JP3123113B2 - Injection molding - Google Patents
Injection moldingInfo
- Publication number
- JP3123113B2 JP3123113B2 JP03114557A JP11455791A JP3123113B2 JP 3123113 B2 JP3123113 B2 JP 3123113B2 JP 03114557 A JP03114557 A JP 03114557A JP 11455791 A JP11455791 A JP 11455791A JP 3123113 B2 JP3123113 B2 JP 3123113B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- liquid crystal
- thermoplastic
- molded article
- injection
- 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
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
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、射出成形品に関する。
さらに詳しくは、酸素ガスバリア性、防湿性等の機能を
必要とする射出成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded product.
More specifically, the present invention relates to an injection-molded article requiring functions such as oxygen gas barrier properties and moisture proof properties.
【０００２】[0002]
【従来の技術】熱可塑性樹脂と、熱可塑性液晶樹脂との
ブレンド技術は、従来より検討されており、種々のブレ
ンド系において、両樹脂成分が非相溶性または、部分相
溶性を有する場合においては熱可塑性液晶樹脂が繊維状
構造あるいは、球状構造をとることが報告されている。
これらの検討の目的は、熱可塑性液晶樹脂を熱可塑性樹
脂にブレンドすることにより、樹脂の耐熱性、機械的強
度を向上させることにあり、耐熱性向上を目的にした場
合には、ブレンド物中の熱可塑性液晶樹脂がどの様な相
構造をとってもほとんど関係なく、配合比率により、耐
熱性が向上する事が判っている。また、機械的強度向上
を目的とした場合には、熱可塑性液晶樹脂の配向度合に
より、配向方向の機械強度の向上のレベルが違うことが
知られている。しかしながら、熱可塑性液晶樹脂を層状
に配向させた射出成形品については、いまだ報告されて
いない。2. Description of the Related Art A blending technique of a thermoplastic resin and a thermoplastic liquid crystal resin has been studied in the past. In various blending systems, when both resin components are incompatible or partially compatible, a It has been reported that a thermoplastic liquid crystal resin has a fibrous structure or a spherical structure.
The purpose of these studies is to improve the heat resistance and mechanical strength of the resin by blending the thermoplastic liquid crystal resin with the thermoplastic resin. It has been found that, regardless of the phase structure of the thermoplastic liquid crystal resin, the heat resistance is improved by the compounding ratio. It is also known that when the purpose is to improve mechanical strength, the level of improvement in mechanical strength in the alignment direction differs depending on the degree of alignment of the thermoplastic liquid crystal resin. However, no injection molded product in which a thermoplastic liquid crystal resin is oriented in a layer has been reported yet.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、エチレン−
酢酸ビニル共重合体ケン化物を含む熱可塑性樹脂に熱可
塑性液晶樹脂をブレンドし、射出成形することにより、
射出成形品の表面層近傍に熱可塑性液晶樹脂を層状に配
向させ、エチレン −酢酸ビニル共重合体ケン化物を含む
熱可塑性液晶樹脂の持つ高ガスバリア性を、最大限に引
き出した成形品を得ようとするものである。The present invention relates to an ethylene-
By blending thermoplastic liquid crystal resin with thermoplastic resin containing saponified vinyl acetate copolymer and injection molding,
Molding that maximizes the high gas barrier properties of the thermoplastic liquid crystal resin containing the saponified ethylene- vinyl acetate copolymer by orienting the thermoplastic liquid crystal resin in a layered manner near the surface layer of the injection molded product. To get the goods.
【０００４】[0004]
【課題を解決するための手段】この目的を達成する為
に、本発明は、エチレン−酢酸ビニル共重合体ケン化物
を含む熱可塑性樹脂と熱可塑性液晶樹脂とを少なくとも
含む２成分以上の樹脂のブレンド物を用いた射出成形品
であり、成形品表面層近傍の熱可塑性液晶樹脂が層構造
を有しており、射出成形加工時における熱可塑性樹脂の
粘度と熱可塑性液晶樹脂の粘度との比が１：４かあるい
はそれよりも小さいことを特徴とする。In order to achieve this object, the present invention relates to a saponified ethylene-vinyl acetate copolymer.
