JP3864994B2 - Coating film - Google Patents

Description

【００６７】
【表２】

【００６８】
『確認』
表２のデータから、各実施例については時間が経過しても初期の酸素透過度、水蒸気透過度並びに密着強度を維持していることが確認できる。
【００６９】
これに対し、比較例１においては基材と被覆層との密着強度が充分でなくその耐剥離性能に劣ることが確認された。
【００７１】
【発明の効果】
請求項１〜６の発明によれば、
金属若しくは金属酸化物から成る被覆層が成膜される側に耐熱性材料により構成された第二コーティング層を備えているため、上記被覆層の成膜時に第二コーティング層表面が高温に晒されても第二コーティング層の軟化、溶融が起こり難く、しかもこの下側に位置する第一コーティング層や高分子フィルムから成る基材が軟化、溶融しても第二コーティング層の平滑性は保持される。
【００７２】
従って、第二コーティング層上にピンホールやクラック等の無い膜特性良好な被覆層を形成できるためそのガス遮断性を大幅に改善できる効果を有する。
【００７３】
また、耐熱性材料により構成される第二コーティング層は、第一コーティング層を介して基材に接着されているため基材から第二コーティング層が剥がれ難く、しかも、第二コーティング層は、ガラス転移温度Ｔ _g2 が４０℃以上の前述した樹脂材料群、熱硬化型樹脂、無機高分子から成る材料により構成されているため第二コーティング層からの上記被覆層の剥離も起こり難い。
【００７４】
従って、基材からの第二コーティング層並びに被覆層の経時的な剥離現象を防止できるためその耐剥離性能も大幅に改善できる効果を有している。
【図面の簡単な説明】
【図１】実施例１に係る被覆フィルムの断面図。
【符号の説明】
１ 被覆フィルム
１０ 基材
１１ 第一コーティング層
１２ 第二コーティング層
１３ 被覆層[0001]
[Industrial application fields]
The present invention comprises a base material made of a polymer film and a coating layer made of metal or metal oxide formed by vapor deposition such as vapor deposition and sputtering on at least one surface of the base material. In particular, coating films widely used for packaging materials in the fields of pharmaceuticals, foods, etc., in particular, can improve the adhesion between the coating layer to be formed and the substrate, and oxygen, water vapor, aroma (fragrance) The present invention relates to an improvement of a coating film that can maintain a gas barrier property such as an odor component).
[0002]
[Prior art]
In recent years, as a gas barrier film replacing an aluminum foil, a covering film formed by forming a metal thin film such as aluminum on a base material made of a polymer film has been used as a packaging material. Recently, a coated film in which a metal oxide thin film such as silicon oxide or aluminum oxide is formed in place of a metal thin film such as aluminum has been put into practical use. And these coated films with metal oxide thin films have transparency and easy incineration that the metal thin film does not have, so their development is attracting attention from today's global environmental problems. Has been.
[0003]
By the way, these coating films are conventionally manufactured by vapor phase growth methods such as vacuum deposition and sputtering. However, when the coating layer made of the metal or metal oxide is formed, the metal or metal oxide particles having an appropriate kinetic energy collide with the surface of the base material made of the polymer film. The low molecular gas contained in the film is released from the polymer film constituting the material, or the surface of the base material is exposed to a high temperature to be softened and melted, so that the smoothness of the film is easily lost. There existed a problem that a pinhole, a crack, etc. arise in a coating layer, or adhesive strength of a base material and a coating layer cannot fully be taken out. In particular, when the coating layer is made of a metal oxide, the melting point of the metal oxide is higher than that of the metal, so the above problem is significant because the electron beam method is used as the heating method during film formation. It was. For this reason, the gas barrier property of the obtained coating film was inadequate, and there was room for improvement such as peeling of the substrate and the coating layer over time.
