JP2002371147A - Coated molding for ultraviolet shielding and gas barrier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide coated moldings for UV shielding and gas barrier that has a variety of excellent characteristics, for example, gas barrier properties, UV shielding properties, adhesion to the substrate, transparency, flexibility. SOLUTION: The substrate is coated with a composition that includes a silicon compound bearing amino group and SiOR<1> group (R<1> is H or a 1-4C alkyl group), an organic compound bearing amino group-reactive functional group in the molecule, an organometallic compound represented by the general formula: R<2> m (OR<3> )n (wherein M is Si or a metal element; R<2> is a 1-4C alkyl or a 1-4C alkyl bearing a functional group unreactive toward amino group; R<3> is H or a 1-4C alkyl; n is an integer of >=1 and the value of m+n coincides the atomic value of M) and/or a hydrolyzate thereof) and further coated with the UV coating layer to obtain the molded products with UV-blocking and gas barrier coating layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel UV-shielded gas barrier coating molding.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide, water vapor and the like in the field of packaging materials and the like. Further, the demand for ultraviolet ray blocking materials having extremely low transmittance of ultraviolet rays is increasing in the field of food packaging materials such as fried foods such as potato chips and alcoholic beverages such as alcoholic beverages, the taste of which changes when exposed to ultraviolet rays. I have. In packaging materials such as beverages and food containers, in order to impart gas barrier properties to molded materials such as plastic films or sheets, ethylene-vinyl alcohol copolymers,
Forming molded objects with gas impermeable materials such as vinylidene chloride copolymers and aromatic nylons, laminating or coating these gas impermeable materials with other materials, laminating aluminum foil on film materials Do
A method such as vapor deposition of a metal oxide is used.

However, among these gas-impermeable materials, ethylene-vinyl alcohol copolymer and aromatic nylon are inferior in moisture resistance, and have a problem that gas barrier properties are greatly reduced as the humidity of the atmosphere increases. In addition, since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. Also, in the above aluminum foil laminated film, the packaged contents cannot be seen from the outside, and the metal oxide vapor-deposited film is inferior in flexibility, so it is difficult to apply it to food packaging materials, and cracks are formed in the vapor-deposited layer. There is a problem in that it is likely to occur and causes a decrease in gas barrier properties.

[0004] As a molded material such as a plastic film or a sheet having the above-mentioned gas barrier properties and ultraviolet shielding properties, the above-mentioned aluminum vapor-deposited or aluminum foil-laminated film or metal oxide-deposited film is often used. However, as described above, there are problems that the packaged contents cannot be seen from the outside, it is difficult to apply the packaged materials to food packaging materials, and the gas barrier property and the ultraviolet shielding property are deteriorated.

In general, ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate),
Molded products (processed products) made of various plastics (substrates) such as polystyrene, PP (polypropylene), PC (polycarbonate), and acrylic resin are more resistant to deterioration such as yellowing when exposed to ultraviolet rays than glass substrates. Easy to occur. Therefore, conventionally, it has been practiced to prevent ultraviolet light deterioration by laminating a weather-resistant resin film on the surface of these plastic molded products.

[0006] However, even when the above-mentioned laminating resin film is exposed to ultraviolet rays, its progress is slightly delayed, but deterioration such as yellowing remains unchanged, and its weather resistance is insufficient. . That is, the resin film for lamination has a problem that the protective effect of the underlayer and the effect of preventing yellowing are poor and the weather resistance is poor.

Therefore, for example, Japanese Patent Laid-Open Publication No.
Japanese Patent Application Laid-Open Publication No. H11-216, proposes that a weather resistance is imparted to the above-mentioned molded article by using a fluororesin composition obtained by copolymerizing a benzotriazole-based ultraviolet-absorbing monomer and a fluorine-containing monomer. ing. However, the fluororesin composition is inferior in adhesion and adhesion to plastics (substrates and the like) as molded articles. Further, the fluororesin composition has a problem that it is expensive and is easily stained (easily stained).

[0008]

Further, with respect to food packaging materials used for such food and beverage containers and packaging materials, there are strict checks by consumers at the time of product purchase. If there is a problem with the adhesion to the material or the flexibility, there is a problem with peeling, transparency, or poor printing, it will not be purchased regardless of the quality of the food or beverage itself. In some cases, the standards for food packaging materials used for food and beverage containers and packaging materials are extremely severe, and in addition to gas barrier properties and UV shielding properties, High performance requirements are required for adhesion to substrates, transparency, flexibility, printability, weather resistance, gloss, moisture resistance, water resistance, solvent resistance, etc. UV shielding that can provide materials The development of the gas barrier coating molded body is in urgent need.

[0009] Accordingly, an object of the present invention is to provide a gas barrier property and an ultraviolet blocking property,
Furthermore, the present invention provides a novel UV-blocking gas barrier coating molded article having excellent adhesion to a substrate or the like, transparency, flexibility, and the like, and capable of stably exhibiting these properties.

