JPH05112709A - Resin composition for molding - Google Patents
Resin composition for moldingInfo
- Publication number
- JPH05112709A JPH05112709A JP3252210A JP25221091A JPH05112709A JP H05112709 A JPH05112709 A JP H05112709A JP 3252210 A JP3252210 A JP 3252210A JP 25221091 A JP25221091 A JP 25221091A JP H05112709 A JPH05112709 A JP H05112709A
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- JP
- Japan
- Prior art keywords
- resin
- molding
- liquid crystal
- strength
- resin composition
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱可塑性樹脂と液晶樹
脂との複合材よりなる成形用樹脂組成物に関する。より
詳しくは本発明は、再成形可能な成形用樹脂組成物に関
する。FIELD OF THE INVENTION The present invention relates to a molding resin composition comprising a composite material of a thermoplastic resin and a liquid crystal resin. More specifically, the present invention relates to a remoldable molding resin composition.
【０００２】[0002]
【従来の技術】従来、高強度で高剛性を有する合成樹脂
製成形品としては、熱硬化性樹脂にガラス繊維を混合し
たものや、スタンパブルシートと称される熱可塑性樹脂
に長繊維ガラスを混合したものなどを所定形状に成形す
ることにより得られるものが知られている。また、上記
ガラス繊維の代わりに炭素繊維を用いてなる高強度且つ
高剛性の合成樹脂も知られている。2. Description of the Related Art Conventionally, as a synthetic resin molded article having high strength and high rigidity, a thermosetting resin mixed with glass fiber, or a thermoplastic resin called a stampable sheet is made of long fiber glass. A material obtained by molding a mixed material into a predetermined shape is known. Further, a high-strength and high-rigidity synthetic resin in which carbon fiber is used instead of the glass fiber is also known.
【０００３】さらに、ガラス繊維や炭素繊維が混合され
ない高強度で高剛性を有する合成樹脂成形品として、特
開平１−３２０１２８号公報に示されるように、熱可塑
性樹脂と液晶樹脂(液晶ポリマー)とからなる複合材を液
晶樹脂の液晶転移温度以上の温度下で延伸しながら押出
すことにより得たストランドを１〜４０mmの長さに切断
し、得られた切断物を液晶樹脂の液晶転移温度以下の温
度で押出成形することにより得られるものも知られてい
る。Further, as a synthetic resin molded article having high strength and high rigidity in which glass fibers and carbon fibers are not mixed, as shown in JP-A-1-320128, a thermoplastic resin and a liquid crystal resin (liquid crystal polymer) are used. Strands obtained by extruding a composite material consisting of the above at a temperature above the liquid crystal transition temperature of the liquid crystal resin are cut into lengths of 1 to 40 mm, and the obtained cut products are below the liquid crystal transition temperature of the liquid crystal resin. What is obtained by extrusion molding at the temperature of is also known.
【０００４】ところで、近時、資源保護等の観点から成
形品となった合成樹脂体をリサイクル(再成形)すること
が望まれている。合成樹脂体よりなる成形品をリサイク
ルする場合には、合成樹脂体を粉砕して合成樹脂よりな
る粉砕片を得た後、該粉砕片を加熱して溶融し、次に、
溶融状態の合成樹脂材を所定形状の成形品に成形する
か、又は溶融状態の合成樹脂を押出成形して成形用素材
を得た後、その成形用素材を所定形状の成形品に成形す
るものである。By the way, recently, from the viewpoint of resource protection and the like, it is desired to recycle (re-mold) the synthetic resin body which has been molded. When recycling a molded article made of a synthetic resin body, the synthetic resin body is crushed to obtain a crushed piece made of a synthetic resin, and the crushed piece is heated and melted.
Molding a molten synthetic resin material into a molded product of a specified shape, or extruding a molten synthetic resin to obtain a molding material, and then molding the molding material into a molded product of a specified shape Is.
【０００５】従来、高強度で高剛性を有する合成樹脂体
をリサイクルする場合には、ガラス繊維や炭素繊維等の
強化用繊維を合成樹脂に混合してなる繊維強化樹脂体が
対象になっていた。Heretofore, in the case of recycling a synthetic resin body having high strength and high rigidity, a fiber reinforced resin body prepared by mixing reinforcing fibers such as glass fibers and carbon fibers with a synthetic resin has been a target. ..