[0004]
Therefore, in order to solve such a problem, a specific copolymer component is blended with the polymer film component constituting the substrate to improve the adhesion with the coating layer (see Japanese Patent Publication No. 55-232). ), Improving the adhesion by physically modifying the substrate surface by corona treatment, plasma treatment, flame treatment, etc. (see JP-A-57-87357, etc.), or gelatin, casein, cellulose, Cellulose derivatives, polyvinyl alcohol, polyvinyl methyl ether and other water-soluble resins that dissolve in water or various emulsions represented by acrylic emulsions are used to form a coating layer on the substrate. To improve gas barrier properties (see Japanese Examined Patent Publication Nos. 59-51427, 54-16557, etc.) Methods have been proposed.
[0005]
[Problems to be solved by the invention]
However, in the method of blending a specific copolymer component, although the adhesion to the coating layer is improved, the mechanical strength and heat resistance of the film base material are likely to be lowered, and the coating layer is particularly composed of a metal oxide. In the coated film, the film base material cannot withstand the thermal load at the time of film formation, and there is a problem that its gas barrier property is greatly lowered.
[0006]
In addition, in the method of physically modifying the substrate surface, the improvement of the adhesion is insufficient, and cracks are likely to occur at the interface between the substrate and the coating layer, and there is still a problem in the gas barrier property. ing.
[0007]
On the other hand, in the method of providing a coating layer on the surface of the substrate, the thermal load during film formation is certainly improved and its gas barrier property is improved, but on the other hand, it is hydrophobic with a polymer film. Since the chemical affinity between the conductive substrate and the coating layer composed of an aqueous resin or various emulsions is difficult, there is a problem that the coating layer is easily peeled off from the substrate over time.
[0008]
The present invention has been made paying attention to such problems, and the problem is that the adhesion between the coating layer to be formed and the substrate can be improved, and a gas such as oxygen or water vapor can be used. An object of the present invention is to provide a coating film capable of maintaining the barrier property over a long period of time.
[0009]
[Means for Solving the Problems]
Under such a technical background, the present inventor tried to apply a hydrophobic material having an affinity for a polymer film as a material constituting the coating layer. That is, a polyolefin-based resin or the like was selected as the coating material focusing on the adhesion to the polymer film, and the above-described coated film was prototyped. However, in this coating film, the peel resistance between the coating layer and the substrate was greatly improved as expected, but the coating layer surface was softened and melted due to the thermal load during film formation. As a result, it was confirmed that pinholes and the like were easily formed in the coating layer formed, and that there was a problem in the gas barrier property. On the other hand, a hydrophobic material having heat resistance such as a thermosetting resin was selected as the coating material focusing on the thermal load at the time of film formation, and a similar coating film was produced as a prototype. However, when the coating layer is composed of such a material, there is still a problem in adhesion to the base material as in the case where the coating layer is composed of the above-mentioned aqueous resin or various emulsions, and the gas barrier property is Although improved, it has been found that the peel resistance is still insufficient. In order to find a coating material that has excellent adhesion to the polymer film and can withstand the thermal load during the film formation, no effort was made to find a coating material. And after passing through such a technical examination, when the said coating layer was comprised with two types of layers from which material differs, it came to discover that the gas barrier property and peeling-proof performance of a coating film are improved dramatically. It was. The present invention has been completed through such technical studies.
[0010]
  That is, the coating film according to the present invention is composed of a base material made of a polymer film and a coating layer made of a metal or metal oxide formed on at least one surface of the base material by a vapor phase growth method. The glass transition temperature T between the substrate and the coating layer_g1Is in the range of −70 ° C. to −15 ° C.Composed of materialIt is assumed that the first coating layer and the second coating layer composed of a heat-resistant material are provided in order from the base material side.
[0011]
And since the coating film which concerns on this invention is equipped with the 2nd coating layer comprised with the heat resistant material in the side by which the coating layer which consists of a metal or a metal oxide is formed into a film, film-forming of the said coating layer Sometimes even if the surface of the second coating layer is exposed to a high temperature, the second coating layer is unlikely to soften or melt, and the base material composed of the first coating layer and the polymer film located below is softened and melted. Also, the smoothness of the second coating layer is maintained. Accordingly, since a coating layer having good film characteristics free from pinholes and cracks can be formed on the second coating layer, the gas barrier property can be greatly improved.
