JP2002192647A - Plastic product and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic product having an antireflection layer particularly excellent in abrasion resistance and a method for producing the same. SOLUTION: A cured material layer of a coating composition (A) containing a compound (a) having one or more active energy ray-curable polymerizable functional groups and polysilazane is formed on at least one surface of a plastic substrate. Then, an antireflection layer is formed on the surface. The antireflection layer is preferably a light-absorbing antireflection layer composed of at least two layers of a high refractive index layer and a low refractive index layer in order from the substrate side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic article having an anti-reflection layer, which is excellent in abrasion resistance and anti-reflection property, and a method for producing the same.

[0002]

2. Description of the Related Art Products having an anti-reflection property on the surface of a plastic substrate are provided in the form of films and sheets, for window materials for construction and vehicles, various displays (CRTs, plasma displays, liquid crystal displays, etc.). Or, it is used as a protective plate, a mirror, goggles, or the like.

[0003] As a method of imparting antireflection properties to the surface of a plastic substrate, a method of applying an antireflection coating to the surface of the substrate, a method of forming a metal deposition film, or an active energy ray-curable resin or a thermosetting resin A method of forming a low-refractive-index antireflection layer on the surface of a cured resin layer is exemplified.

Among these methods, a method of forming an antireflection layer having a low refractive index on the surface of a cured material layer of an active energy ray-curable resin or a thermosetting resin is known. This is an effective method for imparting wear properties. As a method for forming a low-refractive-index antireflection layer made of an inorganic material having excellent durability, a gas layer method such as sputtering, ion plating, or vapor deposition, or a sol-gel method is employed.

However, the gas layer method requires a complicated apparatus and the productivity is not sufficient, and the sol-gel method cures at a high temperature, so that the plastic substrate has a problem in heat resistance. Further, the performance of conventional plastic products having an anti-reflection layer has not been sufficient, particularly in applications requiring surface abrasion resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a plastic article having an antireflection layer having particularly excellent wear resistance and a method for producing the same.

[0007]

Means for Solving the Problems To achieve the above object, one of the present invention is to form a transparent cured product layer and an antireflection layer on at least one surface of a plastic substrate in order from the substrate side. Wherein the transparent cured product layer is a cured product layer of a coating composition (A) containing a compound (a) having at least one active energy ray-curable polymerizable functional group and polysilazane. A plastic product characterized in that:

In the above invention, the anti-reflection layer comprises:
It is preferable that the light-absorbing anti-reflection layer is composed of at least two layers of a high refractive index layer and a low refractive index layer in order from the substrate side. According to this aspect, a plastic product having excellent scratch resistance, sufficient low reflectivity in a wide wavelength range, appropriate visible light absorption for securing high contrast, and low cost and excellent productivity is obtained. Can be

Preferably, the polysilazane is a perhydropolysilazane.

The absolute value of the difference between the refractive index of the plastic substrate and the refractive index of the cured product of the coating composition (A) is 0.1.
It is preferably 15 or less. According to this aspect, it is possible to improve the appearance problem due to the occurrence of color unevenness.

Further, it is preferable that the plastic substrate is a plastic substrate selected from the group consisting of an aromatic polycarbonate resin, a polymethyl methacrylate resin or a polyethylene terephthalate resin.

Another aspect of the present invention is the method for producing a plastic product, wherein the compound (a) having at least one active energy ray-curable polymerizable functional group on at least one surface of the plastic substrate. A method for producing a plastic product, comprising: forming a cured product layer of a coating composition (A) containing a polysilazane and an antireflection layer on the surface of the cured product layer.

In the above invention, a coating composition (A) containing a compound (a) having at least one active energy ray-curable polymerizable functional group and polysilazane on at least one surface of a plastic substrate. After coating, curing of the compound (a) by irradiation with active energy rays and curing of the polysilazane are performed in any order or simultaneously to form a cured layer of the coating composition (A). Further, it is preferable to form an antireflection layer on the surface of the cured product layer.

