JP2001322207A - Gas barrier plastic molded article and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier plastic molded article having a cured matter layer (gas barrier film) excellent in gas barrier properties, abrasion resistance and the adhesion with a base material, and a method for manufacturing the same. SOLUTION: An outermost layer comprising cured matter of a coating composition (B) based on polysilazane, and an inner layer in contact with the outermost layer and comprising a layer of cured matter of a coating composition (A) containing a polyfunctional compound (a) having two or more active energy beam curable polymerizable functional groups and polysilazane, are formed for a gas barrier layer on the surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of a gas barrier plastic having a cured layer having excellent gas barrier properties, abrasion resistance and adhesion to a substrate, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the need for a transparent plastic substrate having gas barrier properties has increased. As a transparent plastic substrate having such a gas barrier property, a resin having a high gas barrier property such as a vinylidene chloride-based resin, a polyolefin-based resin, and a polyvinyl alcohol-based resin,
Examples thereof include those obtained by coating the surface of a substrate with these resins, and those obtained by depositing a metal oxide such as alumina or silica on the surface of the substrate.

[0003] For example, a substrate used for a liquid crystal display device or an electroluminescence display device is required to have a gas barrier property, so that glass having a high gas barrier property is generally used. However, glass is vulnerable to impact,
Also, because of its heavy weight, a transparent plastic substrate having gas barrier properties has been used as a substitute.
As a gas-barrier plastic substrate for display devices, a gas-barrier coating is applied to the surface of a highly transparent resin substrate by a physical method such as a vacuum evaporation method or a sputtering method or a gas-phase method such as a chemical method such as CVD. For example, those having a metal oxide film formed thereon are widely used.

[0004]

However, the gas barrier film formed by the vapor phase method as described above has not been satisfactory in terms of gas barrier properties, scratch resistance, durability and the like. In addition, since the formation of the film requires precise atmosphere control in a high vacuum system, the apparatus becomes complicated and large,
Inevitably, the manufacturing cost was high.

[0005] For example, in Japanese Patent Application Laid-Open Nos. 8-281861 and 11-151774, an inorganic oxide vapor-deposited film is provided on the surface of a synthetic resin film, and polysilazane is coated on the surface to form a gas barrier. A gas barrier film having a functional coating has been proposed. These gas barrier films can provide satisfactory performance to some extent in terms of gas barrier properties, but still do not have sufficient performance in terms of abrasion resistance and adhesion to a substrate.

An object of the present invention is to provide a gas barrier plastic molded article having a cured product layer having excellent gas barrier properties, abrasion resistance and adhesion to a substrate, and a method for producing the same.

[0007]

That is, the first aspect of the present invention is as follows.
Is a gas-barrier plastic molded article having two or more cured product layers formed on at least one surface of a transparent plastic substrate, wherein the inner layer in contact with the outermost layer of the two or more cured product layers has the following coating composition ( It is a layer of the cured product of A), and the outermost layer is a layer of a cured product of the following coating composition (B).

Coating composition (A): polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups
Active energy ray-curable coating composition comprising: and polysilazane. Coating composition (B): a curable coating composition containing polysilazane as a main component.

In a second aspect of the present invention, in the method for producing a gas-barrier plastic molded article, a layer of a cured product of the coating composition (A) is formed on at least one surface of the transparent plastic substrate, and the surface thereof is further formed. To form a layer of an uncured or partially cured product of the coating composition (B), and then irradiate with an active energy ray, or further heat after the irradiation,
A method for producing a gas barrier plastic molded product, comprising curing the coating composition (B) by leaving the coating composition (B) at room temperature or exposing it to a vapor atmosphere of a curing catalyst solution.

According to the present invention, there is provided a gas-barrier plastic molded article having a gas-barrier coating having a cured product layer having extremely excellent abrasion resistance, excellent adhesion to a substrate, and excellent gas barrier properties. Goods can be provided.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following description, a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups is simply referred to as a polyfunctional compound (a). Also,
An acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group, and the same applies to expressions such as a (meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate.

