JPH059317A - Production of resin molding with gas barrier property imparted thereto - Google Patents
Production of resin molding with gas barrier property imparted theretoInfo
- Publication number
- JPH059317A JPH059317A JP3158712A JP15871291A JPH059317A JP H059317 A JPH059317 A JP H059317A JP 3158712 A JP3158712 A JP 3158712A JP 15871291 A JP15871291 A JP 15871291A JP H059317 A JPH059317 A JP H059317A
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- resin
- resin molding
- thin film
- resin molded
- 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
- Wrappers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はガスバリアー性の付与さ
れた樹脂成形品の製造方法に関するものであり、さらに
詳しくは、樹脂成形品の使用時において、これが多少変
形したり、延伸されたりしても、樹脂成形品のガスバリ
アー性が低下しない樹脂成形品の製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin molded product having a gas barrier property. More specifically, when the resin molded product is used, it may be deformed or stretched to some extent. However, the present invention also relates to a method for producing a resin molded product, which does not deteriorate the gas barrier property of the resin molded product.
【０００２】[0002]
【従来の技術】食品等の包装において、外部からの酸素
が透過しないようにすれば、内容物の酸化が抑制され、
その品質を長期に保つことができることが知られてい
る。そのため、最近、Ｓi、Ａl、Ｚn、Ｚr等の無機物の
酸化物の薄膜（厚さ３００〜３０００Å）を、蒸着等の
方法で、ナイロン、ＰＥＴ、ケン化ＥＶＡ等の樹脂成形
品の表面に形成させることにより、成形品に高いガスバ
リアー性を付与させている。2. Description of the Related Art In packaging foods and the like, if oxygen from the outside is prevented from permeating, oxidation of the contents is suppressed,
It is known that its quality can be maintained for a long time. Therefore, recently, a thin film of an oxide of an inorganic material such as Si, Al, Zn, and Zr (thickness 300 to 3000Å) is formed on the surface of a resin molded product such as nylon, PET, or saponified EVA by a method such as vapor deposition. By doing so, a high gas barrier property is imparted to the molded product.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、樹脂の
ような有機材料の上に、上記のような無機酸化物からな
る薄膜を形成させても、樹脂成形品と薄膜との密着力が
弱く、取り扱い上に制約があるものであった。すなわ
ち、例えば樹脂フィルム上に蒸着された無機酸化物から
なる薄膜は、樹脂フィルムと弾性率や伸びが異なるた
め、樹脂フィルムの温度変化による寸法変化に追従でき
ず、そのためクラック等のミクロな破壊が薄膜におこ
り、無機酸化物薄膜が蒸着されたフィルムのガスバリア
ー性が低下していた。本発明は、上記のような課題を解
決し、樹脂成形品の使用時において、これが多少変形し
たり、延伸されたりしても、付与されたガスバリアー性
が低下しない樹脂成形品の製造方法を提供することを目
的とするものである。However, even if a thin film made of the above inorganic oxide is formed on an organic material such as a resin, the adhesion between the resin molded product and the thin film is weak and the handling is difficult. There was a constraint on it. That is, for example, a thin film made of an inorganic oxide vapor-deposited on a resin film has a different elastic modulus and elongation from the resin film, and cannot follow the dimensional change due to the temperature change of the resin film, so that microscopic damage such as cracks occurs. This occurred in the thin film, and the gas barrier property of the film on which the inorganic oxide thin film was deposited was lowered. The present invention solves the above problems, and when using a resin molded product, even if it is deformed or stretched to some extent, a method for producing a resin molded product in which the imparted gas barrier property does not decrease. It is intended to be provided.
【０００４】[0004]
【課題を解決するための手段】本発明者らは鋭意検討の
結果、上記のような従来の課題を解決することができ
た。すなわち本発明は、樹脂成形品の表面に、酸化ケイ
素の薄膜を形成し、その上にＳiＯ2粒子を含有する樹脂
の水および／またはアルコール溶液あるいは水性エマル
ジョンをコーティングし、続いて乾燥することを特徴と
する、ガスバリアー性の付与された樹脂成形品の製造方
法を提供するものである。As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems. That is, according to the present invention, a thin film of silicon oxide is formed on the surface of a resin molded article, and a water and / or alcohol solution of a resin containing SiO 2 particles or an aqueous emulsion is coated thereon, followed by drying. The present invention provides a characteristic method for producing a resin molded article having a gas barrier property.