【０００６】[0006]
【発明が解決しようとする課題】しかるに、上記のよう
な繊維強化樹脂体を再成形する場合、繊維強化樹脂体を
粉砕して得られた粉砕片においては合成樹脂体に混入さ
れている強化用繊維が短く切断されているために、再成
形により得られた成形用素材においても強化用繊維が切
断されたままである。このため、リサイクルによる得ら
れた再成形品は、当初の成形品に比べて強度及び剛性の
点で低下せざるを得なかった。However, when re-molding the fiber-reinforced resin body as described above, the crushed pieces obtained by crushing the fiber-reinforced resin body are mixed with the synthetic resin body for reinforcement. Since the fiber is cut into short pieces, the reinforcing fiber remains cut even in the molding material obtained by the re-molding. For this reason, the remolded product obtained by recycling had to be reduced in strength and rigidity as compared with the original molded product.
【０００７】上記に鑑み、本発明は、高強度で高剛性を
有する合成樹脂体を再成形して得られる再成形品の強度
及び剛性を当初の合成樹脂体よりも低下しないようにす
ることを目的とする。In view of the above, the present invention aims to prevent the strength and rigidity of a remolded product obtained by remolding a synthetic resin body having high strength and high rigidity from being lower than that of the original synthetic resin body. To aim.
【０００８】[0008]
【課題を解決するための手段】即ち本発明は、マトリッ
クス樹脂がポリカーボネートである成形用樹脂組成物が
マトリックス樹脂より高い融点を有する液晶性ポリマー
を３〜７０重量％含有し、且つ成形物中に複合された液
晶性ポリマーの液晶化物がアスペクト比３以上を有する
ことを特徴とする成形用樹脂組成物を、提供する。That is, according to the present invention, a molding resin composition in which a matrix resin is a polycarbonate contains 3 to 70% by weight of a liquid crystalline polymer having a melting point higher than that of the matrix resin, and There is provided a molding resin composition characterized in that a liquid crystal compound of a compounded liquid crystalline polymer has an aspect ratio of 3 or more.
【０００９】本発明の樹脂組成物に於いて使用されるマ
トリックス樹脂は、市販品として入手出来る。具体的に
は市販品としては、例えば１４１(日本ＧＥプラスチッ
クス(株)製)、パンライトＬ１２５０(帝人化成(株)
製)、ユーピロンＳ−１０００(三菱互斯化学(株)製)等
が挙げられ、これらの１種以上使用してよい。マトリッ
クス樹脂の含有量は、樹脂組成物全重量に対し８０〜９
８重量％が好ましい。マトリックス樹脂が８０重量％未
満だと樹脂組成物の成形性が低下し、又９８重量％を超
過すると成形物の強度が十分でなくなる。The matrix resin used in the resin composition of the present invention is commercially available. Specifically, as commercially available products, for example, 141 (manufactured by Japan GE Plastics Co., Ltd.), Panlite L1250 (Teijin Kasei Co., Ltd.)
Manufactured by Mitsubishi Mutual Chemical Co., Ltd., etc., and one or more of them may be used. The content of the matrix resin is 80 to 9 based on the total weight of the resin composition.
8% by weight is preferred. If the amount of the matrix resin is less than 80% by weight, the moldability of the resin composition will decrease, and if it exceeds 98% by weight, the strength of the molded product will be insufficient.