According to the present invention, it is possible to provide a plastic product having an antireflection layer having particularly excellent wear resistance and a method for producing the same.

The antireflection layer is not directly laminated on a relatively soft plastic substrate, but maintains high adhesion on a cured layer of the hard coating composition (A) having high scratch resistance. It is considered that since the antireflection layer is displaced by external force, the displacement of the antireflection layer is reduced and the wear resistance is excellent.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic product of the present invention comprises a plastic substrate, a transparent cured layer formed on at least one surface thereof, and an antireflection layer formed on the surface. The transparent cured product layer may be composed of two or more different types of cured product layers,
In general, it is preferable to consist of one layer. In addition, a third layer made of a synthetic resin or the like (for example, a layer of a thermoplastic resin such as a thermoplastic acrylic resin or a layer of an adhesive) exists between the plastic substrate and the transparent cured material layer. Good. In this case, the third layer preferably has sufficient adhesion to the plastic substrate and the transparent cured product layer, and the absolute value of the difference between the refractive index of the layer and the refractive index of the plastic substrate is 0.1.
It is preferably 15 or less.

As the plastic substrate, various transparent synthetic resins can be used. For example, transparent synthetic resins such as aromatic polycarbonate resin, polymethyl methacrylate resin (acrylic resin), polyethylene terephthalate resin, and polystyrene resin are exemplified. In the present invention, an aromatic polycarbonate resin, a polymethyl methacrylate resin or a polyethylene terephthalate resin is preferred from the viewpoint of compatibility with a solvent.

The transparent cured layer is a coating composition containing a compound (a) having at least one active energy ray-curable polymerizable functional group (hereinafter simply referred to as compound (a)) and polysilazane. It is a cured product layer of A). In the following description, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group,
Acryloyloxy group, (meth) acrylic acid, (meth)
The same applies to expressions such as acrylate.

Among the compounds (a), a compound having one polymerizable functional group polymerizable by an active energy ray (hereinafter, simply referred to as a monofunctional compound) includes (meth)
A compound having an acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. In addition, it may have a functional group such as a hydroxyl group and an epoxy group. Examples of the monofunctional compound include the following.

Alkyl (meth) acrylate (alkyl group having 1 to 13 carbon atoms), allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol Things (meta)
Acrylate, t-butylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth)
Acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Meth) acrylates,

N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, Ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth)
Acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate , 3- (meth) acryloyloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene Glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate,

Morpholine (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy (meth) acrylate,
Polypropylene glycol (meth) acrylate, sodium sulfonic acid (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate, N-vinylcaprolactam, N- Vinylpyrrolidone, N-vinylformamide, morpholino (meth) acrylate, 2-morpholinoethyl (meth) acrylate.

As compounds having two or more active energy ray-curable polymerizable functional groups (hereinafter simply referred to as polyfunctional compounds), JP-A-11-240103, paragraphs [0016] to [0020], and [0023] Compounds described in Nos. To 0047 are preferred.

Preferred polyfunctional compounds include compounds having two or more (preferably 2 to 50, more preferably 3 to 30) at least one polymerizable functional group selected from (meth) acryloyl groups. No. Among them, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of a compound having two or more hydroxyl groups such as a polyhydric alcohol and (meth) acrylic acid is preferable. Further, compounds having various functional groups or bonds other than the polymerizable functional groups may be used. In particular, a (meth) acryloyl group-containing compound having a urethane bond (hereinafter, referred to as acrylic urethane) and a (meth) acrylate compound having no urethane bond are preferable.

The acrylic urethane is 1) acrylurethane which is a reaction product of pentaerythritol or its polymer, polypentaerythritol, polyisocyanate, and hydroxyalkyl (meth) acrylate, and which is active energy ray-curable. Of polyfunctional compounds having 3 or more (more preferably 4 to 20) polymerizable functional groups, or 2) reaction of pentaerythritol or poly (meth) acrylate containing hydroxyl group of polypentaerythritol with polyisocyanate Acryl urethane, and three or more active energy ray-curable polymerizable functional groups (more preferably 4 to 4).
20) having a polyfunctional compound.