Further, in addition to the above-mentioned objects, the present invention provides weather resistance, gloss, moisture resistance, water resistance, solvent resistance, mechanical strength, An object of the present invention is to provide a novel UV-blocking gas barrier coating molded article capable of constantly stably expressing properties such as durability, impact resistance, heat resistance, light resistance, flexibility, and printability.

[0011]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of diligent study of the above problems, these objects express a high gas barrier property, and further have a coating layer having properties such as adhesion to a substrate and the like, transparency, flexibility, UV blocking properties,
By expressing a high UV blocking property and further laminating a coating layer having properties such as adhesion to the substrate, transparency, flexibility and gas barrier properties on the substrate, it can be used for food packaging materials, etc. The present inventors have found that they can meet the required strict requirements, are excellent in visibility, and can maintain the quality (taste, aroma, color, etc.) of the contents, and have completed the present invention.

[0012] That is, the object of the present invention is to provide
(1) A silicon compound (I) having an amino group and a SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in a molecule, and a functional group capable of reacting with the amino group. An organic compound (II) having a compound represented by the following general formula (1)

[0013]

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(Wherein, M is Si or a metal element; R ² is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group; R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is the same as the valence of M.) And / or a hydrolytic condensate thereof; and (2) a UV-blocking gas barrier coating molded article having a UV-blocking coating layer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The substrate which can be used for the UV-shielding gas-barrier coating molded article of the present invention includes various applications in which UV-shielding and gas-barrier properties are required, such as foods (including beverages; the same applies hereinafter). A plastic substrate used for a container, a packaging material, or the like can be used. Specifically, since the required properties required for the base material differ for each of these uses, it cannot be uniquely defined, and according to each required property (for example, mechanical properties, optical properties, etc.), The optimum base material should be appropriately selected, and is not particularly limited.

Examples of the substrate include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene isophthalate, and the like.
Polyester resins such as polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof, polyamides, polystyrene, ABS resin, poly (meth) acrylate, polyacrylonitrile,
Thermoplastic resins such as polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide, polysulfone, polyetherketone, ionomer resin, and fluororesin, melamine resin, polyurethane resin, epoxy resin, phenolic resin, unsaturated polyester resin, Thermosetting resin such as urea resin, alkyd resin, silicon resin,
Composite materials such as fiber reinforced plastic (FRP) and the like can be mentioned. The optimum base material varies depending on the application as described above. For example, when used as a food container or packaging material, the mechanical strength, transparency, heat resistance (boiling resistance), Polycarbonate (PC), high-impact polystyrene (HIPS), polyethylene terephthalate (PE) are used from the viewpoints of moldability, coloring, and low burn calorie.
T), ethylene vinyl alcohol copolymer (EVO
H), gas barrier resins, polyolefin-based resins such as polyethylene and polypropylene, polyacrylonitrile, polyamide, and cellophane are preferred, and thermoplastic resins such as polypropylene, polyamide, and PET are particularly preferred because of their ease of processing and versatility. Is more preferred. These may be used alone or in combination of two or more. In addition, these base materials themselves may be formed into a multilayer structure with materials having different properties in order to obtain required characteristics that cannot be obtained with a single material. In the present invention, the use of a plastic base material having transparency as described above is most common, but the use of a translucent or opaque plastic base material, and further the application of glass, ceramics, metal, etc. (by vapor deposition, etc.) Including the case of applying to some of them).

The shape of the substrate is not particularly limited, and has a characteristic that it can be formed into an arbitrary shape, and can be appropriately selected according to the intended use. Therefore, the gas barrier coating layer on such a substrate, the UV-shielding gas barrier coating molded body of the present invention obtained by forming a UV-shielding coating layer, the name should not be limited, for example, Any form used for food containers and packaging materials should be included in the scope of the present invention. The shape of the substrate may be a sheet shape, or a molded shape such as a bottle shape (including a PET bottle) or a tray shape, in addition to the film shape. Further, it may be a film or sheet, or may have a curved surface.

Since the thickness of the above-mentioned base material varies depending on the intended use, it is difficult to uniquely define the thickness, and it should be appropriately selected according to the intended use. For example, when it is used for food containers and packaging materials, it is usually in the range of 7 to 100 μm, preferably 10 to 30 μm.

When a transparent plastic substrate or the like is used as the substrate, for example, its surface is subjected to plasma treatment or corona discharge treatment in advance, or the surface of the substrate (substrate) is exposed to oxygen. 200 to 40 in an atmosphere containing
It is preferable to form the gas barrier coating layer and the V-blocking coating layer after irradiating ultraviolet rays having a wavelength near 0 nm.

If the composition cannot be uniformly coated by repelling the above-mentioned composition or the like depending on the adhesion state of the dirt on the above-mentioned substrate (substrate to be coated), it can be improved by washing or modifying the surface of the substrate. it can. Methods of cleaning and surface modification include degreasing cleaning with an organic solvent such as alcohol, acetone, and hexane, cleaning with an alkali or acid, polishing the surface with an abrasive, cleaning methods such as ultrasonic cleaning, and ultraviolet irradiation treatment. And surface modification methods such as ultraviolet ozone treatment, plasma treatment, corona discharge treatment, and heat treatment.

