JP2010179506A - Laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film used as a transparent gas-barrier material even in an environment of high temperature and high humidity. <P>SOLUTION: The laminated film is obtained by subjecting at least one side of a substrate made of polyethylene terephthalate (PET) to preparatory treatment by reactive ion etching (RIE), laminating a primer layer on the treated surface of the substrate, laminating an inorganic compound layer on the primer layer, and laminating a gas-barrier coat layer on the inorganic compound layer. The preparatory treatment by RIE is carried out at least once using a mixed gas containing one of argon gas, nitrogen gas, oxygen gas, hydrogen gas, and carbon dioxide gas is used. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a laminated film, and in particular, as a gas barrier material having transparency, it is used in the packaging field of foods, pharmaceuticals, precision electronic parts and the like, and in the industrial material field.

  In recent years, packaging materials used for packaging foods, non-foods, pharmaceuticals, etc. have altered oxygen, water vapor, and other contents that permeate the packaging material in order to suppress the alteration of the contents and retain their functions and properties. It is necessary to prevent the influence of the gas to be generated, and it is required to have a gas barrier property and the like for blocking these. Therefore, conventionally, a packaging material using a metal foil such as aluminum, which is less affected by temperature and humidity, as a gas barrier layer has been generally used.

  However, packaging materials that use metal foils such as aluminum are not affected by temperature and humidity and have excellent gas barrier properties. However, the contents cannot be confirmed through the packaging material. Had disadvantages such as having to be treated as an incombustible material and being unable to use a metal detector during inspection.

  Therefore, as a packaging material that overcomes these disadvantages, a film in which a vapor deposition film of an inorganic compound such as silicon oxide or aluminum oxide is formed on a polymer film by a forming means such as a vacuum vapor deposition method or a sputtering method has been developed. (Patent Document 1, Patent Document 2). These vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having transparency and gas barrier properties that cannot be obtained with metal foil or the like. .

  However, the conventional vapor deposition film cannot exhibit sufficient adhesion to the vapor deposition layer when it comes into contact with moisture for a long period of time, such as a solar cell backsheet.

Therefore, as a gas barrier laminated film that has overcome these drawbacks, at least one surface of a base material made of polyethylene naphthalate (PEN) is subjected to pretreatment by reactive ion etching (RIE), and the base subjected to the pretreatment is applied. Patent Document 3 discloses a laminated film characterized by laminating a transparent primer layer on a material surface and laminating an inorganic compound layer on the transparent primer layer.
However, polyethylene naphthalate used as a base material absorbs ultraviolet rays and turns yellow, so that it is not suitable for use outdoors such as a back sheet for a solar cell from the viewpoint of design. Further, since polyethylene naphthalate is very expensive, there is a problem in cost.

U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 JP 2008-80540 A

  This invention makes it a subject to provide the laminated | multilayer film which can be utilized as a transparent gas barrier material also in a hot and humid environment.

  As means for achieving the above object, the invention according to claim 1 is characterized in that a pretreatment by reactive ion etching (RIE) is performed on at least one surface of a base material made of polyethylene terephthalate (PET), and the pretreatment is performed. A laminated film characterized by laminating a primer layer on the surface of the substrate subjected to the above, laminating an inorganic compound layer on the primer layer, and laminating a gas barrier coating layer on the inorganic compound layer.

  In the invention according to claim 2, the pretreatment by the RIE is performed once or more using a mixed gas containing at least one of argon gas, nitrogen gas, oxygen gas, hydrogen gas, and carbon dioxide gas. The laminated film according to claim 1, wherein the laminated film is implemented.

According to a third aspect of the present invention, in the pretreatment by RIE, the plasma self-bias value is 200 V or more and 2000 V or less, and the Ed value (plasma density × treatment time) is 100 W · s · m ^{−2 to} 10000 W · s · 3. The laminated film according to claim 1, wherein the laminated film is a low-temperature plasma treatment of m ⁻² or less.

  Further, in the invention according to claim 4, the primer layer is made of a composite material of a silane coupling agent or a hydrolyzate thereof, a polyol and an isocyanate compound. It is a laminated film of description.

  The invention according to claim 5 is characterized in that the silane coupling agent or a hydrolyzate thereof contains a functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of a bifunctional or higher functional isocyanate compound. The laminated film according to claim 4.

