JP2001179872A - Coated molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated molded article wherein a cured matter layer excellent in abrasion resistance is formed on the surface of a synthetic resin base material. SOLUTION: A cured matter layer comprising a coating composition containing a polyfunctional compound having more than two active energy beam curable polymerizable functional groups and a polymer containing a methyl methacrylate polymerizing unit and not containing polysilazane and a cured matter layer comprising a coating composition containing polysilazane are formed on the surface of a synthetic resin base material in this order.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated molded article having a hardened layer having excellent abrasion resistance, scratch resistance and weather resistance on the surface of a synthetic resin substrate. More specifically, the inner layer in contact with the outermost layer of the cured layer is a cured layer derived from an active energy ray (especially ultraviolet) curable coating composition, and the outermost layer is a cured layer of a coating composition containing polysilazane. And a coated molded article.

[0002]

2. Description of the Related Art In recent years, a synthetic resin (such as an aromatic polycarbonate resin) has been used as a transparent material in place of inorganic glass (hereinafter, also simply referred to as glass). But,
Synthetic resins have the disadvantage that the surface hardness is not sufficient to be used in place of glass, and they are easily damaged or worn.
Therefore, the following attempts have been made to improve the scratch resistance and abrasion resistance of the aromatic polycarbonate resin.

(1) A curable compound having two or more polymerizable functional groups such as an acryloyl group in a molecule is applied to a substrate,
A method of curing with heat or active energy rays (such as ultraviolet rays) (one of the most common methods). (2) A method in which polysilazane is applied to a substrate and cured by heat.

However, in the above method (1), since the cured product is composed only of an organic substance, there is a limit in the expression level of the scratch resistance of the surface. In addition, the method (2) has a drawback that the cured product is liable to peel off or crack due to poor adhesion between the cured film and the substrate.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coated molded article having a surface having high abrasion resistance almost equivalent to that of glass and having excellent surface properties and good appearance.

[0006]

Means for Solving the Problems The present inventors have improved the wettability with a base material by adding a polymer containing polymerized units of methyl methacrylate to a coating composition (A), thereby facilitating coating. I found out. The polymer containing the polymerized unit of methyl methacrylate has a high affinity for the substrate and improves the adhesion to the substrate, so that sufficient adhesion can be ensured even if the drying time is short. Thereby, continuous coating on the base material becomes possible, and the productivity can be improved.

That is, the present invention relates to a coated molded article having a synthetic resin base material and two or more hardened material layers formed on part or all of the surface of the synthetic resin base material. A coated molded article characterized in that the inner layer in contact with the outer layer is a cured layer of the following coating composition (A), and the outermost layer is a cured layer of the following coating composition (B). Coating composition (A): a polymer containing polymerized units of a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and methyl methacrylate [hereinafter, this polymer is referred to as polymer (a). Abbreviated. And a coating composition containing no polysilazane. Coating composition (B): a coating composition containing polysilazane.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The cured product layer in the present invention has at least two layers, a cured product layer forming an outermost layer and a cured product layer forming an inner layer directly in contact with the outermost layer. The cured product layer preferably comprises only two layers, an outermost layer and an inner layer. The inner layer is a cured product layer of a coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and a polymer (a) and containing no polysilazane.

A third layer made of a thermoplastic resin (such as a thermoplastic acrylic resin) or an adhesive exists between the synthetic resin substrate (hereinafter, also simply referred to as a substrate) and the inner layer. Is also good. If a third layer is present, it preferably has sufficient adhesion to the substrate and the inner layer.

The wear resistance of the inner layer, that is, JIS-R3
The haze value (difference between the haze value after the test and the haze value before the test) after 100 times of the abrasion resistance test in 212 was 15
%, Particularly preferably 10% or less, particularly preferably 5% or less.

In the present specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to expressions such as (meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate. In the present invention, among these groups and compounds, more preferred are those having an acryloyl group, for example, an acryloyloxy group, acrylic acid, acrylate and the like.

