JPH02220821A - Multi-layered molded product - Google Patents
Multi-layered molded productInfo
- Publication number
- JPH02220821A JPH02220821A JP4263389A JP4263389A JPH02220821A JP H02220821 A JPH02220821 A JP H02220821A JP 4263389 A JP4263389 A JP 4263389A JP 4263389 A JP4263389 A JP 4263389A JP H02220821 A JPH02220821 A JP H02220821A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- resin
- molded product
- crystal resin
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 34
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 238000001746 injection moulding Methods 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 27
- 230000004888 barrier function Effects 0.000 abstract description 18
- 238000002347 injection Methods 0.000 abstract description 11
- 239000007924 injection Substances 0.000 abstract description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 8
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 8
- 239000012792 core layer Substances 0.000 abstract description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 abstract description 3
- YUBJPYNSGLJZPQ-UHFFFAOYSA-N Dithiopyr Chemical compound CSC(=O)C1=C(C(F)F)N=C(C(F)(F)F)C(C(=O)SC)=C1CC(C)C YUBJPYNSGLJZPQ-UHFFFAOYSA-N 0.000 abstract 1
- -1 containers Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- LTFHNKUKQYVHDX-UHFFFAOYSA-N 4-hydroxy-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1O LTFHNKUKQYVHDX-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0079—Liquid crystals
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、熱可塑性樹脂層と熱可塑性液晶樹脂層の少な
くとも２層からなる多層成形物に関し、より詳細には、
ガスバリア性プラスチック容器、容器の蓋材、あるいは
音響用振動減衰盤、プリント基板に用いる多層成形物で
ある。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a multilayer molded product consisting of at least two layers, a thermoplastic resin layer and a thermoplastic liquid crystal resin layer, and more specifically,
It is a multilayer molded product used for gas barrier plastic containers, container lids, acoustic vibration damping boards, and printed circuit boards.
〈従来技術〉
例えば、容器、フィルム、シート等の包材材料において
、ガスバリア性樹脂を用いガスバリア性多層成形物とす
ることは、従来から行われている。<Prior Art> For example, in packaging materials such as containers, films, and sheets, gas barrier resins have been conventionally used to form gas barrier multilayer molded products.
エチレン−酢酸ビニル共重合体ケン化物（以下エチレン
−酢酸ビニル共重合体ケン化物（以下２ＶＯＨと称す）
やポリ塩化ビニリデン（以下ＰＶ［ｌＣと称す）は高い
酸素バリア性を有する樹脂と知られ、フィルム、シート
等の表面に塗布したり、ポリエチレン、ポリプロピレン
等の熱可塑性樹脂と一緒に塗布したり、ポリエチレン、
ポリプロピレン等の熱可塑性樹脂と一緒に用いることに
より用いるのが一般的であった。Saponified ethylene-vinyl acetate copolymer (hereinafter referred to as 2VOH)
Polyvinylidene chloride (hereinafter referred to as PV [lC]) is known as a resin with high oxygen barrier properties, and can be applied to the surface of films, sheets, etc., or applied together with thermoplastic resins such as polyethylene, polypropylene, etc. polyethylene,
It was generally used in combination with a thermoplastic resin such as polypropylene.
しかし、これらの樹脂は、熱溶融加工が難しかったり、
レトルト殺菌等において水分の影響をえける状態では、
ガスバリア性が低下し、本来の能力が発揮できない等の
問題があった。However, these resins are difficult to process by hot melting,
In conditions where the influence of moisture can be avoided during retort sterilization, etc.
There were problems such as a decrease in gas barrier properties and an inability to demonstrate the original ability.
上記ＥＶＯＨを用いた多層構成で水分の影響を排除して
、ガスバリア性の低下を小さくする手段として、例えば
特公昭６１−３４３９２号公報に示されるように、前記
樹脂からなるガスバリア層の両側に乾燥剤を配合した樹
脂からなる樹脂層を配した多層構造体が示されている。As a means of eliminating the influence of moisture and reducing the deterioration of gas barrier properties with a multilayer structure using EVOH, for example, as shown in Japanese Patent Publication No. 61-34392, drying is applied to both sides of the gas barrier layer made of the resin. A multilayer structure is shown with a resin layer made of a resin loaded with an agent.