In the invention according to claim 6, in the composite material, the general formula M (OR) _n (M: metal element, R: alkyl group such as CH ₃ , C ₂ H ₅ , n: oxidation number of metal element) The metal alkoxide represented by these or the hydrolyzate of the said metal alkoxide is added, It is a laminated film of Claim 4 or 5 characterized by the above-mentioned.

  The invention according to claim 7 is the laminated film according to any one of claims 1 to 6, wherein the primer layer has a thickness of 0.01 to 1 μm.

  The invention according to claim 8 is characterized in that the inorganic compound contains at least one of aluminum oxide, silicon oxide, magnesium oxide, tin oxide, and zinc oxide. It is a laminated | multilayer film as described in a term.

  The invention according to claim 9 is characterized in that the gas barrier coating layer contains at least one of a water-soluble polymer compound and a metal alkoxide and / or a hydrolyzate thereof and / or a polymer thereof. Laminated film of any one of -8

  The invention according to claim 10 is characterized in that the water-soluble polymer compound contains at least one of polyvinyl alcohol or ethylene-vinyl alcohol copolymer, cellulose, and starch. It is a laminated film.

  The invention according to claim 11 is the laminated film according to claim 6 or 9, wherein the metal in the metal alkoxide contains at least one of Si, Al, Ti, and Zr.

  In the present invention, at least one surface of a base material made of polyethylene terephthalate (PET) is subjected to pretreatment by reactive ion etching (RIE), and a primer layer is laminated on the pretreated base material surface. Even in a hot and humid environment, the adhesion between the substrate and the primer layer is improved, and the gas barrier property can be maintained.

Sectional drawing showing an example of the gas barrier laminated film 5 of this invention

  FIG. 1 is a sectional view showing an example of the gas barrier laminated film 5 of the present invention. In the gas barrier laminate film of the present invention, at least one main surface of the resin base material 1 having two main surfaces is subjected to a pretreatment by reactive ion etching (RIE) using plasma, and the primer layer 2 and the inorganic compound layer 3 and a gas barrier coating layer 4 are laminated.

  The above-mentioned resin base material 1 is polyethylene terephthalate (PET), and the thickness of the base material is preferably 3 to 200 μm practically.

  Further, various known additives and stabilizers such as an antistatic agent, a plasticizer, a lubricant, and an antioxidant can be applied to the surface of the resin substrate 1 as necessary.

  In order to reinforce the adhesion between the resin base material 1 and the primer layer 2, it is effective to perform pretreatment by reactive ion etching (RIE) using plasma on the surface. By performing this RIE treatment, the surface of the resin base material 1 is provided with a functional group by the generated radicals and ions, and the surface is ion-etched to remove impurities and smooth the surface. These two physical effects can be obtained simultaneously.

  RIE is a method for powerfully treating a substrate to be treated with ions generated from plasma generated on the substrate to be treated. At this time, the key point is how to maintain a high-frequency plasma-specific potential called self-bias between the plasma potential and the substrate. In the normal mode plasma, although self-bias is applied, it appears as a potential difference between the plasma and the electrode, and a large potential difference is not generated between the plasma and the substrate. In order to improve this, it is possible to maintain the RIE mode by, for example, installing an electrode on the base material side and perform strong processing.

  Argon, oxygen, nitrogen, hydrogen, and carbon dioxide can be used as gas species for performing pretreatment by RIE. These gases may be used alone, or two or more kinds of gases may be mixed and used. Moreover, you may process continuously using two processing apparatuses.

The processing conditions indicated by the processing speed, energy level, and the like should be set as appropriate according to the type of substrate, application, discharge device characteristics, and the like. However, the self-bias value of the plasma 200V or 2000V or less, Ed = Ed values defined in plasma density × processing time is necessary to below 100W · s · ^{m -2} or more 10000W · s · ^{m -2} Even at a value slightly lower than this, a certain degree of adhesion is exhibited, but the superiority is not high as compared with the untreated product. On the other hand, if the value is high, a strong treatment is applied excessively, the surface of the base material is deteriorated, and the adhesiveness is lowered. Regarding the gas for plasma and its mixture ratio, etc., the flow of the introduced gas varies depending on the device depending on the pump performance, exhaust port mounting position, etc., so the gas flow rate is set appropriately according to the application, substrate, and device characteristics Should do.