The polyfunctional compound having two or more active energy ray-curable polymerizable functional groups in the coating composition (A) is described in JP-A-11-240103 [001].
The compounds described in [5] to [0096] are preferred. The polyfunctional compound may be one kind of polyfunctional compound, or plural kinds of compounds may be used. In the case of a plurality of compounds, they may be different compounds in the same category, or may be compounds in different categories.

The active energy ray-curable polymerizable functional group in the polyfunctional compound is an α, β-unsaturated group such as a (meth) acryloyl group, a vinyl group, an allyl group or a group having the same. It is preferably a (meth) acryloyl group. In addition, polyfunctionality means having two or more of these polymerizable functional groups. That is, as the polyfunctional compound, a compound having two or more polymerizable functional groups selected from an acryloyl group and a methacryloyl group is preferable, and among them, a compound having two or more acryloyl groups which are more easily polymerized by ultraviolet rays. Is more preferable. In addition, the ratio of these preferable polyfunctional compounds is preferably 30% by mass or more, and particularly preferably 50% by mass or more based on all the polyfunctional compounds.

Further, a monofunctional compound having one polymerizable functional group polymerizable by an active energy ray (hereinafter, referred to as a monofunctional compound) may be contained together with the polyfunctional compound. The monofunctional compound may have a functional group such as a hydroxyl group and an epoxy group. Preferred monofunctional compounds are (meth) acrylates.

As the monofunctional compound, methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like can be mentioned.

When the monofunctional compound is used in the coating composition (A), the ratio of the monofunctional compound to the total of the polyfunctional compound and the monofunctional compound is not particularly limited, but may be 60 mass%. % Or less, preferably 3% or less.
0 mass% or less is preferable. If the proportion of the monofunctional compound is too large, the hardness of the cured product layer may decrease and the abrasion resistance may be insufficient.

The coating composition (A) contains a polymer (a). Preferred examples of the polymer (a) include a homopolymer of methyl methacrylate, a copolymer of methyl methacrylate and another copolymerizable monomer, or a compound having its terminal modified.

The glass transition temperature of the polymer (a) is preferably at least 90 ° C., particularly preferably at least 95 ° C. The coating composition (A) containing the polymer (a) has improved adhesion to a substrate and is easy to apply. The molecular weight of the polymer (a) is preferably 5,000 or more, particularly preferably 10,000 or more.

The proportion of the polymer (a) in the coating composition (A) is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 3% by mass.
0% by mass is preferred. If the amount of the polymer (a) is too small, the adhesion to the substrate becomes insufficient, and the coating becomes difficult. On the other hand, if the amount is too large, the hardness of the cured product layer of the coating composition (A) decreases, and the abrasion resistance may be insufficient.

As the polymer (a), a commercially available polymer can be used. As a commercially available product, "Dianal" (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) is preferable. Among them, a thermoplastic acrylic resin "Dianal LR248 (glass transition temperature: 102 ° C., molecular weight: about 150,000, solid content: 30% by mass)" or "Dianal LR269" is preferred.

In order to cure the polyfunctional compound, the coating composition (A) usually contains a photopolymerization initiator. Known photopolymerization initiators can be used, and commercially available photopolymerization initiators are particularly preferable. A plurality of photopolymerization initiators may be used in the cured product layer.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.),
Examples include an acylphosphine oxide-based photopolymerization initiator, a diacylphosphine oxide-based photopolymerization initiator, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide-based photopolymerization initiator and a diacylphosphine oxide-based photopolymerization initiator is preferred. Further, the photopolymerization initiator may be used in combination with a photosensitizer such as an amine.