Examples of the (meth) acrylate compound having no urethane bond include pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate. In addition, pentaerythritol-based poly (meth) acrylate is
A polyester of pentaerythritol or polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 active energy ray-curable polymerizable functional groups). Also, isocyanurate-based poly (meth)
Acrylate is a polyester of tris (hydroxyalkyl) isocyanurate or a compound obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate, and (meth) acrylic acid. (Preferably having 2 to 3 active energy ray-curable polymerizable functional groups).

In the present invention, the above-mentioned preferred polyfunctional compound and another polyfunctional compound having two or more active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol) May be used in combination.

In the compound (a), the ratio of the monofunctional compound or the polyfunctional compound is not particularly limited.

As the polysilazane contained in the coating composition (A), polysilazanes described in paragraphs 0067 to 0068 of JP-A-11-268196 are preferably exemplified. In the present invention, perhydropolysilazane is particularly preferred from the viewpoint of low firing temperature and denseness of a cured product after firing. The number average molecular weight of the polysilazane is preferably from 200 to 50,000. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured product even if it is fired, and if it exceeds 50,000, it becomes difficult to dissolve in a solvent, and the coating composition (A) may become viscous.

The mixing ratio of the polysilazane in the coating composition (A) can be appropriately selected depending on the abrasion resistance and the adhesion to the plastic substrate and the antireflection layer. In particular, when the balance between the abrasion resistance and the adhesion is taken into consideration. Include a compound (a)
With respect to 100 parts by mass, polysilazane is preferably from 1 to 1000 parts by mass, particularly preferably from 5 to 100 parts by mass. If the blending ratio of the polysilazane is less than the above, the abrasion resistance becomes insufficient, and if it is more than the above, the adhesion to the plastic substrate becomes insufficient, which is not preferable.

The coating composition (A) may contain the following solvents and various functional ingredients in addition to the above basic components.

The solvent is usually an essential component, and a solvent is used unless the compound (a) is a liquid having a particularly low viscosity. As the solvent, a solvent in which both the compound (a) and the polysilazane are soluble is used. In addition, it is preferable to use an appropriate solvent according to the type of the resin serving as the base material. In particular, in consideration of storage stability of polysilazane, a solvent containing no hydroxyl group in the molecule is preferable, and examples thereof include hydrocarbons, halogenated hydrocarbons, ketones, ethers, and esters. Specifically, Japanese Patent Application Laid-Open
The solvent described in paragraph number 0074 of 268196 is mentioned. In the present invention, xylene or dibutyl ether is particularly preferred.

The amount of the solvent can be appropriately changed depending on conditions such as the required viscosity of the composition, the desired thickness of the cured product layer, and the drying temperature. In the present invention, the solvent is used in an amount of 100 times or less, preferably 0.1 to 50 times by mass, relative to the compound (a) in the coating composition (A).

The functional compounding agents include a photopolymerization initiator, an ultraviolet absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a defoaming agent, a thickener, a sedimentation inhibitor, a pigment (organic Coloring pigments, inorganic pigments), coloring dyes, infrared absorbers, fluorescent whitening agents, dispersants, antifouling agents, fingerprint removing agents, conductive fine particles, antistatic agents, antifogging agents, curing catalysts, cups One or more functional compounding agents selected from the group consisting of ring agents are included.

The coating composition (A) preferably contains a photopolymerization initiator in order to cure the compound (a) efficiently. Known photopolymerization initiators can be used,
Particularly, commercially available products that are easily available are preferable.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (eg, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, α -Acyloxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. No. Specifically, Japanese Unexamined Patent Application Publication No. 11-268196
Compounds described in Paragraph Nos. 0063 to 0065 of Japanese Patent Application Laid-Open Publication No. H10-163, 1988 are exemplified. A plurality of photopolymerization initiators may be used in combination, or may be used in combination with a photosensitizer such as an amine.