[0012]
  On the other hand, since the second coating layer composed of a heat-resistant material is adhered to the base material via the first coating layer, the second coating layer is difficult to peel off from the base material., Glass transition temperature T _g2 Consists of a resin material group described later at 40 ° C. or higher, a thermosetting resin, and an inorganic polymerSince it is made of a material, the coating layer is hardly peeled off from the second coating layer. Therefore, the second coating layer and the coating layer from the base material can be prevented from being peeled over time, so that the peel resistance can be greatly improved.
[0013]
In such technical means, the polymer film constituting the substrate is preferably a material excellent in dimensional stability, heat resistance and mechanical strength, for example, polyolefins such as polyethylene, polypropylene, polybutene; Vinyl alcohol copolymer; polystyrene; polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate; nylon-6, nylon-11, aromatic polyamide; polycarbonate; polyvinyl chloride, polyvinylidene chloride; polyimide, etc. However, the film is not limited to these films as a matter of course. Further, as these polymer films, it is preferable to apply a film stretched in the vertical and horizontal directions from the viewpoint of strength, dimensional stability, heat resistance and the like. Moreover, about these polymer films, well-known additives, such as an antistatic agent, a ultraviolet absorber, a depopulation agent, a lubricant, and a coloring agent, may be mix | blended. Moreover, there is no restriction | limiting in particular about the thickness dimension of the base material which consists of polymer films, However, A film with a thickness of 3 micrometers-400 micrometers is used from the point of intensity | strength. As will be described later, the thickness is preferably in the range of 6 μm to 200 μm from the viewpoint of vapor phase film-formation workability, as well as handling during printing and laminating as secondary processing.
[0014]
  Next, as a material constituting the first coating layer provided on the substrate, a glass transition temperature T_g1Is in the range of −70 ° C. to −15 ° C.belowPolyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, poly It is selected from butyl acrylate and derivatives thereof.
[0015]
  On the other hand, as a material constituting the second coating layer provided on the first coating layer, heat-resistant polystyrene, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl isobutyral, polyvinyl chloride, polymethacrylonitrile , Polyacrylic acid, polyacrylonitrile, polyacrylate, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polyisobutyl methacrylate, polyethylene glycol dimethacrylate, polycyanoethyl methacrylate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, bisphenol A carbonate, cellulose acetate, cellulose tributyrate and derivatives thereof Et al selected glass transition temperature T_g240 ° C or higher, preferably 70 ° C to 80 ° C or higher.IsThe
[0016]
When the first coating layer and the second coating layer are constituted by these resin systems, the glass transition temperature of the material constituting the first coating layer is set to T_g1The glass transition temperature of the heat-resistant material constituting the second coating layer is T_g2T_g1 <T_g2 And T_g2 It is desirable to select each material so as to satisfy the condition of ≧ 40 ° C. When the first coating layer and the second coating layer are made of materials having such conditions, the glass transition temperature of the second coating layer is 40 ° C. or higher and higher than the glass transition temperature of the first coating layer. Even if the surface of the second coating layer is exposed to a high temperature during the formation of the coating layer, the second coating layer remains in a glass state and is difficult to soften and melt, and the first coating layer is softened and melted. By sufficiently maintaining the adhesive strength between the second coating layer and the substrate, it is possible to obtain a coating film excellent in peeling resistance and gas barrier properties by these actions.
[0017]
In addition to the above resin-based materials, known thermosetting, such as polyureas (urea resins) that are addition condensation reaction products of urea and formaldehyde, and phenol resins that are addition condensation reaction products of phenols and aldehydes. You may comprise a 2nd coating layer using a mold resin.