Specific examples of the photopolymerization initiator include the following compounds. 2,2-dichloro-4'-
Phenoxyacetophenone, 4'-t-butyl-2,2
-Dichloroacetophenone, 4'-t-butyl-2,
2,2-trichloroacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methyl-propan-1-one, -Hydroxycyclohexylphenyl ketone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, 4-hydroxybenzophenone, acrylate Benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone,
9,10-phenanthrenequinone, camphorquinone,
Dibenzosuberone, 2-ethylanthraquinone, 1,3
-Phenylenebis (4-ethylbenzoyl), α-acyloxime esters (eg, 2-propionyloxyimino-1-phenylpropan-1-one), methyl phenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

The addition amount of the photopolymerization initiator in the coating composition (A) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the curable component (total of the polyfunctional compound and the monofunctional compound). And particularly preferably 0.1 to 10 parts by mass.

In the coating composition (A), a solvent and various functional additives can be added in addition to the above basic components. The solvent is usually an essential component, and the solvent is used unless the polyfunctional compound is a liquid having a particularly low viscosity. As the solvent, a solvent usually used for a coating composition containing a polyfunctional compound as a curing component can be used. Further, it is preferable to select and use an appropriate solvent depending on the type of the base material.

Specifically, lower alcohols, ketones, ethers, cellosolves, esters, n-acetic acid
Butyl, diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons and the like. When an aromatic polycarbonate resin having low solvent resistance is used for the substrate, lower alcohols, cellosolves, esters, a mixture thereof, and the like are preferable.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the drying temperature conditions, and the like. Usually 10 to the curable component in the composition
The mass is preferably 0 times or less, particularly preferably 0.1 to 50 times.

Functional compounding agents include ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, anti-settling agents, pigments (organic color pigments, inorganic pigments) ), Coloring dyes, infrared absorbers, fluorescent brighteners, dispersants, antifouling agents, rust inhibitors, conductive fine particles, antistatic agents, antifogging agents, coupling agents, and curing catalysts. One or more functional ingredients selected.

The active energy ray for curing the coating composition (A) is not particularly limited, but is preferably an ultraviolet ray. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used as the ultraviolet light source.

The thickness of the cured product layer formed using the coating composition (A) is preferably from 1 to 50 μm, more preferably from 2 to 30 μm.
μm is preferred. When the thickness is more than 50 μm, curing by active energy rays becomes insufficient and the adhesion to the substrate is easily damaged. When the thickness is less than 1 μm, the abrasion resistance of this layer may be insufficient. There is a possibility that the abrasion resistance and abrasion resistance of the outermost layer cannot be sufficiently exhibited.

The coating composition (B) for forming the outermost layer contains polysilazane. As this polysilazane, JP-A-11-240103, [0097] to [0114]
Are preferred. In particular, perhydropolysilazane is preferred from the viewpoint of low firing temperature and denseness of a cured film after firing. Note that a cured product in which polysilazane is sufficiently cured is silica containing almost no nitrogen element.

The coating composition (B) usually contains a solvent that dissolves polysilazane. Solvents for dissolving polysilazane include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones and the like. Specifically, the following are mentioned.

Pentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene,
Hydrocarbons such as ethylbenzene. Methylene chloride, chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane,
Halogenated hydrocarbons such as tetrachloroethane. Ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran and tetrahydropyran. Esters such as n-butyl acetate and diethylene glycol monoacetate.

The solvent may be used by mixing a plurality of types of solvents in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent to be used can be appropriately selected depending on the coating method to be employed, the structure of polysilazane, the average molecular weight, and the like.

The coating composition (B) may contain various functional additives in addition to the above basic components. Examples of the functional compounding agent include the functional compounding agents described above.

In order to cure the polysilazane into silica, heating which is usually called firing is performed. Since the substrate is a synthetic resin, the firing temperature is limited. For example, when an aromatic polycarbonate resin is used as the base material, the firing temperature is preferably set to 180 ° C. or lower.

In order to cure polysilazane at a low temperature, it is preferable to use a catalyst, and curing can be performed at room temperature depending on the type and amount of the catalyst. The curing is preferably performed in an atmosphere in which oxygen is present, such as in air.