Next, in the UV-shielding gas barrier coating molded article of the present invention, a gas-barrier coating layer and a UV-shielding coating layer are formed on the above substrate. Here, the lamination order of the gas barrier coating layer and the UV-blocking coating layer is not particularly limited, and the gas barrier coating layer and then the UV-blocking coating layer may be laminated on the substrate. Then, a UV blocking coating layer and then a gas barrier coating layer may be laminated on the substrate in this order. Further, the gas barrier coating layer and the UV blocking coating layer may be formed directly on the base material, or may be other coating layers (adhesive layer, decorative layer, etc.) other than the gas barrier coating layer and the UV blocking coating layer. ) May be formed indirectly. Preferably, from the viewpoint of preventing the gas barrier coating layer from swelling, it is desirable to provide the gas barrier coating layer on the substrate side (lower layer side) and to provide the UV blocking coating layer on the upper layer side.

Among them, one of the main components of the composition used for forming the gas barrier coating layer,
The silicon compound (I) is not particularly limited as long as it has an amino group and a SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in the molecule. is not. The silicon compound (I) is a compound serving as a Si source in a coating layer obtained by coating a substrate with a gas barrier coating agent together with an organometallic compound (III) described later.

The silicon compound (I) is an organic compound (I) having a functional group capable of reacting with an amino group described later in the molecule.
In addition to reacting with I), the compound has a hydrolyzable Si (OR ¹ ) group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in the molecule. Compound (II)
Before or after the reaction with the hydrolysis hydrolysis condensation proceeds,
In addition, since condensation polymerization proceeds by causing co-hydrolytic condensation with a hydrolyzable condensed group of the organometallic compound (III) described below, a dense coating layer having excellent hard coat properties can be formed quickly. . Further, it also has an effect of increasing the adhesion between the coating layer (film) and the substrate (or another object to be coated such as a coating layer). As the composition, the silicon compound (I) may be used alone or in advance, or the organometallic compound (III) may be used.
And (co) hydrolytic condensation polymerization. This can prevent the silicon compound (I) and the organometallic compound (III) from permeating at the time of coating the composition on a substrate (or another object to be coated such as a coating layer). This is because a coating layer (coating film) can be formed on the substrate. When a low molecular weight compound is used as the organic compound (II), it is preferable to carry out hydrolysis and condensation in advance.

Here, R ^{1 in the} SiOR ¹ group is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, the alkyl group having 1 to 4 carbon atoms is not particularly limited, and is a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a branched chain alkyl group such as an isopropyl group, and a cyclopropyl group. And a cyclic (alicyclic) alkyl group of a cyclobutyl group. R ¹ is preferably a methyl group or an ethyl group from the viewpoints of excellent hydrolytic condensation reactivity, advantages in forming a dense film, and ease of reaction.

The silicon compound (I) having the above amino group and SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in the molecule includes, specifically,
N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ
-Aminopropyltriisopropoxysilane, N-β
(Aminoethyl) -γ-aminopropyltributoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldibutoxysilane, N-β (aminoethyl)-
γ-aminopropylethyldimethoxysilane, N-β
(Aminoethyl) -γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) -γ-aminopropylethyldibutoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyl Diisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, γ-
(2-ureidoethyl) aminopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ
-Aminopropyltrimethoxysilane and the like. These may be used alone or in combination of two or more. Preferably, from the viewpoint of ease of reaction, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane.

The organic compound (II), which is one of the main components of the composition used for forming the gas barrier coating layer of the molded article for UV blocking gas barrier of the present invention, reacts with an amino group. Any organic compound having a possible functional group in the molecule may be used, and is not particularly limited.

Here, the functional group capable of reacting with the amino group is not particularly restricted but includes, for example, an epoxy group, a carboxyl group, an isocyanate group, a thioisocyanate group, an oxazolinyl group, a (meth) acryl group, Examples include an aldehyde group, a ketone group, and an alkyl halide group. Preferably, ease of reaction with an amino group,
It is an epoxy group from the viewpoint of hot water resistance.

As described above, the organic compound (II) having a functional group capable of reacting with an amino group in the molecule is not particularly limited. For example, specific examples of the epoxy group-containing compound include: 2-ethylhexyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether , Tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol jig Aliphatic mono- and diglycidyl ethers such as sidyl ether and trimethylolpropane diglycidyl ether; glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, trimethylolpropane triglycidyl ether , Polyglycidyl ethers such as pentaerythritol tetraglycidyl ether; aliphatic and aromatic mono- such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester and phenylglycidyl ether;
Diglycidyl esters; bisphenol A diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisiphenol S diglycidyl ether, bisphenol F diglycidyl ether, and compounds represented by the following formula;

[0030]

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Glycidyls having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative); or oligomers having a glycidyl group as a functional group (for example, in the case of bisphenol A diglycidyl ether oligomer, Can be expressed);

[0032]

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And the like.

Hexamethylene diisocyanate,
Isocyanates such as tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; dicarboxylic acids such as tartaric acid and adipic acid; polyacrylic A carboxyl group-containing polymer such as an acid; an oxazolinyl group-containing polymer can also be used as the organic compound (II). These may be used alone or in combination of two or more. In addition, among the organic compounds (II) exemplified above, compounds having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative) have a water resistance of a gas barrier coating layer (film) formed by coating the composition. This is advantageous in that it has an effect of improving.

