JP2564697B2 - Heat-resistant multilayer sheet and its molded products - Google Patents
Heat-resistant multilayer sheet and its molded productsInfo
- Publication number
- JP2564697B2 JP2564697B2 JP2255403A JP25540390A JP2564697B2 JP 2564697 B2 JP2564697 B2 JP 2564697B2 JP 2255403 A JP2255403 A JP 2255403A JP 25540390 A JP25540390 A JP 25540390A JP 2564697 B2 JP2564697 B2 JP 2564697B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- heat
- weight
- sheet
- layer
- 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.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、薬品、玩具及び電気部品の包装容器で、特
に透明性、耐熱性及び熱成形性に優れた耐熱多層シート
及びその成形品に関する。Description: TECHNICAL FIELD The present invention relates to a heat-resistant multilayer sheet excellent in transparency, heat resistance and thermoformability, and a molded article thereof in a packaging container for medicines, toys and electric parts. .
（従来の技術） 従来、塩化ビニル樹脂シートは、透明性、耐衝撃性及
び熱成形性にすぐれ、しかも製造コストが安いため薬
品、玩具及び電気部品の包装容器として、ブリスターパ
ック等に用いられてきた。(Prior Art) Conventionally, vinyl chloride resin sheets have been used for blister packs, etc. as packaging containers for chemicals, toys, and electric parts because of their excellent transparency, impact resistance, and thermoformability, and their low manufacturing costs. It was
しかし最近、欧米を中心とした地球環境問題の高まり
において、塩化ビニル樹脂は廃棄燃焼物が酸性雨の原因
及び発癌性物質視されており、すでに一部の国において
は、塩化ビニル樹脂の包装容器への使用制限が開始され
ている。However, recently, due to the growing global environmental problems mainly in Europe and the United States, vinyl chloride resin has been regarded as a cause of acid rain and carcinogenic substances in waste combustion products. In some countries, vinyl chloride resin packaging containers have already been used. Restrictions on use have started.
一方これら包装容器と同様の性能を有し、しかも塩化
ビニル樹脂に替わりうる樹脂としては、たとえばスチレ
ン−ブタジエン共重合樹脂、透明ABS樹脂、ポリカーボ
ネート樹脂及びポリエチレンテレフタレート樹脂（以下
PET樹脂という）が挙げられる。そしてPET樹脂は、透明
性、機械的強度及び製品コスト等のバランスから、最も
可能性が高い。On the other hand, as a resin which has the same performance as those of these packaging containers and can replace the vinyl chloride resin, for example, styrene-butadiene copolymer resin, transparent ABS resin, polycarbonate resin and polyethylene terephthalate resin (hereinafter
PET resin). And PET resin has the highest possibility because of the balance of transparency, mechanical strength and product cost.
しかしPET樹脂は、耐熱性、吸湿性がやや劣り高温多
湿の場所に長時間放置されると、成形品が変形するため
ブリスターパックの包装容器には適さない問題がある。However, the PET resin has a problem that it is not suitable for a blister pack packaging container because the molded product is deformed when left in a hot and humid place for a long time because the PET resin is slightly inferior in heat resistance and hygroscopicity.
PET樹脂の耐熱性を改良する方法としては、ポリカー
ボネート樹脂またはポリアリレート樹脂（以下PAL樹脂
いう）とのポリマーブレンドの方法が提案されている。As a method of improving the heat resistance of PET resin, a method of polymer blending with a polycarbonate resin or a polyarylate resin (hereinafter referred to as PAL resin) has been proposed.
しかし、ポリカーボネート樹脂とのポリマーブレンド
では、良好な耐熱性と耐衝撃性は得られるが、透明性が
低下し包装容器として使用した際に内容物がよく見えな
い欠点がある。またPAL樹脂とのポリマーブレンドで
は、耐熱性と透明性は向上するが、耐衝撃性と熱成形性
が低下する欠点がある。However, although a polymer blend with a polycarbonate resin can provide good heat resistance and impact resistance, it has a drawback that the transparency is lowered and the contents cannot be seen well when used as a packaging container. Further, a polymer blend with a PAL resin improves heat resistance and transparency, but has a drawback of lowering impact resistance and thermoformability.
