JP2012193303A - Coated plastic molding and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated plastic molding which can improve gas barrier properties regardless of material quality of the plastic molding, by coating the surface of the plastic molding with a layer providing a role as a gas barrier layer, a role as an adhesion layer and a role as a ground layer suitably expressing the performance of a thin film.SOLUTION: This coated plastic molding 90 includes: a plastic molding 91; and a hardened layer 92 formed on the surface of the plastic molding 91 and made by condensation reaction of a compound expressed by general formula: R-M-(CH)(OR'). In general formula, M represents silicon or a metal; R represents a hydrocarbon chain having an amino group; R' represents a 1-4C alkyl group; and n denotes 0, 1 or 2.

Description

  The present invention relates to a coated plastic molded body that can be combined with a gas barrier thin film and a method for producing the same.

  Plastics have the advantages of transparency, lightness, impact resistance, corrosion resistance, and processability, are inexpensive, and can be used for high-mix low-volume production, so they can be used for packaging food, beverages, pharmaceuticals, cosmetics, etc. Suitable as packaging material. However, compared with other packaging materials such as metal or glass, plastic has a problem that it has a low gas barrier property and is not suitable as a packaging material for contents that hate oxidation or contents containing gas such as beer. .

  Accordingly, a coated plastic molded body having a thin film having gas barrier properties (hereinafter sometimes referred to as a gas barrier thin film) has been proposed. For example, a gas barrier film having excellent gas barrier properties in which a coating film made of a water-insoluble resin fine particle and one or more metal oxides selected from the group consisting of silica, zirconia, alumina, and titania is formed on a plastic substrate. It has been proposed (see, for example, Patent Document 1). In addition, a metal oxide anchor coat layer having a thickness of 0.5 to 5.0 nm is formed between the base film and a metal such as silicon, aluminum, magnesium, titanium, zirconia, or tin, or a thin film layer thereof. A laminated gas barrier film has been proposed (see, for example, Patent Document 2).

  In recent years, as a means for imparting gas barrier properties to a plastic container, it has been proposed to cover the surface of the plastic container with a DLC (Diamond Like Carbon) film (see, for example, Patent Document 3 or 4). The DLC film is a film having an amorphous three-dimensional structure with carbon atoms and hydrogen atoms, and is a hard carbon film that is hard, excellent in insulation, has a high refractive index, and has a very smooth morphology. In Patent Document 3, a diamond-like carbon (DLC) film having a film thickness of 5 to 35 nm is formed on the surface of a plastic container by plasma chemical vapor deposition (CVD). In Patent Document 4, CVD plasma treatment using a methane-argon mixed gas on the surface of a polymer substrate to form a carbon interlayer film, and further using a hydrocarbon-containing gas on the carbon interlayer film The technique of forming a DLC film having excellent adhesion on the surface of a polymer substrate by forming a diamond-like carbon film is disclosed.

  However, while these gas barrier thin film technologies are currently put to practical use mainly with polyethylene terephthalate (PET) base materials, they are widely used not only in packaging containers but throughout the industry, and they are versatile. However, the practical use of polyolefin base materials such as polyethylene base materials has not progressed. The reason is, for example, that these polyolefin base materials are made of a chemically inert polymer, and the surface tends to become rough due to the influence of spherulite properties and moldability. Therefore, a technique for performing plasma treatment on the surface of a polypropylene film for surface activation has been disclosed (see, for example, Patent Document 5). In order to smooth the surface, before forming a vapor-deposited film of silicon oxide by ion plating, one or two kinds of resins are used as the main components of the vehicle on the surface of the polypropylene film, and a curing agent is added thereto. A technique for providing a plasma-resistant protective layer with a curable resin composition added is disclosed (see, for example, Patent Document 6). In order to improve the adhesion between the gas barrier coating and the plastic substrate by forming a gas barrier coating having an alkali metal polysilicate as the main component on the plastic substrate mainly composed of polyolefin, A technique for further adding a nitrogen compound and / or a water-soluble polymer to a silicate is disclosed (see, for example, Patent Document 7). In order to reinforce the adhesive strength between the base sheet made of olefin resin and the thermoplastic resin layer made of olefin resin, a technique of adding a silane coupling agent is disclosed (for example, see Patent Document 8). In order to improve adhesion, a transparent primer layer made of a composite of a silane coupling agent, an acrylic polyol and an isocyanate compound is provided on the surface of a polypropylene film substrate, and a deposited thin film layer made of an inorganic oxide is formed thereon. The technique to provide is disclosed (for example, refer patent document 9).

JP 2009-269217 A JP 2010-605 A JP 2008-230648 A Japanese Patent Laying-Open No. 2005-2377 JP 2008-248374 A JP-A-11-105218 JP 2002-113826 A JP-A-8-230113 JP 2000-254994 A JP-A-08-53116 WO2006 / 126777 Publication

  The gas barrier film described in Patent Document 1 forms a metal oxide structure constituting a gas barrier coating film by hydrolyzing and polycondensing a metal alkoxide for the purpose of improving gas barrier properties. . This hydrolysis / polycondensation reaction requires, for example, a reaction time of 1.5 hours at 110 ° C., so that the treatment takes time, and there is a concern about damage to the substrate due to heat. In addition, a gas barrier coating film is formed by applying and drying a coating solution on a base film by a so-called wet method, which is suitable for forming a film on a planar object such as a plastic film. It is not suitable for forming a film on a three-dimensional object such as a bottle. In the gas barrier film described in Patent Document 2 or Patent Document 6, a thin film is formed using a physical vapor deposition method, but the physical vapor deposition method is expensive because the manufacturing apparatus is expensive and the film formation speed is slow. It is difficult to say that it is an effective means as a method for producing a plastic molded article as an application.

  In Patent Document 5, a so-called weak boundary layer is generated on the polypropylene surface by the plasma treatment, and there is a fear that the adhesion strength between the polypropylene film and the thin film is insufficient. In Patent Documents 7 to 9, the silane coupling agent has an original role, that is, a function of binding both by bonding to surfaces having different chemical properties by functional groups having different properties at both ends. It's being used. However, in any case, the gas barrier thin film is used as an intermediate layer, and it is not mentioned that the thin film can be applied to an application in direct contact with food or beverage.

