JPH06192454A - Gas-barrier material - Google Patents
Gas-barrier materialInfo
- Publication number
- JPH06192454A JPH06192454A JP4344088A JP34408892A JPH06192454A JP H06192454 A JPH06192454 A JP H06192454A JP 4344088 A JP4344088 A JP 4344088A JP 34408892 A JP34408892 A JP 34408892A JP H06192454 A JPH06192454 A JP H06192454A
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- barrier material
- metal alkoxide
- water
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は食品、医薬品等の包装分
野に用いられるガスバリア材に関するものである。FIELD OF THE INVENTION The present invention relates to a gas barrier material used in the field of packaging foods, pharmaceuticals and the like.
【０００２】[0002]
【従来の技術】プラスチック基材表面にガスバリア被膜
を設けてなるガスバリア材としてポリ塩化ビニリデン樹
脂（ＰＶＤＣ）等のガスバリア性に優れた樹脂をラミネ
ートしたりコーティングしたものが知られており、食品
などの内容物の品質を長期保存するために包装材料とし
て用いられている。2. Description of the Related Art As a gas barrier material having a gas barrier coating provided on the surface of a plastic base material, it is known that a resin excellent in gas barrier property such as polyvinylidene chloride resin (PVDC) is laminated or coated. It is used as a packaging material to preserve the quality of contents for a long time.
【０００３】しかし、これらの樹脂系のバリア材では酸
素バリア性が１ｃｃ／ｍ2 ・ｄａｙ・ａｔｍ以下のハイ
ガスバリア材を実現するのは困難であり、また焼却処理
やリサイクリングなどの廃棄物処理に難点が多い。However, it is difficult to realize a high gas barrier material having an oxygen barrier property of 1 cc / m 2 · day · atm or less with these resin-based barrier materials, and waste treatment such as incineration and recycling. There are many difficulties.
【０００４】一方、真空蒸着法、スパッタリング法、あ
るいはプラズマ化学気相成長（ＣＶＤ）法などの真空プ
ロセスによってＳｉＯ2 等の無機化合物の被膜を設けた
バリア材が開発されている。On the other hand, barrier materials provided with a film of an inorganic compound such as SiO 2 have been developed by a vacuum process such as a vacuum vapor deposition method, a sputtering method or a plasma chemical vapor deposition (CVD) method.
【０００５】これらのバリア材は樹脂系のバリア材では
実現できないハイバリア性能を有しており、焼却処理さ
れても有毒ガスの発生することなく、また無機物の被膜
もその厚みが数百オングストロームと非常に薄く、樹脂
基材としてのリサイクリングも可能である。These barrier materials have a high barrier performance which cannot be realized by a resin-based barrier material, no toxic gas is generated even if they are incinerated, and the thickness of the inorganic coating film is as high as several hundred angstroms. It is extremely thin and can be recycled as a resin substrate.
【０００６】しかし、これらの無機系のバリア材はバリ
ア層である無機の被膜が可とう性に欠ける、基材との密
着性が悪い、などから取扱いに注意を要する。また、こ
れらの真空プロセスでは装置が高価であったり、生産性
が悪かったりコスト的にかなり高価であるなどの欠点が
残されている。However, these inorganic barrier materials require careful handling because the inorganic coating as the barrier layer lacks flexibility and has poor adhesion to the substrate. Further, these vacuum processes have drawbacks such as expensive equipment, poor productivity, and high cost.
【０００７】この様な課題を解決する技術として、基材
に金属アルコキシドの被膜を設けたガスバリア材が提案
されている（特開昭６２−２９５９３１号公報等）。As a technique for solving such a problem, a gas barrier material having a metal alkoxide coating film on a substrate has been proposed (Japanese Patent Laid-Open No. 62-295931).
【０００８】このガスバリア材は、乱雑な取扱いにも耐
え得る可とう性を有し、金属アルコキシドは無害なもの
であるので環境に優しく、また被膜は薄いので廃棄処理
あるいはリサイクリングが可能でコスト的にも安価であ
る。This gas barrier material is flexible enough to withstand messy handling, and is harmless to metal alkoxides because it is harmless to the environment. Also, since the film is thin, it can be disposed of or recycled because it is thin. It is also cheap.