[0018]
Further, a structure having Si—N in the main chain and hydrogen or an alkyl group in the side chain (SiH_lN_m)_n A coating solution containing a polysilazane precursor represented by the above or a modified product thereof or a mixture thereof is heated or subjected to low-temperature plasma treatment to cure and polymerize the polysilazane precursor or modified product thereof or a mixture thereof. An inorganic polymer made of silicon oxide, silicon nitride, or a mixture thereof, or H_ThreeSi (NHSiH₂)_nNHSiH_ThreeAs a constituent material of the second coating layer, an inorganic polymer composed of a silicon oxide system, a silicon nitride system, or a mixed system formed by heating and drying a coating solution containing the silicon compound or derivative thereof shown in FIG. Applicable. Further, the second coating layer may be composed of silicon oxide, silicon nitride, or a mixed system thereof converted into silicon oxide by heating and oxidation treatment. In this case, since the chemical stability is increased as compared with an inorganic polymer composed of silicon oxide, silicon nitride, or a mixed system thereof, the gas barrier property has an advantage that it is difficult to deteriorate over a long period of time. In addition, as a specific polysilazane constituting the second coating layer, (SiH_lN_m)_n The polysilazane represented by [where l = 1 to 3, m = 0.1, n = 600 to 2100] is exemplified.
[0019]
In addition, the polysilazane precursor or a modified product thereof or a mixture thereof, or the H_ThreeSi (NHSiH₂)_nNHSiH_ThreeAs the solvent for dissolving or dispersing the silicon compound or its derivative, a single component or a mixed solvent selected from benzene, toluene, xylene, diethyl ether, tetrahydroxyfuran, methylene chloride, carbon tetrachloride and the like is applied. The
[0020]
Next, regarding the thickness dimension of these coating layers, the thickness of the first coating layer is set to M.₁, The thickness of the second coating layer is M₂In this case, it is desirable to set so as to satisfy the following conditions.
[0021]
50nm ≦ M₁≤ 2000nm, M₂≦ 1000nm
That is, about the 1st coating layer, 50 nm <= M according to the material which comprises the base material which consists of a polymer film, and the 2nd coating layer.₁≦ 2000 nm can be set as appropriate. However, the thickness M of the first coating layer₁When the thickness exceeds 2000 nm, the first coating layer is instantaneously softened due to the effect of thermal addition applied during the formation of the coating layer, and the second coating layer formed on the first coating layer is softened due to this softening. Since physical stress is easily applied to the coating layer due to deformation, expansion and contraction, cracks and the like may occur in the formed coating layer. Also, the thickness M of the first coating layer₁When the thickness is less than 50 nm, adhesion failure with the second coating layer formed thereon may occur.
[0022]
On the other hand, for the second coating layer, M₂≦ 1000 nm is preferably as thin as possible within a range that satisfies the condition. The thickness M of the second coating layer₂When the thickness exceeds 1000 nm, the flexibility of the coating layer is impaired, and the second coating layer is likely to be cracked or cracked, which may cause cracks or the like in the coating layer.
[0023]
The thickness relationship between the first coating layer and the second coating layer depends on the thickness M of the second coating layer.₂Since the thinner the better, M₁≧ M₂In addition, the total thickness of the first coating layer and the second coating layer is set to a range of 100 nm to 3000 nm, preferably 500 nm to 1000 nm.
[0024]
In addition, about the formation method of these 1st coating layers and 2nd coating layers, the gravure coat, roll coat, air which apply | coats the coating liquid containing the resin mentioned above, a polysilazane precursor, etc. on a base material or a 1st coating layer. It can carry out using well-known coating means, such as a knife coat and a blade coat. Hereinafter, the case where a base material composed of a biaxially stretched polyester film is used as an example will be described, and the coating liquid for the first coating layer is applied to at least one surface of the polyester film before the oriented crystal is completed, After stretching the polyester film in the vertical and horizontal directions, the coating solution for the second coating layer is applied on the first coating layer of the polyester film that has been heat-set, and the oriented crystal is completed. The coating liquid for the first coating layer and the coating liquid for the second coating layer are sequentially applied to at least one surface of the polyester film before the coating, and then each of the coating layers is formed by performing longitudinal and transverse stretching treatment and heat setting treatment. it can.