【００１０】本発明の樹脂組成物は、液晶性ポリマーを
含有する。液晶性ポリマーは、樹脂組成物の成形物中に
於いて、後述のアスペクト比を有する繊維形状をなし、
成形物の強化材となる。このような液晶性ポリマーとし
ては、上記マトリックス樹脂より融点が高いもの、好ま
しくは２０℃以上高いものである。融点がマトリックス
樹脂より低いと、液晶性ポリマーが成形物中に於いて繊
維状とならず又配向も一定せず十分な強度が得られな
い。液晶ポリマーとしては従来公知の各種のものが適用
出来、特に限定されるものではない。液晶ポリマーとし
ては、各種のものが知られているが、本発明で特に好ま
しく用いられるものは熱可塑性の液晶ポリエステル、ま
た液晶ポリエステルアミドである。かかるものとして、
特に好ましく用いられるものとしては、下記に記載する
ものが挙げられる。即ちThe resin composition of the present invention contains a liquid crystalline polymer. The liquid crystalline polymer has a fiber shape having an aspect ratio to be described later in the molded product of the resin composition,
It serves as a reinforcing material for molded products. Such a liquid crystalline polymer has a melting point higher than that of the above matrix resin, and is preferably 20 ° C. or higher. When the melting point is lower than that of the matrix resin, the liquid crystalline polymer does not become fibrous in the molded product, the orientation is not constant, and sufficient strength cannot be obtained. As the liquid crystal polymer, various conventionally known ones can be applied and are not particularly limited. Although various kinds of liquid crystal polymers are known, those particularly preferably used in the present invention are thermoplastic liquid crystal polyesters and liquid crystal polyester amides. As such,
Particularly preferably used are those described below. I.e.
【００１１】[0011]
【化１】 [Chemical 1]
【００１２】[0012]
【化２】 [Chemical 2]
【００１３】[0013]
【化３】 [Chemical 3]
【００１４】[0014]
【化４】 [Chemical 4]
【００１５】[0015]
【化５】 [Chemical 5]
【００１６】ここで、Σni＝１００である。そして、特
に好ましいのは各構造式のniが４以上である。Here, Σni = 100. And it is particularly preferable that ni in each structural formula is 4 or more.
【００１７】また、各式において、ハロゲン等をはじ
め、各種の置換基が付加されていても良い。これらに示
されるものは本発明の変性ポリエステルと良好に溶融成
形しやすいので特に好ましい。また、高強度・高弾性率
の複合繊維としやすい。Further, in each formula, various substituents such as halogen may be added. Those shown in these are particularly preferable because they can be easily melt-molded with the modified polyester of the present invention. Further, it is easy to form a composite fiber having high strength and high elastic modulus.
【００１８】同様に液晶ポリエステルアミドも従来公知
のものが適用できなんら制限されるものではない。特に
好ましいものとして下記の構造式に示されるものが挙げ
られる。即ちSimilarly, as the liquid crystal polyesteramide, a conventionally known one can be applied and is not limited at all. Particularly preferred are those represented by the following structural formulas. I.e.
【００１９】[0019]
【化６】 [Chemical 6]
【００２０】[0020]
【化７】 [Chemical 7]
【００２１】[0021]
【化８】 [Chemical 8]
【００２２】ここで、各構造式においてΣni＝１００で
ある。そして、特に好ましいのは各構造式のniが１５以
上である。また、各式ともハロゲン等をはじめ、各種の
置換基が付加されていてもよい。これらに示されるもの
はポリアーリレートからなる液晶ポリマーと同様に溶融
成形性があり、かつ高強度である。液晶性ポリマーの含
有量は、樹脂組成物全重量に対し２〜２０重量％であ
る。含有量が３重量％未満だと成形物に十分な強度を付
与できず、又２０重量％を超過すると樹脂組成物の成形
性が低下する。Here, Σni = 100 in each structural formula. And, it is particularly preferable that ni in each structural formula is 15 or more. Further, in each formula, various substituents such as halogen may be added. Those shown in these materials have melt moldability and high strength as in the case of the liquid crystal polymer composed of polyarylate. The content of the liquid crystalline polymer is 2 to 20% by weight based on the total weight of the resin composition. If the content is less than 3% by weight, sufficient strength cannot be imparted to the molded product, and if it exceeds 20% by weight, the moldability of the resin composition is deteriorated.
【００２３】本発明の樹脂組成物にはその他添加剤とし
て、耐光剤、酸化防止剤、可塑剤等を加えてよい。Other additives such as a light resistance agent, an antioxidant and a plasticizer may be added to the resin composition of the present invention.