【０００９】しかし、この金属アルコキシドの被膜を設
けたガスバリア材は、基材単体の場合と較べ、酸素バリ
ア性の向上は見られるものの、絶対的なガスバリア性の
点で満足がいくものではなかった。However, although the gas barrier material provided with this metal alkoxide coating shows an improvement in oxygen barrier property as compared with the case of the base material alone, it is not satisfactory in terms of absolute gas barrier property. .
【００１０】[0010]
【発明が解決しようとする課題】本発明は、かかる問題
点に鑑みてなされたもので、乱雑な取扱いにも耐え得る
可とう性を有し、環境に優しい廃棄処理あるいはリサイ
クリングが可能でコスト的にも安価であることは無論の
こと、ガスバリア性が遙に優れたガスバリア材を提供す
ることを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, has flexibility to withstand messy handling, and is environmentally friendly for disposal or recycling, and is cost effective. It is, of course, inexpensive to provide a gas barrier material having a far superior gas barrier property.
【００１１】[0011]
【課題を解決するための手段】請求項１記載の発明は、
プラスチックからなる基材の少なくとも片面に、金属ア
ルコキシドあるいは金属アルコキシドの加水分解物と、
水酸基を有する水溶性樹脂との複合物からなる被膜を有
することを特徴とするガスバリア材である。The invention according to claim 1 is
At least one surface of the base material made of plastic, a metal alkoxide or a hydrolyzate of a metal alkoxide,
A gas barrier material having a coating film made of a composite with a water-soluble resin having a hydroxyl group.
【００１２】請求項２記載の発明は、請求項１記載の発
明を前提とし、該金属アルコキシドあるいは金属アルコ
キシドの加水分解物中の金属が、Ｓｉ、Ａｌであること
を特徴とするガスバリア材である。The invention according to claim 2 is based on the invention according to claim 1, and is a gas barrier material characterized in that the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si or Al. .
【００１３】請求項３記載の発明は、請求項１、２記載
の発明を前提とし、該水溶性樹脂がポリビニルアルコー
ルであることを特徴とするガスバリア材である。The invention according to claim 3 is based on the invention according to claims 1 and 2, and is a gas barrier material characterized in that the water-soluble resin is polyvinyl alcohol.
【００１４】請求項４記載の発明は、請求項１、２、３
記載の発明を前提とし、該被膜中の金属アルコキシドあ
るいは金属アルコキシドの加水分解物を金属酸化物に換
算したときの金属酸化物と水溶性樹脂との重量比率が、
２０：８０〜９５：５であることを特徴とするガスバリ
ア材である。The invention as claimed in claim 4 is as follows.
Based on the invention described, the weight ratio of the metal oxide and the water-soluble resin when the metal alkoxide in the coating film or the hydrolyzate of the metal alkoxide is converted into the metal oxide,
The gas barrier material is characterized by having a ratio of 20:80 to 95: 5.
【００１５】[0015]
【作用】本発明に係わるガスバリア材は、プラスチック
からなる基材の少なくとも片面に、金属アルコキシドあ
るいはその加水分解物とポリビニルアルコールなどの水
溶性樹脂との複合被膜を設けたものであり、ハイレベル
のガスバリア性を有する。The gas barrier material according to the present invention comprises a base material made of plastic, and a composite coating of a metal alkoxide or its hydrolyzate and a water-soluble resin such as polyvinyl alcohol provided on at least one surface of the base material. Has gas barrier properties.
【００１６】本発明において用いられるプラスチック基
材とは、ポリオレフィン（ポリエチレン、ポリプロピレ
ン等）、ポリエステル（ポリエチレンテレフタレート、
ポリブチレンテレフタレート、ポリエチレンナフタレー
ト等）、ポリアミド（ナイロン−６、ナイロン−６６
等）、ポリ塩化ビニル、ポリイミド等、あるいはこれら
の高分子の共重合体などの通常の包装材料として用いら
れるものである。The plastic substrate used in the present invention includes polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate,
Polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66)
Etc.), polyvinyl chloride, polyimide and the like, or copolymers of these polymers and the like, which are used as usual packaging materials.