[0012] The gas-barrier plastic molded article of the present invention comprises, on at least one side of a substrate, an inner layer made of a cured product of the coating composition (A) in contact with the outermost layer, and a cured product of the coating composition (B). A gas barrier coating having at least two or more cured product layers including an outer layer is formed. In the present invention, the layer of the cured product of the coating composition (B) is preferably formed directly on the surface of the layer of the cured product of the coating composition (A). Since the coating composition (A) contains polysilazane, it can ensure high adhesion to the layer of the coating composition (B),
High scratch resistance and adhesion are obtained.

[0013] Further, between the substrate and the layer of the cured product of the coating composition (A), a layer such as an adhesive layer or a synthetic resin paint, or another synthetic resin such as a thermoplastic acrylic resin. A third layer made of a thermoplastic resin layer may be present.

First, the coating composition (A) will be described. Polyfunctional compound (a) contained in coating composition (A)
Preferable examples thereof include compounds described in paragraphs 0014 to 0019 and 0021 to 0043 of JP-A-11-268196.

Preferred polyfunctional compounds (a) include:
A compound having two or more (preferably 2 to 50, more preferably 3 to 30) one or more polymerizable functional groups selected from (meth) acryloyl groups is exemplified. 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. 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.

Examples of the acrylic urethane include acrylic urethane, which is a reaction product of pentaerythritol or its multimer, polypentaerythritol, polyisocyanate, and hydroxyalkyl (meth) acrylate; An acrylic urethane that is a reaction product of a (meth) acrylate and a polyisocyanate, and a polyfunctional compound having three or more (more preferably 4 to 20) active energy ray-curable polymerizable functional groups, No.

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
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 (meth) acrylic acid with an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or 1 mol of tris (hydroxyalkyl) isocyanurate. (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.

The coating composition (A) is a monofunctional compound having one polymerizable functional group polymerizable by an active energy ray together with the polyfunctional compound (a) (hereinafter, simply referred to as a monofunctional compound). )).

As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. In addition, other hydroxyl groups,
It may have a functional group such as an epoxy group.

Preferred monofunctional compounds are (meth) acrylic acid esters, that is, (meth) acrylates, and specific examples thereof include those described in JP-A-11-268196, paragraph [0045].

When a monofunctional compound is used, it is based on the total of the polyfunctional compound (a) and the monofunctional compound (hereinafter referred to as active energy ray-curable components) in the coating composition (A). The proportion of the monofunctional compound is
Although not particularly limited, it is preferably at most 60% by mass, particularly preferably at most 30% by mass. If the proportion of the monofunctional compound is too large, the cured product of the coating composition (A) becomes too soft, and the abrasion resistance when the outermost layer is formed decreases.

As the polysilazane contained in the coating composition (A), polysilazane (perhydropolysilazane) substantially free of an organic group, an alkyl group, an alkenyl group,
A hydrolyzable group such as an aryl group, a cycloalkyl group, or a polysilazane or an alkoxy group in which a hydrogen atom bonded to a carbon atom of these groups is partially or entirely substituted with a substituent is bonded to a silicon atom is silicon. Examples include polysilazane bonded to an atom, and polysilazane in which an organic group such as an alkyl group is bonded to a nitrogen atom.

The silica formed from polysilazane is different from the silica formed from the hydrolyzable silane compound.
A denser silica is formed. For example, silica formed from perhydropolysilazane is more dense than silica formed from a tetrafunctional hydrolyzable silane compound (eg, tetraalkoxysilane),
Excellent properties such as gas barrier properties and abrasion resistance.

When polysilazane has a hydrolyzable group at the silicon atom, it forms silica substantially free of organic groups by a hydrolysis reaction at the time of curing. In particular, perhydropolysilazane is preferred in view of its low firing temperature and denseness of a cured product after firing. A cured product obtained by sufficiently curing perhydropolysilazane becomes silica containing almost no nitrogen atoms.