At least a thermoplastic resin containing and a thermoplastic liquid crystal resin
2 is injection-molded article blend was used of components more resins, thermoplastic liquid crystal resins of the molded article surface layer vicinity has a layer structure, viscosity and thermoplastic of the thermoplastic resin during injection molding comprising It is characterized in that the ratio to the viscosity of the liquid crystal resin is 1 : 4 or smaller .
【０００５】本発明の射出成形品は、エチレン−酢酸ビ
ニル共重合体ケン化物を含む熱可塑性樹脂と熱可塑性液
晶樹脂の混合物からなる。熱可塑性樹脂は、成形品を基
本的に構成する樹脂であり、通常、混合体積比において
５０％以上を該樹脂が占める。熱可塑性液晶樹脂は、熱
可塑性樹脂の性能を向上させる為にブレンドされる樹脂
であり、通常において５０％以下を該樹脂が占める。[0005] The injection molded article of the present invention is made of ethylene-vinyl acetate.
It is composed of a mixture of a thermoplastic resin containing a saponified benzyl copolymer and a thermoplastic liquid crystal resin . The thermoplastic resin is a resin that basically constitutes a molded product, and usually accounts for 50% or more of the mixed volume ratio. The thermoplastic liquid crystal resin is a resin blended to improve the performance of the thermoplastic resin, and usually accounts for 50% or less of the resin.
【０００６】かかる熱可塑性樹脂としては、酸素バリア
性に優れる樹脂として知られているエチレン−酢酸ビニ
ル共重合体ケン化物を少なくとも含み、成形品の使用目
的に応じて種々の樹脂を混合して使用することも出来
る。混合する樹脂としては、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樹脂である。あるい
は、エチレン−酢酸ビニル共重合体であっても良い。ま
た、ポリカーボネート、ポリエステル、ポリアミド、ポ
リオキシメチレン、ポリサルホン、ポリアリレート、ポ
リエーテルサルホン、ポリスチレン、アクリロニトリル
−スチレン共重合体、アクリロニトリル−ブタジエン−
スチレン共重合樹脂等を使用することもできる。As such a thermoplastic resin, an oxygen barrier
Ethylene-vinyl acetate known as a resin with excellent properties
The resin contains at least a saponified copolymer, and various resins can be mixed and used depending on the purpose of use of the molded article. The resin to be mixed is, for example, a polyolefin resin such as polyethylene and polypropylene. Alternatively, it may be an ethylene-vinyl acetate copolymer. Also, polycarbonate, polyester, polyamide, polyoxymethylene, polysulfone, polyarylate, polyethersulfone, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-
A styrene copolymer resin or the like can also be used.
【０００７】かかる熱可塑性液晶樹脂としては、例え
ば、ポリエステル系液晶樹脂が知られている。すなわ
ち、ヒドロキシナフトイックアシッドとヒドロキシベン
ゾイックアシッドとの共重合物、ヒドロキシベンゾイッ
クアシッドとエチレングリコールとテレフタール酸との
共重合物である。なお、ヒドロキシナフトイックアシッ
ドとしては２−ヒドロキシ−６−ナフトエ酸、ヒドロキ
シベンゾ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、パラヒドロキシ安息香
酸、あるいは４−ヒドロキシ−３−メチル安息香酸等が
例示できる。本発明においてはこれらのいずれも使用で
き、これらのうちの２種類以上の混合物であっても良
い。As such a thermoplastic liquid crystal resin, for example, a polyester liquid crystal resin is known. That is, a copolymer of hydroxynaphthoic acid and hydroxybenzoic acid, and a copolymer of hydroxybenzoic acid, ethylene glycol and terephthalic acid. The hydroxynaphthoic acid is 2-hydroxy-6-naphthoic acid, and the hydroxybenzoic acid is 4-hydroxy-3-naphthoic acid.
Examples thereof include chlorobenzoic acid, vanillic acid, parahydroxybenzoic acid, and 4-hydroxy-3-methylbenzoic acid. In the present invention, any of these can be used, and a mixture of two or more of these may be used.