  In spite of the aforementioned problems, the so-called wet method, in which a plastic bottle surface is coated and dried using a coating solution, is active against the inertness and / or roughness of the polyolefin substrate surface described above. In addition, it is a promising means for forming a gas barrier thin film on a polypropylene base material or a polyethylene base material from the viewpoint that the smoothness (leveling) can be imparted at the same time and that the moldability of the container is not affected. It can be. However, the coating solution to be used can adhere to both the polypropylene or polyethylene and the gas barrier thin film, and can perform high-speed processing that can follow the properties of the underlying layer that develops the gas barrier properties of the thin film and the speed of container production. Properties are required. Furthermore, in order to use for containers for beverages and foods, safety to the human body is required. As far as the present inventors know, a coating solution that can be applied to a three-dimensional object such as a container, a treatment method using an underlayer of a gas barrier thin film, and a gas barrier container obtained as a result are not known.

  An object of the present invention is to cover the surface of a plastic molded body with a layer having a role as a gas barrier layer, a role as an adhesion layer, and a role as an underlayer that makes the performance of a thin film appear well. The object is to provide a coated plastic molded body capable of improving the gas barrier property regardless of the material. A second object of the present invention is to provide a method for producing a coated plastic molded body that can improve gas barrier properties safely and at high speed using a production apparatus that does not require expensive equipment.

  The inventors of the present invention do not use a coupling agent having an amino group as a coupling agent but a condensation reaction as a raw material of a cured layer that covers the surface of a plastic molded body, so that the cured layer becomes an adhesion layer. The present invention was completed by discovering that the cured layer itself has a gas barrier property, as well as a role as a base layer that satisfactorily expresses the performance of the thin film and the performance of the thin film.

The coated plastic molded body according to the present invention includes a plastic molded body and a cured layer obtained by condensation reaction of a compound represented by the general formula (Chemical Formula 1) formed on the surface of the plastic molded body. .
(Chemical Formula 1) R-M- (CH ₃ ) _n (OR ′) _3-n
In the general formula (Formula 1), M represents silicon or metal. R represents a hydrocarbon chain having an amino group. R ′ represents an alkyl group having 1 to 4 carbon atoms. N represents 0, 1 or 2.

  In the coated plastic molded body according to the present invention, the compound represented by the general formula (Formula 1) is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3. Includes forms that are -aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, or N-phenyl-3-aminopropyltrimethoxysilane.

  In the coated plastic molded body according to the present invention, the cured layer has an element concentration ratio of O of 3.0 to 4.5 and C of 3.0 to 16 when the element concentration of M is 1. 5, It is preferable that it is a layer containing 0.5 to 2.5 N. The layer is substantially colorless, and has a high barrier property and a physicochemical stability in an aqueous solution in a weakly acidic to neutral range (hereinafter, also referred to as content resistance in the present specification). .

  The coated plastic molded body according to the present invention includes a form in which the plastic molded body is polypropylene, polyethylene, or a mixture thereof. Even if the plastic molding is a material that is chemically inert and has a relatively rough surface, gas barrier properties can be imparted.

  In the coated plastic molded body according to the present invention, it is preferable that a thin film is further provided on the cured layer. By interposing a cured layer between the plastic molded body and the thin film, the adhesion of the thin film can be improved.

  In the coated plastic molded body according to the present invention, the thin film is preferably a gas barrier thin film. Further, high gas barrier properties can be imparted.

  The coated plastic molded body according to the present invention includes a form in which the gas barrier thin film is a DLC film, a SiC film, or an oxide film.

  The coated plastic molded body according to the present invention includes a form in which the plastic molded body is a container. By covering at least one of the inner wall surface and the outer wall surface of the container, the container can be made excellent in the preservation of contents.

  The method for producing a coated plastic molded body according to the present invention includes a coating step in which a coating liquid comprising a compound represented by the general formula (Chemical Formula 1) is applied to the surface of a plastic molded body to form a coating layer; And a curing step of proceeding a condensation reaction of the compound represented by (Chemical Formula 1) to cure the coating layer to form a cured layer.

  In the manufacturing method of the covering plastic molding which concerns on this invention, it is preferable to have the film-forming process which forms a thin film on the said application layer further after the said application | coating process. By forming a cured layer between the plastic molded body and the thin film, the adhesion or / and gas barrier properties of the thin film can be improved.

  In the method for producing a coated plastic molded body according to the present invention, the film forming step is preferably a step performed before the compound represented by the general formula (Chemical Formula 1) completes the condensation reaction. The gas barrier property of the thin film can be further enhanced.

  In the manufacturing method of the covering plastic molding which concerns on this invention, it is preferable that the said hardening process is a process performed at 0 to 40 degreeC. Within this temperature range, the condensation reaction can be prevented from occurring rapidly, and a crack-free cured layer can be formed, and the condensation reaction can be completed within a practical time.

  The present invention covers the surface of a plastic molded body with a layer having a role as a gas barrier layer, a role as an adhesion layer, and a role as an underlayer that makes the performance of a thin film appear well. Regardless, it is possible to provide a coated plastic molded body that can improve gas barrier properties. Moreover, this invention can provide the manufacturing method of the covering plastic molding which can improve gas barrier property safely and at high speed using the manufacturing apparatus which does not require expensive equipment.

It is sectional drawing which shows an example of the covering plastic molding which concerns on this embodiment. It is sectional drawing which shows another example of the covering plastic molding which concerns on this embodiment.

  Next, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these descriptions. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.

FIG. 1 is a cross-sectional view showing an example of a coated plastic molded body according to this embodiment. The coated plastic molded body 90 according to the present embodiment includes a plastic molded body 91 and a cured layer 92 obtained by condensation reaction of a compound represented by the general formula (Formula 1) formed on the surface of the plastic molded body 91.
(Chemical Formula 1) R-M- (CH ₃ ) _n (OR ′) _3-n
In the general formula (Formula 1), M represents silicon or metal. R represents a hydrocarbon chain having an amino group. R ′ represents an alkyl group having 1 to 4 carbon atoms. N represents 0, 1 or 2.