【００２４】本発明の樹脂組成物は一旦溶融状態、即ち
液晶性ポリマーの融点より高い温度に加熱し、ポリマー
分子に配向性を付与する状態で成形あるいは成形用材料
化する。ポリマー分子に配向性を付与する状態は押出成
形、射出成形等の方法により与えられるのが一般的であ
る。この方法で直接、成形して、高い配向性(分子方向
性)を有する成形物品を得てもよい。しかし、通常押出
成形した後、ペレット状の成形用材料にする。この成形
用材料を用いて、再度押出機や射出成形器等で溶融して
成形してもよい。尚、この再溶融する時の温度はマトリ
ックス樹脂の融点より高くかつ液晶ポリマーの融点より
低い温度である方が、液晶樹脂が繊維状態を保持してい
るので好ましい。成形用材料としては平板状のものを用
いてもよい。この場合成形用材料板を重ねて型内成形し
てもよい。特に、配向方向を同一または異なる方向にす
ることにより、成形物品の特性を変えることができる。The resin composition of the present invention is molded or made into a molding material in a molten state, that is, in a state where it is heated to a temperature higher than the melting point of the liquid crystalline polymer to impart orientation to the polymer molecules. The state of imparting orientation to the polymer molecules is generally given by a method such as extrusion molding or injection molding. It may be directly molded by this method to obtain a molded article having high orientation (molecular orientation). However, it is usually formed into a pellet-shaped molding material after extrusion molding. The molding material may be melted and molded again by an extruder, an injection molding machine or the like. The temperature at the time of remelting is preferably higher than the melting point of the matrix resin and lower than the melting point of the liquid crystal polymer, because the liquid crystal resin retains a fibrous state. A flat material may be used as the molding material. In this case, the molding material plates may be overlapped and molded in the mold. In particular, the characteristics of the molded article can be changed by making the orientation directions the same or different.
【００２５】上記成形物中に複合された繊維状液晶化ポ
リマーは、アスペクト比(即ち、長さ／太さ)３以上、好
ましくは１０以上有する。The fibrous liquid crystalline polymer compounded in the above molded product has an aspect ratio (that is, length / thickness) of 3 or more, preferably 10 or more.
【００２６】[0026]
【発明の効果】上記成形物を原料として、これを必要に
応じ粉砕等を行い、上記製造法に従って再溶融、再成形
を行うことにより、再成形物が得られる。このようにし
て得られた再成形物中の繊維状液晶化ポリマーは本質的
に原料成形物中のそれと同じであり、アスペクト比３以
上を有し、従って再成形物は原料成形物の強度と実質的
に同等である。このような再成形物も更に、何度でも再
成形出来、実質的に強度低下のない再成形物を与える。EFFECTS OF THE INVENTION A remolded product is obtained by using the above molded product as a raw material, crushing it if necessary, and remelting and remolding according to the above-mentioned manufacturing method. The fibrous liquid crystalline polymer in the remolded product thus obtained is essentially the same as that in the raw material molded product and has an aspect ratio of 3 or more. Substantially equivalent. Further, such a re-molded product can be re-molded any number of times to give a re-molded product having substantially no strength reduction.
【００２７】[0027]
【実施例】以下、本発明を実施例により具体的に説明す
る。まず、液晶樹脂としてポリプラスチックス(株)製の
ベクトラＡ９５０(芳香族ポリエステル、液晶転移温度:
約２８０℃)を用い、ＰＣとしては日本ＧＥプラスチッ
クス(株)製の１４１を用い、両者を所定の割合に混合し
て液晶樹脂複合材を得た。EXAMPLES The present invention will be specifically described below with reference to examples. First, as a liquid crystal resin, Vectra A950 manufactured by Polyplastics Co., Ltd. (aromatic polyester, liquid crystal transition temperature:
A liquid crystal resin composite material was obtained by using 141 of Nippon GE Plastics Co., Ltd. as a PC and mixing them at a predetermined ratio.