As the catalyst, fine particles of a metal such as gold, silver, palladium, platinum and nickel (JP-A-7-19698)
No. 6) or a carboxylic acid complex thereof (Japanese Unexamined Patent Publication No.
93275) and the like. Further, a method of contacting a catalyst solution (an aqueous amine solution or the like) or exposing it to a vapor for a certain period of time instead of adding the catalyst to the coating composition (B) (Japanese Unexamined Patent Publication No. Hei 9-31333) may also be mentioned. Can be

The thickness of the cured product layer of the coating composition (B) is
It is preferably from 0.05 to 10 μm, particularly preferably from 0.1 to 3 μm. If the thickness is more than 10 μm, further improvement in surface characteristics such as scratch resistance cannot be expected, and the layer becomes brittle, and cracks and the like are liable to occur even by slight deformation. If it is less than 0.05 μm, abrasion resistance and scratch resistance may not be sufficiently exhibited.

The two types of coating compositions (A) described above,
Various methods can be adopted as a method for forming the two cured product layers formed by using (B). When the coating compositions (A) and (B) contain a solvent, the coating composition is dried after removing the solvent, and then cured. The coating composition (A) is preferably cured by irradiating ultraviolet rays or the like, and the coating composition (B) is cured by heating, leaving it at room temperature, or exposing it to the vapor of a curing catalyst solution. Is preferred.

The means for applying the coating compositions (A) and (B) is not particularly limited, and examples thereof include a dip method, a flow coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, and a blade. Known methods such as a coating method, an air knife coating method, a spin coating method, a slit coating method, and a microgravure coating method can be employed.

The timing of curing of the coating composition (A) and application to curing of the coating composition (B) are as follows. 1) A method of applying the coating composition (A), irradiating a sufficient amount of active energy rays to complete the curing, and then applying the coating composition (B) to the surface to cure the composition. . 2) After coating the coating composition (A) and coating the coating composition (B) on its surface, the coating composition (A) is cured by irradiating a sufficient amount of active energy rays, Coating composition (B)
Curing by leaving at room temperature or exposing to the vapor of a catalyst solution. 3) After applying the coating composition (A), the minimum active energy ray (to about 300 mJ / cm ² ) which becomes dry to the touch is obtained.
Is irradiated once to form a partially cured layer of the coating composition (A), and then the coating composition (B) is applied to the surface thereof, and then the coating composition (A) is sufficiently coated. A method in which the coating composition (B) is cured by irradiating it with an amount of active energy rays and leaving the coating composition (B) at room temperature or exposing it to vapor of a catalyst solution.

In order to increase the adhesion between the two cured product layers, the above method 2) or 3) is preferable. However,
In the case of 2), if the coating composition (B) is applied by a dipping method, the components of the uncured product of the coating composition (A) may contaminate the dip solution of the coating composition (B).

In the present invention, two or more cured layers are formed on both sides or one side of the substrate. Since the coated molded product of the present invention has a surface property such as abrasion resistance and scratch resistance which is almost equal to that of glass, it has been used in various applications such as a window material for vehicles in which glass has been conventionally used. Can be used for applications.

Various synthetic resins can be used as the base material. For example, a synthetic resin such as an aromatic polycarbonate-based resin, a polymethyl methacrylate-based resin (acrylic resin), an aromatic polyester-based resin, and a polystyrene-based resin can be used as the base material. In particular, a substrate made of an aromatic polycarbonate resin is preferable.

The substrate may be a molded one, for example, a sheet-like substrate such as a flat plate or a corrugated sheet, a film-like substrate, a substrate molded into various shapes, or at least a surface layer composed of various synthetic resins. And the like. In particular, a film-like or flat-plate-like substrate is preferably used. The thickness of the substrate can be appropriately selected depending on the application,
m to 10 mm, and particularly preferably 20 to 400 μm when used in a continuous film coating apparatus.

[0050]

EXAMPLES The present invention is described by way of Synthesis Examples (Examples 1 and 2), Examples (Examples 3 to 18, 21, 22) and Comparative Examples (Examples 19, 20, 2).
A description will be given based on (3, 24). The measurement and evaluation of various physical properties were performed by the following methods, and the results are shown in Table 1.