In the case of polysilazane in which an organic group such as an alkyl group is bonded to a silicon atom, silica containing an organic group formed has a gas barrier property and abrasion resistance which are lower than those of silica formed from perhydropolysilazane. Although it may be inferior in properties such as properties, a tougher cured product layer is obtained,
In addition, it may be preferable to perhydropolysilazane for some purposes because the layer can be made thicker.

These polysilazanes are composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture having a plurality of these structures in the molecule. The molecular weight of polysilazane is preferably 200 to 50,000 in number average molecular weight. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured product even when firing. The number average molecular weight is 5
If it exceeds 10,000, it is difficult to dissolve in a solvent and the coating composition (A) may become viscous, which is not preferable.

The mixing ratio of the polysilazane to the polyfunctional compound (a) in the coating composition (A) can be appropriately selected depending on the abrasion resistance and the compatibility. Is preferably 1 to 80 parts by mass of polysilazane based on 100 parts by mass of the polyfunctional compound (a). If the blending ratio of the polysilazane to the polyfunctional compound (a) is less than 1 part by mass, sufficient abrasion resistance cannot be obtained, and if it is more than 80 parts by mass, the adhesion to the substrate tends to decrease.

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

In the coating composition (A), a solvent is usually an essential component, and a solvent is used unless the active energy ray-curable component is a liquid having a particularly low viscosity.

As the solvent, a solvent in which both the active energy ray-curable component and the polysilazane are soluble is used. In addition, paragraph 005 of JP-A-11-268196.
The dispersing medium used for modifying the colloidal silica described later in item 1 can also be used as a solvent as it is. In addition, it is preferable to select and use an appropriate solvent depending on the type of the base material. In particular, when the storage stability of polysilazane is considered, a solvent containing no hydroxyl group in the molecule, for example, a hydrocarbon or a halogenated hydrocarbon , Ketones, ethers, esters and the like. Specifically, a solvent described in paragraph No. 0074 of JP-A-11-268196 can be used. In the present invention, xylene and dibutyl ether are particularly preferred.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured product layer, the drying temperature conditions, and the like. In the present invention, the solvent is used in an amount of 100 times or less, preferably 0.1 to 50 times by mass the active energy ray-curable component in the coating composition (A).

The coating composition (A) preferably contains a photopolymerization initiator in order to efficiently cure the active energy ray-curable component. As the photopolymerization initiator, known photopolymerization initiators can be used, and commercially available photopolymerization initiators are particularly preferable.

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 acylphosphine oxide-based photopolymerization initiators, diacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators.

Specific examples include compounds described in paragraphs 0063 to 0065 of JP-A-11-268196. In the present invention, an aryl ketone-based photopolymerization initiator is particularly preferred. 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 preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the active energy ray-curable component. .

Further, it is preferable to use colloidal silica in order to increase the wear resistance and hardness of the gas barrier coating.

As colloidal silica, JP-A No.
No. 268196, paragraphs [0046] to [0060], a surface-unmodified colloidal silica or a colloidal surface modified with a compound having a hydrolyzable silicon group or a hydroxyl-bonded silicon group (modifier). Silica (hereinafter simply referred to as modified colloidal silica) can be used. In the present invention, it is preferable to use modified colloidal silica. The average particle size of the colloidal silica is preferably 200 nm or less, more preferably 1 to 100 nm, and particularly preferably 1 to 50 nm.

The amount of the colloidal silica to be used is preferably 5 to 300 parts by mass, more preferably 10 to 250 parts by mass, based on 100 parts by mass of the active energy ray-curable component.
-50 parts by mass is more preferred. When the amount is less than 5 parts by mass, it is difficult to obtain sufficient abrasion resistance, and when the amount is more than 300 parts by mass, clouding (haze) is likely to occur, and a crack is easily generated in the formed cured product layer. Absent.