またｐｖｏｃは、その吸湿度は、Ｅ Ｖ Ｏ１１と比較
して少なく、吸湿によるガスバリア性の低下は大きな間
題とはならないが、ＰＶＤＣは、熱溶融温度と熱分解温
度°とが非常に近接しているため、溶融加工の技術が非
常に難しく、生産効率、収率等の点で問題があった。In addition, PVOC absorbs less moisture than EVO11, and the reduction in gas barrier properties due to moisture absorption is not a major problem, but PVDC has a thermal melting temperature and a thermal decomposition temperature very close to each other. As a result, the melt processing technology is extremely difficult, leading to problems in terms of production efficiency, yield, etc.
一方、近年熱可塑性液晶樹脂が出現し、熱液晶ポリエス
テル樹脂を他の熱可塑性樹脂と積層し、この積層体を延
伸して用いたガスバリア性のすぐれた容器が特開昭６２
−１８７０３３号公報に開示されている。On the other hand, thermoplastic liquid crystal resins have appeared in recent years, and a container with excellent gas barrier properties was produced by laminating thermoliquid crystal polyester resin with other thermoplastic resins and stretching this laminate.
It is disclosed in the publication No.-187033.
しかしながら、前記熱可塑性液晶樹脂は、耐熱性、ガス
バリア性、寸法安定性、低熱膨張性、低収縮性と優れた
物性を有する反面、溶融時に特殊な流動挙動を示すため
、ポリエチレン、ポリプロピレン等の熱可塑性樹脂と一
緒に共押出し成形、および延伸成形を行うことは、困難
であるため、特定の範囲の熱可塑性液晶樹脂において可
能であった。However, although the thermoplastic liquid crystal resin has excellent physical properties such as heat resistance, gas barrier properties, dimensional stability, low thermal expansion, and low shrinkage, it exhibits special flow behavior when melted, so it Coextrusion and stretch molding with plastic resins is difficult and has been possible with a certain range of thermoplastic liquid crystal resins.
〈発明が解決しようとする課題〉
本発明はポリエステル系の液晶樹脂と他の熱可塑性樹脂
からなる２層以上の吸湿によりガスバリア性の低下が小
さく、耐熱、性、寸法安定性の優れた多層成形物を提供
することを目的とする。<Problems to be Solved by the Invention> The present invention provides multilayer molding with less deterioration in gas barrier properties and excellent heat resistance, toughness, and dimensional stability due to moisture absorption of two or more layers made of a polyester-based liquid crystal resin and another thermoplastic resin. The purpose is to provide something.
く課題を解決するための手段〉
本発明では、熱可塑性樹脂層と芳香族ポリエステル系液
晶樹脂の液晶樹脂層の少なくとも２層からなる多層射出
成形法により成形された多層成形物である。Means for Solving the Problems The present invention is a multilayer molded product formed by a multilayer injection molding method, which is formed of at least two layers: a thermoplastic resin layer and a liquid crystal resin layer made of an aromatic polyester liquid crystal resin.
次に本発明の多層成形物の製造について説明する。Next, the production of the multilayer molded article of the present invention will be explained.
まず、第１図に示すようにキャビティＡ内に熱可塑性樹
脂１を射出する。First, a thermoplastic resin 1 is injected into a cavity A as shown in FIG.
次に、射出のタイミングを若干遅らせて液晶樹脂２をキ
ャビティＡ内に射出し、成形する。Next, the liquid crystal resin 2 is injected into the cavity A by slightly delaying the injection timing and molded.
第３図に示すように、熱可塑性樹脂１がスキン層を形成
し、コア層として液晶樹脂２が存在する構成の多層成形
物が製造される。As shown in FIG. 3, a multilayer molded product is manufactured in which the thermoplastic resin 1 forms a skin layer and the liquid crystal resin 2 exists as a core layer.
なお、前述の方法は、３１１の多層成形物の製造につい
て説明したが、シリンダーの数等を変えることにより層
の数をさらに多くすることができることはいうまでもな
い。In addition, although the above-mentioned method was explained about manufacturing a multilayer molded product of 311, it goes without saying that the number of layers can be further increased by changing the number of cylinders, etc.