Further, as another one of the main constituent components of the above composition used for forming the gas barrier coating layer of the molded article for UV blocking gas barrier coating of the present invention, the following general formula (1):

[0036]

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[0037] (wherein, M is Si or metal element, R ² is an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an alkyl group or an amino group having 1 to 4 carbon atoms, R ³ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is the same as the valence of M.)
And / or a hydrolyzed condensate thereof. When the composition contains an organometallic compound (III) and / or a hydrolytic condensate thereof, it enhances adhesion to a substrate (substrate to be coated), hard coat properties, and heat resistance, and packages food and beverages. Because it can maintain a sufficiently high gas barrier property even under a severe storage environment (for example, at a high humidity of about 20 ° C. and 90% Rh) after boiling sterilization, which can be said to be inevitable when used as a material. It is suitable. The organometallic compound (III) can be distinguished from the organic compound (II) in that it does not have a functional group capable of reacting with the functional group of the silicon compound (I).

M in the above general formula (1) is not particularly limited as long as it is Si or a metal element. However, from the viewpoint of easy handling during the coating treatment operation, M is preferably Si, It is one kind selected from Ti, Zr, and Al, and is particularly preferably Si.

R ² in the above general formula (1) has 1 to 1 carbon atoms.
Any alkyl group having 1 to 4 carbon atoms having a functional group that does not react with an alkyl group of 4 or an amino group may be used. here,
The functional group that does not react with the amino group is not particularly limited, and includes, for example, an amino group and a vinyl group. The alkyl group having 1 to 4 carbon atoms is not particularly limited, and may be a methyl group, an ethyl group, a propyl group, a linear alkyl group such as a butyl group, a branched chain alkyl group such as an isopropyl group, a cyclopropyl group, Any of a cyclo (alicyclic) alkyl group of a cyclobutyl group may be used, but it is preferably excellent in the reactivity of hydrolytic condensation, advantageous in forming a dense film, and from the viewpoint of ease of reaction. These are a methyl group and an ethyl group. Therefore, R ² is preferably an alkyl group having 1 to 4 carbon atoms having a vinyl group from the viewpoint of heat resistance and boiling resistance. When m is 2 or more, R ² may be the same or different.

R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is not particularly limited, and may be a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a branched chain alkyl group such as an isopropyl group, a cyclopropyl group, or a cyclobutyl group. May be any of the cyclic (alicyclic) alkyl groups. R ³ is preferably a methyl group or an ethyl group from the viewpoint of excellent hydrolytic condensation reactivity and the advantage of forming a dense film. Note that R ³
May be the same or different when n is 2 or more.

In the general formula (1), n is an integer of 1 or more, m is an integer of 0 or more, and m + n is equal to the valence of M. For example, when M is Si, m
+ N = 4, and from the viewpoints of heat resistance, boiling resistance, and water resistance of the gas barrier coating layer obtained by coating the composition,
Preferably, m = 0 and n = 4.

Specific examples of the organometallic compound (III) represented by the above general formula (1) include, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyl Trimethoxysilane, methyltriethoxysilane,
Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, alkoxysilanes such as γ-methacryloxypropyltriethoxysilane, titanium tetraethoxide, titanium tetraisopropoxide, Titanium alkoxides such as titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium alkoxides such as zirconium tetrabutoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum alkoxides such as aluminum tributoxide, or These complex compounds, methyltriacetoxysilane, trimethylsilanol, etc. Organic compounds, etc. are mentioned, it is possible to use one or more of these. Above all, the reactivity and the resulting gas barrier coating layer obtained show good boiling resistance, moisture resistance, and water resistance,
Tetramethoxysilane, tetraethoxysilane, or oligomers thereof are preferred.

The reason that the organic metal compound (III) represented by the above general formula (1) may contain a hydrolyzed condensate may be that the organic compound (II) and the organic metal compound (III) are This is because, in order to prevent drying when forming the gas barrier coating layer, it is preferable to carry out hydrolysis and condensation in advance. In other words, in the composition,
Those in which these hydrolysis condensates can exist can be said to be preferable. These (co) hydrolytic condensation reactions proceed with moisture in the air, but can be performed efficiently using a known catalyst such as an acid or a base. In addition, the hydrolysis reaction is preferably performed in a solvent, and the above composition containing such a solvent also facilitates a coating operation on a substrate (or another coating layer, an adhesive layer, or the like).