As the primer layer 2, for example, an organic polymer obtained by a two-component reaction of a polyol selected from acrylic polyol, polyvinyl acetal, polyester polyol, polyurethane polyol, and the like with a bifunctional or higher isocyanate compound, or a polyisocyanate compound And organic compounds having urea bonds by reaction with water, polyethyleneimine or derivatives thereof, polyolefin emulsions, polyimides, melamines, phenols, inorganic silicas such as organically modified colloidal silica, silane coupling agents and hydrolysates thereof The thing which has such an organic silane compound as a main ingredient is mentioned. In particular, a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is preferable. When the primer layer 2 made of this combination is used, stable high adhesion can be obtained between the resin base material 1 and the inorganic compound layer 3.

  Examples of the isocyanate compound include various diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hydrogenated products thereof. Monomers can be used. In addition, adduct types obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette types reacted with water, and trimers utilizing self-polymerization of isocyanate groups. Trifunctional derivatives such as (isocyanurate) type or higher polyfunctional derivatives may be used.

  As an example of the silane coupling agent, a silane coupling agent containing any organic functional group can be used. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, Y-chloropropylmethyldimethoxysilane, Y-chloropropyl. Use one or more silane coupling agents such as trimethoxysilane, glycidoxypropyltrimethoxysilane, Y-methacryloxypropyltrimethoxysilane, Y-methacryloxypropylmethyldimethoxysilane, or hydrolysates thereof. Can

  Further, among these silane coupling agents, those having a functional group that reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing an isocyanate group such as Y-isocyanatopropyltriethoxysilane, Y-isocyanatopropyltrimethoxysilane, those containing a mercapto group such as Y-mercaptopropyltriethoxysilane, Y-aminopropyltriethoxysilane, Some include amino groups such as Y-aminopropyltrimethoxysilane, N-β- (aminoethyl) -Y-aminopropyltriethoxysilane, Y-phenylaminopropyltrimethoxysilane. Further, those containing an epoxy group such as Y-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyl (β-methoxyethoxy) silane, etc. Such a silane coupling agent may be added with alcohol or the like and added with a hydroxyl group or the like, and one or more of these may be used. These silane coupling agents have a silane cup containing a functional group in which an organic functional group present at one end exhibits an interaction in a composite material composed of a polyol and an isocyanic compound or reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. A stronger transparent primer layer 2 is formed by providing a covalent bond by using a ring agent, and a silanol group generated by hydrolysis of an alkoxy group at the other end is formed on the metal in the inorganic compound or the surface of the inorganic compound. High adhesiveness with an inorganic compound is expressed by a strong interaction with a highly active hydroxyl group or the like, and desired physical properties can be obtained. Therefore, you may use what hydrolyzed the said silane coupling agent with the metal alkoxide. In addition, there is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group, etc., and these alkoxy groups, chloro groups, acetoxy groups, etc. are hydrolyzed to form silanol groups. Can be used in this composite material.

A polyol has two or more hydroxyl groups in a polymer and is reacted with an isocyanate group in an isocyanate compound added later. Among them, an acrylic polyol which is a polyol obtained by polymerizing an acrylic acid derivative monomer or a polyol obtained by copolymerizing an acrylic acid derivative monomer and other monomers is particularly preferable. Among these, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxylbutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

  The blending ratio of the polyol and the silane coupling agent is preferably in the range of 1/1 to 1000/1 in terms of weight ratio, more preferably in the range of 2/1 to 100/1. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, A mixture of aromatic hydrocarbons such as toluene and xylene alone and arbitrarily can be used. However, since an aqueous solution such as hydrochloric acid may be used to hydrolyze the silane coupling agent, it is preferable to use a solvent in which isopropyl alcohol or the like and ethyl acetate that is a polar solvent are arbitrarily mixed as a cosolvent.

Further, a reaction catalyst may be added to promote the reaction when the silane coupling agent and the polyol are blended. Examples of the catalyst to be added include tin compounds such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ), tin axoxide, and titanium chelate in terms of reactivity and polymerization stability. It is preferable that In particular, it is preferable to use titanium chelate from the environmental viewpoint. If the addition amount is too small or too large, the catalytic effect cannot be obtained, and therefore it is preferably in the range of 1/10 to 1/10000 in terms of molar ratio with respect to the trifunctional organosilane. It is desirable to be in the range of 100 to 1/2000.