【０００５】以下に、本発明をさらに詳細に説明する。
本発明は、樹脂成形品に無機酸化物として酸化ケイ素を
コーティングし、その上にＳiＯ2粒子を含有する樹脂の
水および／またはアルコール溶液あるいは水性エマルジ
ョンをさらにコーティングし、乾燥させることにより、
樹脂成形品が寸法変化しても、ガスバリアー性薄膜にミ
クロな破壊が起こらず、実用上満足なガスバリアー性を
維持する樹脂成形品を提供するものである。本発明に使
用できる樹脂成形品の素材は、とくに限定されるもので
はない。例えば、ポリエチレン、ポリプロピレン等のポ
リオレフィン、ナイロン、ポリエステル、ポリスチレ
ン、ポリ塩化ビニル等が挙げられる。これらの樹脂成形
品の形状は、様々な形態であることができる。例えば、
フィルム、容器等が挙げられる。The present invention will be described in more detail below.
According to the present invention, a resin molded article is coated with silicon oxide as an inorganic oxide, and a water and / or alcohol solution of a resin containing SiO 2 particles or an aqueous emulsion is further coated on the resin molded article, followed by drying,
It is intended to provide a resin molded product that maintains a practically satisfactory gas barrier property without causing microscopic damage to the gas barrier thin film even when the resin molded product changes in dimension. The material of the resin molded product that can be used in the present invention is not particularly limited. Examples thereof include polyolefins such as polyethylene and polypropylene, nylon, polyester, polystyrene, polyvinyl chloride and the like. The shape of these resin molded products can be various forms. For example,
Examples include films and containers.
【０００６】樹脂成形品にガスバリアー性薄膜を形成さ
せる方法は、以下のようにして行う。まず、樹脂成形品
の表面に酸化ケイ素（ＳiＯx）をコーティングする。こ
のコーティングは、物理蒸着、化学蒸着等の公知のコー
ティング法を使用できる。コーティング膜の物性上、ｘ
は１.５〜２.０、膜厚は３００〜３０００Åが好まし
い。この範囲において、コーティング膜の透明さ、ガス
バリアー性、生産性が優れている。A method of forming a gas barrier thin film on a resin molded product is performed as follows. First, the surface of the resin molded product is coated with silicon oxide (SiOx). For this coating, known coating methods such as physical vapor deposition and chemical vapor deposition can be used. X due to the physical properties of the coating film
Is preferably 1.5 to 2.0 and the film thickness is preferably 300 to 3000Å. Within this range, the coating film is excellent in transparency, gas barrier property and productivity.