さらに特開平２−147640号公報には、熱可視性ポリエ
ステル樹脂とこの樹脂にPLA樹脂をポリマーブレンドし
たものとの多層シートが開示されている。しかしこの多
層シートでは本発明が目的とする薄肉製品でしかも深絞
り成形する、たとえばブリスターパックでは熱成形性及
び耐衝撃性が低下する欠点があり、実用的でない。Further, JP-A-2-147640 discloses a multilayer sheet of a heat-visible polyester resin and a polymer blend of this resin with a PLA resin. However, this multi-layered sheet is not practical because it is a thin product for the purpose of the present invention and deep drawing is performed, for example, in the case of a blister pack, the thermoformability and impact resistance are deteriorated.
（発明が解決しようとする課題） 本発明は、かかる欠点を解決したものであり、PET樹
脂と該樹脂とPAL樹脂との樹脂組成物からなる耐熱多層
シートで、しかも各層の割合を重量構成比率で特定する
ことにより、透明性、耐熱性及び耐衝撃性、熱成形性に
すぐれ、高温多湿の雰囲気でも成形品の変形がない耐熱
多層シート及びその成形品を見出し本発明を完成するに
至った。(Problems to be Solved by the Invention) The present invention is to solve the above drawbacks, and is a heat-resistant multilayer sheet made of a resin composition of PET resin and the resin and PAL resin, and the ratio of each layer is the weight composition ratio. The present invention has completed the present invention by finding a heat-resistant multi-layer sheet having excellent transparency, heat resistance, impact resistance, and thermoformability and having no deformation of the molded article even in a hot and humid atmosphere, and its molded article. .
（課題を解決するための手段） すなわち本発明は、スキン層が、エチレングリコー
ル、テレフタル酸及び1,4−シクロヘキサンジメタノー
ルの共重合体からなるポリエチレンフタレート樹脂80〜
95重量％とポリアリレート樹脂５〜20重量％とを主成分
とする樹脂組成物、コア層が少なくとも85重量％以上の
該ポリエチレンテレフタレート樹脂からなる耐熱多層シ
ートであって、該耐熱多層シートに対するスキン層の重
量構成比率が10〜50重量％であることを特徴とする耐熱
多層シート及び該耐熱多層シートを熱成形してなる成形
品である。(Means for Solving the Problems) That is, according to the present invention, the skin layer has a polyethylene phthalate resin 80 to 80 made of a copolymer of ethylene glycol, terephthalic acid and 1,4-cyclohexanedimethanol.
A heat-resistant multi-layer sheet comprising a resin composition containing 95% by weight and a polyarylate resin of 5 to 20% by weight as a main component, and a polyethylene terephthalate resin having a core layer of at least 85% by weight, and a skin for the heat-resistant multi-layer sheet. The heat-resistant multilayer sheet is characterized by having a layer weight composition ratio of 10 to 50% by weight, and a molded article obtained by thermoforming the heat-resistant multilayer sheet.
以下本発明を詳細に説明する。 The present invention will be described in detail below.
本発明に用いるPET樹脂はエチレングリコールとテレ
フタル酸及び1,4シクロヘキサンジメタノールとの共重
合体からなるPET樹脂が透明性、熱成型性及び耐衝撃性
にすぐれていることから好適である。The PET resin used in the present invention is preferable because the PET resin composed of a copolymer of ethylene glycol, terephthalic acid and 1,4 cyclohexanedimethanol has excellent transparency, thermoformability and impact resistance.
本発明に用いるPAL樹脂は、芳香族ジカルボン酸と二
価フェノールからなる重合生成物を使用するものである
が特に限定するものではない。The PAL resin used in the present invention uses a polymerization product composed of an aromatic dicarboxylic acid and a dihydric phenol, but is not particularly limited.
次に本発明の耐熱多層シートに用いるスキン層を構成
する樹脂組成物は、PET樹脂80〜95重量％及びPAL樹脂５
〜20重量％の含有量からなり、PAL樹脂が５重量％未満
では、高温多湿下に成形品を長時間放置すると変形が生
じて改良の効果が得られず、また20重量％を越えると多
層シートの熱成形性と成形品の耐衝撃性が低下するの
で、好ましくない。樹脂組成物の混合方法は、シート押
出しする際に直接押出機に投入するか、PET樹脂とPAL樹
脂との高濃度マスターペレットでPET樹脂を希釈しても
よい。Next, the resin composition constituting the skin layer used for the heat-resistant multilayer sheet of the present invention is composed of 80 to 95% by weight of PET resin and 5% of PAL resin.