【００１７】また、これらの高分子に公知の添加剤、例
えば帯電防止剤、紫外線吸収剤、可塑剤、滑剤、着色剤
などを含んだものであっても良い。Further, these polymers may contain known additives such as antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants and the like.
【００１８】次に、基材上に形成される複合被膜につい
て詳細に説明する。本発明において用いられる金属アル
コキシドとは、テトラエチルオルソシリケート（Ｓｉ
（ＯＣ2 Ｈ5 ）4 ）、トリイソプロピルアルミニウム
（Ａｌ（ＯＣ3Ｈ7 ）3 ）．など一般式Ｍ（ＯＲ）
n （ＭはＳｉ，Ｔｉ，Ａｌ，Ｚｒなどの金属、ＲはＣＨ
3 ，Ｃ2 Ｈ5 などのアルキル基）で表せるものである。
その中でもＭがＳｉ，Ａｌである金属アルコキシドの特
性が優れている。Next, the composite coating formed on the substrate will be described in detail. The metal alkoxide used in the present invention is tetraethyl orthosilicate (Si
(OC 2 H 5) 4) , triisopropyl aluminum (Al (OC 3 H 7) 3). General formula M (OR)
n (M is a metal such as Si, Ti, Al, Zr, R is CH
3 , an alkyl group such as C 2 H 5 ).
Among them, the characteristic of the metal alkoxide in which M is Si or Al is excellent.
【００１９】水酸基を有する水溶性樹脂とは、ポリビニ
ルアルコール、ポリビニルピロリドン、デンプン、メチ
ルセルロース、カルボキシメチルセルロース、アルギン
酸ナトリウムなどである。その中でもポリビニルアルコ
ールのバリア特性が優れている。The water-soluble resin having a hydroxyl group includes polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. Among them, polyvinyl alcohol has excellent barrier properties.
【００２０】被膜はこのような金属アルコキシドを直接
あるいはあらかじめ加水分解反応させたものを水溶性樹
脂と混合して複合物溶液を作成し、基材にコーティング
して形成させるものである。The coating film is formed by coating such a metal alkoxide directly or by previously hydrolyzing it with a water-soluble resin to prepare a composite solution and coating it on a substrate.
【００２１】とりわけ複合物の割合は金属アルコキシド
あるいはその加水分解物を金属酸化物に換算したときに
金属酸化物と水溶性樹脂との重量比率が２０：８０〜９
９：１の範囲がバリア性、可とう性ともに優れている。Particularly, the ratio of the composite is such that, when the metal alkoxide or its hydrolyzate is converted into the metal oxide, the weight ratio of the metal oxide and the water-soluble resin is 20: 80-9.
The range of 9: 1 is excellent in both barrier property and flexibility.
【００２２】コーティングの方法は通常用いられるディ
ッピング法、ロールコティング法、スクリーン印刷法、
スプレー法、などいずれの方法を用いても良い。The coating method is a commonly used dipping method, roll coating method, screen printing method,
Any method such as a spray method may be used.
【００２３】被膜の厚さは、用いる複合物の種類によっ
ても異なるが、約０．０１〜１０００μｍの範囲内であ
れば良い。しかし、５０μｍ以上では膜にクラックが入
り易くなるため、０．０１〜５０μｍの範囲内にあるこ
とがより望ましい。The thickness of the coating varies depending on the type of composite used, but may be in the range of about 0.01 to 1000 μm. However, if the thickness is 50 μm or more, cracks are likely to occur in the film, so it is more preferable that the thickness is in the range of 0.01 to 50 μm.
【００２４】このような複合被膜を設けたガスバリア材
上に、必要に応じてヒートシール可能な熱可塑性樹脂層
を積層したり、印刷層を設けたり、また複数の樹脂を接
着層を介して積層して使用することも出来る。On the gas barrier material provided with such a composite coating, a heat-sealable thermoplastic resin layer may be laminated if necessary, a printing layer may be provided, or a plurality of resins may be laminated via an adhesive layer. You can also use it.