The above-mentioned composition used for forming the gas-barrier coating layer of the UV-shielding gas-barrier coating molding of the present invention contains a solvent capable of suitably dissolving (or dispersing) the above-mentioned main components and the like. May be included.
Examples of the solvent include those capable of dissolving the silicon compound (I), the organic compound (II), and the organometallic compound (III) and / or a hydrolyzed condensate thereof, and various additives used as necessary. If it is not particularly limited, for example, methanol, ethanol,
Alcohols such as 2-propanol, butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone;
Ketones such as cyclohexanone; toluene, benzene,
Aromatic hydrocarbons such as xylene; hexane, heptane,
Hydrocarbons such as octane; acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; and others, ethyl phenol ether, propyl ether, tetrahydrofuran, water and the like. These may be used alone or as a mixture of two or more. Among them, alcohols such as methanol and ethanol are preferred because they are excellent in stability during hydrolysis reaction and storage stability. In particular, in the present invention, the cross-linking of the obtained gas barrier coating layer becomes dense depending on the type of the other components of the composition other than the solvent, and various properties such as a desired gas barrier property are obtained. It is desirable to appropriately select an appropriate solvent so that the expression can be effectively performed.

The composition used for forming the gas barrier coating layer of the molded article for UV blocking gas barrier of the present invention may further comprise a curing catalyst, a wettability improver, a plasticizer, a defoamer, if necessary. An appropriate amount of various inorganic or organic additives such as an agent and a thickener can also be added.

Next, the compounding amount of the silicon compound (I) depends on the organic compound (II) and the organometallic compound (III).
And / or the presence / absence of the use of other additives cannot be unambiguously defined because the ratio varies depending on the compounding ratio of the hydrolyzed condensate of the organometallic compound (III) and the presence or absence of other additives. , Excluding the solvent), usually 5 to 70% by mass, preferably 10 to 6% by mass.
0 mass%, more preferably 15 to 40 mass%. When the compounding amount of the silicon compound (I) is less than 5% by mass, the film forming property of the gas barrier coating layer may be poor. On the other hand, if it exceeds 70% by mass, the flexibility and water resistance of the gas barrier coating layer may be poor.

The compounding amount of the organic compound (II) depends on the silicon compound (I), the organometallic compound (III) and / or
Alternatively, it cannot be uniquely defined because it differs depending on the compounding ratio of the hydrolysis-condensation product, the presence or absence of other additives, and the like, but the components of the composition (however,
(Excluding the solvent), usually 1 to 50% by mass, preferably 3 to 30% by mass, more preferably 5 to 1% by mass.
The range is 5% by mass. If the amount of the organic compound (II) is less than 1% by mass, the flexibility of the gas barrier coating layer may be poor. On the other hand, if it exceeds 50% by mass, the water resistance of the gas barrier coating layer may be poor.

The amount of the organometallic compound (III) and / or the hydrolytic condensate thereof may be determined depending on the mixing ratio of the silicon compound (I) or the organic compound (II), the presence or absence of other additives, and the like. Although it cannot be unambiguously defined because of the difference, the components of the composition (however,
(Excluding solvent), usually 10 to 80% by mass, preferably 20 to 70% by mass, more preferably 3 to 80% by mass.
It is in the range of 0 to 60% by mass. The above organometallic compounds (II
I) and / or the amount of the hydrolyzed condensate is 80
If the amount is more than mass%, the flexibility of the gas barrier coating layer may be poor. On the other hand, if it is less than 10% by mass, the water resistance of the gas barrier coating layer may be poor.

Although the amount of the solvent is not particularly limited, the total weight of the composition (including the solvent in this case) is 1%.
10% to 95% by mass, preferably 50% to 90% by mass, and more preferably 70% to 90% by mass,
Range. If the compounding amount of the solvent is less than 10% by mass, the reaction stability of the composition may be poor, and the viscosity of the composition may increase during coating, making uniform coating impossible. There is. On the other hand, if it exceeds 95% by mass, the productivity in forming the gas barrier coating layer may be poor, and the active ingredient may be too low in concentration, so that the required film thickness of the gas barrier coating layer cannot be secured. There are cases.

The above-mentioned silicon compound (I), organic compound (II), organometallic compound (III) and / or a hydrolytic condensate thereof, a curing catalyst other than a solvent, a wettability improver, a plasticizer, With respect to the compounding amount of various inorganic or organic additives such as an antifoaming agent and a thickening agent, various characteristics of the additive can be sufficiently exhibited, and the silicon compound (I) and the organic compound (II) ), The organometallic compound (III) and / or its hydrolytic condensate, and the solvent are not particularly limited as long as they do not affect the gas barrier properties and the like of the present invention.

The above composition containing the silicon compound (I), the organic compound (II), the organometallic compound (III) and / or a hydrolytic condensate thereof, and other additives (excluding the solvent) ) Is always 100% by mass in any combination.

The method of preparing the composition used for forming the gas barrier coating layer of the UV-shielding gas barrier coating molded article according to the present invention is not particularly limited. For example, (1) the silicon compound (I)
And the organic compound (II) and the organometallic compound (II
A compounding component containing I) and / or a hydrolysis condensate thereof, and a solvent (other optional components may be contained)
(2) performing a functional group reaction between the silicon compound (I) and the organic compound (II) in the presence of a solvent in advance, and then mixing the organometallic compound (III) and / or a hydrolyzate thereof. A method of adding a decomposition condensate, (3) a method of co-hydrolyzing and condensing the silicon compound (I) and the organometallic compound (III) in the presence of the organic compound (II) and a solvent, and (4) A method of co-hydrolyzing and condensing the above-mentioned silicon compound (I) and the above-mentioned organometallic compound (III) in the presence and then reacting with the above-mentioned organic compound (II). Not something. It is desirable that the above-mentioned solvent be appropriately replenished or added in a timely manner depending on the preparation step and method.