If the content of PAL resin is less than 5% by weight, the molded product will be deformed when left in a high temperature and high humidity for a long time and the improvement effect will not be obtained. It is not preferable because the thermoformability of the sheet and the impact resistance of the molded product are reduced. As a method for mixing the resin composition, the resin composition may be directly put into an extruder at the time of sheet extrusion, or the PET resin may be diluted with a high-concentration master pellet of the PET resin and the PAL resin.
また本発明の耐熱多層シートに用いるコア層として
は、少なくとも85重量％以上のPET樹脂により構成され
ているが、PET樹脂以外の成分としては、多層シートの
バリアー性付与を目的としたエチレン−ビニルアルコー
ル共重合樹脂やポリアミド樹脂が用いられ、さらに本発
明の多層シートの再生品であってもよい。PET樹脂が85
重量％未満では、成形品の耐衝撃性が低下して使用が難
しくなる。The core layer used in the heat-resistant multilayer sheet of the present invention is composed of at least 85% by weight or more of PET resin, but as a component other than the PET resin, ethylene-vinyl for the purpose of imparting barrier properties to the multilayer sheet. An alcohol copolymer resin or a polyamide resin is used, and the multilayer sheet of the present invention may be a recycled product. PET resin is 85
If it is less than 10% by weight, the impact resistance of the molded product decreases and it becomes difficult to use.
本発明の耐熱多層シートの構成はスキン層とコア層と
の二層シート、好ましくはコア層の両面にスキン層があ
る三層シートである。そしてスキン層は、耐熱多層シー
トに対するスキン層の重量構成比率が10〜50重量％であ
り、重量構成比率が10重量％未満では、高温多湿下に成
形品を長時間放置すると変形が生じて改良の効果が得ら
れず、また50重量％を越えるとシートの熱成形性と成形
品の耐衝撃性が低下し、さらにシート再生品の混合割合
が低下してコスト高になる欠点がある。The heat-resistant multilayer sheet of the present invention has a two-layer sheet including a skin layer and a core layer, preferably a three-layer sheet having skin layers on both sides of the core layer. The weight ratio of the skin layer to the heat-resistant multilayer sheet is 10 to 50% by weight. If the amount exceeds 50% by weight, the thermoformability of the sheet and the impact resistance of the molded product deteriorate, and the mixing ratio of the recycled product of the sheet decreases, resulting in high cost.
本発明の耐熱多層シートは、少なくともスキン層とコ
ア層との二層シート、好ましくは三層シートであり、ま
たその他の多層シートであっても何ら差し支えない。そ
してコア層の両面がスキン層からなる三層シートの場合
は、スキン層の両面の構成比率が極端に相違すると、成
形品とした後の高温多湿に長時間にわたって成形品を放
置すると変形の要因となって好ましくなく、スキン層両
面の構成比率は40:60〜50:50の範囲とすることが好まし
い。The heat-resistant multilayer sheet of the present invention is a two-layer sheet having at least a skin layer and a core layer, preferably a three-layer sheet, and may be another multilayer sheet without any problem. And, in the case of a three-layer sheet having both sides of the core layer made of skin layers, if the composition ratio of both sides of the skin layer is extremely different, if the molded article is left for a long time in high temperature and high humidity after it is formed, it may cause deformation. This is not preferable, and the composition ratio on both sides of the skin layer is preferably in the range of 40:60 to 50:50.
本発明の耐熱多層シートは、着色剤、安定剤などを添
加することもできる。また成成品は帯電防止剤、防曇
剤、摺動剤及び摺接剤を後処理剤として使用することも
可能である。The heat resistant multilayer sheet of the present invention may also contain a colorant, a stabilizer and the like. Further, the product may use an antistatic agent, an antifogging agent, a sliding agent and a sliding contact agent as a post-treatment agent.
（実施例） 次に実施例により本発明を更に詳細に説明するが、本
発明はこれによって限定されるものではない。尚本発明
の透明性、熱成形性、多湿下耐熱性及び耐衝撃性は、次
の方法によって測定した。(Examples) Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The transparency, thermoformability, heat resistance under high humidity and impact resistance of the present invention were measured by the following methods.