  The hardened layer 92 includes M (silicon or metal), O (oxygen), C (carbon), N (nitrogen), and H (hydrogen) as constituent elements. In the coated plastic molded body 90 according to this embodiment, the cured layer 92 has an element concentration ratio of O of 3.0 to 4.5 and C of 3.0 to 16 when the element concentration of M is 1. .5, and a layer containing 0.5 to 2.5 N is preferable. More preferably, when the element concentration of M is 1, the element concentration ratio includes O of 3.1 to 4.2, C of 3.3 to 16.2, and N of 0.9 to 2.1. To do. By making the elemental concentration of O and the elemental concentration of C within the above ranges, a layer that is physicochemically stable even when directly or indirectly in contact with the contents of weakly acidic to neutral regions often found in beverages or foods Can do. Moreover, the effect of improving the gas barrier property of the cured layer 92 itself can be obtained by setting the element concentration of N in the above range. Furthermore, adhesion between the plastic molded body 91 and the cured layer 92 can be ensured. Further, when a thin film is formed on the cured layer 92, the adhesion of the thin film can be ensured. M, O, C, and N element concentrations can be measured by various elemental analysis methods. For example, a method using X-ray photoelectron spectroscopy (XPS analysis) or a method using an energy dispersive X-ray fluorescence (EDX) apparatus provided in a scanning electron microscope (SEM).

  Examples of the resin constituting the plastic molded body 91 include polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, cycloolefin copolymer resin (COC, cyclic olefin copolymer), and ionomer resin. , Poly-4-methylpentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyamideimide resin, polyacetal resin Polycarbonate resin, polysulfone resin, tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin. One of these may be used as a single layer or two or more may be stacked.

  In the coated plastic molded body 90 according to the present embodiment, the plastic molded body 91 is more preferably polypropylene, polyethylene, or a mixture thereof. Polypropylene includes, for example, a homopolymer, a random polymer, and a block polymer. The polyethylene is, for example, high density polyethylene (HDPE), low density polyethylene (LDPE), or linear low density polyethylene (LLDPE). Further, polypropylene, polyethylene or a mixture thereof is not particularly limited as long as polypropylene and polyethylene are the main components. For example, a polymer alloy of polypropylene or polyethylene and the above-described resin other than polypropylene or polyethylene, or various additives such as an antioxidant, a lubricant, an antiblocking agent, a plasticizer, and a softener are added to polypropylene or polyethylene.

  The coated plastic molded body 90 according to the present embodiment includes a form in which the plastic molded body 91 is a container or a film. Examples of the container include a container that is used with a lid, a stopper, or a seal, or a container that is used without being used. The size of the opening can be appropriately set according to the contents. The container includes a container having a predetermined thickness having moderate rigidity and a container formed of a sheet material having no rigidity. Examples of the contents include beverages such as water, tea, soft drinks, carbonated drinks and fruit juice drinks, liquids, viscous bodies, powders or solid foods. Further, the container may be either a returnable container or a one-way container. Moreover, as a film, a elongate sheet-like thing and a cut sheet are included. It does not matter whether the film is stretched or unstretched. In the present embodiment, the shape of the plastic molded body 91 can be appropriately set according to the purpose and application, and is not particularly limited. Further, the present invention is not limited to the method for manufacturing the plastic molded body 91.

  The thickness of the plastic molded body 91 can be appropriately set according to the purpose and application, and is not particularly limited. For example, when the plastic molded body 91 is a container such as a beverage bottle, the thickness of the bottle is preferably 100 to 500 μm, and more preferably 150 to 300 μm. Moreover, when the plastic molded object 91 is a film which comprises a packaging bag, it is preferable that the thickness of a film is 3-200 micrometers, More preferably, it is 10-100 micrometers.

  When the plastic molded body 91 is a container, the hardened layer 92 is provided on one or both of the inner wall surface and the outer wall surface. When the plastic molded body 91 is a film, the hardened layer 92 is provided on one side or both sides. In particular, in the case where the plastic molded body 91 is a container for beverages or foods, when the hardened layer 92 is formed on the inner wall surface of the container, the reaction between oxygen dissolved in the container wall and the content, the content to the container wall It is possible to effectively suppress the quality deterioration of the content such as the sorption of the content aroma component. On the other hand, when the hardened layer 92 is formed on the outer wall surface of the container, the hardened layer 92 can be formed more easily. In particular, when the container material is made of a heat-resistant resin such as polypropylene, it can be a heat-resistant container that enables heat treatment such as boiling sterilization, and it is particularly significant to improve gas barrier properties.

  FIG. 2 is a cross-sectional view showing another example of the coated plastic molded body according to the present embodiment. The coated plastic molded body 90 according to the present embodiment preferably further includes a thin film 93 on the cured layer 92. The kind of the thin film 93 is not particularly limited, and can be appropriately selected according to the function to be imparted. When the thin film 93 is formed, the hardened layer 92 becomes an intermediate layer. Even when the plastic molded body 91 has a surface with fine irregularities such as, for example, polypropylene or polyethylene, the hardened layer 92 smoothes the surface so that the surface is suitable for forming the thin film 93. be able to. Therefore, the performance of the obtained thin film 93 can be expressed satisfactorily.

  In the coated plastic molded body 90 according to this embodiment, the thin film 93 is preferably a gas barrier thin film. As shown in FIG. 1, the coated plastic molded body 90 according to the present embodiment exhibits a high gas barrier property in a state where only the cured layer 92 is provided, but further improves the gas barrier property by providing a gas barrier thin film. be able to. The type of the gas barrier thin film is not particularly limited. In addition to the gas barrier property, the gas barrier thin film has heat resistance and non-sorption properties, makes the best use of the advantages of the plastic molded body 91, and can compensate for insufficient performance. A DLC film, SiC film, SiCO film, SiCN film, or SiCNO film is preferable. In the coated plastic molded body 90 according to this embodiment, the gas barrier thin film is preferably a DLC film, a SiC film, or an oxide film from the viewpoint of higher gas barrier properties.

  The thickness of the thin film 93 is preferably 5 to 100 nm. More preferably, it is 10-80 nm. If it is less than 5 nm, gas barrier properties or other functions may not be obtained. If it exceeds 100 nm, cracks may occur due to internal stress, and gas barrier properties or other functions may deteriorate.