[Substrate] An aromatic polycarbonate resin film (150 mm × 300 mm) having a thickness of 380 μm.

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method in No. 2, a haze was measured with a haze meter after a 500 g weight was combined with each of two CS-10F abrasion wheels and rotated 500 times. The haze was measured at four points of the wear cycle orbit, and the average value was calculated. The initial haze indicates the value (%) of the haze before the test, and the abrasion resistance indicates the value (%) of (haze after the test)-(haze before the test).

[Abrasion resistance after moisture resistance test]
After holding for 2 weeks at a temperature of 95 ° C. and a relative humidity of 95%, the abrasion resistance was evaluated.

[Adhesion] 11 cuts were made on the sample at intervals of 1 mm each in the vertical and horizontal directions with a razor blade to make 100 grids. Then, after closely attaching a commercially available cellophane tape, the number of squares (m) of the coating remaining without peeling when peeled sharply in the forward direction by 90 degrees is m / 100.
Expressed by

[Adhesion after Moisture Resistance Test]
After holding for 2 weeks under the condition of a relative humidity of 95%, the above-mentioned adhesion was evaluated.

[Appearance] The number of foreign substances having a diameter of 0.5 mmφ or more within a range of 30 cm × 30 cm of the sample is 4 or less “○”, 5 to 6 foreign substances “△”, and 7 or more “×” was assigned.

[Weather Resistance] Using a sunshine weather meter, the sample was exposed for 3000 hours at a black panel temperature of 63 ° C. in a cycle of 12 minutes of rainfall and 48 minutes of drying, and the appearance was evaluated.

[Example 1] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by mass, average particle size: 11 nm)
By adding 5 parts by mass of 3-mercaptopropyltrimethoxysilane and 3.0 parts by mass of 0.1 mol / L hydrochloric acid to 100 parts by mass, heating and stirring at 100 ° C. for 6 hours, and then aging at room temperature for 12 hours. To obtain a mercaptosilane-modified colloidal silica dispersion.

[Example 2] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by mass, average particle size: 11 nm)
5 parts by mass of 3-acryloyloxypropyltrimethoxysilane and 3.0 mol of 0.1 mol / L hydrochloric acid were added to 100 parts by mass.
Then, the mixture was heated and stirred at 100 ° C. for 6 hours.
By aging at room temperature for 2 hours, an acrylsilane-modified colloidal silica dispersion was obtained.

Example 3 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 4 g of isopropyl alcohol, 16 g of butyl acetate, 300 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
[4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4 -[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl]
-4,6-bis (2,4-dimethylphenyl) -1,
1700 mg of a mixture of 3,5-triazine and N-
Methyl-4-methacryloyloxy-2,2,6,6-
400 mg of tetramethylpiperidine, "Dianal
6.5 g of “LR248” (hereinafter referred to as LR) was added and dissolved.

Subsequently, 10 g of urethane acrylate (containing an average of 15 acryloyl groups per molecule) which is a reaction product of dipentaerythritol polyacrylate having a hydroxyl group and partially nullated hexamethylene diisocyanate, and tris (2-acryloyloxyethyl) ) 10 g of triacrylate of isocyanurate-caprolactone 1 mol adduct was added, and the mixture was stirred at room temperature for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 1). .

The coating liquid 1 was applied to the base material using a bar coater (wet thickness: 14 μm; hereinafter, the thickness is referred to as “wet thickness”) and kept in a hot-air circulating oven at 90 ° C. for 1.5 minutes. did. Then, in an air atmosphere, using a high-pressure mercury lamp, 2000 mJ / cm ² (wavelength 300 to 390 n)
m-region ultraviolet integrated energy amount, the same applies hereinafter. ) Was applied to form a cured product layer having a thickness of 7 μm.