Furthermore, in order to improve the liquid stability during the preparation of the above mixture, a metal alkoxide or a hydrolyzate thereof may be added. This metal alkoxide is a general formula M (OR) _n (M: metal element, R: CH) such as tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), tripropoxyaluminum (Al (OC ₃ H ₇ ) ₃ ), etc. ₃ or an alkyl group represented by a general formula C _n H _{2n + 1} such as C ₂ H _5, or a hydrolyzate thereof. Of these, tetraethoxysilane, tripropoxyaluminum, or a mixture of both is preferable because it is relatively stable in an aqueous solvent. The metal alkoxide hydrolyzate may be hydrolyzed together with the silane coupling agent, or may be added after adding an acid alone.

  The primer layer 2 is obtained by directly or previously hydrolyzing such a silane coupling agent or hydrolyzed together with a metal alkoxide (in this case, the above-mentioned reaction catalyst or the like may be added together) Is mixed with a polyol or an isocyanate compound to prepare a composite solution, or a silane coupling agent and a polyol are mixed in advance in a solvent (the above-described reaction catalyst and metal alkoxide may be added together). Among those that have undergone a hydrolysis reaction, or just a mixture of a silane coupling agent and a polyol (in this case, it is possible to add the above-mentioned reaction catalyst and metal alkoxide together) Then, an isocyanate compound is added to prepare a composite liquid, which is formed by coating the resin substrate 1.

The thickness of the primer layer 2 is generally a thickness after drying, and it is desirable to coat the primer layer 2 in a range of 0.005 to 5 μm, and more preferably 0.01 to 1 μm. 0
. If the thickness is less than 01 μm, it is difficult to obtain a uniform coating film from the viewpoint of coating technology, and conversely if it exceeds 1 μm, it becomes uneconomical.

  Examples of the material used for the inorganic compound layer 3 include oxides such as silicon, aluminum, titanium, zirconium, tin, and magnesium, nitrides thereof, and fluorides thereof, and oxides, nitrides, and the like. Fluoride composite material. Among these, a material containing at least one of aluminum oxide, silicon oxide, magnesium oxide, tin oxide, and zinc oxide is desirable. In particular, silicon oxide is preferable because it has high barrier properties, maintains high barrier properties even under high temperature and high humidity, and has high safety.

The inorganic compound layer 3 can be formed by a film forming process such as a vacuum deposition method or an ion plating method. For example, when a silicon oxide vapor deposition layer is formed on one side of a film, silicon monoxide or silicon dioxide is used as a vapor deposition material, and resistance heating, induction heating, or electron beam is applied under a vacuum of 10 ⁻³ to 10 ⁻⁵ Torr. A film can be formed by a vacuum evaporation method by heating and evaporating. A reactive vapor deposition method performed while supplying oxygen gas can also be employed. In this case, metallic silicon may be used. The inorganic compound layer 3 can also be formed by a film forming process such as sputtering or CVD.

  The film thickness of the inorganic compound layer 3 varies depending on the application and the film thickness of the gas barrier coating layer 4, but is preferably several tens to 5000 mm. Furthermore, if it is 50 mm or less, a continuous thin film cannot be obtained, and if it exceeds 3000 mm, cracks are likely to occur. Therefore, a more preferable film thickness is 50 mm to 3000 mm.

  The gas barrier coating layer 4 is a coating layer having gas barrier properties, and uses a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof. It is formed. For example, a solution obtained by mixing a water-soluble polymer dissolved in an aqueous (water or water / alcohol mixed) solvent with a metal alkoxide directly or previously hydrolyzed is used as a solution. After coating this solution on the inorganic compound layer 3, it is formed by heating and drying.

  Examples of the water-soluble polymer used in the coating solution for the gas barrier coating layer 4 include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used as the coating agent for the gas barrier coating layer 4, the gas barrier property is most excellent, which is preferable. PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only several percent of acetic acid groups remain can be used from so-called partially saponified PVA in which several tens percent of acetic acid groups remain, and other materials may be used.

The metal alkoxide is a compound represented by a general formula, M (OR) _n (M: metal such as Si, Ti, Al, Zr, R: alkyl group such as R ₃ CH ₃ , C ₂ H ₅ ). Specific examples include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] and triisopropoxyaluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], among which tetraethoxysilane and triisopropoxy. Aluminum is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

  It is also possible to add known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants to the solution as long as the gas barrier properties are not impaired. is there.