The amount of the photopolymerization initiator in the coating composition (A) is 0.01 to 2 with respect to 100 parts by mass of the compound (a).
0 parts by mass is preferable, and 0.1 to 10 parts by mass is particularly preferable.

As the ultraviolet absorber, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, and phenyltriazine-based ultraviolet absorbers, which are used as synthetic resin ultraviolet absorbers, are preferred. Specifically, Japanese Unexamined Patent Application Publication No. 11-268196
And the compounds described in paragraph No. 0078 of the publication. In the present invention, 2- {2-hydroxy-5-
(2-acryloyloxyethyl) phenyl} benzotriazole, 2-hydroxy-3-methacryloyloxypropyl-3- (3-benzotriazole-4-hydroxy-5-t-butylphenyl) propionate, 2
1 mol of-[4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and methacryloyloxy Those having a photopolymerizable functional group in the molecule, such as a reaction product with 1 mol of ethyl isocyanate, are preferred. Above all, 2- [4- (2-
Hydroxy-3-dodecyloxypropyloxy) -2
-Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and one mole of methacryloyloxyethyl isocyanate in a molecule, such as a reaction product. A triazine-based ultraviolet absorber having a functional group having no acidity is particularly preferable because it does not cause a problem such as yellowing of the cured product layer.

As the light stabilizer, a hindered amine light stabilizer used as a light stabilizer for a synthetic resin is preferable. Specifically, the compounds described in paragraph No. 0080 of JP-A-11-268196 can be mentioned. In the present invention, such as N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine,
Those having a polymerizable functional group in the molecule are particularly preferred.

Examples of the antioxidant include hindered phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, and phosphorus-based antioxidants such as triphenylphosphite. Examples of the leveling agent include a silicone resin-based leveling agent and an acrylic resin-based leveling agent.

Examples of the antifoaming agent include silicone resin antifoaming agents such as polydimethylsiloxane. Examples of the thickener include polymethyl methacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.

Examples of the infrared absorber include polymethine, phthalocyanine, metal complex, aminium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, and triarylmethane compounds. Is mentioned.

Examples of the antifouling agent include silicone resin antifouling additives and fluororesin antifouling additives.
Examples of the conductive fine particles include metal powders such as zinc, aluminum, and nickel, iron phosphide, and antimony-doped tin oxide.

Examples of the coupling agent include a silane coupling agent and a titanate coupling agent. Examples of the antistatic agent include a nonionic antistatic agent, a cationic antistatic agent, and an anionic antistatic agent. Examples of the curing catalyst include curing catalysts selected from acids, alkalis, and salts.

In the present invention, it is preferable that the absolute value of the difference between the refractive index of the plastic substrate and the refractive index of the cured product layer of the coating composition (A) is as small as possible. By reducing the difference in the refractive index, color unevenness is reduced, and appearance quality is improved. Specifically, the absolute value of the difference between the refractive index of the plastic substrate and the refractive index of the cured product layer of the coating composition (A) is 0.15.
The following is preferred.

When the refractive index of the cured product layer of the coating composition (A) is lower than the refractive index of the plastic substrate, a compound having a structure or a functional group that enhances the refractive index and / or high refractive index ultrafine particles may be used. It is preferable that the difference in the refractive index between the two is reduced by blending it in the coating composition (A). In particular, when the absolute value of the difference between the refractive index of the plastic substrate and the refractive index of the cured product layer of the coating composition (A) is large, it is preferable to use the above compound in combination with high refractive index ultrafine particles.

The compound having a structure or a functional group for increasing the refractive index includes the compound (a) having an aromatic ring or a halogen atom in the molecule.

The high refractive index ultrafine particles include Z
_{nO, TiO 2, Sb 2 O} 5, Y 2 O 3, La 2 O 3, Zr
O ₂ , Al ₂ O ₃ , ITO, In ₂ O ₃ , SnO ₂ and Ce
O _{2 and the} like.