Next, a xylene solution of perhydropolysilazane curable at a low temperature (solid content: 20% by mass,
Tonen Co., Ltd., product name “L110” (hereinafter referred to as coating liquid 2) is coated (3 μm) using a bar coater,
After removing the solvent by holding in a hot air circulating oven for 2 minutes in an air atmosphere, 2000 mJ /
Irradiated with ultraviolet light of cm ² . Subsequently, the outermost layer was sufficiently hardened by holding in a hot air circulating oven at 100 ° C. for 120 minutes. IR analysis confirmed that the outermost layer was almost complete silica. Thus, a cured product layer having a total thickness of 7.6 μm was formed on the surface of the base material. The measurement was performed using this sample.

On the other hand, when the abrasion resistance of the surface of a sample in which the cured product layer of only the coating liquid 1 was formed on the surface of the substrate was evaluated, the abrasion resistance after 100 rotations was 3.0%. Was.

Example 4 The sample preparation method was changed as follows. In Example 3, coating liquid 1 was applied, and 90 ° C.
Example 3 except that after holding for 1.5 minutes in a hot air circulation oven, 150 mJ / cm ² ultraviolet rays were irradiated using a high-pressure mercury lamp in an air atmosphere to form a 7 μm-thick partially cured layer. I did the same. The measurement was performed using this sample.

Example 5 The sample preparation method was changed as follows. Example 4 was repeated in the same manner as in Example 4 except that curing was performed in an environment of 23 ° C. and a relative humidity of 55% for one day, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

Example 6 The sample preparation method was changed as follows. In Example 3, except that the coating liquid 2 was changed to a catalyst-free xylene solution of perhydropolysilazane (solid content concentration: 20% by mass, trade name “V110” manufactured by Tonen Corporation) (hereinafter referred to as coating liquid 3). Was the same as in Example 3. The measurement was performed using this sample.

[Example 7] The sample preparation method was changed as follows. In Example 6, the coating liquid 1 was coated and held in a hot air circulating oven at 90 ° C. for 1.5 minutes.
150 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere
Was applied to form a partially cured layer having a thickness of 7 μm. Then, instead of keeping the coating liquid 3 in a hot air circulating oven at 100 ° C. for 120 minutes,
The procedure was the same as in Example 6, except that curing was carried out for one day in an environment at 55 ° C. and a relative humidity of 55%. The measurement was performed using this sample.

Example 8 The sample preparation method was changed as follows. In Example 7, lastly 23 ° C. and 55% relative humidity
%, Except that it was kept on a bath of a 3% aqueous solution of triethylamine kept at 25 ° C. for 2 minutes instead of being cured in a 1% environment for 1 day. The measurement was performed using this sample.

Example 9 The sample preparation method was changed as follows.

In Example 5, instead of the coating liquid 2, a xylene solution of polysilazane in which a part of hydrogen atoms bonded to silicon atoms of perhydropolysilazane was substituted with a methyl group (solid content: 20% by mass, Product name "N" manufactured by Tonensha
L710 ”) (hereinafter referred to as coating liquid 4), except that Example 5 was used. The measurement was performed using this sample.

Example 10 The sample preparation method was changed as follows. In Example 5, instead of the coating liquid 2, a xylene solution of polysilazane in which a part of hydrogen atoms bonded to silicon atoms of perhydropolysilazane was substituted with a trimethylsilyl group (solid content concentration: 20% by mass, manufactured by Tonensha Co., Ltd.)
The procedure was the same as Example 5 except that the trade name "N310") (hereinafter referred to as coating liquid 5) was used. The measurement was performed using this sample.

[Example 11] 4 g of isopropyl alcohol
Was used instead of 4.3 g, butyl acetate was used instead of 16 g and 17.2 g, and LR was used instead of 6.5 g and 3.3 g.
Except for using, a coating composition (hereinafter, referred to as coating liquid 6) was obtained in the same manner as in Step A of Example 3. The same procedure as in Example 3 was carried out except that the coating liquid 6 was used instead of the coating liquid 1. The measurement was performed using this sample. On the other hand, when the abrasion resistance of the surface of the sample in which the cured product layer of only the coating liquid 6 was formed on the surface of the substrate was evaluated, the abrasion resistance after 100 rotations was 2.6.
%Met.