  The thin film 93 can be formed by various known methods. Known methods are, for example, chemical vapor deposition (CVD) methods such as plasma CVD methods and heating element CVD methods, and physical vapor deposition (PVD) methods such as vacuum deposition methods, sputtering methods, and ion plating methods. In this specification, the heating element CVD method refers to a CVD method called a heating element CVD method, a Cat-CVD method, or a hot wire CVD method. When the plastic molded body 91 is a container for beverages or foods, it is more preferably a plasma CVD method or a heating element CVD method. These can be applied to various three-dimensional container shapes, and can be formed at a low cost as compared with other methods.

  Next, the compound represented by the general formula (Formula 1) will be described.

  In the general formula (Formula 1), M is silicon (Si) or a metal. The metal is preferably titanium (Ti) or zirconium (Zr). In the present embodiment, it is particularly preferable that M is silicon. An inexpensive compound can be used, and the obtained cured layer 92 can have a safe and relatively flexible structure.

In the general formula (Formula 1), R is a hydrocarbon chain having an amino group. The amino group is —NH ₂ , ═NH or —NH—. More preferably, the amino group is at the end of the hydrocarbon chain. R is linear and preferably has 3 to 5 carbon atoms. As a result, the resulting hardened layer 92 can have a relatively dense and flexible structure.

  In the general formula (Chemical Formula 1), R ′ is an alkyl group having 1 to 4 carbon atoms. Specifically, R ′ is a methyl group, an ethyl group, a propyl group, or a butyl group. Among these, R ′ is more preferably a methyl group. That is, OR ′ is preferably a methoxy group. In addition, although it can also be set as the structure which has an acetyl group or an acyl group as R ', it is preferable to set it as an alkyl group from a viewpoint of a cure rate.

  In the general formula (Formula 1), n represents 0, 1 or 2. n is preferably 1, and more preferably 0.

  A known amine coupling agent can be used as the compound represented by the general formula (Chemical Formula 1). For example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxytitanium, 3-aminopropyltrimethoxyzirconium. Among these, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-, in that M is silicon and OR ′ is a methoxy group. Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane are preferred. Further, 3-aminopropyltrimethoxysilane is particularly preferable in that M is silicon, OR ′ is a methoxy group, and n is 0.

  When the compound represented by the general formula (Formula 1) is silicon, OR ′ is a methoxy group, and n is 0, such as 3-aminopropyltrimethoxysilane, The hardened layer 92 can have a high gas barrier property and a dense structure. On the other hand, there is a tendency to become a structure that is relatively hard and prone to cracking. However, as described above, by ensuring the structure of the hydrocarbon chain, the flexibility of the resulting intermediate layer is ensured, and when cured Generation of cracks can be suppressed.

  Overall, the compound represented by the general formula (Chemical Formula 1) is generally used as an amine coupling agent, and can be obtained safely and relatively inexpensively. In addition, a certain gas barrier property improvement effect can be expected. Moreover, adhesiveness with a polypropylene or polyethylene is securable by containing an amino group. Furthermore, it is excellent in adhesiveness with a thin film, and a higher gas barrier property can be secured. Furthermore, in the general formula (Chemical Formula 1), OR ′ is a methoxy group, n is 0, and R is a hydrocarbon chain having the above-mentioned carbon number. The structure can be stored stably under pressure. And when the coating liquid which consists of a compound represented by general formula (Chemical Formula 1) is apply | coated to the surface of the plastic molding 91, the compound represented by General formula (Chemical Formula 1) will carry out special hardening under normal temperature and a normal pressure. The condensation reaction proceeds without the initiator, the coating layer is cured, and the cured layer 92 can be formed. In connection with these physical properties, the hardened layer 92 can be formed at low cost and at high speed without using expensive equipment.

  The hardened layer 92 has a role as a gas barrier layer, a role as an adhesion layer between the plastic molded body 91 and the thin film 93, and a role as a base layer that develops the performance of the thin film. In the hardened layer 92, the alkoxysilane structure (—Si—OR ′) in the molecule of the compound represented by the general formula (Chemical Formula 1) is hydrolyzed by, for example, moisture in the air to form a silanol group (—Si—OH). ), A siloxane bond (Si—O—Si) is formed by a condensation reaction between molecules. The reason is not clear because this siloxane bond forms a three-dimensional network, but the cured layer 92 exhibits high adhesion to the plastic molded body 91 and high gas barrier properties. Furthermore, the hardened layer 92 is formed on the surface of the plastic molded body 91 having irregularities such as polypropylene or polyethylene, so that the surface is smoothed and becomes a surface suitable for film formation, and the thin film formed thereon Performance (for example, gas barrier property when the thin film is a gas barrier thin film) can be exhibited well. The compound represented by the general formula (Chemical Formula 1) is generally used as an amine-based coupling agent, but the coupling agent generally has functional groups having different properties at both ends of the molecular structure. Each functional group binds to a surface having a different chemical property (for example, an organic surface and an inorganic surface), thereby linking the two. Therefore, it is often used mainly as a primer layer or an anchor coat layer for forming a gas barrier thin film. In such a general use method, for example, when the organic substance is polypropylene or polyethylene, it is known that a coupling agent having a vinyl group or a methacryloxy group as a functional group that easily binds to these is suitable. It has been. However, in the present invention, since a coupling agent having an amino group is selected, it can be said that this coupling agent having an amino group is not used in a general utilization method as a coupling agent. In the present invention, by using a coupling agent having an amino group, the reason is not clear. However, the cured layer 92 not only serves as an adhesion layer, but the cured layer 92 itself has a high gas barrier property. As a layer, it acts as a base layer for smoothing the surface of the plastic molded body 91 to form a thin film.

  Next, a method for forming the hardened layer 92 formed on the surface of the plastic molded body 91 will be described.

  The method for producing a coated plastic molded body according to the present embodiment includes a coating step in which a coating liquid composed of a compound represented by the general formula (Chemical Formula 1) is applied to the surface of the plastic molded body 91 to form a coating layer; A curing step of proceeding a condensation reaction of the compound represented by the general formula (Chemical Formula 1) to cure the coating layer to form the cured layer 92 is included.