（１）透明性 成形された容器底部から測定用サンプルを切出しJIS
K−6718に準拠して測定した。(1) Transparency JIS cut out a sample for measurement from the bottom of the molded container
It was measured according to K-6718.
（２）成形性 実施例で得られた各多層シートを使用して、第１図に
示す容器を真空成形機で成形する際に、賦形性良好な容
器を得るに要した成形前のシート加熱時間幅で求めた。(2) Formability When using the multilayer sheets obtained in the examples to form the container shown in FIG. 1 with a vacuum forming machine, the sheet before forming required to obtain a container with good shapeability It was determined by the heating time range.
（３）多湿下耐熱性 （２）で得られた容器を用いて60℃、80RH％の環境試
験機に８時間放置した後の形状保持度合いを肉眼で評価
した。(3) Heat resistance under high humidity Using the container obtained in (2), the degree of shape retention after being left for 8 hours in an environmental tester at 60 ° C and 80RH% was visually evaluated.
判定基準 ○：容器の変形が見られず △：容器のコーナー部分に僅かな変形が発生 ×：容器全体に顕著な変形が発生 （４）耐衝撃性 （２）項で得られた容器の底部から判定用サンプルを
切出し落錘衝撃強度（デュポン式）を求めた（Ｊ＝1N・
ｍ）。Judgment Criteria ○: No deformation of the container was observed. △: Slight deformation was generated in the corner of the container. ×: Significant deformation was generated in the entire container. (4) Impact resistance. Bottom of the container obtained in item (2). The sample for judgment was cut out from the sample and the impact strength (Dupont type) was calculated (J = 1N ・
m).
実施例１〜２ 比較例１〜４ エチレングリコール、テレフタル酸及び1,4−シクロ
ヘキサンジメタノールの共重合からなるPET樹脂（イー
ストマンコダック射製、商品名PET 10388）とPAL樹脂
（ユニチカ（株）製、商品名Ｕポリマー）とを表−１に
示す割合とし、３台の押出機（65mm １台、40mm ２
台）を用いて0.4mmの三層シートを押出した。Examples 1 to 2 Comparative Examples 1 to 4 PET resin (manufactured by Eastman Kodak Co., trade name PET 10388) consisting of copolymerization of ethylene glycol, terephthalic acid and 1,4-cyclohexanedimethanol and PAL resin (Unitika Ltd.) Made by the trade name of U polymer) and the ratios shown in Table-1 are three extruders (65mm 1 unit, 40mm 2
A 0.4 mm three-layer sheet was extruded using a table.
尚、三層シート全体に占めるスキン層の重量構成比率
は30重量％であり、コア層両面のスキン層配分は50/50
であった。The weight composition ratio of the skin layer in the entire three-layer sheet is 30% by weight, and the distribution of the skin layers on both sides of the core layer is 50/50.
Met.
表−１に評価結果を示すが、スキン層に占めるPAL樹
脂の構成比率が５〜20重量％の範囲では、熱成形時のシ
ート加熱時間幅が広く、耐衝撃製及び多湿下耐熱性も良
好であった。Table-1 shows the evaluation results. When the composition ratio of PAL resin in the skin layer is in the range of 5 to 20% by weight, the sheet heating time width during thermoforming is wide, and impact resistance and heat resistance under high humidity are also good. Met.
実施例３〜５ 比較例５〜６ コア層を構成するPET樹脂とPAL樹脂とを 表−２に示すとおりとした以外は、実施例１と同様な
操作を行った。評価結果を表−２に示す。Examples 3 to 5 Comparative Examples 5 to 6 The same operation as in Example 1 was performed except that the PET resin and PAL resin forming the core layer were as shown in Table-2. The evaluation results are shown in Table-2.
コア層を構成するPET樹脂の重量比率が85重量％未満
では、耐衝撃性が低下する。If the weight ratio of the PET resin forming the core layer is less than 85% by weight, the impact resistance is lowered.
実施例６〜７ 比較例７ 三層シートに対するスキン層の重量構成比率を表−３
に示す割合とした以外は、実施例１と同様な操作を行っ
た。評価結果を表−３に示す。Examples 6 to 7 Comparative Example 7 Table 3 shows the weight composition ratio of the skin layer to the three-layer sheet.