ポリプロピレン、ポリスチレン等のポリオレフィン、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、ポリオチレンナフタレート、ポリエチレンイソフタ
レート等のポリエステル、６゜６ポリアマイド、６ポリ
アマイド、４．６ポリアマイド、 ６．１０ポリアマイ
ド等のポリアマイド、ポリカーボネート、ポリオキシメ
チレン等のポリエーテル、ポリエーテルサルホン また
はポリウレタンが使用可能である。Polyolefins such as polypropylene and polystyrene; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyethylene isophthalate; polyamides such as 6°6 polyamide, 6 polyamide, 4.6 polyamide, and 6.10 polyamide; polycarbonate; Polyethers such as oxymethylene, polyether sulfones or polyurethanes can be used.
また、液晶樹脂としては、ヒドロキシナフトイ・ンクア
シンドとヒドロキシベンツ゛イ・ンクアシ・ンドの共重
合物、ヒドロキシベンゾイックアシッドとポリエチレン
テレフタレートの共重合物が使用できる。Further, as the liquid crystal resin, a copolymer of hydroxynaphthoic acid and hydroxybenzoic acid and a copolymer of hydroxybenzoic acid and polyethylene terephthalate can be used.
そして、前記ヒドロキシナフトイックアシッドとしては
、４−ヒドロキシ−３−クロロ安息香酸、バニリン酸、
あるいは４−ヒドロキシ−３−メチル安息香酸が挙げら
れる。The hydroxynaphthoic acids include 4-hydroxy-3-chlorobenzoic acid, vanillic acid,
Alternatively, 4-hydroxy-3-methylbenzoic acid may be mentioned.
く作用〉
液晶樹脂は、第４図に示すように非常に高いシェアによ
る見かけの溶融粘度が低いので、狭い間隔をぬって移動
することができる。このため熱可塑性樹脂により形成さ
れたスキン層の形成以後にできた実質上通過可能な狭い
領域を通って射出形成し、コア層を形成することができ
る。Effect> As shown in FIG. 4, the liquid crystal resin has a low apparent melt viscosity due to a very high shear, so it can move through narrow spaces. Therefore, the core layer can be formed by injection molding through a narrow area that is substantially passable after the formation of the skin layer made of thermoplastic resin.
液晶樹脂の射出成形可能なＬ／Ｔ （Ｌ ：流動長。Injection moldable L/T of liquid crystal resin (L: flow length.
Ｔ；キャビティの厚み）を他の熱可塑性樹脂と比較する
と、第５図から明らかなように、高せん断速度において
、非常に低い見掛けの溶融粘度を示し、多段射出成形に
より第３図に示すようなスキン層の間にコア層を有する
多層成形物を容易に製造可能となった。When comparing the T (cavity thickness) with other thermoplastic resins, it is clear from Figure 5 that it shows a very low apparent melt viscosity at high shear rates, and by multi-stage injection molding, as shown in Figure 3. It has become possible to easily produce a multilayer molded product having a core layer between two skin layers.
本発明の多層成形物は、例えば容器として用いた場合、
ガスバリヤ性、耐熱性が高く、従来、ガスバリア材料と
して広く用いられているＥ Ｖ ＯＨと比較し、高湿度
雰囲気下においても、ガスバリア性が著しく低下する恐
れがない。For example, when the multilayer molded product of the present invention is used as a container,
Compared to EV OH, which has high gas barrier properties and high heat resistance and has been widely used as a conventional gas barrier material, there is no fear that the gas barrier properties will deteriorate significantly even in a high humidity atmosphere.
従って、レトルト殺菌を行う食品用の容器として用いて
も、従来のＥＶＯＨを用いた容器のように、レトルト殺
菌による著しいガスバリア性の低下が防止できる。Therefore, even when used as a food container that undergoes retort sterilization, it is possible to prevent a significant decrease in gas barrier properties due to retort sterilization, unlike containers using conventional EVOH.
また、コア層に液晶樹脂を用いたので、成形後の成形物
の収縮、および線膨張が小さ（、高い寸法精度の多層成
形物とすることができる。Furthermore, since a liquid crystal resin is used for the core layer, shrinkage and linear expansion of the molded product after molding are small (and a multilayer molded product with high dimensional accuracy can be obtained).
そして、スキン層に用いる熱可塑性樹脂として、例えば
ポリウレタン、ポリエチレン、あるいはポリプロピレン
のように非常に伸びのよい樹脂を用いれば均一な厚さの
薄肉多層成形物とすることができる。If a thermoplastic resin used for the skin layer is a highly extensible resin such as polyurethane, polyethylene, or polypropylene, a thin multilayered molded product with uniform thickness can be obtained.