Other functional compounding agents include high molecular weight compounds such as polymethyl methacrylate resin (PMMA), ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers From thickeners, anti-settling agents, pigments, coloring dyes, infrared absorbers, fluorescent brighteners, dispersants, antistatic agents, anti-fog agents, curable catalysts (acids, alkalis, salts), silane coupling agents 1 selected from the group
More than one functional compound may be included. In the present invention, it is particularly preferable to use an ultraviolet absorber and / or a light stabilizer.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers which are commonly used as ultraviolet absorbers for synthetic resins.
Salicylic acid-based UV absorbers and phenyltriazine-based UV absorbers are preferred. Specifically, Japanese Patent Laid-Open No. 11-2
Compounds described in paragraph No. 0078 of 68196 are exemplified. In the present invention, the coating composition (A)
Contains the polyfunctional compound (a), so that 2- [4
-[(2-hydroxy-3-dodecyloxypropyl)
Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy ] -2-Hydroxyphenyl]-
4,6-bis (2,4-dimethylphenyl) -1,3
A phenyltriazine-based ultraviolet absorber such as 5-triazine is preferred.

As the light stabilizer, a hindered amine light stabilizer which is also commonly used as a light stabilizer for a synthetic resin is also preferable. Specifically, Japanese Patent Application Laid-Open No. H11-26
Compounds described in paragraph No. 0080 of JP-A-8196 are exemplified. In the present invention, those having a polymerizable functional group in the molecule, such as N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, are particularly preferable.

The thickness of the inner layer formed by the coating composition (A) is preferably 1 to 50 μm, particularly preferably 2 to 30 μm. When the thickness of the inner layer is more than 50 μm, the curing by the active energy ray becomes insufficient, and the adhesion to the base material is easily damaged. On the other hand, if the thickness of the inner layer is less than 1 μm, the abrasion resistance of this layer may be insufficient, and the abrasion resistance and scratch resistance of the outermost layer may not be sufficiently exhibited.

Hereinafter, the coating composition (B) will be described. As the polysilazane contained in the coating composition (B), the polysilazane used in the coating composition (A) can be used.

The coating composition (B) can contain, in addition to the above basic components, the same solvents and various functional additives as those used in the coating composition (A).

The thickness of the outermost layer formed by the coating composition (B) is preferably from 0.01 to 10 μm, particularly preferably from 0.05 to 10 μm.
３3 μm is preferred. If the thickness of the outermost layer is less than 0.01 μm, sufficient gas barrier properties and abrasion resistance cannot be obtained. Further, even if the thickness of the outermost layer exceeds 10 μm, further improvement in gas barrier properties and abrasion resistance cannot be expected, and the layer becomes rather brittle, and even the slightest deformation easily causes cracks and the like in the outermost layer.

The gas barrier coating having the cured layers of the coating compositions (A) and (B) as described above has an oxygen permeability of 10 (mL / m ² · 24 hr · (1.013 × 1
0 ⁵ Pa)) or less and water vapor permeability of 10
(G / m ² · 24 hr) or less. That is, the gas barrier plastic molded article of the present invention is:
Oxygen permeability is 10 (mL / m ² · 24 hr · (1.01
3 × 10 ⁵ Pa)) or less, and a water vapor permeability of 10 (g / m ² · 24 hr) or less.

Since the gas-barrier plastic molded article of the present invention has excellent gas-barrier properties, it can be used for liquid crystal display devices,
It is particularly suitably used for a substrate for a display element such as an electroluminescence display element.

Next, the base material will be described. Various transparent synthetic resins can be used as the transparent plastic substrate,
For example, an aromatic polycarbonate resin, a polystyrene resin, a polymethyl methacrylate resin, an aromatic polyester resin, a polyimide resin, and a polyarylate resin are preferably exemplified. Other examples include polyethersulfone-based resins, polysulfone-based resins, polyamide-based resins, and cellulose triacetate-based resins. In the present invention, aromatic polycarbonate resins, polymethyl methacrylate resins, aromatic polyester resins, and polyarylate resins are particularly preferred.