The method for coating the above composition on the surface of a substrate or another coating layer (hereinafter also simply referred to as a substrate or the like in the present specification) is not particularly limited. Known techniques can be appropriately used, for example, roll coating, dip coating, bar coating, nozzle coating, die coating, spray coating, spin coating, curtain coating,
Various printing methods, such as a flow coating method, screen printing, gravure printing, and curved surface printing, or a combination thereof can be employed. Among them, the die coating method is preferable for increasing the stability of the composition.

After coating the above composition, the coating layer (gas barrier coating layer) is cured and dried. In such curing and drying, heating or heating
Humidification is preferred in that a dense coating layer (gas barrier coating layer) having excellent hard coat properties can be formed quickly. When heating here, it is preferable to heat at a temperature lower than the heat-resistant temperature of the substrate or other coating layer. From the viewpoint of preventing evaporation of the organometallic compound (III) at the time of drying, it is preferable to use the above composition comprising a hydrolyzed condensate of the organometallic compound (III).

Further, the SiOR ^{1 of the} unreacted silicon compound (I) in the coating layer (gas barrier coating layer)
It is desirable to reduce the MOR ³ group of the organometallic compound (III) and the organometallic compound (III) in order to maintain a sufficient gas barrier property even in a high-temperature and high-humidity environment. After coating by the method, the coating layer (gas barrier coating layer) is cured and dried, and then the unreacted SiOR ¹ group of the silicon compound (I) and the organometallic compound (III) in the coating layer are dried. It is preferable to carry out an aging (aging) treatment for reacting (condensing) the MOR ³ groups. For example, after applying and drying the above composition on the surface of a substrate or the like, an effective heat treatment for reducing unreacted groups ( For example, a method of performing heat treatment at a temperature between 40 to 60 ° C. for 1 to 7 days), a method of performing corona treatment, and the like are preferable. However, the aging process is
(1) The composition may be applied to the surface of a substrate or the like and dried and cured to form a gas-barrier coating layer, and then immediately, or (2) As described in Examples described later, the composition may be used. The method may be carried out after the product is applied to the surface of a substrate or the like, dried and cured to form a gas barrier coating layer, and then after forming a UV blocking coating layer and further another coating layer. Here, the heat-resistant temperature of the base material or the like is substantially the upper limit temperature at which the properties of the base material or the like can be maintained, and for a glass base material, for example, the softening point or the devitrification temperature (normally 600 to 700 ° C.) ), For example, a glass transition point, a crystallization temperature, a decomposition point, and the like. Before the application of the composition,
It goes without saying that another coating layer such as a known anchor coat layer such as a urethane resin or an adhesive layer may be provided on the surface of the base material or the like.

By the above curing, drying and heat treatment, a gas barrier coating layer obtained from the above composition can be formed on the surface of a substrate or the like. The thickness of the gas barrier coating layer after drying cannot be uniquely defined because it differs depending on the intended use. However, it exhibits high gas barrier properties and further exhibits adhesion, transparency, and flexibility with a substrate or the like. Any material that can have moisture resistance and the like may be used, and is usually 0.01 to 20 μm, preferably 0.1 to 10 μm.
μm, more preferably in the range of 0.5 to 5 μm. The thickness of the gas barrier coating layer after drying is 0.01 μm
If it is less than 1, the coating will not be uniform, and properties such as gas barrier properties, adhesion to substrates and the like, transparency, flexibility, and moisture resistance will not be sufficiently exhibited. On the other hand, when the thickness of the gas barrier coating layer after drying exceeds 20 μm, cracks tend to occur in the coating.

In the gas barrier coating layer obtained by coating the above composition on a substrate or the like, the same type (composition) of the above composition may be separately applied to the substrate or the like. Alternatively, by separately applying the above compositions of different types (compositions), a multilayer structure having a different composition and thickness for each layer (even if a UV blocking coating layer or another coating layer is interposed in the middle) Good) gas barrier coating layer.

Next, the UV-blocking coating layer is not particularly limited, and can be formed by using various known UV-blocking coating agents.
Any barrier coating layer may be used, but it exhibits high UV blocking properties, and further has adhesion to a substrate or the like (including the gas barrier coating layer), transparency, flexibility, weather resistance, gloss, and water resistance. ,
A coating layer having characteristics such as solvent resistance is preferable. Specifically, for example, the following general formula (2)

[0059]

Embedded image

(Wherein R ⁴ is a hydrogen atom or a carbon atom having 1 to
8 represents a hydrocarbon group, R ⁵ represents a linear or branched alkylene group having 1 to 6 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a halogen group. , A hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group), and the following general formula (3)

[0061]

Embedded image

(Wherein R ⁷ is a hydrogen atom or a group having 1 to 1 carbon atoms)
2 represents a hydrocarbon group, and Z represents a cycloalkyl group which may have a substituent). Coalescing layer (UV blocking coating layer);

Hereinafter, the copolymer layer will be described as a preferred embodiment of the UV blocking coating layer of the present invention. However, the UV blocking coating layer of the present invention should not be limited to these. Needless to say.