【０００８】熱可塑性樹脂と熱可塑性液晶樹脂は、熱可
塑性樹脂５０〜９５重量部に対して、熱可塑性液晶樹脂
５０〜５重量部の混合割合で、目的に応じて混ぜれば良
い。熱可塑性液晶樹脂がこれより少ないと、熱可塑性樹
脂の性能向上のレベルが小さく、改善効果が期待出来な
いことが多い。The thermoplastic resin and the thermoplastic liquid crystal resin may be mixed according to the purpose at a mixing ratio of 50 to 5 parts by weight of the thermoplastic liquid crystal resin to 50 to 95 parts by weight of the thermoplastic resin. If the amount of the thermoplastic liquid crystal resin is less than this, the level of improvement in the performance of the thermoplastic resin is small and the improvement effect cannot be expected in many cases.
【０００９】なお、熱可塑性樹脂の粘度と、熱可塑性液
晶樹脂の粘度との比は、射出成形加工時において１：４
かあるいはそれよりも小さいことが好ましい。また両樹
脂の界面張力があまりにも大きいと、熱可塑性液晶樹脂
の変形がおこりにくく、希望の配向状態が得られない事
がある。従って、両樹脂相間の界面張力は、５ｄｙｎｅ
／ｃｍ程度以下が望ましい。The ratio of the viscosity of the thermoplastic resin to the viscosity of the thermoplastic liquid crystal resin is 1 : 4 during injection molding.
Or smaller . When interfacial tension or both resins is too large, difficult to occur deformation of the thermoplastic liquid crystal resins, sometimes it can not be obtained orientation of desired. Therefore, the interfacial tension between both resin phases is 5 dyne
/ Cm or less is desirable.
【００１０】なお、本発明の射出成形品は、熱可塑性樹
脂と熱可塑性液晶樹脂の外に、この両者の相溶性を向上
する為に、相溶化剤を混合することが出来る。例えば、
熱可塑性非液晶樹脂がポリオレフィンから成る場合はポ
リオレフィンと熱可塑性液晶樹脂が互いに相溶性に乏し
いため、相溶性を向上して均一な成形品を製造するた
め、酸変性ポリオレフィンを混合することが望ましい。
かかる酸変性ポリオレフィンとしては、オレフィンと、
マレイン酸または無水マレイン酸、アクリル酸、メタア
クリル酸、あるいはこれらのエステル等をグラフトまた
はランダム重合した樹脂である。酸変性ポリオレフィン
は、熱可塑性液晶樹脂と熱可塑性非液晶樹脂の混合物１
００重量部に対し、２〜１０重量部混合すれば良い。The injection-molded article of the present invention can contain a compatibilizer in addition to the thermoplastic resin and the thermoplastic liquid crystal resin in order to improve the compatibility between the two. For example,
When the thermoplastic non-liquid crystal resin is composed of a polyolefin, the polyolefin and the thermoplastic liquid crystal resin have poor compatibility with each other. Therefore, it is desirable to mix an acid-modified polyolefin in order to improve the compatibility and produce a uniform molded article.
As such an acid-modified polyolefin, an olefin,
It is a resin obtained by grafting or randomly polymerizing maleic acid or maleic anhydride, acrylic acid, methacrylic acid, or an ester thereof. The acid-modified polyolefin is a mixture of a thermoplastic liquid crystal resin and a thermoplastic non-liquid crystal resin.
It is sufficient to mix 2 to 10 parts by weight with respect to 00 parts by weight.
【００１１】本発明の射出成形品は、２層以上の層構成
を有しても良い。例えば、上記ブレンド物を表裏両外層
を構成する層とし、中心層（コア層）としては、通常の
プラスチックを用いることも出来る。該構成の射出成形
品は、図１に示すように、外側層（１）が、上記ブレン
ド物であり、中心層（コア層）（２）は、通常のプラス
チックとなり、本発明の目的である、熱可塑性液晶樹脂
の層状構造は、外側層（１）の表面近傍に発現する。以
下実施例を用いて本発明を詳細に説明する。The injection-molded article of the present invention may have two or more layers. For example, the above-mentioned blend can be used as a layer constituting both front and back outer layers, and a normal plastic can be used as a center layer (core layer). As shown in FIG. 1, in the injection molded article having the above configuration, the outer layer (1) is the above-mentioned blend, and the center layer (core layer) (2) is a normal plastic, which is the object of the present invention. the layered structure of the thermotropic liquid crystal resin is expressed in the vicinity of the surface of the outer layer (1). Hereinafter, the present invention will be described in detail with reference to Examples.