The thickness of the gas barrier coating layer 4 after drying is not particularly limited. However, if the thickness exceeds 50 μm or more, cracks are likely to occur. As a method for forming the gas barrier coating layer 4, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like can be used. It coats on the inorganic compound layer 3 using these coating methods.

  If the drying method of the gas barrier coating layer 4 is a method of heating the gas barrier coating layer 4 such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, etc., and blowing off a solvent such as water or alcohol, these methods are used. In any case, two or more of these may be combined.

A printing layer can be laminated on the gas barrier coating layer 4 as necessary. Or it is also possible to laminate | stack several resin through an adhesive agent. Also, a plurality of resins can be laminated on the opposite side of the surface of the resin substrate 1 provided with the primer layer 2, the inorganic compound layer 3, and the gas barrier coating layer 4 through a printing layer, a heat seal layer, and an adhesive. .
Hereinafter, the gas barrier laminate of the present invention will be further described with reference to specific examples.

A pretreatment was performed by reactive ion etching (RIE) using plasma using a 12 μm-thick biaxially-stretched PET (Futamura Co., Ltd., FE2001) as a base material. At this time, a high frequency power source with a frequency of 13.56 MHz was used for the electrodes, and argon was used for the processing gas. The primer layer solution (A) was mixed at the following ratio to obtain a coating solution. The pretreated surface was coated using a bar coater, dried at 120 ° C. for 1 minute with a dryer, and a 0.2 μm primer layer was applied.
On this primer layer, silicon oxide was heated by an electron beam method, adjusted so as to have a predetermined film composition, and a silicon oxide vapor deposition layer having a thickness of 400 mm was formed.
A gas barrier coating layer solution comprising a combination of polyvinyl alcohol, tetraethoxysilane, and a silane coupling agent is applied to the upper surface of the silicon oxide vapor deposition layer using a bar coater, and dried at 120 ° C. for 1 minute in a dryer. A gas barrier coating layer having a thickness of about 0.3 μm was formed to obtain a gas barrier laminated film.
<Primer layer solution (A)>
In a diluting solvent, 9 parts by weight of acrylic polyol and 1 part by weight of polyester polyol are weighed and mixed and stirred with respect to 1 part by weight of Y-isocyanatopropyltrimethoxysilane. Subsequently, a primer layer solution (A) was prepared by diluting a mixed solution in which tolylene diisocyanate was added as an isocyanate compound so that NCO groups were equivalent to OH groups of acrylic polyol and polyester polyol to an arbitrary concentration.

A laminated film of Example 2 was produced in the same manner as in Example 1 except that the primer layer solution (B) prepared by the following method was used for the primer layer.
<Primer layer solution (B)>
9 parts by weight of acrylic polyol and 1 part by weight of polyester polyol with respect to 1 part by weight of mixed solution of Y-glycidoxypropyltrimethoxysilane or its hydrolyzate, tetraethoxysilane or its hydrolyzate, and titanium chelate in the diluting solvent Weigh and mix and stir. Next, a primer layer solution (B) was prepared by diluting a mixed solution in which tolylene diisocyanate as an isocyanate compound was added so that the NCO group was equivalent to the OH groups of the acrylic polyol and polyester polyol to an arbitrary concentration.

<Comparative Example 1>
In the PET substrate, reactive ion etching (RIE) using plasma.
The laminated film of Comparative Example 2 was produced in the same manner as in Example 1 except that the pretreatment was not performed and the corona treatment was performed.

<Comparative example 2>
The PET base material was the same as in Example 1 except that the pretreatment by reactive ion etching (RIE) using plasma was not performed, the PET base material was subjected to corona treatment, and the primer layer was not used. By the method, a laminated film of Comparative Example 2 was produced.

  About each said laminated | multilayer film by dry lamination using the polycarbonate-type adhesive agent on the laminated | multilayer film of Examples 1-2 and Comparative Examples 1-2, hydrolysis-resistant polyethylene terephthalate (50 micrometers) / laminated film / water resistance Each laminated sample of degradable polyethylene terephthalate (50 μm) was produced.