The thickness of the cured product layer formed using the coating composition (A) is preferably from 0.1 to 50 μm, more preferably from 1 to 2 μm.
0 μm is preferred. When the thickness is more than 50 μm, curing by active energy rays becomes insufficient, and the adhesion to the plastic substrate and the antireflection layer is easily deteriorated.
If it is less than m, the abrasion resistance may be insufficient.

Next, the antireflection layer will be described. As the antireflection layer formed on the surface of the cured product layer of the coating composition (A), a low refractive index layer formed of a single layer, or a high refractive index layer and a low refractive index layer formed of multiple layers Examples include:

In the present invention, the above coating composition (A)
Since the cured product layer contains silica having a relatively low refractive index, the antireflection layer is preferably a multilayer in which a high refractive index layer and a low refractive index layer are formed, and in particular, a high refractive index layer and a high refractive index layer are sequentially formed from the substrate side. A light-absorptive antireflection layer composed of at least two layers of a refractive index layer and a low refractive index layer is preferred.

The antireflection layer formed of the high refractive index layer and the low refractive index layer has a simple layer structure of a high refractive index light absorbing layer and a low refractive index layer described in JP-A-10-230558. The light-absorbing anti-reflection layer is preferable because it has high productivity, has excellent anti-reflection properties, has a low surface resistance value that can cope with electromagnetic wave shielding, and can ensure a higher contrast.

When the refractive index of the cured product layer of the coating composition (A) is n ₀ , the refractive index of the high refractive index layer is n ₁ , and the refractive index of the low refractive index layer is n ₂ , There n ₂ = √n ₀ if it is a single layer, anti-reflection effect if the high refractive index layer and a low refractive index layer satisfies the relationship n ₂ = √n ₁ if it is formed in the multilayer most Therefore, it is preferable that the value on the right side and the value on the left side of the above equation be close to each other.

As a material for forming the low refractive index layer, the following inorganic materials or organic materials can be used. Examples of the inorganic material include magnesium fluoride, cerium fluoride, lanthanum fluoride, aluminum fluoride, lithium fluoride, and silane oxide.

As the organic material, polytetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoro (alkoxyethylene) copolymer resin, polyvinylidene fluoride resin, ethylene-tetrafluoroethylene resin Preferred are fluorine-containing polymers such as copolymer resins and polychlorotrifluoroethylene resins. In the present invention, a non-crystalline fluoropolymer is preferred. Amorphous fluoropolymers are excellent in transparency because there is no scattering of light by crystals. Examples of the non-crystalline fluorine-containing polymer include terpolymers of tetrafluoroethylene (37 to 48% by mass), vinylidene fluoride (15 to 35% by mass), and hexafluoropropylene (26 to 44% by mass). And a polymer having a fluorinated aliphatic ring structure. For example, as the polymer having a fluorinated aliphatic ring structure, a polymer obtained by polymerizing a monomer having a fluorinated ring structure (see Japanese Patent Publication No. 63-18964) or a fluorinated compound having two or more double bonds Polymers having a ring structure in the main chain obtained by cyclopolymerization of a monomer (JP-A-63-2381)
No. 11, JP-A-63-238115).

On the other hand, as a material for forming the high refractive index layer, the following inorganic materials or organic materials can be used. As inorganic materials, ZnO, TiO ₂ , Sb ₂ O ₅ , Y ₂ O ₃ ,
La ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , ITO, In ₂ O ₃ , S
metal oxides such as nO ₂ and CeO ₂ .

As organic materials, polystyrene, poly (o-chlorostyrene), poly (2,6-dichlorostyrene), poly (o-bromostyrene), poly (2,6-
Polymers having an aromatic ring in the main chain or side chain, such as dibromostyrene) and polysulfone, and polymers having a sulfur atom in the main chain.

In the present invention, when the antireflection layer is a single low refractive index layer, its thickness is preferably from 60 to 110 nm.
When the high refractive index layer and the low refractive index layer are formed in multiple layers, the thickness of the high refractive index layer is preferably from 2 to 200 nm, and the thickness of the low refractive index layer is preferably from 60 to 110 nm.