【００２８】次に、上記液晶樹脂複合材を初期押出成形
した。この場合の押出成形条件は、押出機としてプラス
チック工学研究所(株)製の２軸押出機(スクリュー径:３
０mm)を用い、樹脂温度は２９０℃に、スクリュー回転
数は１００rpmに、ダイス径は２mmに、剪断速度は１７
００sec-1に、延伸比は２倍に各々設定した。そして、
上記の液晶樹脂複合材を延伸しながら押出成形してテス
ト用の直径:１．４mmのストランド状の初期成形用素材
を得た後、該初期成形用素材の一部を長さ:３mmに切断
して初期ペレット材を得た。Next, the liquid crystal resin composite material was subjected to initial extrusion molding. In this case, the extrusion molding conditions are as follows: A twin-screw extruder manufactured by Plastic Engineering Laboratory Co., Ltd. (screw diameter: 3
0 mm), the resin temperature is 290 ° C., the screw rotation speed is 100 rpm, the die diameter is 2 mm, and the shear rate is 17 mm.
The stretching ratio was set to 00 sec -1 and doubled. And
The above liquid crystal resin composite material is stretched and extruded to obtain a strand-shaped initial molding material having a diameter of 1.4 mm for testing, and then a part of the initial molding material is cut into a length of 3 mm. Then, an initial pellet material was obtained.
【００２９】次に、上記初期ペレット材を射出成形して
液晶樹脂複合体を得た。この場合の射出成形条件は、東
芝機械(株)製の２２０Ｔon射出成形機及びテストピース
型の金型を用い、樹脂温度を２６５℃に設定した。Next, the above initial pellet material was injection molded to obtain a liquid crystal resin composite. The injection molding conditions in this case were a resin temperature of 265 ° C. using a 220 Ton injection molding machine manufactured by Toshiba Machine Co., Ltd. and a test piece mold.
【００３０】次に、上記液晶樹脂複合体を、(株)ホーラ
イ製 Ｖ−３６０の粉砕装置で粉砕し、長さ:３〜４mm
の粉砕片を得た後、該粉砕片をリサイクル押出し成形し
てテスト用の直径:１．４mmのストランド状のリサイク
ル成形用素材を得た後、該リサイクル成形用素材の一部
を長さ:３mmに切断してリサイクルペレット材を得た。
この場合の押出成形条件は初期押出成形の場合と同じで
あった。Next, the above-mentioned liquid crystal resin composite was crushed by a crusher V-360 manufactured by Horai Co., Ltd., and length: 3-4 mm.
After obtaining the crushed pieces, the crushed pieces are recycled and extrusion-molded to obtain a strand-shaped recycle molding material having a diameter of 1.4 mm for testing, and a part of the recycle molding material is length: It was cut into 3 mm to obtain a recycled pellet material.
The extrusion molding conditions in this case were the same as those in the initial extrusion molding.
【００３１】次に、ストランド状の初期成形用素材及び
リサイクル成形用素材に対して引張試験を行なった。測
定機としては島津製作所(株)製の万能試験機(オートグ
ラフ)を用い、引張速度を２０mm／分に設定した。Next, a tensile test was performed on the strand-shaped initial molding material and the recycled molding material. A universal testing machine (Autograph) manufactured by Shimadzu Corporation was used as a measuring machine, and the tensile speed was set to 20 mm / min.
【００３２】図１は初期成形用素材及びリサイクル成形
用素材に対して引張試験を行なった結果を示しており、
液晶樹脂の含有率が２〜４％を超える領域で液晶樹脂の
繊維化が生じ、液晶樹脂含有量の全量域に亘って両者の
引張強度が略同じであること、つまり上記再成形方法に
よると高強度の合成樹脂を再成形するにも拘わらず、強
度が低下しないことが確認できた。尚、３０％の時点で
一旦引張強さが下がる。FIG. 1 shows the results of tensile tests performed on the initial molding material and the recycled molding material.
In the region where the content of the liquid crystal resin exceeds 2 to 4%, fibrosis of the liquid crystal resin occurs, and the tensile strengths of the two are substantially the same over the entire range of the content of the liquid crystal resin, that is, according to the above remolding method. It was confirmed that the strength did not decrease despite remolding the high-strength synthetic resin. Note that the tensile strength temporarily decreases at 30%.
【図１】 実施例により得られた初期成形用素材および
リサイクル成形用素材に対する引張試験の結果を示すグ
ラフである。FIG. 1 is a graph showing the results of a tensile test for an initial molding material and a recycling molding material obtained in Examples.