The substrate is formed in advance, for example, a sheet-like substrate such as a flat plate or a corrugated plate, a film-like substrate,
Examples include a base material formed into various shapes, a laminate in which at least a surface layer is made of the above synthetic resin, and the like. The thickness of the substrate may be appropriately determined depending on the application. For example, when the substrate is used for a substrate of a liquid crystal display device or an electroluminescent display device, the substrate formed into a sheet or film having a thickness of 10 μm to 1 mm is used. Is preferred.

FIG. 1 is a schematic diagram showing a cross section of a gas-barrier plastic molded product according to one embodiment of the present invention.

The gas-barrier plastic molded article 5 is a cured product of the outermost layer 1 which is a cured product of the coating composition (B) and a cured product of the coating composition (A) which is in direct contact with the surface of the transparent plastic substrate 3. A gas barrier coating 4 composed of two layers of the inner layer 2 is formed.

The gas barrier plastic molded article of the present invention can be produced, for example, as follows.

First, on one side of the transparent plastic substrate 3,
The coating compositions (A) and (B) are applied and cured to form the gas barrier coating 4. At this time, the third space between the transparent plastic substrate 3 and the gas barrier coating 4 as described above.
May be formed.

In the present invention, the gas barrier coating may be formed on only one surface of the transparent plastic substrate, or may be formed on both surfaces. By forming gas barrier coatings on both surfaces of the transparent plastic substrate, higher gas barrier properties and durability reliability can be secured.

When a gas barrier coating is formed only on one side of a transparent plastic substrate, the other side has
A hard coat layer may be formed. Examples of the hard coat layer include a cured layer made of a curable resin such as a polyester resin, a urethane resin, a melamine resin, an epoxy resin, a silicon resin, an acrylic resin, and a polyimide resin.

The method for applying the coating compositions (A) and (B) on the surface of the transparent plastic substrate is not particularly limited, and a known method can be employed. For example, various methods such as dip coating, float coating, spray coating, shower coating, ring coating, spin coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, etc. Method can be adopted.

The active energy ray for curing the coating composition (A) is not particularly limited, and ultraviolet rays, electron beams and other active energy rays can be used, but ultraviolet rays are preferred. As the ultraviolet light source, a xenon lamp, a pulse xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, and the like can be used.

Further, as a method of curing the polysilazane contained in the coating composition (B) to obtain silica, paragraphs 0069 to 007 of JP-A-11-268196 can be used.
The method described in No. 1 can be adopted.

However, in the present invention, the low temperature (180
C. or lower) to cure the polysilazane. In order to cure polysilazane at a low temperature, it is necessary to add a catalyst to the coating composition (B). However, it is preferable to use a catalyst that can be cured at a lower temperature, and it can be cured at room temperature depending on the type and amount of the catalyst. . Examples of such a catalyst include fine particles of metals such as gold, silver, palladium, platinum and nickel described in JP-A-7-196886, and those described in JP-A-5-93275. Carboxylic acid complex and JP-A-9
Examples thereof include amines and acids described in JP-A-31333.

The particle size of the metal fine particles is preferably smaller than 0.1 μm, and is preferably smaller than 0.05 μm in order to ensure transparency of the cured product. Further, since the specific surface area increases as the particle diameter decreases, the catalytic ability also increases. Therefore, it is preferable to use a catalyst having a smaller particle diameter from the viewpoint of improving the catalytic performance.

The above amines include, for example, monoalkylamine, dialkylamine, trialkylamine, monoarylamine, diarylamine, cyclic amine and the like.

Examples of the above-mentioned acids include organic acids such as acetic acid and inorganic acids such as hydrochloric acid.