The plastic product of the present invention having the above structure can be manufactured, for example, by the following method.

(1) The coating composition (A) is applied to at least one surface of a plastic substrate and cured to form a transparent cured product layer. When the coating composition (A) contains a solvent, it is preferable that the coating composition is dried after application to remove the solvent, and then cured.

The method for applying the coating composition (A) is not particularly limited, and a known method can be employed. For example,
Various methods such as dipping, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, and microgravure coating are used. it can.

As the active energy ray for curing the compound (a) contained in the coating composition (A), ultraviolet rays are particularly preferable. However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. 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.

On the other hand, in order to cure the polysilazane to silica, heating which is usually called calcination is performed. In the present invention, the calcination temperature of the polysilazane is set to 250 ° C. or less from the viewpoint of heat resistance of the plastic substrate. Is preferred.

It is also preferable to use a catalyst to lower the firing temperature of polysilazane. Depending on the type and amount of the catalyst, it can be calcined at a low temperature, and in some cases, can be cured at room temperature. The atmosphere for curing is preferably an atmosphere in which oxygen is present, such as in air. By firing polysilazane, its nitrogen atoms are replaced by oxygen atoms to produce silica. By firing in an atmosphere in which sufficient oxygen exists, a dense silica layer is formed.

As the catalyst, it is preferable to use a catalyst which cures polysilazane at a lower temperature. Examples of such a catalyst include fine particles of a metal such as gold, silver, palladium, platinum and nickel described in JP-A-7-196886, and the above-mentioned metal described in JP-A-5-93275. And a carboxylic acid complex of Further, the catalyst may be added to the coating composition (A) in advance, and as described in JP-A-9-31333, the coating composition (A) is added to the catalyst solution, specifically, A method of directly contacting with an amine aqueous solution or the like or exposing it to the vapor for a certain time can also be adopted.

JP-A-11-181290 discloses that the curing of polysilazane is promoted by irradiation with an active energy ray in the presence of a photoradical generator. By optimizing the irradiation conditions, it is possible to cure with an active energy ray even when the catalyst is not contained.

In the present invention, as the method for curing the coating composition (A), the following three methods are preferably mentioned.

After applying the coating composition (A), the compound (a) is sufficiently cured by irradiating a sufficient amount of active energy rays, and then heated, left at room temperature, or treated with polysilazane. A method of curing a partially cured or uncured polysilazane by exposing it to the vapor of a curing catalyst solution.

After coating the coating composition (A), the uncured polysilazane is cured by heating, leaving it at room temperature, or exposing it to the vapor of a curing catalyst solution of polysilazane. A method of irradiating an amount of active energy rays to cure the compound (a).

A method in which the curing of compound (a) and the curing of polysilazane by irradiation of the active energy ray are performed almost simultaneously. In this method, the curing of the polysilazane is usually slower than the curing of the compound (a).

(2) An antireflection layer is formed on the surface of the transparent cured product layer. As a method for forming the antireflection layer, a known method such as a wet method, an evaporation method, and a sputtering method can be employed. For example, in the wet method, a low refractive index layer such as MgF ₂ , SiO ₂ or a fluoropolymer, TiO ₂ or Zr
A high refractive index layer such as O ₂ can be formed.

In order to form a low-refractive index layer and a high-refractive index layer of a thin film by a wet method, for example, a low-refractive material and a high-refractive material are respectively dissolved in a solvent to form a liquid composition. A method of applying on a plastic substrate by a coating method such as a dip coating method and a spin coating method can be selected.

In order to form a thin low-refractive index layer and a high-refractive index layer by a dry method, a vapor deposition method, a sputtering method and the like can be selected. In particular, light absorption using a light absorbing material as the high refractive index layer is possible. In the case of employing a reflective antireflection layer, see
The DC sputtering method described in JP-A-230558 is preferable.