The same operation as in Example 1 was carried out except that the ratio was set to. The evaluation results are shown in Table-3.
スキン層の重量構成比率が10重量％、未満では、多湿
下耐熱性が悪い。When the weight composition ratio of the skin layer is less than 10% by weight, the heat resistance under high humidity is poor.
（発明の効果） 以上のとおり本発明は、PET樹脂とPAL樹脂とを特定の
割合とすることにより、成形賦形性にすぐれた多層シー
トが得られ、しかも該多層シートを用いて成形した成形
品は、多湿下耐熱性に耐えることができ、耐衝撃性及び
透明性にもすぐれた効果を有するものである。 (Effect of the invention) As described above, the present invention provides a multilayer sheet having excellent moldability by using the PET resin and the PAL resin in a specific ratio, and molding using the multilayer sheet. The product can withstand heat resistance under high humidity, and has excellent impact resistance and transparency.
第１図は、本発明の実施例で物性測定用に用いた成形品
の斜視図を表すものである。FIG. 1 shows a perspective view of a molded product used for measuring physical properties in an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−204552（ＪＰ，Ａ) 特開 昭61−291131（ＪＰ，Ａ) 特開 昭63−237951（ＪＰ，Ａ) 特開 昭61−135743（ＪＰ，Ａ) 特開 平２−162040（ＪＰ，Ａ) ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-59-204552 (JP, A) JP-A-61-291131 (JP, A) JP-A-63-237951 (JP, A) JP-A-61- 135743 (JP, A) JP-A-2-162040 (JP, A)
Claims (2)
タル酸及び1,4−シクロヘキサンジメタノールの共重合
体からなるポリエチレンフタレート樹脂80〜95重量％と
ポリアリレート樹脂５〜20重量％とを主成分とする樹脂
組成物、コア層が少なくとも85重量％以上の該ポリエチ
レンテレフタレート樹脂からなる耐熱多層シートであっ
て、該耐熱多層シートに対するスキン層の重量構成比率
が10〜50重量％であることを特徴とする耐熱多層シー
ト。1. A skin layer comprising, as a main component, 80 to 95% by weight of a polyethylene phthalate resin composed of a copolymer of ethylene glycol, terephthalic acid and 1,4-cyclohexanedimethanol and 5 to 20% by weight of a polyarylate resin. A resin composition having a core layer of at least 85% by weight or more, which is a heat-resistant multilayer sheet made of the polyethylene terephthalate resin, wherein the weight ratio of the skin layer to the heat-resistant multilayer sheet is 10 to 50% by weight. Heat resistant multi-layer sheet.
てなる成形品。2. A molded product obtained by thermoforming the heat-resistant multi-layer sheet according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255403A JP2564697B2 (en) | 1990-09-27 | 1990-09-27 | Heat-resistant multilayer sheet and its molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255403A JP2564697B2 (en) | 1990-09-27 | 1990-09-27 | Heat-resistant multilayer sheet and its molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04135752A JPH04135752A (en) | 1992-05-11 |
| JP2564697B2 true JP2564697B2 (en) | 1996-12-18 |
Family
ID=17278284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255403A Expired - Fee Related JP2564697B2 (en) | 1990-09-27 | 1990-09-27 | Heat-resistant multilayer sheet and its molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2564697B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0225621D0 (en) | 2002-11-02 | 2002-12-11 | Glaxo Group Ltd | Medicament carrier |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204552A (en) * | 1983-05-10 | 1984-11-19 | 東洋製罐株式会社 | Multilayer oriented polyester bottle |
| JPS61135743A (en) * | 1984-12-07 | 1986-06-23 | ユニチカ株式会社 | Mat film |
| JPS61291131A (en) * | 1985-06-19 | 1986-12-20 | ユニチカ株式会社 | Multilayer structure sheet |
| JP2595960B2 (en) * | 1987-03-26 | 1997-04-02 | 東レ株式会社 | Composite polyester film |
| JPH0628950B2 (en) * | 1988-12-15 | 1994-04-20 | ユニチカ株式会社 | Multilayer structure sheet |
-
1990
- 1990-09-27 JP JP2255403A patent/JP2564697B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04135752A (en) | 1992-05-11 |
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