[0025]
  And claims1-6The present invention relates to an invention that specifies selection conditions for forming the first coating layer and the second coating layer with the resin-based material described above, and an invention that specifies the type of material constituting the second coating layer.
[0026]
  That is, the invention according to claim 1
  It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one surface of the base material. And glass transition temperature T_g1Is in the range of −70 ° C. to −15 ° C.Composed of materialAssuming a coating film in which a first coating layer and a second coating layer composed of a heat-resistant material are provided in order from the substrate side,
  The glass transition temperature of the heat-resistant material constituting the second coating layer is T_g2If
      T_g1 <T_g2 And T_g2 ≧ 40 ℃
The first coating layer and the second coating layer are composed of a material that satisfies the condition ofThe material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate And a heat-resistant material selected from these derivatives and constituting the second coating layer is polystyrene, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl isobutyral, polyvinyl chloride, polymethacrylonitrile, polyacrylic acid , Polyacrylonitrile, polyacrylate, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate Acrylate, polyisobutyl methacrylate, polyethylene glycol dimethacrylate, poly cyanoethyl methacrylate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, bisphenol A carbonate, cellulose acetate, is selected from cellulose tributyrate and derivatives which suchIt is characterized by that.
[0027]
  The invention according to claim 2
  It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one side of the base material, and between the base material and the coating layer. And glass transition temperature T_g1Is in the range of -70 ° C to -15 ° C.Composed of materialAssuming a coating film in which a first coating layer and a second coating layer composed of a heat-resistant material are provided in order from the substrate side,
  The material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate And derivatives thereof, andThe second coating layer is composed of a thermosetting resin,
  The invention according to claim 3
  It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one side of the base material, and between the base material and the coating layer. And glass transition temperature T_g1Is in the range of -70 ° C to -15 ° C.Composed of a certain materialAssuming a coating film in which a first coating layer and a second coating layer composed of a heat-resistant material are provided in order from the substrate side,
  The material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate And derivatives thereof, andThe second coating layer is composed of an inorganic polymer.
[0028]
  Further claims4The invention according to
  Claim3On the premise of the coating film according to the described invention,
  A silicon oxide system formed by heating or low-temperature plasma treatment of a coating liquid containing a polysilazane precursor or a modified product thereof or a mixture thereof to cure and polymerize the polysilazane precursor or a modified product thereof or a mixture thereof. Alternatively, the second coating layer is composed of an inorganic polymer composed of a silicon nitride system or a mixed system thereof,
  Claim5The invention according to
  H_ThreeSi (NHSiH₂)_nNHSiH_ThreeThe second coating layer is composed of an inorganic polymer formed by heating and drying a coating solution containing a silicon compound or a derivative thereof, which is formed of silicon oxide, silicon nitride, or a mixed system thereof. It is characterized by that.
[0029]
  Claims6The invention according to
  Claims 4 to5On the premise of the coating film according to any of the invention,
  The second coating layer is composed of silicon oxide formed by heating / oxidation treatment of an inorganic polymer composed of the silicon oxide type, the silicon nitride type, or a mixed type thereof.
[0030]
In addition, as a means for forming a coating layer made of a metal or a metal compound provided on the second coating layer, a physical vapor deposition method such as a vapor deposition method, an ion plating method or a sputtering method, or a chemical method such as a plasma CVD method is used. Well-known film forming means such as a chemical vapor deposition method can be applied.
[0031]
Examples of the metal constituting the coating layer include silicon, aluminum, tin, zinc, titanium, magnesium, zirconium, nickel, cobalt, iron, lead, copper, and the like, and the metal oxide constituting the coating layer Examples of such materials include oxides of these metals. Further, the coating layer may be formed of a coating made of a single material or a coating made of a plurality of mixed materials. In some cases, the coating layer has a multilayer structure in which a metal thin film and a metal oxide thin film are combined. Also good.