さらに、スキン層に用いる熱可塑性樹脂として、ポリエ
ーテルサルホン、ポリカーボネート、ポリブチレンテレ
フタレートのように耐熱性を有する樹脂を用いれば、耐
熱性を有し、高モジュラスな多層成形物とすることがで
きる。Furthermore, if a heat-resistant resin such as polyether sulfone, polycarbonate, or polybutylene terephthalate is used as the thermoplastic resin for the skin layer, a multilayer molded product with heat resistance and high modulus can be obtained. .
〈実施例１〉
多層射出成形後（１００）ンの型締力、２つのシレンダ
ー）を用い、メインシリンダーにポリプロピレン（メル
トインデックス＝２５）、サブシリンダーにポリエチレ
ンテレフタレートとパラヒドロキシ安息香酸の共重合物
からなる液晶樹脂を供給キシ安息香酸の共重合物からな
る液晶樹脂を供給し、下記条件１に示した条件で共射出
成形し、第６図に示した円盤状の多層成形物を製造した
。<Example 1> After multilayer injection molding, using a mold clamping force of (100) min and two cylinders, the main cylinder was made of polypropylene (melt index = 25), and the sub-cylinder was made of a copolymer of polyethylene terephthalate and para-hydroxybenzoic acid. A liquid crystal resin consisting of a copolymer of xybenzoic acid was supplied and co-injection molded under the conditions shown in Condition 1 below to produce a disc-shaped multilayer molded product as shown in FIG.
（条件１）
メインシリンダー ３５５ｍφ Ｌ／Ｄ＝２０サブシ
リンダー ２０ｍ５φ Ｌ／Ｄ＝２０ヒーター設定
温度
メインバレル■ ２３０℃
■ ２４０°Ｃ
■ ２５０’Ｃ
ノズル ２５０°Ｃ
サブバレル ■ ２４０°Ｃ
■ ２４８°Ｃ
■ ２５５°Ｃ
ノズル ２５５°Ｃ
ホットランナ−■ ２５０℃
■ ２５０°Ｃ
メインスクリュー射出時間 １．０秒サブスクリュー
射出時間 ０．５秒メインスクリュー射出時間
０．１秒まず、メインスクリューからポリプロピレンを
射出し、キビテイへの全充填量の５０〜８０％充填し、
次にサブスクリューから液晶樹脂を、２０〜５０％射出
充填する。(Condition 1) Main cylinder 355mφ L/D=20 Sub-cylinder 20m5φ L/D=20 Heater setting temperature Main barrel ■ 230°C ■ 240°C ■ 250'C Nozzle 250°C Sub-barrel ■ 240°C ■ 248°C ■ 255°C Nozzle 255°C Hot Runner ■ 250°C ■ 250°C Main screw injection time 1.0 seconds Subscrew injection time 0.5 seconds Main screw injection time
0.1 seconds First, polypropylene is injected from the main screw, filling 50 to 80% of the total filling amount into the kibity.
Next, 20 to 50% of liquid crystal resin is injected and filled from the sub-screw.
この時、第１図から第３図から明らかなようにまず、ポ
リプロピレンがキャビティ内に部分的に充填され、次に
サブスクリューから射出充填された液晶樹脂が、前記ポ
リプロピレンの溶融部分を押し退けて充填される。At this time, as is clear from Figures 1 to 3, polypropylene is first partially filled into the cavity, and then the liquid crystal resin injected and filled from the sub-screw displaces the molten part of the polypropylene and fills the cavity. be done.
このような液晶樹脂の特異な性質により、キャビティの
壁面側のスキン層は、ポリプロピレンにより構成され、
コア層は、液晶樹脂により構造される。Due to the unique properties of liquid crystal resin, the skin layer on the wall side of the cavity is made of polypropylene.
The core layer is constructed of liquid crystal resin.
そして、最後に、ポリプロピレン樹脂を射出することに
より、ホットライナー中に若干量残った液晶樹脂を押し
出してしまうことにより、次のサイクルにおいて、最初
にキャビティ内に射出される樹脂は、混入の少ないポリ
プロピレンとすることができる。Finally, by injecting polypropylene resin, a small amount of liquid crystal resin remaining in the hot liner is extruded, so that in the next cycle, the first resin injected into the cavity is polypropylene with less contamination. It can be done.