For example, when the metal fine particles are previously added to the coating composition (B) as a catalyst, the amount added is
0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of polysilazane. If the amount is less than 0.01 part by mass, a sufficient catalytic effect cannot be expected. If the amount exceeds 10 parts by mass, aggregation of the catalysts tends to occur, which may impair the transparency.

The above-mentioned amines and acids may be added to the coating composition (B) in advance and used. Solutions of amines and acids (including aqueous solutions) and vapors thereof (vapors from the aqueous solution) may be used. May be included). Moreover, you may leave it in the air whose humidity was adjusted.

The combination (timing) of the curing of the coating composition (A) and the application and curing of the coating composition (B) includes the following timings 1) to 3).

1) After coating the coating composition (A), the coating composition (A) is irradiated with an active energy ray enough to sufficiently cure, and then the coating composition (B) is coated. The coating composition (B) is cured.

2) After coating the coating composition (A), the coating composition (A) is irradiated with active energy rays to obtain a partially cured product of the coating composition (A), and then the coating composition (B) is coated. Thereafter, the partially cured product of the coating composition (A) and the curing of the coating composition (B) are
This step is performed by irradiating with an active energy ray and heating or exposing the coating composition (B) to a curing catalyst solution in a vapor atmosphere.

3) After applying the coating composition (A), the coating composition (B) is applied. Thereafter, the coating compositions (A) and (B) are cured by irradiating with an active energy ray and heating or by exposing the composition to a vapor atmosphere of a curing catalyst solution of the coating composition (B).

In the present invention, in order to increase the adhesion between the two cured product layers, it is preferable to perform the above-mentioned 2) or 3) timing. When the coating composition contains a solvent, it is preferable that the coating composition is dried after drying to remove the solvent, and then cured.

[0071]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples (Examples 1 to 6) and Comparative Examples (Examples 7 to 18), but the present invention is not limited thereto. In addition, Examples 1 to 13, 17, 1 and 1
8, an aromatic polycarbonate resin film having a thickness of 250 μm, Example 14 an aromatic polyarylate resin film having a thickness of 250 μm, Example 15 a polyethylene terephthalate resin film having a thickness of 188 μm, and Example 16 having a thickness of 2
A 50 μm polymethyl methacrylate resin film was used. The measurement and evaluation of various physical properties of the samples obtained in Examples 1 to 18 were performed by the following methods, and the results are shown in Table 1.

[Adhesion] The sample was cut with eleven vertical and horizontal lines at 1 mm intervals with a razor blade to make 100 grids. Then, when a commercially available cellophane tape is closely adhered and then rapidly peeled in the forward direction by 90 degrees, the number (m) of the grids remaining without peeling off the coating is represented by m / 100. The initial adhesion after sample preparation and the humidity resistance after storage for 7 days in an atmosphere at 60 ° C. and a relative humidity of 95% were measured (JIS-K1979).

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method in No. 2, a haze meter was used to measure the haze value when a 500 g weight was combined with each of the 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 abrasion test, and the abrasion resistance indicates the value (%) of (haze after the abrasion test)-(haze before the abrasion test).

[Oxygen permeability] JIS-K7126, Method A (25 ° C) [mL / m ² · 2
4 hr · (1.013 × 10 ⁵ Pa)]

[Water Vapor Permeability] JIS-K7129, Method A (40 ° C.) [g / m ² · 24
hr]

[Example 1] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 36 g of xylene, 27 g of dibutyl ether and 240 mg of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one were added and dissolved, followed by dipentaerythritol hexaacrylate. 6.4 g and 9.6 g of tris (2-acryloyloxyethyl) isocyanurate were added. Further, 2- [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 480m of a mixture of 1,3,5-triazine
g, and N-methyl-4-methacryloyloxy-
160 mg of 2,2,6,6-tetramethylpiperidine were added. The mixture was stirred at room temperature for 1 hour, and 20 g of a non-catalyzed xylene solution of perhydropolysilazane (solid content: 20% by mass, manufactured by Tonen Corp., trade name "V110") was added.
Coating liquid 1 was obtained.