[0032]
Moreover, about the film thickness of the said coating layer, it is normally set to 5 nm-1000 nm. In addition, in order to fully provide a gas barrier property to a coating film, it is preferable to set to 5 nm-50 nm. If the thickness is less than 5 nm, the structure of the coating layer becomes non-uniform and the gas barrier property becomes insufficient. This is because the adhesion with the layer is lowered.
[0033]
[Action]
  Claims 1 to6According to the coating film according to the described invention,
  Since the second coating layer made of a heat-resistant material is provided on the side on which the coating layer made of metal or metal oxide is formed, the surface of the second coating layer is exposed to a high temperature when the coating layer is formed. However, the second coating layer is not easily softened or melted, and the smoothness of the second coating layer is maintained even if the underlying substrate made of the first coating layer or polymer film is softened or melted. The Accordingly, since a coating layer having good film characteristics free from pinholes and cracks can be formed on the second coating layer, the gas barrier property can be greatly improved.
[0034]
  In addition, the second coating layer composed of a heat-resistant material is adhered to the base material via the first coating layer, so that the second coating layer is difficult to peel off from the base material., Glass transition temperature T _g2 Consisting of the above-mentioned resin material group of 40 ° C. or higher, thermosetting resin, and inorganic polymerSince it is made of a material, the coating layer is hardly peeled off from the second coating layer. Therefore, the second coating layer and the coating layer from the base material can be prevented from being peeled over time, so that the peel resistance can be greatly improved.
[0035]
【Example】
Examples of the present invention will be described in detail below.
[0036]
[Example 1]
A polyethylene terephthalate film having a thickness of 12 μm was used as the base material 10, and polyurethane (T_g1: -15 ° C) and polyester (T_g2: 65 ° C.) is applied by a roll coating method to form a first coating layer 11 and a second coating layer 12 each having a thickness after drying of 100 nm, and then a vacuum is formed on the second coating layer 12 40nm thick silicon oxide (SiO2) by vapor deposition_X, X: 1-2), a coating layer (vapor deposition film) 13 was formed to obtain a coating film 1 (see FIG. 1).
[0037]
Next, this coated film 1 and an unstretched polypropylene film were laminated by a dry lamination method via a two-component curable polyurethane adhesive to obtain a laminated material, and then a bag was created by heat sealing using this laminated material. .
[0038]
And, this bag is filled with tap water as contents, and left in an environment at room temperature (25 ° C.) and 40 ° C., oxygen permeability (gas barrier property), water vapor permeability (gas barrier property) of the bag, And the time change of adhesive strength (adhesiveness, ie, peeling resistance) was measured. The results are shown in Table 2 below.
[0039]
Each measurement is performed according to the following test method.
[0040]
(1) Oxygen permeability test
The oxygen gas permeability was measured by the isobaric method of JISK7126.
[0041]
Measuring instrument: MOCON OXTRAN 50/100 (ModernControll)
Measurement conditions: 27 ° C.-100% RH
In Table 2, only numerical values are displayed, but the unit is (cc / m²/ Day / atm).
[0042]
(2) Water vapor permeability test
The JISK7129 B method (infrared sensor method) was adopted.
[0043]
Measuring device: MOCON PERMATRAN W6
In Table 2, only numerical values are displayed, but the unit is (cc / m²/ Day / atm).
[0044]
(3) Adhesion strength test
In order to investigate the adhesion between the formed coating layer (deposition film) and the polyester film, the peel strength was measured with a Tensilon tester based on JISK7127, and how much the coating layer (deposition film) remained on the polyester film. Was detected as the signal intensity per fixed area by the fluorescent X-ray method, and compared with the intensity value measured in advance, the following ranking was performed and evaluated.
[0045]
Evaluation criteria
Rank 1: No coating layer (deposited film) remains.
[0046]
Rank 2: Less than 40% of the coating layer (deposited film) remains.
[0047]
Rank 3: 40% or more and less than 80% of the coating layer (deposited film) remains.
[0048]
Rank 4: The coating layer (deposited film) remains 80% or more and less than 100%.
[0049]
Rank 5: 100% of the coating layer (deposited film) remains.