【００２５】[0025]
【実施例】以下、本発明の実施例を説明するが、本発明
は実施例に記載の材料に限定されるものではない。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the materials described in the examples.
【００２６】＜実施例１＞テトラエチルオルソシリケー
ト（Ｓｉ（ＯＣ2 Ｈ5 ）4 ：ＴＥＯＳと略記）８．３ｇ
に塩酸でＰＨを１に調整した水３．６ｇを加え３０分撹
拌し加水分解溶液を作成した後、水約３６ｇを加えＳｉ
Ｏ2 分として固形分濃度が５％になるように調整した。
これにポリビニルアルコール（重合度約２０００，鹸化
度８８％）（以下ＰＶＡと略記），可溶性デンプン，カ
ルボキシメチルセルロース（Ｎａ塩）（以下ＣＭＣと略
記），ゼラチンの５％水溶液を重量比で１／１（アルコ
キシドはＳｉＯ2 換算）になるように混合して、４種の
複合溶液を作成した。これらの溶液を基材のポリエチレ
ンテレフタレート（ＰＥＴ）フィルム（２５μｍ，コロ
ナ処理）の片面にバーコーターでコーティング後、乾燥
機で１００℃−１０ｍｉｎ乾燥して膜厚１．０μｍの被
膜を形成し、試験体を得た。Example 1 Tetraethyl orthosilicate (abbreviated as Si (OC 2 H 5 ) 4 : TEOS) 8.3 g
After adding 3.6 g of water whose pH was adjusted to 1 with hydrochloric acid and stirring for 30 minutes to prepare a hydrolysis solution, add about 36 g of water and add Si.
The solid content concentration was adjusted to 5% as O 2 content.
To this, polyvinyl alcohol (polymerization degree: about 2000, saponification degree: 88%) (hereinafter abbreviated as PVA), soluble starch, carboxymethyl cellulose (Na salt) (hereinafter abbreviated as CMC), and a 5% aqueous solution of gelatin in a weight ratio of 1/1. (Alkoxides are converted into SiO 2 ) so that 4 kinds of composite solutions were prepared. These solutions were coated on one side of a polyethylene terephthalate (PET) film (25 μm, corona treated) as a base material with a bar coater and then dried at 100 ° C. for 10 minutes with a drier to form a film with a thickness of 1.0 μm and tested. Got the body
【００２７】これらのガスバリア性を酸素透過度測定装
置（モダンコントロール社製ＭＯＣＯＮ ＯＸＴＲＡＮ
１０／５０Ａ）を用い２５℃−１００％ＲＨ雰囲気の
条件で測定した。比較例として未処理のＰＥＴフィルム
と同様の条件で作成したアルコキシドおよび樹脂単体の
被膜を施したものについても測定を行ったので合わせて
その結果を表１に示す。These gas barrier properties are measured by an oxygen permeability measuring device (MOCON OXTRAN manufactured by Modern Control Co., Ltd.).
10/50 A) at 25 ° C.-100% RH atmosphere. As a comparative example, an alkoxide prepared under the same conditions as the untreated PET film and a film coated with a resin alone were also measured, and the results are also shown in Table 1.
【００２８】[0028]
【表１】 [Table 1]
【００２９】いずれの樹脂もアルコキシドと複合化する
ことでガスバリア性が著しく向上し、アルコキシド単体
のものよりも優れている。なかでもＰＶＡについては酸
素透過度が１ｃｃ／ｍ2 ・ｄａｙ・ａｔｍ以下のハイバ
リアのものが得られた。The gas barrier property of each of the resins is remarkably improved by forming a composite with the alkoxide, and is superior to that of the alkoxide alone. Among them, PVA with a high barrier having an oxygen permeability of 1 cc / m 2 · day · atm or less was obtained.