The plastic product of the present invention is, for example,
Display front panel, optical lens, automotive window glass,
Suitable for applications such as front panels of instruments.

[0075]

The present invention will be specifically described below with reference to Example 1 (Example) and Example 2 (Comparative Example). In each example, a transparent aromatic polycarbonate resin film (hereinafter, simply referred to as a film) having a thickness of 380 μm was used as a plastic substrate. Various properties of the obtained sample were measured by the following methods, and the results are shown in Table 1.

[Initial luminous average transmittance (TV)] JIS-
Measured using a spectrophotometer according to Z8701.

[Initial luminous average reflectance (RV)] JIS-
Measured using a spectrophotometer according to Z8701.

[Initial haze (H)] JIS-K7105
It measured according to.

[Abrasion Resistance] Based on the abrasion resistance test method in JIS-R3212, a luminous transmittance after 100 rotations or 500 rotations of the two CS-10F wear wheels combined with a 500 g weight respectively. (TV) and haze (H) were measured.

[Adhesion] A sample was placed in a thermo-hygrostat (50
(At 90 ° C., relative humidity: 95%) for 48 hours, rubbed the gauze impregnated with ethanol for 10 reciprocations under a load of about 2 kg / cm ² , and visually observed whether or not the layer was peeled off.

Example 1 A 100 mL four-necked flask equipped with a stirrer and a condenser was charged with 12 g of dibutyl ether, 13 g of xylene, and 2 g of xylene.
-[4- (2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 0.2 g, 2- Methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one 0.15
g, and 0.2 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate were added and dissolved.

Subsequently, a xylene solution of 4.8 g of tris (2-acryloyloxyethyl) isocyanurate, 3.2 g of dipentaerythritol hexaacrylate and a low-temperature curable perhydropolysilazane (solid content: 20% by mass,
(Clariant Japan, product name "D110") 10
g was added and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating liquid 1.

The coating liquid 1 was applied to the surface of the film by a bar coating method (wet thickness: 12 μm), and kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, in an air atmosphere, ultraviolet rays of 2,000 mJ / cm ² (integrated ultraviolet energy in a wavelength range of 300 to 390 nm, the same applies hereinafter) were irradiated using a high-pressure mercury lamp, and then 23 ° C. and a relative humidity of 50 were applied.
% Environment for 24 hours to form a transparent cured layer having a total thickness of 2.4 μm.

Next, in a vacuum chamber, metal titanium and N-type silicon (phosphorus-doped single crystal) having a specific resistance of 1.2 Ω · cm were set on the cathode as targets, and 10 cm
The film on which the transparent cured product layer cut into the corner was formed was placed on a substrate holder.

Then, after evacuation of the vacuum chamber to 1.33 mPa, an antireflection layer was formed as follows to obtain a sample.

(1) Argon is introduced as a discharge gas,
The conductance was adjusted so that the pressure became 133 mPa. Next, the substrate holder (surface area about 1,200 c
m ² ), RF power of 200 W was applied for 1 minute to perform RF plasma processing. At this time, the self-bias voltage of the electrode was -280 V.

(2) The discharge gas is switched to a mixed gas of argon and nitrogen (25 vol% nitrogen), and the pressure is set to 266 mP.
a, a voltage was applied to the silicon target, and a silicon nitride film (adhesion layer) having a geometrical film thickness of 2 nm was formed by intermittent DC sputtering of the silicon target.

(3) The discharge gas is switched to a mixed gas of argon and nitrogen (20 vol% nitrogen), and the pressure is set to 266 mP.
After adjusting to a, a negative DC voltage was applied to the titanium cathode, and a titanium nitride film (high-refractive-index light-absorbing layer) having a geometric film thickness of 26 nm was formed by DC sputtering of a titanium target.

(4) In the same discharge gas atmosphere as in (3), a voltage is applied to the silicon target, and a silicon nitride film (fine absorption film) having a geometric film thickness of 26 nm is formed by intermittent DC sputtering of the silicon target. Formed.