表１から、ＰＥＴ基材１の表面に対してＲＩＥの前処理を行うことで、高温多湿の環境下でも、ＰＥＴ基材１とこの表面に積層したプライマー層２との密着性低下が抑制され、なおかつ、水蒸気バリア性を維持できることがわかる。 Using each of the above laminated samples, a pressure cooker test (PCT) for 48 hours and 96 hours was performed at 105 ° C. × 100% RH. The change in the water vapor barrier property of each of the above laminated samples was measured under an atmosphere of 40 degrees and a relative humidity of 90% using PERMATRAN 3/31 manufactured by Modern Control Co., in accordance with JIS K7129 B method. Moreover, the change of the laminate strength between the laminated film and the hydrolysis-resistant polyethylene terephthalate in each of the laminated samples was measured using an Orientec Tensilon universal tester RTC-1250 (conforming to JIS Z1707). Was measured. The results are shown in Table 1.

From Table 1, by performing the RIE pretreatment on the surface of the PET substrate 1, a decrease in the adhesion between the PET substrate 1 and the primer layer 2 laminated on the surface is suppressed even in a hot and humid environment. In addition, it can be seen that the water vapor barrier property can be maintained.

  In the present invention, at least one surface of a base material made of polyethylene terephthalate (PET) is pretreated by reactive ion etching (RIE), and a primer layer is laminated on the pretreated base material surface, The present invention relates to a film in which an inorganic compound layer is laminated on the primer layer, and a gas barrier coating layer is laminated on the inorganic compound layer. Since the film can improve the adhesion between the base material and the primer layer and maintain the gas barrier property even in a hot and humid environment, the film is in contact with moisture for a long period of time, for example, a solar cell backsheet. However, it can be provided at low cost for industrial material applications that require the maintenance of gas barrier properties and adhesion.

DESCRIPTION OF SYMBOLS 1 ... Resin base material 2 ... Primer layer 3 ... Inorganic compound layer 4 ... Gas barrier coating layer 5 ... Gas barrier laminated film

Claims (11)

  A pretreatment by reactive ion etching (RIE) is performed on at least one surface of a base material made of polyethylene terephthalate (PET), and a primer layer is laminated on the pretreated base material surface. An inorganic compound layer is laminated on the substrate, and a gas barrier coating layer is laminated on the inorganic compound layer.   The pretreatment by RIE is performed one or more times using a mixed gas containing at least one of argon gas, nitrogen gas, oxygen gas, hydrogen gas, and carbon dioxide gas. Item 2. The laminated film according to Item 1. Pretreatment with the RIE is, the low temperature plasma treatment the plasma self-bias value is set to 200V or 2000V following, Ed value (plasma density × processing time) and 100W · s · ^{m -2} or more 10000W · s · ^{m -2} or less The laminated film according to claim 1 or 2, wherein:   The laminated film according to any one of claims 1 to 3, wherein the primer layer is made of a composite material of a silane coupling agent or a hydrolyzate thereof, and a polyol and an isocyanate compound.   The laminated film according to claim 4, wherein the silane coupling agent or a hydrolyzate thereof includes a functional group that reacts with at least one of a hydroxyl group of a polyol or an isocyanate group of a bifunctional or higher functional isocyanate compound. . In the composite material, a metal alkoxide represented by the general formula M (OR) _n (M: metal element, R: alkyl group such as CH ₃ , C ₂ H ₅ , n: oxidation number of metal element) or the metal The laminated film according to claim 4 or 5, wherein a hydrolyzate of alkoxide is added.   The thickness of the said primer layer is 0.01-1 micrometer, The laminated | multilayer film of any one of Claims 1-6 characterized by the above-mentioned.   The laminated film according to any one of claims 1 to 7, wherein the inorganic compound contains at least one of aluminum oxide, silicon oxide, magnesium oxide, tin oxide, and zinc oxide.   9. The gas barrier coating layer according to claim 1, wherein the gas barrier coating layer contains at least one of a water-soluble polymer compound and a metal alkoxide and / or a hydrolyzate thereof and / or a polymer thereof. The laminated film as described.   The laminated film according to claim 9, wherein the water-soluble polymer compound contains at least one of polyvinyl alcohol or ethylene-vinyl alcohol copolymer, cellulose, and starch.   The laminated film according to claim 6 or 9, wherein the metal in the metal alkoxide contains at least one of Si, Al, Ti, and Zr.

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