The coating liquid 1 was applied to one surface of the substrate using a spin coater (wet thickness: 15 μm) and kept in a hot air circulating oven at 90 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 1500 mJ / cm ² (wavelength 3
Ultraviolet integrated energy in the range of 00 to 390 nm, the same applies hereinafter. ) Was applied to form a cured product layer having a thickness of 3 μm.

Next, a xylene solution (solid content: 20% by mass, trade name “L110”, manufactured by Tonen Co.) of a low-temperature curing type perhydropolysilazane (hereinafter referred to as “coating liquid 2”)
That. ) Was applied (wet thickness 2 μm) using a spin coater, and kept in a hot air circulating oven at 90 ° C. for 5 minutes to remove the solvent, and then kept in a hot air circulating oven at 100 ° C. for 120 minutes. The outermost layer was sufficiently cured. By IR analysis, it was confirmed that the outermost layer was almost completely silica. Thus, a total film thickness of 3.
A cured product layer of 4 μm was formed.

[Example 2] In Example 1, instead of holding in a hot air circulating oven at 100 ° C for 120 minutes, 1500 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere.
Irradiation with UV light, followed by curing for one day in an environment of 23 ° C. and a relative humidity of 55%, was performed in the same manner as in Example 1.

[Example 3] The coating liquid 1 was applied (wet thickness 15 μm) to one surface of the substrate using a spin coater,
C. for 5 minutes in a hot air circulating oven. Then, it was irradiated with 150 mJ / cm ² ultraviolet rays using a high-pressure mercury lamp in an air atmosphere to form a 3 μm-thick touch-dry layer. The coating liquid 2 was coated thereon (wet thickness 2 μm) using a spin coater, and kept in a hot air circulating oven at 90 ° C. for 5 minutes to remove the solvent. UV light of 1500 mJ / cm ² and then cured for 1 day in an environment of 23 ° C. and 55% relative humidity. By IR analysis, it was confirmed that the outermost layer was almost completely silica. Thus, a cured product layer having a total film thickness of 3.4 μm was formed on the substrate surface.

[Example 4] The coating liquid 1 was applied to one surface of the base material using a spin coater (wet thickness: 15 µm), and 90
C. for 5 minutes in a hot air circulating oven. Further, the coating liquid 2 is applied using a spin coater (wet thickness 2 μm).
m) and kept in a hot-air circulating oven at 90 ° C. for 5 minutes to remove the solvent, and then irradiate with ultraviolet light of 1500 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere.
Cured for 1 day in an environment at a temperature of 55 ° C. and a relative humidity of 55%. By IR analysis, it was confirmed that the outermost layer was almost completely silica. Thus, a cured product layer having a total film thickness of 3.4 μm was formed on the substrate surface.

Example 5 The procedure of Example 2 was repeated, except that the coating amount of the coating liquid 2 was changed to a wet thickness of 1 μm.

Example 6 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 20 g of xylene, 20 g of dibutyl ether and 150 mg of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one were added and dissolved, followed by dipentaerythritol hexaacrylate. 4 g and tris (2-acryloyloxyethyl) isocyanurate 6 g were added. Further, 2- [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) -1,3,5-triazine (300 mg) and N-methyl-4-methacryloyloxy-2 , 2,
150 mg of 6,6-tetramethylpiperidine was added.
The mixture was stirred at room temperature for 1 hour, and 50 g of a catalyst-free xylene solution of perhydropolysilazane (solid content: 20% by mass, manufactured by Tonen Corp., trade name: “V110”) was added to obtain a coating liquid 3. In Example 1, it carried out similarly to Example 1 except having changed the coating liquid 1 into the coating liquid 3.

Example 7 The procedure of Example 2 was repeated, except that the coating liquid 1 was changed to the coating liquid 3.

Example 8 The procedure of Example 3 was repeated, except that the coating liquid 1 was changed to the coating liquid 3.