[0050]
[Example 2]
By the same method as in Example 1 except that the materials shown in Table 1 were applied as materials constituting the first coating layer and the second coating layer (see also the thickness after drying of each coating layer). A coated film was prepared and subjected to the same measurement.
[0051]
The results are shown in Table 2.
[0052]
[Example 3]
By the same method as in Example 1 except that the materials shown in Table 1 were applied as materials constituting the first coating layer and the second coating layer (see also the thickness after drying of each coating layer). A coated film was prepared and subjected to the same measurement.
[0053]
The results are shown in Table 2.
[0054]
[Example 4]
A coated film was prepared in the same manner as in Example 1 except that aluminum was applied as a constituent material of the coating layer (deposited film) and a 50 nm deposited film was formed, and the same measurement was performed.
[0055]
The results are shown in Table 2.
[0056]
[Example 5]
Aluminum oxide (AlO) as a constituent material of the coating layer (deposited film)_X, X: 1 to 1.5), and a coating film was prepared in the same manner as in Example 1 except that a 30 nm vapor-deposited film was formed, and the same measurement was performed.
[0057]
The results are shown in Table 2.
[0058]
[Example 6]
A polyethylene terephthalate having an intrinsic viscosity of 0.62 containing 650 ppm of silicon dioxide having an average particle diameter of 0.4 μm is formed by melt extrusion under conditions of 285 ° C. to 300 ° C. and cooled while being held by a cooling roll at 15 ° C. Thus, an unstretched film having a thickness of 120 μm was obtained. This unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated at 85 ° C. and having different peripheral speeds, and the following first coating material and second coating material were rolled onto this film. It is applied sequentially by the coating method, dried with hot air at 90 ° C., then stretched 3.5 times in the transverse direction with a tenter at 98 ° C., and further subjected to heat setting treatment at 210 ° C. to 220 ° C. to a film thickness of 12 μm, A base film composed of a biaxially stretched polyester film having a first coating layer thickness of 50 nm and a second coating layer thickness of 50 nm was obtained.
(First coating material)
Polyurethane resin (T_g1: -15 ° C) water / isopropyl alcohol solution (solid content: 15% by weight)
(Second coating material)
Polysilazane precursor (trade name TSX-448, 20 wt% xylene / toluene mixture, manufactured by Tonen)
Next, magnesium oxide (MgO) having a thickness of 50 nm is formed on the second coating layer of the base film._X, X: 1 to 1.5) After forming a coating layer (vapor deposition film) to obtain a coating film, the same measurement as in Example 1 was performed.
[0059]
The results are shown in Table 2.
[0060]
[Example 7]
The materials shown in Table 1 are applied as materials constituting the first coating layer and the second coating layer (see also the thickness after drying of each coating layer) and the composition of the coating layer (deposited film) Tin oxide (SnO as material)_X, X: 1 to 2) was applied, and a coating film was prepared by the same method as in Example 6 except that a deposited film of 30 nm was formed, and the same measurement was performed.
[0061]
The results are shown in Table 2.
[0062]
[Comparative Example 1]
A coated film was prepared by the same method as in Example 1 except that the first coating layer was not formed, and the same measurement was performed.
[0063]
The results are shown in Table 2.
[0066]
[Table 1]

[0067]
[Table 2]

[0068]
"Confirmation"
From the data in Table 2, it can be confirmed that the initial oxygen transmission rate, water vapor transmission rate, and adhesion strength are maintained over time for each example even when time elapses.
[0069]
On the other hand, in Comparative Example 1, it was confirmed that the adhesion strength between the substrate and the coating layer was not sufficient and the peel resistance was poor.
[0071]
【The invention's effect】
  Claims 1 to6According to the invention of
  Since the second coating layer made of a heat-resistant material is provided on the side on which the coating layer made of metal or metal oxide is formed, the surface of the second coating layer is exposed to a high temperature when the coating layer is formed. However, the second coating layer is not easily softened or melted, and the smoothness of the second coating layer is maintained even if the underlying substrate made of the first coating layer or polymer film is softened or melted. The
[0072]
Therefore, since a coating layer having good film characteristics free from pinholes and cracks can be formed on the second coating layer, the gas barrier property can be greatly improved.