【手続補正書】[Procedure amendment]
【提出日】平成４年１０月２２日[Submission date] October 22, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Name of item to be corrected] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３２】図１は初期成形用素材及びリサイクル成形
用素材に対して引張試験を行なった結果を示しており、
液晶樹脂の含有率が２〜４％を超える領域で液晶樹脂の
繊維化が生じ、液晶樹脂含有量の全量域に亘って両者の
引張強度が略同じであること、つまり上記再成形方法に
よると高強度の合成樹脂を再成形するにも拘わらず、強
度が低下しないことが確認できた。尚、３０％の時点で
一旦引張強さが下がる。FIG. 1 shows the results of tensile tests performed on the initial molding material and the recycled molding material.
In the region where the content of the liquid crystal resin exceeds 2 to 4%, fibrosis of the liquid crystal resin occurs, and the tensile strengths of the two are substantially the same over the entire range of the content of the liquid crystal resin, that is, according to the above remolding method. It was confirmed that the strength did not decrease despite remolding the high-strength synthetic resin. Note that the tensile strength temporarily decreases at 30%.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief description of the drawing
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【図１】 実施例により得られた初期成形用素材および
リサイクル成形用素材に対する引張試験の結果を示すグ
ラフである。FIG. 1 is a graph showing the results of a tensile test for an initial molding material and a recycling molding material obtained in Examples.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金子 満晴 広島県安芸郡府中町新地３番１号 マツダ 株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuharu Kaneko 3-1, Shinchi, Fuchu-cho, Aki-gun, Hiroshima Mazda Motor Corporation
Claims (1)
ある成形用樹脂組成物がマトリックス樹脂より高い融点
を有する液晶性ポリマーを３〜７０重量％含有し、且つ
成形物中に複合された液晶性ポリマーの液晶化物がアス
ペクト比３以上を有することを特徴とする成形用樹脂組
成物。1. A liquid crystal compound of a liquid crystalline polymer in which a molding resin composition in which a matrix resin is a polycarbonate contains 3 to 70% by weight of a liquid crystalline polymer having a melting point higher than that of the matrix resin, and which is compounded in the molded product. Has an aspect ratio of 3 or more.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03252210A JP3119508B2 (en) | 1991-09-30 | 1991-09-30 | Method for producing reshaped article containing liquid crystal polymer |
| KR1019920017834A KR960006785B1 (en) | 1991-09-30 | 1992-09-30 | Molding resin composition |
| EP19920116771 EP0535650A3 (en) | 1991-09-30 | 1992-09-30 | Molding resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03252210A JP3119508B2 (en) | 1991-09-30 | 1991-09-30 | Method for producing reshaped article containing liquid crystal polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05112709A true JPH05112709A (en) | 1993-05-07 |
| JP3119508B2 JP3119508B2 (en) | 2000-12-25 |
Family
ID=17234037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03252210A Expired - Fee Related JP3119508B2 (en) | 1991-09-30 | 1991-09-30 | Method for producing reshaped article containing liquid crystal polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3119508B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127466A (en) * | 1996-11-29 | 2000-10-03 | Polyplastics Co., Ltd. | Injection-molded article |
| US6956072B1 (en) | 1999-07-16 | 2005-10-18 | Polyplastics Co., Ltd. | Thermoplastic resin composition and molded object thereof |
| JP2021059622A (en) * | 2019-10-03 | 2021-04-15 | 三菱瓦斯化学株式会社 | Film, security card, passport, and method for producing film |
-
1991
- 1991-09-30 JP JP03252210A patent/JP3119508B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127466A (en) * | 1996-11-29 | 2000-10-03 | Polyplastics Co., Ltd. | Injection-molded article |
| US6956072B1 (en) | 1999-07-16 | 2005-10-18 | Polyplastics Co., Ltd. | Thermoplastic resin composition and molded object thereof |
| JP2021059622A (en) * | 2019-10-03 | 2021-04-15 | 三菱瓦斯化学株式会社 | Film, security card, passport, and method for producing film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3119508B2 (en) | 2000-12-25 |
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