Example 9 The procedure of Example 4 was repeated, except that the coating liquid 1 was changed to the coating liquid 3.

Example 10 The procedure of Example 1 was repeated, except that the one-sided coat was changed to the two-sided coat.

Example 11 The procedure of Example 2 was repeated, except that the one-sided coat was changed to the two-sided coat.

Example 12 The procedure of Example 3 was repeated, except that the one-sided coat was changed to the two-sided coat.

Example 13 The procedure of Example 4 was repeated, except that the one-sided coat was changed to the two-sided coat.

[Examples 14 to 16] Except that the base material was changed,
Same as Example 2.

[Example 17] The coating liquid 1 was applied to one surface of the base material using a spin coater (wet thickness: 15 µm) to give 9
It was kept in a hot air circulating oven at 0 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 1500 mJ / cm ²
To form a cured product layer having a thickness of 3 μm, and then cured for 1 day in an environment of 23 ° C. and 55% relative humidity.
IR analysis confirmed that the perhydropolysilazane had become almost complete silica. Thus, a cured product layer having a total film thickness of 3 μm was formed on the substrate surface.

[Example 18] The coating liquid 2 was applied to one surface of the base material using a spin coater (wet thickness: 15 μm) to give 9
It was kept in a hot air circulating oven at 0 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 1500 mJ / cm ²
To form a cured product layer having a thickness of 3 μm, and then cured for 1 day in an environment of 23 ° C. and 55% relative humidity.
IR analysis confirmed that the outermost layer was almost completely silica. Thus, a cured product layer having a total film thickness of 3 μm was formed on the substrate surface.

[0094]

[Table 1]

[0095]

According to the present invention, it is possible to provide a gas-barrier plastic molded article having a gas-barrier coating having extremely excellent abrasion resistance and excellent adhesion to a substrate and gas barrier properties.

The gas-barrier plastic molded article of the present invention is particularly suitably used for a substrate for a liquid crystal display device, an electroluminescence display device, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a cross section of a gas barrier plastic molded product according to one embodiment of the present invention.

[Explanation of symbols]

 1. Outermost layer 2. Inner layer 3. Transparent plastic substrate 4. Gas barrier coating 5. Gas barrier plastic molded products

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Kondo 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. 72) Inventor Hiroshi Shimoda 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. JB12B JB12C JB14B JB14C JD02 JD03 JD04 JK06 JK09 JN01A YY00 YY00B YY00C

Claims (5)

[Claims] In a gas-barrier plastic molded article having two or more cured product layers formed on at least one surface of a transparent plastic substrate, an inner layer in contact with an outermost layer of the two or more cured product layers has the following coating: A gas-barrier plastic molded product, which is a layer of a cured product of the composition (A), and the outermost layer is a layer of a cured product of the following coating composition (B). Coating composition (A): an active energy ray-curable coating composition containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and polysilazane. Coating composition (B): a curable coating composition containing polysilazane as a main component. 2. A cured product of the coating composition (A) having a layer thickness of 1 to 50 μm, and the coating composition (B)
The gas-barrier plastic molded product according to claim 1, wherein the thickness of the layer of the cured product is 0.01 to 10 µm. 3. An oxygen permeability of 10 (mL / m ² · 24 h)
r · (1.013 × 10 ⁵ Pa)) or less and the water vapor permeability is 10 (g / m ² · 24 hr) or less. 4. A display element substrate comprising the gas-barrier plastic molded product according to claim 1. 5. The method for producing a gas-barrier plastic molded article according to claim 1, wherein a layer of the cured product of the coating composition (A) is provided on at least one surface of the transparent plastic substrate. And further forming a layer of an uncured or partially cured product of the coating composition (B) on the surface thereof, and then irradiating with an active energy ray, or further heating, leaving at room temperature or vapor of a curing catalyst solution after the irradiation. A method for producing a gas barrier plastic molded product, comprising curing the coating composition (B) by exposing the coating composition (B) to an atmosphere.