【００３０】＜実施例２＞テトラメチルオルソシリケー
ト（Ｓｉ（ＯＣＨ3 ）4 ：ＴＭＯＳと略記），テトラプ
ロピルチタネート（Ｔｉ（ＯＣ3 Ｈ7 ）4 ：ＴＰＴと略
記），テトラブチルジルコニウム（Ｚｒ（ＯＣ
4 Ｈ9 ）：ＴＢＺと略記）これら各々０．１ｍｏｌに水
９ｇとエタノール７９ｇとジエチレングリコール２０ｇ
の混合溶媒を加え、１０分撹拌した加水分解溶液とトリ
プロピルアルミニウム（Ａｌ（Ｏ（Ｃ3 Ｈ7）3 ：ＴＰ
Ａと略記）を８０℃の熱水中で溶解した後、塩酸を添加
して解膠させた透明加水分解溶液、ＴＰＡの加水分解溶
液と実施例１で作成したＴＥＯＳの加水分解溶液との１
／１の混合加水分解溶液の５種類の加水分解溶液を作成
した。<Example 2> Tetramethyl orthosilicate (abbreviated as Si (OCH 3 ) 4 : TMOS), tetrapropyl titanate (abbreviated as Ti (OC 3 H 7 ) 4 : TPT), tetrabutyl zirconium (Zr (OC)
4 H 9 ): TBZ abbreviated) 9 g of water, 79 g of ethanol and 20 g of diethylene glycol were added to 0.1 mol of each of these.
Was added for 10 minutes and the hydrolysis solution and tripropylaluminum (Al (O (C 3 H 7 ) 3 : TP
A) (abbreviated as A) is dissolved in hot water at 80 ° C., and then hydrochloric acid is added to peptize the transparent hydrolyzed solution, a hydrolyzed solution of TPA and a hydrolyzed solution of TEOS prepared in Example 1.
Five types of hydrolysis solutions of the mixed hydrolysis solution of / 1 were prepared.
【００３１】これらにＰＶＡ水溶液を重量比で１／１
（アルコキシドは酸化物換算）、固形分濃度が１％にな
るように混合して、３種類の複合溶液を作成した。実施
例１と同様にＰＥＴにコーティングして膜厚０．５μｍ
の被膜を形成し酸素透過度の測定を行った。その結果を
表２に示す。An aqueous PVA solution is added to these in a weight ratio of 1/1
(Alkoxides are converted to oxides) and mixed so that the solid content concentration was 1% to prepare three kinds of composite solutions. Coating on PET as in Example 1 to form a film thickness of 0.5 μm
Was formed to measure the oxygen permeability. The results are shown in Table 2.
【００３２】[0032]
【表２】 [Table 2]
【００３３】いずれのアルコキシドを用いてもＰＶＡと
複合化したものは著しくバリア性が向上した。なかでも
Ｓｉ，Ａｌのアルコキシドあるいは両者の混合系のもの
が特に優れたものが得られた。Whatever alkoxide was used, the composite with PVA had significantly improved barrier properties. Among them, particularly excellent ones were obtained from alkoxides of Si and Al or a mixed system of both.
【００３４】＜実施例３＞実施例１と同様の方法で作成
したＴＥＯＳ（ＳｉＯ2 換算 ２．５％）加水分解水溶
液とＰＶＡの２．５％水溶液の混合比を重量比で１０／
０から０／１０まで変えた複合溶液を作成して、実施例
１と同様にＰＥＴ（フィルム厚５０μｍ）に約０．５μ
ｍ被膜を形成して、酸素透過度の測定を行った。また、
曲げによる変形（曲率半径：１ｍｍ、ＰＥＴ表面の伸び
が約５％）を加えて、被膜の状態を光学顕微鏡あるいは
走査型電子顕微鏡で観察して評価を行った。比較例とし
てＳｉＯ（純度３Ｎ、大阪チタニウム製）を蒸着源とし
て電子線加熱方式による真空蒸着法によって膜厚０．２
μｍの被膜を作成して同様の評価を行ったので合わせて
結果を表３に示す。Example 3 A TEOS (2.5% in terms of SiO 2 ) hydrolyzed aqueous solution prepared in the same manner as in Example 1 and a 2.5% PVA aqueous solution were mixed at a weight ratio of 10 /.