前記工程により製造された多層成形物は、第７図に示す
ように均一な厚さのポリプロピレンからものであった。The multilayer molded article produced by the above process was made of polypropylene of uniform thickness, as shown in FIG.
〈実施例２〉
実施例１において用いた射出成形機を用いて、メインシ
リンダーにポリエチレンテレフタレート（ＩＶ＝０．８
） 、サブシリンダーに実施例１で用いた液晶樹脂を
供給し、下記条件２に示した条件で共射出成形し、第８
図に示した円筒状の容器を製造した。<Example 2> Using the injection molding machine used in Example 1, polyethylene terephthalate (IV = 0.8
), the liquid crystal resin used in Example 1 was supplied to the sub-cylinder, and co-injection molding was performed under the conditions shown in Condition 2 below.
The cylindrical container shown in the figure was manufactured.
（条件２）
メインバレル■ ２４５°Ｃ
■ ２６０°Ｃ
■ ２７０“Ｃ
ノズル ２７０’Ｃ
サブバレル ■ ２４０℃
■ ２５０’Ｃ
■ ２６０”Ｃ
ノズル ２６０’Ｃ
ホットライナー■ ２７０’Ｃ
■ ２７０°Ｃ
メインスクリュー射出時間 １．２秒サブスク
リュー射出時間 ０．４秒メインスクリュー
射出時間 ０．２秒上記条件で製造された容器は
、内、外層がポリエチレンテレフタレート、中間層が、
液晶樹脂からなり、層厚比は、外層：中間層：内層が０
．５：０゜２：０．３であった。(Condition 2) Main barrel ■ 245°C ■ 260°C ■ 270"C Nozzle 270'C Sub-barrel ■ 240°C ■ 250'C ■ 260"C Nozzle 260'C Hot liner ■ 270'C ■ 270°C Main screw Injection time: 1.2 seconds Subscrew injection time: 0.4 seconds Main screw injection time: 0.2 seconds The container manufactured under the above conditions had inner and outer layers made of polyethylene terephthalate, and an intermediate layer made of polyethylene terephthalate.
Made of liquid crystal resin, the layer thickness ratio is 0 for outer layer: middle layer: inner layer.
．． It was 5:0° and 2:0.3.
この製造された容器の開口部をアルミニウム材からなる
蓋材により端部を２重巻締め、密封した。The opening of the manufactured container was sealed by double wrapping the ends with a lid made of aluminum material.
そして、この容器の酸素透過度は、０．００２ｃｃ ／
：個・ｄａｙ ・ａｔｅであった。なお、ポリエチレ
ンテレフタレート単体からなる同じ大きさの容器の酸素
透過度は、０．０２ｃｃ／個−ｄａｙ ・ａｔ−であ
った。The oxygen permeability of this container is 0.002cc/
:Individual/day/ate. Note that the oxygen permeability of a container of the same size made of polyethylene terephthalate alone was 0.02 cc/piece-day·at-.
〈発明の効果〉
本発明は、ガスバリア性、耐熱性、寸法安定性の優れた
液晶樹脂を、他の熱可塑性樹脂と共に射出成形により成
形することにより、性能は優れた樹脂であるにもかかわ
らず、用途が限られていた液晶樹脂の層を含む多層成形
物を得ることができ、容器、蓋、基板等の広い用途での
使用が可能となった。<Effects of the Invention> The present invention uses injection molding to mold a liquid crystal resin with excellent gas barrier properties, heat resistance, and dimensional stability together with other thermoplastic resins. , it was possible to obtain a multilayer molded product containing a layer of liquid crystal resin, which had limited uses, and it became possible to use it in a wide range of applications such as containers, lids, and substrates.
また、射出成形法により成形することにより、液晶樹脂
からなる層が、他の熱可塑性樹脂間に均一な薄層とする
ことができ、容器として用いた場合、優れたガスバリア
性を発揮することができる。In addition, by molding using the injection molding method, the layer made of liquid crystal resin can be made into a uniform thin layer between other thermoplastic resins, and when used as a container, it can exhibit excellent gas barrier properties. can.