【００１２】[0012]
【実施例】（ａ）（熱可塑性樹脂） エチレン−酢酸ビニル共重合体ケン化物。（以下ＥＶＯ
Ｈと略す）。 （ｂ）（熱可塑性液晶樹脂） パラヒドロキシ安息香酸−２−ヒドロキシ−６−ナフト
エ酸共重合物。（以下ＬＣＰと略す）。 （ｃ）（混合比） 熱可塑性樹脂：熱可塑性液晶樹脂＝７：３（重量比）。 （ｄ）（射出成形） 上記樹脂を乾燥後、ドライブレンドし、通常の射出成形
機を用いて幅６μｍ、厚さ２μｍ、長さ７０μｍの試験
片用金型に射出成形した。 （イ）成形温度 バレル温度 ２１０〜２３０℃ 金型温度 ４０℃ （ロ）射出速度 ６０ｍｍ／ｓｅｃ （ハ）成形サイクル １２ｓｅｃ （ｅ）樹脂粘度比 ＥＶＯＨ−１：ＬＣＰ＝１：３．６…ブレンド物Ａ ＥＶＯＨ−２：ＬＣＰ＝１：０．８…ブレンド物Ｂ ＥＶＯＨ−３：ＬＣＰ＝１：０．４…ブレンド物Ｃ （ｆ）成形品物性 射出成形品の水蒸気吸収量を図２に示した。ＥＶＯＨに
対するＬＣＰの粘度比が大きいブレンド物Ａは、比較的
防湿効果が小さく、ＥＶＯＨに対するＬＣＰの粘度比が
小さいブレンド物Ｃは防湿効果が大きかった。 （ｇ）成形品の破断面 図３に、ＥＶＯＨ４とＬＣＰ３のブレンド物Ｃで成形し
た成形品の断面拡大説明図を示した。成形品表面近傍で
は、ＬＣＰ３が層状に配向していた。EXAMPLES (a) (Thermoplastic resin) Saponified ethylene-vinyl acetate copolymer. (Hereinafter EVO
H). (B) (Thermoplastic liquid crystal resin) Parahydroxybenzoic acid-2-hydroxy-6-naphthoic acid copolymer. (Hereinafter abbreviated as LCP). (C) (mixing ratio) thermoplastic resin: thermoplastic liquid crystal resin = 7: 3 (weight ratio). (D) (Injection molding) The above resin was dried, dry blended, and injection molded into a test piece mold having a width of 6 μm, a thickness of 2 μm, and a length of 70 μm using an ordinary injection molding machine. (A) Molding temperature Barrel temperature 210-230 ° C Mold temperature 40 ° C (b) Injection speed 60 mm / sec (c) Molding cycle 12 sec (e) Resin viscosity ratio EVOH-1 : LCP = 1 : 3.6 ... Blend A EVOH-2 : LCP = 1 : 0.8 ... Blend B EVOH-3 : LCP = 1 : 0.4 ... Blend C (f) Properties of molded product Fig. 2 shows the water vapor absorption of the injection molded product. . Blend A having a large viscosity ratio of LCP to EVOH had a relatively small moisture-proof effect, and blend C having a small viscosity ratio of LCP to EVOH had a large moisture-proof effect. (G) Fracture section of molded article FIG. 3 shows an enlarged sectional explanatory view of a molded article molded with a blend C of EVOH4 and LCP3 . In the vicinity of the surface of the molded product, LCP 3 was oriented in a layered manner.
【００１３】[0013]
【発明の効果】本発明の射出成形品は、熱可塑性液晶樹
脂が成形品表面近傍で層状に配向することにより、水蒸
気等のガス遮断効果が大きく、すぐれた成形品としての
物性が得られた。According to the injection molded article of the present invention, since the thermoplastic liquid crystal resin is oriented in a layered manner near the surface of the molded article, the effect of shutting off gas such as water vapor is large, and excellent physical properties as a molded article are obtained. .