【０００７】続いて、コーティングされたＳiＯxの上
に、ＳiＯ2を含有する樹脂の水溶液、アルコール溶液、
水とアルコールの混合溶液、または水性エマルジョンを
さらにコーティングする。本発明に使用するＳiＯ2は、
平均粒径が５０〜２００Å程度のものが好ましい。ま
た、上記のＳiＯ2と混合される樹脂としては、ポリビニ
ルアルコール、アクリル系樹脂、ＳＢＲラテックス、ポ
リ酢酸ビニル等を挙げることができる。これらの樹脂を
水溶液、アルコール溶液または水性分散体として、Ｓi
Ｏ2と混合する。これは、選択された樹脂の性質によ
り、いずれかの形態をとることになり、そのときに応じ
て最適な形態を選択すればよい。ＳiＯ2粒子との混合方
法としては、ＳiＯ2粒子を水またはアルコールに分散さ
せてＳiＯ2ゾルを形成させ、これに上記の樹脂の水、ア
ルコールまたは水性分散体を加えればよい。アルコール
としては、エチルアルコール、メチルアルコール、イソ
プロピルアルコールが使用される。ＳiＯ2と樹脂との固
形分比は、２０：８０〜８０：２０の範囲で用いるのが
よく、好ましくは７５：２５〜５０：５０がよい。Ｓi
Ｏ2が８０％を超えると、得られるガスバリアー性皮膜
の耐擦力性が悪く、ＳiＯ2が２０％未満では、成形品に
外部から応力が加えられた場合、酸化ケイ素薄膜にクラ
ックが発生しやすくなる。このコーティング皮膜の膜厚
は、０.１〜１０μm、好ましくは０.５〜５μmがよい。[0007] Subsequently, on the coated SiOx, a resin containing a SiO 2 aqueous solution, alcoholic solution,
Further coating a mixed solution of water and alcohol, or an aqueous emulsion. The SiO 2 used in the present invention is
The average particle size is preferably about 50 to 200Å. Examples of the resin mixed with SiO 2 include polyvinyl alcohol, acrylic resin, SBR latex, polyvinyl acetate and the like. These resins are treated as an aqueous solution, an alcohol solution or an aqueous dispersion to obtain Si
Mix with O 2 . This will take any form depending on the properties of the selected resin, and the optimum form may be selected depending on the situation. The method of mixing SiO 2 particles, the SiO 2 particles are dispersed in water or alcohol to form a SiO 2 sol, to which water the resin, may be added to the alcohol or aqueous dispersion. Ethyl alcohol, methyl alcohol, or isopropyl alcohol is used as the alcohol. The solid content ratio of SiO 2 and resin is preferably 20:80 to 80:20, and more preferably 75:25 to 50:50. Si
When O 2 exceeds 80%, the resulting gas barrier film has poor abrasion resistance, and when SiO 2 is less than 20%, cracks occur in the silicon oxide thin film when external stress is applied to the molded product. Easier to do. The coating film has a thickness of 0.1 to 10 μm, preferably 0.5 to 5 μm.
【０００８】[0008]
【作用】本発明は、ＳiＯxの上にコーティングされたＳ
iＯ2と樹脂との混合物の層が、樹脂成形品に外部応力が
加わり変形した時に生じやすい酸化ケイ素皮膜に生じる
ミクロな破壊（マイクロクラック）の広がりを押え、ク
ラック部位をコーティング皮膜で保護することにより、
樹脂成形品のガスバリアー性の低下を防ぐものと考えら
れる。The present invention is based on the S coated on the SiOx.
A layer of a mixture of io 2 and resin suppresses the spread of micro-cracks (microcracks) that occur in the silicon oxide film, which tends to occur when external stress is applied to the resin molded product, and protects the cracked part with the coating film. Due to
It is considered to prevent deterioration of the gas barrier property of the resin molded product.
【０００９】[0009]
【実施例】以下、本発明を実施例によって説明する。実施例１ 肉厚が１２μmのポリエチレンテレフタレートフィルム
（酸素透過率：１００cc／m2・atm・２４時間（JISZ170
7-75）に真空蒸着装置を用い、ＳiＯ2を電子線で蒸発さ
せ、前記フィルム上にＳiＯ1.5の薄膜（１５００Å）を
形成させた（酸素透過率２.０cc／m2・atm・２４時
間）。次いで平均粒径１００ÅのＳiＯ2粒子が水に分散
した（４０重量％濃度）液体（ＳiＯ2ゾル）６０重量
部、およびメタクリル酸（２５重量％）とメタクリル酸
ブチル（７５重量％）との共重合体のアンモニウム塩水
溶液（４０重量％濃度、イソプロピルアルコール１０重
量％含有）４０重量部の混合物を、前記酸化ケイ素薄膜
上にコーティングし、１分間、１００℃で熱風乾燥し、
１μmの皮膜を形成させてガスバリアー性フィルムを得
た。このようにして得られた樹脂成形品の断面図を図１
に示す。EXAMPLES The present invention will be described below with reference to examples. Example 1 Polyethylene terephthalate film having a wall thickness of 12 μm (oxygen permeability: 100 cc / m 2 · atm · 24 hours (JISZ170
7-75) using a vacuum evaporation apparatus, SiO 2 was evaporated by an electron beam to form a thin film of SiO 1.5 (1500 Å) on the film (oxygen permeability 2.0 cc / m 2 · atm · 24 hours). ). Next, 60 parts by weight of a liquid (SiO 2 sol) in which SiO 2 particles having an average particle size of 100 Å are dispersed in water (40% by weight concentration), and methacrylic acid (25% by weight) and butyl methacrylate (75% by weight) A mixture of 40 parts by weight of an aqueous solution of an ammonium salt of a polymer (concentration of 40% by weight, containing 10% by weight of isopropyl alcohol) was coated on the silicon oxide thin film and dried with hot air at 100 ° C. for 1 minute,
A film having a thickness of 1 μm was formed to obtain a gas barrier film. A cross-sectional view of the resin molded product thus obtained is shown in FIG.