The ultraviolet absorbing monomer represented by the above general formula (2) (hereinafter referred to as ultraviolet absorbing monomer (2))
In the formula, a substituent represented by R ⁴ is a hydrogen atom or a group having 1 carbon atom.
And a substituent represented by R ⁵ is a linear or branched alkylene group having 1 to 6 carbon atoms, and a substituent represented by R ⁶ is a hydrogen atom. Or a benzotriazole composed of a methyl group, wherein the substituent represented by X is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. Kind.

As the ultraviolet absorbing monomer (2),
Specifically, for example, 2- [2′-hydroxy-5′-
(Methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′-
(Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxypropyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyhexyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-3'-
t-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5- Methoxy-
2H-benzotriazole, 2- [2′-hydroxy-
5 '-(methacryloyloxyethyl) phenyl] -5
-Cyano-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole,
Examples thereof include 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, but are not particularly limited. One kind of these ultraviolet absorbing monomers (2) may be used alone, or two or more kinds thereof may be appropriately mixed and used.

The unsaturated monomer represented by the above general formula (3) has a substituent represented by R ⁷ which is a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and is represented by Z Wherein the substituent is a cycloalkyl group which may have a substituent.

The cycloalkyl group in the substituent represented by Z is, for example, a monocyclic saturated hydrocarbon residue such as a cyclopentyl group, a cyclohexyl group or a cyclododecyl group. And the cycloalkyl group may have a C1-C7 alkyl group as a substituent. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and a heptyl group.

Specific examples of the unsaturated monomer (hereinafter, referred to as a cycloalkyl group-containing monomer) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (Meth) acrylate, cyclododecyl (meth)
Examples include acrylates, but are not particularly limited. As the cycloalkyl group-containing monomer, only one type may be used, or two or more types may be appropriately mixed and used.

The method for forming the above-mentioned UV-blocking coating layer on the surface of a substrate or the like is not particularly limited. For example, by preparing a coating composition obtained by adding a crosslinking agent to a polymer composition containing a copolymer obtained by copolymerizing a monomer composition, and applying the coating composition or the like. A UV-blocking coating layer may be formed. Also, once the coating composition is formed into a film, the film is fused, thermocompressed, or adhered to the surface of a substrate or the like to thereby form a UV-blocking coating. A coating layer may be formed. Further, after a UV-blocking coating layer is once formed on the molding surface of the mold, the UV-blocking coating layer may be transferred to the substrate.

In the coating composition, the content of each of the monomers in the monomer composition is not particularly limited. 3
The range is preferably 0% by mass, more preferably 1 to 20% by mass, and particularly preferably 2 to 15% by mass. Further, the cycloalkyl group-containing monomer is 2-95.
It is preferably within the range of 5% by mass, more preferably within the range of 5 to 85% by mass, and particularly preferably within the range of 10 to 75% by mass.

The UV-blocking coating has a light transmittance at a wavelength of 360 nm of preferably 30% or less, more preferably 1% or less.
0% or less.

The UV-shielding gas barrier coating molded article of the present invention is excellent in gas barrier properties and ultraviolet ray blocking properties, and is also excellent in adhesion to substrates and the like, transparency, flexibility and the like. As long as it can be expressed stably, the gas barrier properties must be uniquely defined because the required standards differ depending on the intended use, and also vary depending on the type of substrate and the overall laminated structure. Although it is not possible, for example, it is used as a film for containers and packaging of foods and drinks such as potato chips and alcoholic beverages that are easily oxidized, loses flavor due to ultraviolet rays, and easily discolors (yellowing) if,
Gas (oxygen) permeability under high humidity (20 ° C. 90% Rh) is 30 ml / m ² · 24 hrs or less, preferably 20 ml
/ M ² · 24 hrs or less, more preferably 10 ml / m ²
・ It is desirable to be 24 hours or less. If the gas (oxygen) permeability exceeds 30 ml / m ² · 24 hrs, a gas such as oxygen cannot be sufficiently cut by the UV-shielding gas barrier coating molded body, and a considerable amount of oxygen permeates. As a result, the flavor of potato chips, alcoholic beverages, and the like is lost or discolored (yellowing) due to oxygen and the like over time, and the shelf life of such foods is prolonged (high-quality long-term Retention) cannot be achieved sufficiently.

Examples of the coating molded article for UV barrier gas barrier according to the present invention include, in particular, films for containers and packaging of foods and beverages, plastic molded articles such as tanks and containers, household electrical appliances, steel and the like. Examples include, but are not limited to, products, large structures, automotive interior / exterior parts, building materials, woodwork, glass products, and the like.

[0074]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the present invention in any way, and can be modified and implemented without departing from the spirit of the preceding and the following. Everything is included in the technical scope of the present invention. The “parts” representing the amounts of the respective components are all “parts by mass”.