  Since the compound represented by the general formula (Chemical Formula 1) is a compound having a stable and appropriate viscosity, a coating liquid composed of the compound represented by the General Formula (Chemical Formula 1) is used without using a solvent. It can apply | coat on the surface of the molded object 91. FIG. And since a solvent is not used, in the drying after application | coating, a gas barrier property does not fall by the void | hole formed when a solvent volatilizes. The coating process is preferably a technique capable of forming a layer on the surface of the plastic molded body 91 under normal pressure or reduced pressure. The application method is not particularly limited, and various methods called application or spraying can be used. Specific examples include bar coating, spin coating, spray coating, evaporation or spraying in vacuum, and dipping in a coating solution. The thickness of the coating layer is not particularly limited, but it is preferable that the thickness of the cured layer 92 obtained by curing the coating layer is 0.5 nm to 100 μm. More preferably, it is 5 nm-30 micrometers. Most preferably, it is 50 nm-300 nm. If the thickness is less than 0.5 nm, the uniform cured layer 92 may not be obtained. If it exceeds 100 μm, the curing time increases, which is uneconomical. A surface modification effect such as surface activation can be obtained even with a monomolecular layer, but a high adhesion improvement effect can be stably obtained by setting the thickness to 5 nm or more. As described above, the surface of polypropylene or polyethylene tends to be rough due to the influence of the properties of spherulites and moldability. However, when the thickness is 50 nm or more, the surface smoothing effect and the gas barrier property of the hardened layer 92 itself. The effect of expression is easily obtained. On the other hand, when the thickness exceeds 100 μm, an increase in curing time and a decrease in economic efficiency become remarkable.

  Prior to the coating step, it is preferable to perform a process for improving wettability so that the coating liquid is uniformly distributed on the surface of the plastic molded body 91. Specific examples include plasma treatment with nitrogen, oxygen or argon, corona discharge, ozone treatment, and other various chemical treatments. Among these, nitrogen plasma treatment is more preferable. The effect of improving the wettability and the adhesion of the cured layer 92 is easily obtained without roughening the surface of the plastic molded body 91.

  When the compound represented by the general formula (Chemical Formula 1) is applied to the surface of the plastic molded body 91 and left in an environment of normal temperature and normal pressure, the condensation reaction proceeds without the addition of a special curing initiator. And harden. In the manufacturing method of the covering plastic molding which concerns on this embodiment, it is preferable that a hardening process is a process performed at 0 to 40 degreeC. More preferably, it is 10 degreeC or more and 30 degrees C or less. If it is less than 0 degreeC, it will take time for hardening and it will become difficult to become a realistic production method. In particular, it becomes impractical for packaging container applications. If the temperature exceeds 40 ° C., the curing proceeds rapidly, so that cracks are likely to occur in the resulting layer, and the gas barrier property improving effect and other functions may be reduced. Therefore, in order to promote the condensation reaction, it is preferable not to perform a promotion step such as holding at a high temperature. Although time required for hardening changes according to the temperature which performs a hardening process, it is preferable that it is 30 to 500 minutes, for example.

  Next, a method for forming the thin film 93 will be described.

  In the manufacturing method of the covering plastic molding which concerns on this embodiment, it is preferable to have the film-forming process which forms the thin film 93 on an application layer further after an application | coating process. In the present embodiment, the method for forming the thin film 93 is not particularly limited, and can be appropriately selected depending on the type of the thin film 93. For example, when the thin film 93 is a DLC film, it can be formed mainly by a plasma CVD method. For example, JP-A-8-53116, JP-A-8-53117, JP-A-9-272567. There exists a gazette or Unexamined-Japanese-Patent No. 10-226884. In addition, when the thin film is a SiC film or an oxide film, it can be formed by a heating element CVD method, for example, WO2006 / 126667, JP2008-127053, JP2008-127054. There is a gazette.

  In the method for producing a coated plastic molded body according to this embodiment, the film forming step is preferably a step performed before the compound represented by the general formula (Formula 1) completes the condensation reaction. By performing the film forming step before completing the condensation reaction, higher gas barrier properties can be generated than when the film forming step is performed after the condensation reaction is completed. Specifically, after the coating process, it is preferable to perform the film forming process within a predetermined time without substantially drying and promoting processes. For example, the predetermined time is preferably within 5 minutes, and more preferably within 1 minute. Thus, gas barrier property can be improved by performing an application | coating process and a film-forming process continuously, without passing through the acceleration | stimulation process for accelerating | stimulating a condensation reaction. At this time, even if a thin film is directly formed on the cured layer before the completion of the condensation reaction, a thin film having functions such as gas barrier properties is obtained, and aging is not required. Therefore, since a special accelerating process and an aging process are not required, the coated plastic molded body can be manufactured at high speed and at low cost. In addition, since the curing process proceeds simultaneously in the film forming process and can be completed after the film forming process, the total process time can be shortened. In particular, after the film formation step, the formed film surface can be regarded as being in a dry and cured state, so that the plastic molded body after film formation can be easily handled.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.

Example 1
(Plastic molding production process)
A 100 μm thick polypropylene film was used as the plastic molding. 0.25 g of polypropylene film (molecular weight 190,000) made by Sigma-Aldrich, and a commercially available press machine (AH-2003 made by As One Corporation) were used as a mold between the stainless steel plates at 180 ° C. for 5 minutes. After sandwiching weakly under the conditions, the sandwiching pressure was increased to 15 MPa, and a film having a thickness of 0.1 mm was formed at 180 ° C. for 5 minutes.

(Hydrophilic treatment process)
One side of the obtained film was first made hydrophilic in a plasma ion bombardment apparatus (PIB-10 manufactured by Vacuum Device Inc.) by selecting a hard mode for output for 90 seconds with air plasma. The current display value at that time was 10 mA.

(Coating process)
3-aminopropyltrimethoxy, which is a compound represented by the general formula (Chemical Formula 1), as a coating solution on a hydrophilic treatment surface using a spin coater (MS-A100 manufactured by Mikasa) under conditions of 3000 rpm and 10 minutes. Using 50 μl of silane (KBM903 manufactured by Shin-Etsu Silicone Co., Ltd.), a coating layer was formed by spin coating to a thickness of about 200 nm.

(Curing process)
The coated layer was cured in a room at 23 ° C. for 8 hours to obtain a coated plastic molded body.