Shown in.
【００１０】実施例２〜３および比較例１〜２ 実施例１において、ＳiＯ2ゾルと、共重合体のアンモニ
ウム水溶液中に含まれる樹脂のそれぞれの固形分の比
（重量比）が７５：２５（実施例２）、４０：６０（実
施例３）、０：１００（比較例１）、９０：１０（比較
例２）となるようにしたほかは、実施例１と同様にして
ガスバリアー性フィルムを得た。上記実施例および比較
例で得たガスバリアー性フィルムをゲルボテスター（名
立計器社製品）で１０回繰り返し変形させた後、JIS Z
1707-75に従って酸素透過率を測定した。また、変形さ
せる前の酸素透過率（初期酸素透過率）も測定した。そ
の結果を表１に示す。 Examples 2-3 and Comparative Examples 1-2 In Example 1, the solid content ratio (weight ratio) of the SiO 2 sol and the resin contained in the aqueous ammonium solution of the copolymer was 75:25. (Example 2), 40:60 (Example 3), 0: 100 (Comparative Example 1), 90:10 (Comparative Example 2), except that the gas barrier properties were the same as in Example 1. I got a film. The gas barrier films obtained in the above Examples and Comparative Examples were repeatedly deformed 10 times with a gel bot tester (manufactured by Meitetsu Keiki Co., Ltd.), and then JIS Z
Oxygen permeability was measured according to 1707-75. Further, the oxygen transmission rate before deformation (initial oxygen transmission rate) was also measured. The results are shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【発明の効果】本発明によって、樹脂成形品の使用時に
おいて、これが多少変形しても、樹脂成形品のガスバリ
アー性が低下しない樹脂成形品の製造方法を提供するこ
とができ、これによって、各種の使用条件で、内容物を
保護する包装材料として利用することができる。Industrial Applicability According to the present invention, it is possible to provide a method for producing a resin molded product, which does not deteriorate the gas barrier property of the resin molded product even when the resin molded product is used and is deformed to some extent. It can be used as a packaging material for protecting contents under various usage conditions.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の一実施例によって作製した樹脂成形品
の断面図である。FIG. 1 is a cross-sectional view of a resin molded product manufactured according to an example of the present invention.
