS-10F wear wheel and 1,000 rotations under a load of 500 g). . 9. The polycarbonate resin window glass according to claim 8, wherein the window glass is a window glass for an automobile in a driving field of view. 10. The melamine coat is ASTM D10.
The change in haze value is within a range of 0.5% or more and 5% or less as a result of a wear test by a Taber wear test according to No. 44 (using a CS-10F wear wheel, 100 rotations under a load of 500 g). Polycarbonate resin window glass. 11. The polycarbonate resin window glass according to claim 1, wherein the inner surface is printed.