A composite solution was prepared by changing it from 0 to 0/10, and about 0.5 μm was added to PET (film thickness 50 μm) as in Example 1.
The m coating was formed and the oxygen permeability was measured. Also,
After deformation by bending (curvature radius: 1 mm, elongation of PET surface is about 5%), the state of the coating film was observed and evaluated by an optical microscope or a scanning electron microscope. As a comparative example, SiO (purity 3N, made by Osaka Titanium) is used as a vapor deposition source, and a film thickness of 0.2 is obtained by a vacuum vapor deposition method using an electron beam heating method.
Since a film having a thickness of μm was formed and the same evaluation was performed, the results are also shown in Table 3.
【００３５】[0035]
【表３】 [Table 3]
【００３６】可とう性の評価、◎：異常無し、○：僅か
にクラック発生、×：著しくクラック発生。Evaluation of flexibility, ⊚: No abnormality, ∘: Slight cracks occurred, ×: Significant cracks occurred.
【００３７】ＳｉのアルコキシドとＰＶＡの組成比、す
なわちＳｉのアルコキシド（ＳｉＯ 2 換算）／ＰＶＡの
比率が２／８から９／１の被膜がバリア性が良好で可と
う性にも優れている。Ｓｉのアルコキシド単体では可と
う性、バリア性ともに悪く、蒸着被膜ではバリア性は優
れているが、可とう性が著しく劣っている。The composition ratio of Si alkoxide and PVA,
That is, Si alkoxide (SiO 2Conversion) / PVA
A coating with a ratio of 2/8 to 9/1 has good barrier properties and is acceptable.
It is also excellent in caries. Si alkoxide alone is acceptable
The barrier and barrier properties are poor, and the barrier properties of vapor-deposited coatings are excellent.
However, the flexibility is extremely poor.
【００３８】[0038]
【発明の効果】以上説明したように、本発明に係わるガ
スバリア材は、プラスチックからなる基材の少なくとも
片面に、金属アルコキシドあるいはその加水分解物とポ
リビニルアルコールなどの水溶性樹脂との複合被膜を設
けたものであり、ハイレベルのガスバリア性を有すると
ともに、可とう性に優れるので、乱雑な取扱いにもバリ
ア性を損なうことなく、食品など内容物の長期保存を可
能にするものである。また、焼却されたとしても有毒ガ
ス、有害物質を発生することなく廃棄処理も可能であ
り、製造方法も簡単で特殊な装置も必要としないので生
産性も高く安価に製造することができるものである。As described above, in the gas barrier material according to the present invention, a composite coating of a metal alkoxide or its hydrolyzate and a water-soluble resin such as polyvinyl alcohol is provided on at least one side of a plastic substrate. Since it has a high level of gas barrier property and is excellent in flexibility, it enables long-term storage of contents such as foods without impairing the barrier property even in messy handling. Also, even if it is incinerated, it can be disposed of without generating toxic gas and harmful substances, the manufacturing method is simple, and no special equipment is required, so it is highly productive and can be manufactured at low cost. is there.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 101/00 ＰＣＳ 7415−4Ｊ 129/04 ＰＦＭ 6904−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C09D 101/00 PCS 7415-4J 129/04 PFM 6904-4J
Claims (4)
面に、金属アルコキシドあるいは金属アルコキシドの加
水分解物と、水酸基を有する水溶性樹脂との複合物から
なる被膜を有することを特徴とするガスバリア材。1. A gas barrier material comprising a base material made of plastic and having a film made of a composite of a metal alkoxide or a hydrolyzate of a metal alkoxide and a water-soluble resin having a hydroxyl group on at least one surface.
シドの加水分解物中の金属が、Ｓｉ、Ａｌであることを
特徴とする請求項１記載のガスバリア材。2. The gas barrier material according to claim 1, wherein the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si or Al.
ることを特徴とする請求項１、２記載のガスバリア材。3. The gas barrier material according to claim 1, wherein the water-soluble resin is polyvinyl alcohol.