[0073]
  In addition, the second coating layer composed of a heat-resistant material is adhered to the base material via the first coating layer, so that the second coating layer is difficult to peel off from the base material., Glass transition temperature T _g2 Consisting of the above-mentioned resin material group of 40 ° C. or higher, thermosetting resin, and inorganic polymerSince it is made of a material, the coating layer is hardly peeled off from the second coating layer.
[0074]
Therefore, since the peeling phenomenon with time of the second coating layer and the coating layer from the substrate can be prevented, the peeling resistance performance can be greatly improved.
[Brief description of the drawings]
1 is a cross-sectional view of a coating film according to Example 1. FIG.
[Explanation of symbols]
1 Coating film
10 Base material
11 First coating layer
12 Second coating layer
13 Coating layer

Claims (6)

It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one side of the base material, and between the base material and the coating layer. In addition, a first coating layer made of a material having a glass transition temperature T _{g1 in} the range of −70 ° C. to −15 ° C. and a second coating layer made of a heat-resistant material are sequentially provided from the substrate side. In the coated film
When the glass transition temperature of the heat-resistant material constituting the second coating layer is T _g2 ,
T _g1 <T _g2 and T _g2 ≧ 40 ° C.
The first coating layer and the second coating layer are constituted by a material satisfying the following conditions, and the material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, A heat-resistant material selected from polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate and derivatives thereof, and constituting the second coating layer is polystyrene, polyvinyl alcohol , Polyvinyl formal, polyvinyl acetal, polyvinyl isobutyral, polyvinyl chloride, polymethacrylonitrile, polyacrylic acid, polyacrylonitrile Polyacrylate, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polyisobutyl methacrylate, polyethylene glycol dimethacrylate, polycyanoethyl methacrylate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, bisphenol A carbonate, cellulose acetate, cellulose tri A coated film selected from butyrate and derivatives thereof. It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one side of the base material, and between the base material and the coating layer. In addition, a first coating layer made of a material having a glass transition temperature T _{g1 in} the range of −70 ° C. to −15 ° C. and a second coating layer made of a heat-resistant material are sequentially provided from the substrate side. In the coated film
The material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate coated film and which is selected from the derivatives of this like, and the second coating layer, characterized in that it is constituted by a thermosetting resin. It is composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed by vapor deposition on at least one side of the base material, and between the base material and the coating layer. In addition, a first coating layer made of a material having a glass transition temperature T _{g1 in} the range of −70 ° C. to −15 ° C. and a second coating layer made of a heat-resistant material are sequentially provided from the substrate side. In the coated film
The material constituting the first coating layer is polyethylene, ethylene propylene copolymer, polybutadiene, polypropylene, polyurethane, polybutene, polypentene, polychloropyrene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate and it is selected from the derivatives of this like, and coating film the second coating layer, characterized in that it is constituted by an inorganic polymer.   A silicon oxide system formed by heating or low-temperature plasma treatment of a coating liquid containing a polysilazane precursor or a modified product thereof or a mixture thereof to cure and polymerize the polysilazane precursor or a modified product thereof or a mixture thereof. 4. The coated film according to claim 3, wherein the second coating layer is composed of an inorganic polymer composed of silicon nitride or a mixed system thereof. By an inorganic polymer composed of a silicon oxide system, a silicon nitride system, or a mixed system formed by heating and drying a coating solution containing a silicon compound represented by H ₃ Si (NHSiH ₂ ) _n NHSiH ₃ or a derivative thereof. The said 2nd coating layer is comprised, The coating film of Claim 3 characterized by the above-mentioned.   5. The second coating layer is composed of silicon oxide formed by heating / oxidizing an inorganic polymer composed of the silicon oxide, silicon nitride, or mixed system thereof. The coating film according to any one of 5.

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