(5) The introduction of the discharge gas was stopped, the inside of the vacuum chamber was evacuated to a high vacuum, and a mixed gas of argon and oxygen (67 vol% oxygen) was introduced as the discharge gas, and the pressure was increased to 266 m.
It was adjusted to Pa. Next, a voltage was applied to the silicon target, and a silicon film (having a refractive index of 1.4) having a geometric film thickness of 70 nm was formed by intermittent DC sputtering of the silicon target.
7 low refractive index layer).

Example 2 In a 100 mL four-necked flask equipped with a stirrer and a condenser, 9 g of dibutyl ether, 16 g of xylene,
[4- (2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 0.2 g, 2-methyl -1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one 0.15
g, and 0.2 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate were added and dissolved.

Subsequently, 4.8 g of tris (2-acryloyloxyethyl) isocyanurate and 3.2 g of dipentaerythritol hexaacrylate were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating liquid 2.

The coating liquid 2 was applied to the surface of the film by a bar coating method (wet thickness: 10 μm), and was kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, ultraviolet rays of 2,000 mJ / cm ² were irradiated using a high-pressure mercury lamp in an air atmosphere to form a transparent cured layer having a thickness of 2.5 μm. An anti-reflection layer was formed on the surface of the transparent cured product layer in the same manner as in Example 1 to obtain a sample.

[0094]

[Table 1]

[0095]

According to the present invention, a cured layer of a hard coating composition (A) having high scratch resistance is formed on at least one surface of a plastic substrate, and an antireflection layer is formed on the surface. Thereby, the displacement of the antireflection layer due to external force is reduced, and a plastic product having the antireflection layer having particularly excellent wear resistance can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Shibuya 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. (72) Inventor Tomohiro Yamada 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Terms (reference) 2K009 AA05 BB24 CC03 CC06 CC09 CC12 CC26 CC42 DD02 4F100 AA20 AD04 AD05 AH06B AK01A AK01B AK25A AK42A AK45A AL05B AR00B AR00C AR00D BA04 BA07 BA10A BA10D EH46 EHJ JBJB18J12 GB14

Claims (7)

[Claims] 1. A plastic product having a transparent cured product layer and an antireflection layer formed on at least one surface of a plastic substrate in order from the substrate side, wherein the transparent cured product layer has an active energy ray-curable property. A plastic product characterized by being a cured layer of a coating composition (A) containing a compound (a) having at least one polymerizable functional group and polysilazane. 2. The plastic product according to claim 1, wherein the antireflection layer is a light-absorbing antireflection layer composed of at least two layers of a high refractive index layer and a low refractive index layer in order from the substrate side. 3. The plastic product according to claim 1, wherein the polysilazane is a perhydropolysilazane. 4. The absolute value of the difference between the refractive index of the plastic substrate and the refractive index of the cured product of the coating composition (A) is 0.15.
The plastic product according to claim 1, wherein: 5. The plastic substrate according to claim 1, wherein the plastic substrate is a plastic substrate selected from the group consisting of an aromatic polycarbonate resin, a polymethyl methacrylate resin and a polyethylene terephthalate resin. Plastic products. 6. The method for producing a plastic product according to claim 1, wherein at least one surface of the plastic substrate has at least one active energy ray-curable polymerizable functional group. A method for producing a plastic product, comprising: forming a cured product layer of a coating composition (A) containing (a) and polysilazane, and then forming an antireflection layer on the surface of the cured product layer. 7. A coating composition comprising a compound (a) having at least one active energy ray-curable polymerizable functional group and at least one polysilazane on at least one surface of a plastic substrate in the method for producing a plastic product. The composition (A) is applied, and then the curing of the compound (a) and the curing of the polysilazane by irradiation of active energy rays are performed in any order or at the same time, so that a cured product of the coating composition (A) is obtained. The method for producing a plastic product according to claim 6, wherein after forming the layer, an antireflection layer is further formed on the surface of the cured product layer.