アルコキシドの加水分解物を金属酸化物に換算したとき
の金属酸化物と水溶性樹脂との重量比率が、２０：８０
〜９５：５であることを特徴とする請求項１、２、３記
載のガスバリア材。4. The weight ratio of the metal oxide to the water-soluble resin when the metal alkoxide or the hydrolyzate of the metal alkoxide in the coating film is converted to the metal oxide is 20:80.
The gas barrier material according to claim 1, 2, or 3, characterized in that the gas barrier material has a ratio of up to 95: 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34408892A JP3401807B2 (en) | 1992-12-24 | 1992-12-24 | Gas barrier material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34408892A JP3401807B2 (en) | 1992-12-24 | 1992-12-24 | Gas barrier material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06192454A true JPH06192454A (en) | 1994-07-12 |
| JP3401807B2 JP3401807B2 (en) | 2003-04-28 |
Family
ID=18366564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34408892A Ceased JP3401807B2 (en) | 1992-12-24 | 1992-12-24 | Gas barrier material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3401807B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11962A (en) * | 1997-06-13 | 1999-01-06 | Toppan Printing Co Ltd | Gas barrier film and packaging material using the same |
| WO2000018838A1 (en) * | 1998-09-28 | 2000-04-06 | Kuraray Co., Ltd. | Process for producing vinyl alcohol polymer composition |
| WO2000075248A1 (en) * | 1999-06-04 | 2000-12-14 | Jsr Corporation | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| JP2004315781A (en) * | 2003-04-04 | 2004-11-11 | Tokuyama Corp | Gas barrier-coating agent and gas barrier type film |
| WO2006120534A1 (en) * | 2005-05-06 | 2006-11-16 | Dynea Oy | Methods of preparing organic-inorganic hybrid binder compositions and nonwoven products |
| US7157147B2 (en) | 2001-09-18 | 2007-01-02 | Tokuyama Corporation | Gas-barrier film and gas-barrier coating agent, and method for production thereof |
| JP2007253477A (en) * | 2006-03-23 | 2007-10-04 | Kohjin Co Ltd | Gas barrier film and gas barrier laminated material |
| US7341782B2 (en) * | 2002-09-19 | 2008-03-11 | Fujifilm Corporation | Polymer composition containing organic modified layered silicate, film and gas barrier film as well as substrate and image display device using them |
| US7375349B2 (en) | 2003-11-19 | 2008-05-20 | Fujifilm Corporation | Radiation-image conversion panel and process of producing the same |
| WO2008142794A1 (en) * | 2007-05-24 | 2008-11-27 | Ceramission Hanbai Co., Ltd. | Coating composition, products of curing, coatings for electrical insulation, coatings for heat release, and flexible printed wiring boards |
| JP2014191171A (en) * | 2013-03-27 | 2014-10-06 | Fujifilm Corp | Film mirror |
| JP2014218007A (en) * | 2013-05-08 | 2014-11-20 | 凸版印刷株式会社 | Heat-sealable packaging material |
| WO2022004073A1 (en) * | 2020-06-29 | 2022-01-06 | サカタインクス株式会社 | Barrier coating composition and barrier composite film |
-
1992
- 1992-12-24 JP JP34408892A patent/JP3401807B2/en not_active Ceased
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11962A (en) * | 1997-06-13 | 1999-01-06 | Toppan Printing Co Ltd | Gas barrier film and packaging material using the same |
| WO2000018838A1 (en) * | 1998-09-28 | 2000-04-06 | Kuraray Co., Ltd. | Process for producing vinyl alcohol polymer composition |
| AU728755B2 (en) * | 1998-09-28 | 2001-01-18 | Kuraray Co., Ltd. | Process for producing vinyl alcohol polymer compositions |
| US6444751B1 (en) | 1998-09-28 | 2002-09-03 | Kuraray Co., Ltd. | Process for producing vinyl alcohol polymer composition |
| WO2000075248A1 (en) * | 1999-06-04 | 2000-12-14 | Jsr Corporation | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| EP1211295A1 (en) * | 1999-06-04 | 2002-06-05 | JSR Corporation | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| EP1211295A4 (en) * | 1999-06-04 | 2003-05-02 | Jsr Corp | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| US6656602B1 (en) | 1999-06-04 | 2003-12-02 | Jsr Corporation | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| US7157147B2 (en) | 2001-09-18 | 2007-01-02 | Tokuyama Corporation | Gas-barrier film and gas-barrier coating agent, and method for production thereof |