[Example 12] The sample preparation method was changed as follows. In Example 11, coating liquid 6 was applied and
It was kept in a hot air circulating oven at 0 ° C. for 1.5 minutes, and irradiated with ultraviolet rays of 150 mJ / cm ² in an air atmosphere using a high-pressure mercury lamp to form a 7 μm-thick partially cured product layer. Then, it carried out similarly to Example 11 except having cured at 23 degreeC and the environment of 55% of relative humidity for 1 day instead of keeping it for 120 minutes in a 100 degreeC hot-air circulation oven finally. The measurement was performed using this sample.

Example 13 The sample adjustment method was changed as follows. Example 12 was repeated except that the coating liquid 3 was used instead of the coating liquid 2. The measurement was performed using this sample.

Example 14 The sample adjustment method was changed as follows. The procedure of Example 13 was repeated except that the sample was kept in a 3% aqueous solution of triethylamine at 25 ° C. for 2 minutes instead of being cured for 1 day in an environment of 23 ° C. and 55% relative humidity. I did the same. The measurement was performed using this sample.

Example 15 The method of adjusting the sample was changed as follows. In Example 12, it carried out similarly to Example 12 except having used the coating liquid 4 instead of the coating liquid 2. The measurement was performed using this sample.

Example 16 The sample adjustment method was changed as follows. In Example 12, it carried out similarly to Example 12 except having used the coating liquid 5 instead of the coating liquid 2. The measurement was performed using this sample.

Example 17 To the same amount of the coating liquid 1 obtained in the same manner as in the step A of Example 3, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added. After stirring for a minute, a coating composition (hereinafter referred to as coating liquid 7) was obtained. Example 7 using coating liquid 7 instead of coating liquid 1
A sample was prepared in the same manner as described above. The measurement was performed using this sample. On the other hand, when the abrasion resistance of the surface of the sample in which the cured product layer of only the coating liquid 7 was formed on the surface of the substrate was evaluated, the abrasion resistance after 100 rotations was 1.9%.

Example 18 To the same amount of the coating liquid 1 obtained in the same manner as in Step A of Example 3, 30.3 g of the acrylsilane-modified colloidal silica dispersion synthesized in Example 2 was added. After stirring for a minute, the coating composition (hereinafter referred to as coating liquid 8)
I got A sample was prepared in the same manner as in Example 7, except that the coating liquid 8 was used instead of the coating liquid 1. The measurement was performed using this sample. On the other hand, when the abrasion resistance of the surface of a sample in which the cured product layer of only the coating liquid 8 was formed on the surface of the substrate was evaluated, the abrasion resistance after 100 rotations was 1.7%.

[Example 19] Coating was carried out in the same manner as in Step A of Example 3 except that LR was not used, 4.6 g of isopropyl alcohol was used instead of 4 g, and 18.2 g of butyl acetate was used instead of 16 g. Composition (hereinafter, referred to as coating liquid 9)
I got A sample was prepared in the same manner as in Example 7, except that the coating liquid 9 was used instead of the coating liquid 1. The measurement was performed using this sample. On the other hand, when the abrasion resistance of the surface of the sample in which the cured product layer of only the coating liquid 9 was formed on the surface of the substrate was evaluated, the abrasion resistance after 100 rotations was 2.1%.

Example 20 The sample adjustment method was changed as follows. Example 19 was the same as Example 19 except that the drying time after the application of the coating liquid 9 was changed to 5 minutes instead of 1.5 minutes.
Same as. The measurement was performed using this sample.

Example 21 The sample adjustment method was changed as follows. Example 13 was repeated except that the substrate was a polymethyl methacrylate resin plate (2 mm thick). The measurement was performed using this sample.