(Example 2)
In Example 1, N-2- (aminoethyl) -3-aminopropylmethyl which is a compound represented by the general formula (Chemical Formula 1) is used instead of 3-aminopropyltrimethoxysilane as a coating solution used in the coating process. A coated plastic molded body was obtained in the same manner as in Example 1 except that dimethoxysilane (KBM602 manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

(Example 3)
In Example 1, as a coating solution used in the coating process, N-2- (aminoethyl) -3-aminopropyltri is a compound represented by the general formula (Formula 1) instead of 3-aminopropyltrimethoxysilane. A coated plastic molded body was obtained in the same manner as in Example 1 except that methoxysilane (KBM603 manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

Example 4
In Example 1, a coated plastic molded body was obtained in the same manner as in Example 1 except that the curing process was accelerated by high-temperature treatment at 70 ° C. for 35 seconds.

(Example 5)
On the cured layer of the coated plastic molded body of Example 1, a DLC film was formed as a thin film. The DLC film was formed by a film forming process described below.

(Film formation process)
The coated plastic molded body of Example 1 was placed along the inner wall surface of a 500 ml PET bottle (height 200 mm, trunk outer diameter 66 mm, mouth outer diameter 24 mm, mouth inner diameter 22 mm, wall thickness 300 μm and resin amount 29 g). The cured layer was fixed in a state facing the inner space of the container, and a 20 nm DLC film was formed using the plasma CVD film forming apparatus disclosed in Patent Document 10. At that time, the PET bottle was accommodated in a vacuum chamber, and the pressure was reduced until 5.0 Pa was reached. Next, acetylene gas was supplied at a flow rate of 80 sccm, and high frequency power of 800 W at 13.56 MHz was applied for 2 seconds. After the film formation, the coated plastic molded body was taken out from the PET bottle to obtain a coated plastic molded body of Example 5.

(Example 6)
In Example 5, a coated plastic molded body was obtained in the same manner as in Example 5 except that the coated plastic molded body of Example 2 was used.

(Example 7)
In Example 5, a coated plastic molded body was obtained in the same manner as in Example 5 except that the coated plastic molded body of Example 3 was used.

(Example 8)
In Example 1, as a curing process, a process of curing for 8 hours in a room at 23 ° C. is not performed before the film forming process, but a film forming process is performed immediately after the coating process, and then left in a room at 23 ° C. for 8 hours. Then, the curing process was completed to obtain a coated plastic molded body of Example 8. The film forming process was performed in the same manner as in Example 5.

Example 9
In Example 1, a coated plastic molded body was obtained in the same manner as in Example 1 except that a polyethylene film was used instead of the polypropylene film. The polyethylene film used 5 g of high-density polyethylene resin (molecular weight: 125,000) manufactured by Sigma-Aldrich in place of polypropylene resin in the plastic molding process of Example 1 and the temperature used in the press machine. It was produced in the same manner as a polypropylene film except that the temperature was 150 ° C.

(Example 10)
In Example 5, a coated plastic molded body was obtained in the same manner as in Example 5 except that the coated plastic molded body of Example 9 was used.

(Example 11)
In Example 1, a coated plastic molded body was obtained in the same manner as in Example 1 except that a PET film (Lumirror manufactured by Toray Industries, Inc.) was used instead of the polypropylene film.

(Example 12)
In Example 5, a coated plastic molded body was obtained in the same manner as in Example 5 except that the coated plastic molded body of Example 11 was used.

(Example 13)
A silicon oxide (SiO) film was formed as a thin film on the cured layer of the coated plastic molded body of Example 1. The SiO film was formed by the following film forming process. That is, using a plasma CVD apparatus (PD-10 apparatus manufactured by SAMCO), the cured layer of the coated plastic molded body of Example 1 was fixed to one side of a parallel plate in a state facing the reaction chamber side, and 40 sccm of trimethylsilane and A high-frequency power of 200 W at 13.56 MHz was applied to a mixed gas of oxygen at 60 sccm for 150 seconds, and a 50 nm silicon oxide thin film was formed by plasma CVD.

(Example 14)
A silicon carbide (SiC) film was formed as a thin film on the cured layer of the coated plastic molded body of Example 1. The SiC film was formed by the following film forming process. That is, a 30 nm silicon carbide film was formed by a heating element CVD method using the apparatus described in FIG. Specifically, the coated plastic molded body of Example 1 was fixed along the inner wall surface of a 500 ml PET bottle with the cured layer facing the inner space of the container, and the PET bottle was placed in the vacuum chamber 6. Housed and depressurized until reaching 1.0 Pa. Subsequently, two molybdenum wires having a diameter of 0.5 mm and a length of 43 cm were used as the thermal catalyst 18, 24 V was applied to the thermal catalyst 18 to generate heat at 2000 ° C. Thereafter, using a gas flow controller, 50 sccm of vinylsilane was supplied as a source gas, and a silicon carbide film containing oxygen and hydrogen was deposited on the cured layer. After the film formation, the coated plastic molded body was taken out from the PET bottle to obtain a coated plastic molded body of Example 14.

(Comparative Example 1)
In Example 1, the film made from polypropylene which has not performed the application | coating process and the hardening process was made into the comparative example 1.

(Comparative Example 2)
In Example 1, the DLC film was formed on the hydrophilic treatment surface of the polypropylene film without performing the coating process and the curing process. The DLC film was formed in the same manner as the film forming process of Example 5.

(Comparative Example 3)
In Example 1, after the hydrophilic treatment step, a DLC film was formed on the treated surface that was further treated with oxygen plasma for 2 seconds. In the oxygen plasma treatment, the plastic molded body is cured along the inner wall surface of a 500 ml PET bottle (height 200 mm, body outer diameter 66 mm, mouth outer diameter 24 mm, mouth inner diameter 22 mm, wall thickness 300 μm, resin amount 29 g). The layer was fixed in a state where it was directed toward the inner space of the container, and the plasma CVD film forming apparatus disclosed in Patent Document 10 was used. At that time, the PET bottle was accommodated in a vacuum chamber, and the pressure was reduced until 5.0 Pa was reached. Next, oxygen gas was supplied at a flow rate of 80 sccm, and high frequency power of 800 W at 13.56 MHz was applied for 2 seconds. In the subsequent DLC film formation, the supply of oxygen gas is stopped and the vacuum state is maintained, acetylene gas is supplied at a flow rate of 80 sccm, 13.56 MHz high frequency power 800 W is applied for 2 seconds, and 20 nm A DLC film was formed. After the film formation, the coated plastic molded body was taken out from the PET bottle to obtain a coated plastic molded body of Comparative Example 3.