| CN100360309C (en) * | 2001-09-18 | 2008-01-09 | 株式会社德山 | Gas-barrier film and gas-barrier coating agent, and method for production thereof |
| US7341782B2 (en) * | 2002-09-19 | 2008-03-11 | Fujifilm Corporation | Polymer composition containing organic modified layered silicate, film and gas barrier film as well as substrate and image display device using them |
| JP2004315781A (en) * | 2003-04-04 | 2004-11-11 | Tokuyama Corp | Gas barrier-coating agent and gas barrier type film |
| US7375349B2 (en) | 2003-11-19 | 2008-05-20 | Fujifilm Corporation | Radiation-image conversion panel and process of producing the same |
| WO2006120534A1 (en) * | 2005-05-06 | 2006-11-16 | Dynea Oy | Methods of preparing organic-inorganic hybrid binder compositions and nonwoven products |
| JP2007253477A (en) * | 2006-03-23 | 2007-10-04 | Kohjin Co Ltd | Gas barrier film and gas barrier laminated material |
| WO2008142794A1 (en) * | 2007-05-24 | 2008-11-27 | Ceramission Hanbai Co., Ltd. | Coating composition, products of curing, coatings for electrical insulation, coatings for heat release, and flexible printed wiring boards |
| JPWO2008142794A1 (en) * | 2007-05-24 | 2010-08-05 | セラミッション販売株式会社 | Coating composition, cured product, coating film for electrical insulation, coating film for heat dissipation, and flexible printed wiring board |
| JP2014191171A (en) * | 2013-03-27 | 2014-10-06 | Fujifilm Corp | Film mirror |
| JP2014218007A (en) * | 2013-05-08 | 2014-11-20 | 凸版印刷株式会社 | Heat-sealable packaging material |
| WO2022004073A1 (en) * | 2020-06-29 | 2022-01-06 | サカタインクス株式会社 | Barrier coating composition and barrier composite film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3401807B2 (en) | 2003-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3401807B2 (en) | Gas barrier material | |
| EP0878495B1 (en) | Gas barrier laminated material | |
| JP2790054B2 (en) | Gas barrier laminate film and packaging material using this laminate film | |
| US7288313B2 (en) | Laminated body | |
| JP4816848B2 (en) | Coating agent and laminated material using the coating agent | |
| JPH07126419A (en) | Gas-barrier laminate | |
| JP4816842B2 (en) | Gas barrier material | |
| KR100547296B1 (en) | Vapor deposition film and packaging material | |
| JP2000254994A (en) | Vapor-deposited film laminated packaging material | |
| JPH0970917A (en) | Transparent laminate with gas barrier properties | |
| JP2007210262A (en) | Transparent barrier film and its manufacturing method | |
| JP3736130B2 (en) | Strong adhesion gas barrier transparent laminate and packaging body using the same | |
| JP2000218726A (en) | Strong adherence transparent laminate | |
| JPH11147276A (en) | Gas barrier transparent laminate | |
| JP3438257B2 (en) | Gas barrier material with boil resistance | |
| JPH08318591A (en) | Barrier material having vapor deposition layer and laminated material using the same | |
| JP3438256B2 (en) | Gas barrier material with boil resistance | |
| JP2002321301A (en) | Gas barrier transparent film | |
| JPH08267637A (en) | Barrier material with vepor deposition layer and laminated material using this barrier material | |
| JPH09117986A (en) | Gas barrier laminated film | |
| JP3119109B2 (en) | Laminated material with excellent barrier properties | |
| JPS62295931A (en) | Thermoplastic resin film or sheet having excellent gas barrier characteristics | |
| JPH1016150A (en) | Gas barrier laminated film | |
| JP3119108B2 (en) | Packaging material with excellent barrier properties with printed layer | |
| JP5412745B2 (en) | Release sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RVOP | Cancellation by post-grant opposition |