Reference Example 1 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole
5 parts, cyclohexyl methacrylate 20.0 parts, 4-
Methacryloyloxy-2,2,6,6-tetramethylpiperidine 1.2 parts, methacrylic acid 0.3 parts, hydroxyethyl acrylate 6.0 parts, butyl acrylate 1
0.0 part and 10.0 parts of methyl methacrylate were mixed with 2,2′-azobis (2-methylbutyronitrile) in a mixed solvent of 30.0 parts of toluene and 19.0 parts of butyl acetate.
Polymerization was performed at 90 ° C. using 0.8 part as a polymerization initiator to obtain a UV blocking coating agent (1).

Example 1 N-β (aminoethyl) -γ-aminopropyltrimethoxysilane {silicon compound (I)} 14 g and bisphenol A diglycidyl ether {organic compound (II)} 2
g, a mixture of 10 g of toluene (solvent) and 30 g of methanol (solvent) at 60 ° C. for 3 hours, and then cooled to room temperature, 2.8 g of water (solvent) and 10 g of methanol (solvent).
g of the mixed solution, and reacted for 30 minutes. Further, 8.5 g of M silicate 51 (tetramethoxysilane oligomer; manufactured by Tama Chemical Co., Ltd., hydrolyzed condensate of organometallic compound (III)) and 20 g of methanol (solvent) Was added and reacted for 1 hour to obtain a coating agent (1).

This coating agent (1) was treated with 25 μm PE
The film was coated on a T film so that the thickness after drying was 1 μm, dried at 100 ° C. for 20 seconds, and the UV blocking coating agent (1) obtained in Reference Example 1 was dried so as to have a thickness of 2 μm. And dried at 100 ° C for 20 seconds.
After aging for a day, a UV-shielding gas barrier coating molded article (1) was obtained, which was laminated on a PET film substrate in the order of a gas-barrier coating layer and a UV-shielding coating layer.

Table 1 below shows the characteristic evaluation of the coated molded article (1).

Comparative Example 1 A comparative coated molded product (1) was obtained in the same manner as in Example 1 except that the UV-blocking coating layer of the UV-blocking coating agent (1) was not provided. .

The evaluation of the properties of the comparative coated molded article (1) is also shown in Table 1 below.

Comparative Example 2 A comparative coated molded article (2) was obtained in the same manner as in Example 1 except that the gas barrier coating layer of the coating agent (1) was not provided.

The evaluation of the properties of the comparative coated molded article (2) is also shown in Table 1 below.

[0083]

[Table 1]

Light transmittance (%) in Table 1: The light transmittance at 360 nm was measured.

Oxygen permeability in Table 1: Measured at 20 ° C. and 90% Rh using an oxygen permeability measuring device manufactured by Modern Controls. The unit is ml / m ² · 24 hrs · atm.

Flexibility in Table 1: Judgment was made by the following tests.

：: The molded article was bent at 180 ° and no crack was generated.

×: Cracks occur when the molded body is bent at 180 °.

[0089]

As described above, the coating product for UV barrier gas barrier of the present invention has excellent UV blocking properties,
Gas barrier properties, adhesion to substrates, etc., transparency, flexibility,
Furthermore, it has properties such as weather resistance, gloss, moisture resistance, water resistance, solvent resistance, mechanical strength, durability, impact resistance, heat resistance, light resistance, flexibility, and printability. ) Can be widely applied in various fields requiring, for example, containers and packaging materials for foods and beverages, in particular, are easily oxidized, lose their flavor due to ultraviolet rays, and discolor (yellow). Containers and packaging materials for foods and beverages such as fried foods such as potato chips and alcoholic beverages (specifically, laminating a gas barrier coating layer and a UV blocking coating layer on a plastic base material) Electronic components (eg, a UV-blocking coating layer of a liquid crystal display, a liquid crystal display device, a portable terminal or a mobile device, etc.) Such as gas barrier coating layer polymer film substrate is formed), medical equipment and medical instruments (e.g., blood storage back, etc.) is applicable to a wide range of applications, such as. In addition, since the properties of each coating layer formed on the substrate are not impaired even when subjected to stress due to shrinkage, shrink films (shrinkable films) used in containers and packaging materials for food and beverages Is also applicable to
It is very widely applicable.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4F006 AA35 AB32 AB34 AB37 AB39 BA05 CA07 4F100 AH03B AH06B AH08B AK25 AK42 AR00C AT00A BA03 BA07 BA10A BA10C EH46 EJ86 GB15 GB23 GB41 GB66 JB07 JD02 JD03 JD09 JD09 JD09 JK17 JL00 JN01 JN21

Claims (1)

[Claims] 1. An amino group and a SiOR ¹ group (R ¹
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) In the molecule and an organic compound (I) having a functional group capable of reacting with an amino group in the molecule.
I) and the following general formula (1) (Where M is Si or a metal element;
² is an alkyl group having 1 to 4 carbon atoms having a functional group that does not react with an alkyl group having 1 to 4 carbon atoms or an amino group;
R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is the same as the valence of M. Organometallic compound (III) represented by
And / or a UV-shielding gas barrier coated molded article having a coating layer obtained from a composition containing a hydrolysis-condensation product thereof and a UV-shielding coating layer.