第１図及至第３図は、本発明の多層成形物の製造工程の
一例を示す説明図、第４図は、液晶樹脂のシェアと粘度
の関係を示すグラフ、第５図は液晶樹脂と他の樹脂の射
出速度と成形性の関係を示すグラフ、第６図は実施例１
における多層成形物の形状を示す説明図、第７図は第６
図の多層成形物の層構成を示す断面図、第８図は実施例
２における多層成形物の形状を示す説明図である。
１・・・熱可塑性樹脂 ２・・・液晶樹脂Ａ・・・
キャビティ
シミアル （ｉ／ｓｅｃ ）
第４図
第３図
ノ
身す ムａ席 （％ン （哨１０４為−）第５図
３８′ｉFigures 1 to 3 are explanatory views showing an example of the manufacturing process of the multilayer molded product of the present invention, Figure 4 is a graph showing the relationship between the share and viscosity of liquid crystal resin, and Figure 5 is a graph showing the relationship between liquid crystal resin and other materials. A graph showing the relationship between injection speed and moldability of the resin, Figure 6 is Example 1.
Fig. 7 is an explanatory diagram showing the shape of the multilayer molded product in Fig. 6.
FIG. 8 is an explanatory diagram showing the shape of the multilayer molded product in Example 2. FIG. 1... Thermoplastic resin 2... Liquid crystal resin A...
Cavity Simial (i/sec) Figure 4 Figure 3 Body Seat (%n (for 104-) Figure 5 38'i
Claims (1)
の液晶樹脂層の少なくとも２層からなる多層射出成形法
により成形された多層成形物。(1) A multilayer molded article formed by a multilayer injection molding method, which is formed by at least two layers: a thermoplastic resin layer and a liquid crystal resin layer made of an aromatic polyester liquid crystal resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4263389A JPH02220821A (en) | 1989-02-22 | 1989-02-22 | Multi-layered molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4263389A JPH02220821A (en) | 1989-02-22 | 1989-02-22 | Multi-layered molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02220821A true JPH02220821A (en) | 1990-09-04 |
Family
ID=12641418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4263389A Pending JPH02220821A (en) | 1989-02-22 | 1989-02-22 | Multi-layered molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02220821A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0588330A2 (en) * | 1992-09-16 | 1994-03-23 | Toyo Seikan Kaisha, Ltd. | Composition for molding with liquid crystal resin |
| JPH06293044A (en) * | 1993-04-08 | 1994-10-21 | Polyplastics Co | Polyester composite molded product and production thereof |
| US6268026B1 (en) | 1997-10-20 | 2001-07-31 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same |
| US6312772B1 (en) * | 1997-10-20 | 2001-11-06 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer |
| WO2014070875A1 (en) * | 2012-11-01 | 2014-05-08 | Ticona Llc | Multi-layered co-injection molded article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62187033A (en) * | 1986-02-13 | 1987-08-15 | 三菱化学株式会社 | Laminated oritented molded shape |
| JPS6354225A (en) * | 1986-08-26 | 1988-03-08 | Agency Of Ind Science & Technol | Manufacture of multilayer composite molded item |
| JPS6367469A (en) * | 1986-09-10 | 1988-03-26 | Kubota Ltd | Butterfly valve |
-
1989
- 1989-02-22 JP JP4263389A patent/JPH02220821A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62187033A (en) * | 1986-02-13 | 1987-08-15 | 三菱化学株式会社 | Laminated oritented molded shape |
| JPS6354225A (en) * | 1986-08-26 | 1988-03-08 | Agency Of Ind Science & Technol | Manufacture of multilayer composite molded item |
| JPS6367469A (en) * | 1986-09-10 | 1988-03-26 | Kubota Ltd | Butterfly valve |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0588330A2 (en) * | 1992-09-16 | 1994-03-23 | Toyo Seikan Kaisha, Ltd. | Composition for molding with liquid crystal resin |
| EP0588330A3 (en) * | 1992-09-16 | 1994-06-01 | Toyo Seikan Kaisha Ltd | Composition for molding with liquid crystal resin |
| JPH06293044A (en) * | 1993-04-08 | 1994-10-21 | Polyplastics Co | Polyester composite molded product and production thereof |
| US6268026B1 (en) | 1997-10-20 | 2001-07-31 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same |
| US6312772B1 (en) * | 1997-10-20 | 2001-11-06 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer |
| WO2014070875A1 (en) * | 2012-11-01 | 2014-05-08 | Ticona Llc | Multi-layered co-injection molded article |
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