(Comparative Example 4)
In Example 1, after the hydrophilic treatment step, a DLC film was formed on the treated surface that was further treated with nitrogen plasma for 2 seconds. Nitrogen plasma treatment and subsequent DLC film formation were performed in the same manner as in Comparative Example 3 except that nitrogen gas was used instead of oxygen gas in the oxygen plasma treatment of Comparative Example 3.

(Comparative Example 5)
In Comparative Example 2, a SiOx film was formed instead of the DLC film. The SiOx film was formed in the same manner as the film forming process of Example 13.

(Comparative Example 6)
In Example 1, except that 3-glycidoxypropyltriethoxysilane (KBE403 manufactured by Shin-Etsu Silicone) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating step, the same as Example 1. Thus, a coated plastic molded body was produced, and a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5.

(Comparative Example 7)
In Example 1, the same procedure as in Example 1 was used except that 3-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A coated plastic molded body was prepared, and a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5.

(Comparative Example 8)
In Example 1, the same procedure as in Example 1 was used except that 3-mercaptopropyltrimethoxysilane (KBM803 manufactured by Shin-Etsu Silicone) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A coated plastic molding was produced.

(Comparative Example 9)
In Example 5, a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5 except that the coated plastic molded body of Comparative Example 8 was used.

(Comparative Example 10)
In Example 1, coated plastic molding was performed in the same manner as in Example 1 except that vinyltrimethoxysilane (KBM1003 manufactured by Shin-Etsu Silicone) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A DLC film was formed in the same manner as in Example 5 on the cured layer of the coated plastic molded body.

(Comparative Example 11)
In Example 1, coating was performed in the same manner as in Example 1 except that p-styryltrimethoxysilane (KBM1403 manufactured by Shin-Etsu Silicone) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A plastic molded body was produced, and a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5.

(Comparative Example 12)
In Example 1, coated plastic molding was performed in the same manner as in Example 1 except that hexamethyldisiloxane (HMDS3 manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A DLC film was formed in the same manner as in Example 5 on the cured layer of the coated plastic molded body.

(Comparative Example 13)
In Example 1, coated plastic molding was performed in the same manner as in Example 1 except that hexamethyldisilazane (KF96L065CS manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A DLC film was formed in the same manner as in Example 5 on the cured layer of the coated plastic molded body.

(Comparative Example 14)
In Example 1, the same procedure as in Example 1 was used except that titanium tetraisopropoxide (TA-10 manufactured by Matsumoto Trading Co., Ltd.) was used as the coating solution used in the coating process instead of 3-aminopropyltrimethoxysilane. A coated plastic molded body was produced, and a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5.

(Comparative Example 15)
In Example 1, coating was performed in the same manner as in Example 1 except that titanium tetranormal butoxide (TA-25 manufactured by Matsumoto Trading Co., Ltd.) was used instead of 3-aminopropyltrimethoxysilane as the coating solution used in the coating process. A plastic molded body was produced, and a DLC film was formed on the cured layer of the coated plastic molded body in the same manner as in Example 5.

(Comparative Example 16)
In Example 9, a polyethylene film not subjected to the coating process and the curing process was used as Comparative Example 16.

(Comparative Example 17)
In Example 11, the PET film that was not subjected to the coating process and the curing process was referred to as Comparative Example 17.

  Table 1 shows the compositions of the obtained plastic coated articles or plastic molded articles of Examples and Comparative Examples. These were evaluated by the following method.

(Element concentration)
For Examples 1, 2, and 3, the elemental concentration of the cured layer was measured. The element concentration is determined by EDX analysis using an EDX apparatus (EMAX X-Max manufactured by Horiba, Ltd.) in a field of view (100 μm square) obtained by expanding the surface of the cured layer 1000 times with a scanning electron microscope (SU1510 manufactured by Hitachi High-Technologies Corporation). Went. The conditions for EDX analysis are as follows. The analysis was performed at four locations by changing the observed part. Table 2 shows the ratio of O, C, and N element concentrations when the M element concentration is 1.
Acceleration voltage: 8.0 kV
Measuring pressure: 60Pa
Probe current: 67.0 μA

(Gas barrier property-BIF)
Oxygen permeability was measured under the conditions of 23 ° C. and 90% RH using an oxygen permeability measuring device (model: Oxtran 2/21, manufactured by Modern Control), conditioned for 5 hours from the start of measurement, and started measurement. The value after 6 hours had elapsed. The improvement rate of gas barrier property was evaluated by BIF (Barrier Improvement Factor). BIF was determined by Equation 1. The evaluation results are shown in Table 3.
(Expression 1) BIF = [Oxygen permeability of uncoated plastic molding] / [Oxygen permeability of coated plastic molding of Example or Comparative Example]
In Equation 1, the oxygen permeability of the uncoated plastic molding is as follows: when the coated plastic molding is a PP film, the oxygen permeability of the sample of Comparative Example 1, and when the plastic molding is a PE film, Comparative Example 16 When the plastic molded body was a PET film, the oxygen permeability of the sample of Comparative Example 17 was used.

(Adhesion)
A test in which a coated plastic molded body was cut into 20 mm × 20 mm when a pH 4.01 (25 ° C.) phthalate pH standard solution (product number: 168-12145, manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 50 ° C. After immersing the piece, the surface condition immediately after the immersion and 10 days after the immersion was observed with a laser microscope (model: VK-9510, manufactured by Keyence Corporation) for the presence or absence of peeling of the film at a visual field of 100 μm × 100 μm, and a thin film against a weakly acidic aqueous solution The appearance was evaluated. Similarly, the appearance of the thin film with respect to the neutral aqueous solution was evaluated using a phosphate pH standard solution (product number: 165-12155, manufactured by Wako Pure Chemical Industries, Ltd.) having a pH of 6.83 (25 ° C.). Before observation, the test piece was gently shaken in an aqueous solution to facilitate observation of the presence or absence of peeling. The evaluation criteria are as follows. The evaluation results are shown in Table 3.
○: No peeling (practical level)
Δ: Some peeling (unsuitable for practical use)
×: Overall peeling (unsuitable for practical use)