Example 22 The sample adjustment method was changed as follows. Except that the base material was made of polyethylene terephthalate resin film (thickness: 100 μm) with easy adhesion treatment
Same as Example 13. The measurement was performed using this sample.

[Example 23] Coating liquid 1 was applied to a substrate (14 µm) using a bar coater and kept in a hot-air circulating oven at 90 ° C for 1.5 minutes. Then, ultraviolet rays of 2000 mJ / cm ² were irradiated using a high-pressure mercury lamp in an air atmosphere to form a cured layer having a thickness of 7 μm. The measurement was performed using this sample.

[Example 24] A dibutyl ether solution of low-temperature curable perhydropolysilazane (solid content: 20% by mass, trade name “L120”, manufactured by Tonen Co., Ltd.) was coated on a substrate (3 μm) using a bar coater. Then, the mixture was kept in a hot-air circulating oven at 90 ° C. for 2 minutes to remove the solvent, and then irradiated with ultraviolet rays of 2000 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere. Then, in a hot air circulation oven at 100 ° C,
By holding for 20 minutes, a cured product layer was formed. The measurement was performed using this sample.

[0087]

[Table 1]

A sample whose inner layer contains the polymer (a) (Example 3)
To 18) are samples containing no polymer (a) (Example 1).
As compared with 9), the adhesiveness after the moisture resistance test is excellent. Further, as compared with the sample in which only the inner layer is formed (Example 23), it is excellent in abrasion resistance, abrasion resistance after a moisture resistance test and weather resistance. Furthermore, as compared with the sample in which only the outermost layer is formed (Example 24), it is excellent in abrasion resistance, abrasion resistance after a moisture resistance test, adhesion and weather resistance.

The results of Example 20 indicate that the drying time after application of the coating composition (A) was sufficiently ensured, and that the adhesion after the moisture resistance test was improved. Example 21
And from Example 22, even when the substrate is a polymethyl methacrylate resin or a polyethylene terephthalate resin,
It can be seen that performance equivalent to that of the aromatic polycarbonate resin is exhibited.

[0090]

The coated molded article of the present invention is an excellent coated molded article having various functions and high scratch resistance. Also,
By adding the polymer (a) to the inner layer, the adhesion between the substrate and the inner layer is improved, so that sufficient adhesion can be ensured even if the drying time is short. Thereby, continuous coating on the base material is possible, and productivity can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C08J 7/04 CFD C08J 7/04 CFDL CFDM C08L 101: 00 C08L 101: 00 (72) Inventor Shimoda Hiroshi 1150 Hazawa-machi, Kanagawa-ku, Kanagawa-ku, Kanagawa Prefecture F-term (reference) 4A006 AB24 AB39 AB65 AB67 BA02 BA03 DA04 EA03 4F100 AK25B AK25J AK45 AK52C AK52K AL01B AL05B AL05C AT00A BA03 BA07B07B10 JBABBABBABBABBAB 4J038 AA011 CG141 CH031 FA111 HA441 JC35 KA03 KA06 MA13 NA01 NA11 PA17 PA19 PB02 PB08 PC08

Claims (4)

[Claims] 1. A coated molded article having a synthetic resin base material and two or more hardened material layers formed on a part or the whole of the surface of the synthetic resin base material, in contact with the outermost layer among the hardened material layers. A coated molded article, wherein the inner layer is a cured product layer of the following coating composition (A), and the outermost layer is a cured product layer of the following coating composition (B). Coating composition (A): a coating composition containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and a polymer containing polymerized units of methyl methacrylate and containing no polysilazane. Coating composition (B): a coating composition containing polysilazane. 2. The coated molded article according to claim 1, wherein the glass transition temperature of the polymer is 90 ° C. or higher. 3. The coated molded article according to claim 1, wherein the proportion of the polymer in the coating composition (A) is 0.1 to 50% by mass. 4. The coated molded article according to claim 1, wherein the polysilazane is perhydropolysilazane.