１ ポリエチレンテレフタレートフィルム ２ 酸化ケイ素薄膜 ３ ＳiＯ2粒子／樹脂混合物皮膜1 polyethylene terephthalate film 2 silicon oxide thin film 3 SiO 2 particle / resin mixture film
───────────────────────────────────────────────────── 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 // Ｃ０８Ｋ 3/36 ＫＡＨ 7167−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // C08K 3/36 KAH 7167-4J
Claims (1)
を形成し、その上にＳiＯ2粒子を含有する樹脂の水およ
び／またはアルコール溶液あるいは水性エマルジョンを
コーティングし、続いて乾燥することを特徴とする、ガ
スバリアー性の付与された樹脂成形品の製造方法。Claim: What is claimed is: 1. A thin film of silicon oxide is formed on the surface of a resin molded article, and a water and / or alcohol solution or an aqueous emulsion of a resin containing SiO 2 particles is coated thereon. A method for producing a resin molded article having a gas barrier property, which is characterized by subsequent drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15871291A JP3193071B2 (en) | 1991-06-28 | 1991-06-28 | Method for producing resin molded article provided with gas barrier properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15871291A JP3193071B2 (en) | 1991-06-28 | 1991-06-28 | Method for producing resin molded article provided with gas barrier properties |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001104147A Division JP3562482B2 (en) | 2001-04-03 | 2001-04-03 | Method for producing resin molded article provided with gas barrier properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH059317A true JPH059317A (en) | 1993-01-19 |
| JP3193071B2 JP3193071B2 (en) | 2001-07-30 |
Family
ID=15677711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15871291A Expired - Lifetime JP3193071B2 (en) | 1991-06-28 | 1991-06-28 | Method for producing resin molded article provided with gas barrier properties |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3193071B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0646611A1 (en) * | 1993-09-30 | 1995-04-05 | Toppan Printing Co., Ltd. | Gas barrier laminated material |
| WO2006010509A2 (en) * | 2004-07-24 | 2006-02-02 | Krones Ag | Device and method for plasma coating/sterilization |
| JP2006256091A (en) * | 2005-03-17 | 2006-09-28 | Toppan Printing Co Ltd | Gas-barrier film laminate having heat-treatment resistance |
| WO2007026751A1 (en) | 2005-08-31 | 2007-03-08 | Mitsubishi Plastics, Inc. | Gas barrier multilayer film |
| US7910213B2 (en) | 2004-03-25 | 2011-03-22 | Mitsubishi Plastics, Inc. | Gas-barrier laminate |
| CN114456670A (en) * | 2021-03-02 | 2022-05-10 | 海南赛诺实业有限公司 | Acrylic acid coating silicon oxide plating film and manufacturing method thereof |
-
1991
- 1991-06-28 JP JP15871291A patent/JP3193071B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0646611A1 (en) * | 1993-09-30 | 1995-04-05 | Toppan Printing Co., Ltd. | Gas barrier laminated material |
| US5589252A (en) * | 1993-09-30 | 1996-12-31 | Toppan Printing Co., Ltd. | Gas barrier laminated material |
| US5645923A (en) * | 1993-09-30 | 1997-07-08 | Toppan Printing Co., Ltd. | Gas barrier laminated material |
| EP0878495A3 (en) * | 1993-09-30 | 1998-11-25 | Toppan Printing Co., Ltd. | Gas barrier laminated material |
| US7910213B2 (en) | 2004-03-25 | 2011-03-22 | Mitsubishi Plastics, Inc. | Gas-barrier laminate |
| WO2006010509A3 (en) * | 2004-07-24 | 2006-11-02 | Krones Ag | Device and method for plasma coating/sterilization |
| WO2006010509A2 (en) * | 2004-07-24 | 2006-02-02 | Krones Ag | Device and method for plasma coating/sterilization |
| JP2006256091A (en) * | 2005-03-17 | 2006-09-28 | Toppan Printing Co Ltd | Gas-barrier film laminate having heat-treatment resistance |
| JP4626348B2 (en) * | 2005-03-17 | 2011-02-09 | 凸版印刷株式会社 | Gas barrier film laminate having heat treatment resistance |
| WO2007026751A1 (en) | 2005-08-31 | 2007-03-08 | Mitsubishi Plastics, Inc. | Gas barrier multilayer film |
| EP2537673A1 (en) | 2005-08-31 | 2012-12-26 | Mitsubishi Plastics, Inc. | Gas barrier multilayer film |
| US8658278B2 (en) | 2005-08-31 | 2014-02-25 | Mitsubishi Plastics, Inc. | Gas barrier multilayer film |
| CN114456670A (en) * | 2021-03-02 | 2022-05-10 | 海南赛诺实业有限公司 | Acrylic acid coating silicon oxide plating film and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3193071B2 (en) | 2001-07-30 |
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