In all of Examples 1 to 14, it was confirmed that the gas barrier properties were improved, the adhesiveness was good, and the material had resistance to contents in weakly acidic to neutral range. . Examples 1 to 4 are coated plastic molded bodies provided with a cured layer on a plastic molded body, but the gas barrier property is improved only by the cured layer, and the cured layer is not only as an adhesion layer, but also as a gas barrier layer. Has also been confirmed to work. In Example 11 in which the plastic molding was PET, BIF was 1.7. However, in Example 1 in which the plastic molding was polypropylene, BIF was 127.9 and Example 9 in which the plastic molding was polyethylene was used. Then, BIF was 47.3. As described above, it was confirmed that in the coated plastic molded body according to the present invention, when the plastic molded body is polypropylene or polyethylene, a remarkable effect of improving the gas barrier property can be obtained. In the first place, as can be seen from Comparative Example 1, Comparative Example 16 and Comparative Example 17, PET has a gas barrier property higher than that of polypropylene or polyethylene, so that BIF was small as in Example 11. . However, by forming the gas barrier thin film on the cured layer as in Example 12, the oxygen transmission rate is reduced to 1.9 cc / m ² · day, and the gas barrier of the gas barrier thin film is obtained by the effect of the cured layer as an underlayer. The property could be expressed well.

  In particular, Example 1 had a high gas barrier property. When Example 2 and Example 3 were compared, BIF was larger in Example 3. In the general formula (Chemical Formula 1), it was confirmed that by using a compound in which n is 0 and three methoxy groups are bonded to M (Si in Example 3), there is a larger gas barrier property improving effect. . In Example 4, high temperature treatment was performed to promote the condensation reaction, but when Example 1 was compared with Example 4, Example 1 had higher gas barrier properties. It has been confirmed that it is preferable not to perform an acceleration step such as a high-temperature treatment for promoting the condensation reaction. When Example 5 is compared with Example 8, it can be confirmed that Example 8 has a larger BIF, and the gas barrier property can be further improved by performing the film-forming process before the condensation reaction is completed. It was. And since there is no time for performing the curing process between the coating process and the film forming process, the curing process proceeds simultaneously in the film forming process and can be completed after the film forming process. It was confirmed that the time can be remarkably shortened. This leads to significant cost savings.

  In Comparative Example 2, the DLC film was formed on the hydrophilic treated surface of the polypropylene film, but the BIF was less than 2, and the gas barrier property improvement effect as in Examples 5 to 8 could not be obtained. Moreover, the adhesiveness in aqueous solution as seen in Examples 5-8 could not be obtained. In Comparative Example 3, a DLC film was formed on the surface treated with oxygen plasma, but the BIF was less than 2, and the gas barrier property improvement effect could not be obtained. In Comparative Example 4, a DLC film was formed on the surface treated with nitrogen plasma, but BIF remained at 2.1, and the gas barrier property improvement effect as in Examples 5 to 8 could not be obtained. In Comparative Example 5, a SiOx film was formed on the hydrophilic treated surface of a polypropylene film, but the BIF was less than 2, and adhesion in an aqueous solution as seen in Example 13 could not be obtained. . Moreover, the gas barrier property improvement effect was not able to be acquired. In Comparative Example 6, Comparative Example 7, and Comparative Examples 9 to 15, a cured layer and a DLC film were formed using a coupling agent having no amino group, but all were found in Examples 5 to 8. Such a remarkable improvement in gas barrier properties was not observed, and the effect as an underlayer was insufficient. In particular, the coupling agent used in Comparative Example 7 or Comparative Example 10 is a coupling agent having a methacryloxy group or a vinyl group, which is generally considered to be excellent in adhesion to a polypropylene base material. The improvement of the gas barrier property did not exhibit a significant effect as an underlayer.

  The coated plastic molded body according to the present invention has gas barrier properties and content resistance in weakly acidic to neutral range, so in particular, beverage containers such as water, tea, soft drinks, carbonated drinks, fruit juice drinks, tablets and the like It is suitable as a packaging material constituting a solid pharmaceutical container and food container.

90 Coated plastic molded body 91 Plastic molded body 92 Hardened layer 93 Thin film

Claims (12)

A coated plastic molded body comprising a plastic molded body and a cured layer formed by condensation reaction of a compound represented by the general formula (Chemical Formula 1) formed on the surface of the plastic molded body.
(Chemical Formula 1) R-M- (CH ₃ ) _n (OR ′) _3-n
In the general formula (Formula 1), M represents silicon or metal. R represents a hydrocarbon chain having an amino group. R ′ represents an alkyl group having 1 to 4 carbon atoms. N represents 0, 1 or 2.   Compounds represented by the general formula (Chemical Formula 1) are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino The coated plastic molded article according to claim 1, which is propyltrimethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane.   The cured layer has an element concentration ratio of O of 3.0 to 4.5, C of 3.0 to 16.5, and N of 0.5 to 2. 5. The coated plastic molded body according to claim 1, which is a layer containing 5.   The said plastic molding is a polypropylene, polyethylene, or a mixture thereof, The covering plastic molding as described in any one of Claims 1-3 characterized by the above-mentioned.   The coated plastic molded article according to any one of claims 1 to 4, further comprising a thin film on the cured layer.   The coated plastic molded body according to claim 5, wherein the thin film is a gas barrier thin film.   The coated plastic molded body according to claim 6, wherein the gas barrier thin film is a DLC film, a SiC film, or an oxide film.   The said plastic molding is a container, The covering plastic molding as described in any one of Claims 1-7 characterized by the above-mentioned. An application step of applying an application liquid comprising a compound represented by the general formula (Chemical Formula 1) to the surface of the plastic molded body to form an application layer;
A method for producing a coated plastic molded article, comprising: a step of proceeding a condensation reaction of the compound represented by the general formula (Chemical Formula 1) to cure the coating layer to form a cured layer. After the coating step,
The method for producing a coated plastic molded body according to claim 9, further comprising a film forming step of forming a thin film on the coating layer.   The method for producing a coated plastic molded body according to claim 10, wherein the film forming step is a step performed before the compound represented by the general formula (Chemical Formula 1) completes the condensation reaction.   The said hardening process is a process performed at 0 to 40 degreeC, The manufacturing method of the covering plastic molding as described in any one of Claims 9-11 characterized by the above-mentioned.

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