【図１】多層射出成形品断面図。FIG. 1 is a cross-sectional view of a multilayer injection molded product.
【図２】４０℃における射出成形品の水蒸気吸収量。FIG. 2 shows the water vapor absorption of an injection-molded article at 40 ° C.
【図３】射出成形品破断面の拡大説明図。FIG. 3 is an enlarged explanatory view of a fracture surface of an injection molded product.
１ 外層（ブレンド物層） ２ 中心層（コア層） ３ 層状ＬＣＰ４ ＥＶＯＨ Reference Signs List 1 outer layer (blend layer) 2 center layer (core layer) 3 layered LCP 4 EVOH
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 23:16 29:04 67:04 (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 45/00 - 45/84 C08L 67/00 - 67/08 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 identification code FI C08L 23:16 29:04 67:04 (58) Field surveyed (Int.Cl. 7 , DB name) B29C 45/00-45 / 84 C08L 67/00-67/08
Claims (1)
含む熱可塑性樹脂と熱可塑性液晶樹脂とを少なくとも含
む２成分以上の樹脂のブレンド物を用いた射出成形品で
あり、成形品表面層近傍の熱可塑性液晶樹脂が層構造を
有しており、射出成形加工時における熱可塑性樹脂の粘
度と熱可塑性液晶樹脂の粘度との比が１：４かあるいは
それよりも小さいことを特徴とする射出成形品。1. A saponified ethylene-vinyl acetate copolymer.
Containing at least a thermoplastic resin and a thermoplastic liquid crystal resin.
An injection molded article using a blend of free 2-component or more resins, thermoplastic liquid crystal resins of the molded article surface layer vicinity has a layer structure, viscosity and thermoplastic of the thermoplastic resin during injection molding An injection-molded article characterized in that the ratio to the viscosity of the liquid crystal resin is 1 : 4 or less .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03114557A JP3123113B2 (en) | 1991-05-20 | 1991-05-20 | Injection molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03114557A JP3123113B2 (en) | 1991-05-20 | 1991-05-20 | Injection molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05305626A JPH05305626A (en) | 1993-11-19 |
| JP3123113B2 true JP3123113B2 (en) | 2001-01-09 |
Family
ID=14640790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03114557A Expired - Fee Related JP3123113B2 (en) | 1991-05-20 | 1991-05-20 | Injection molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3123113B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0635666U (en) * | 1992-10-19 | 1994-05-13 | 光洋精工株式会社 | Bearing with sensor |
| US8160870B2 (en) | 2005-01-12 | 2012-04-17 | Nippon Telegraph And Telephone Corporation | Method, apparatus, program, and recording medium for long-term prediction coding and long-term prediction decoding |
| JP7304754B2 (en) | 2019-07-04 | 2023-07-07 | Ntn株式会社 | bearing device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2795671B1 (en) * | 1999-06-29 | 2001-09-14 | Valeo Vision | METHOD FOR MANUFACTURING OPTICAL PARTS FOR LIGHTING OR SIGNALING OF MOTOR VEHICLES |
| JP2006212928A (en) * | 2005-02-03 | 2006-08-17 | Fujitsu Ltd | Molding containing photocatalyst and method for molding containing photocatalyst |
| US8197924B2 (en) * | 2010-10-05 | 2012-06-12 | Ford Global Technologies, Llc | Compostable interior panel for use in a vehicle and method of manufacture |
-
1991
- 1991-05-20 JP JP03114557A patent/JP3123113B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0635666U (en) * | 1992-10-19 | 1994-05-13 | 光洋精工株式会社 | Bearing with sensor |
| US8160870B2 (en) | 2005-01-12 | 2012-04-17 | Nippon Telegraph And Telephone Corporation | Method, apparatus, program, and recording medium for long-term prediction coding and long-term prediction decoding |
| JP7304754B2 (en) | 2019-07-04 | 2023-07-07 | Ntn株式会社 | bearing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05305626A (en) | 1993-11-19 |
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