JP3094656B2 - Internal release agent - Google Patents
Internal release agentInfo
- Publication number
- JP3094656B2 JP3094656B2 JP04134860A JP13486092A JP3094656B2 JP 3094656 B2 JP3094656 B2 JP 3094656B2 JP 04134860 A JP04134860 A JP 04134860A JP 13486092 A JP13486092 A JP 13486092A JP 3094656 B2 JP3094656 B2 JP 3094656B2
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- Japan
- Prior art keywords
- release agent
- weight
- ethylene
- parts
- internal release
- 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)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、樹脂やゴムの混合、成
形の工程において、これらの劣化物、各種配合剤等に起
因する混合機械、成形機械及び成形の型への付着物質が
起こす型汚染、離型性の低下などを防止するための新規
な内部離型剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for mixing and molding resins and rubbers, wherein the degraded products, various compounding agents, etc., cause adhesion to a mixing machine, a molding machine and a molding die. The present invention relates to a novel internal release agent for preventing contamination and a decrease in releasability.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】樹脂や
ゴムの成形加工工程においては、これらの劣化物、各種
配合剤等に起因して、混合機械、成形機械あるいは金型
などに異物が付着蓄積し、外観を損なったり、成形品の
物性を低下させるという問題がよく知られている。2. Description of the Related Art In the resin and rubber molding process, foreign substances adhere to a mixing machine, a molding machine, a mold, or the like due to these degraded products and various compounding agents. Problems of accumulating and impairing the appearance and deteriorating the physical properties of molded articles are well known.
【０００３】その付着防止策として、従来、機械や金型
の表面処理、例えばクロムメッキまたはフッ素樹脂コー
ティング等が行われてきたが、効果の持続性や表面処理
コスト等に問題があった。Conventionally, as a measure for preventing the adhesion, surface treatment of a machine or a mold, such as chromium plating or fluororesin coating, has been carried out, but there have been problems with the continuity of the effect and the surface treatment cost.
【０００４】また、別の方法としては、付着物質が蓄積
した時点で研磨のような物理的清掃、またはアルカリ水
あるいは界面活性剤などによる化学的清掃が行われてき
た。なかでも特開平１−２９２０４４号公報、特開平２
−１７５２１０号公報、特開平３−１４０２１４号公報
などに記載のクリーニング用ゴムのように、汚れを吸着
させる方法が一般的である。[0004] As another method, physical cleaning such as polishing or chemical cleaning with alkaline water or a surfactant has been performed at the time when the deposits accumulate. Above all, Japanese Patent Application Laid-Open Nos. 1-292044 and 2
A method of adsorbing dirt, such as a cleaning rubber described in JP-A-175210 and JP-A-3-140214, is generally used.
【０００５】しかし、これらの方法も連続操業を停止し
て清掃しなければならず、生産性が低下すること、型な
どを傷める等の問題を有していた。[0005] However, these methods also require continuous operation to be stopped for cleaning, which causes problems such as a decrease in productivity and damage to molds and the like.
【０００６】さらに、別の方法としては、離型剤を用い
る方法が知られている。例えば、シリコンやフッ素系化
合物、油脂類等の外部離型剤をスプレー式に塗布する方
法があるが、外部離型剤を用いる方法では、効果の持続
性が不充分であったり、離型剤が成形物表面に付着して
次工程に支障をきたすという問題を有していた。As another method, a method using a release agent is known. For example, there is a method in which an external release agent such as silicon, a fluorine-based compound, or an oil or fat is applied by a spray method. However, in the method using an external release agent, the persistence of the effect is insufficient or the release agent is not used. However, there is a problem that the particles adhere to the surface of the molded product and hinder the next step.
【０００７】また、内部離型剤として離型性のよい物
質、例えば無機粉末や高分子界面活性剤、高分子化合物
などを練り込む方法が知られている（特公平３−４８８
４５号公報、特開平３−１９５７６７号公報）。しかし
ながら、これらの方法でも効果が不十分であったり、樹
脂やゴムの物性を低下させるなどの問題を有していた。Further, a method of kneading a substance having good releasability as an internal release agent, for example, an inorganic powder, a polymer surfactant, a polymer compound or the like is known (Japanese Patent Publication No. 3-488).
No. 45, JP-A-3-195767). However, these methods also have problems such as insufficient effect and deterioration of physical properties of resin and rubber.
【０００８】[0008]
【課題を解決するための手段】かかる事情に鑑み、本発
明者らは樹脂やゴムの混合、成形の工程において、それ
らの劣化物、各種配合剤等に起因する混合機械、成形機
械や成形の型への付着物質が起こす型汚染、離型性の低
下などを防止するための新規な内部離型剤について鋭意
検討した結果、特定のエチレン−ビニルアルコール共重
合体グラフト物が内部離型剤として優れた効果を奏する
ことを見出し、さらに種々の検討を加えて本発明を完成
するに至った。SUMMARY OF THE INVENTION In view of the above circumstances, the present inventors, in the process of mixing and molding resins and rubbers, used a mixing machine, a molding machine or a molding machine caused by their degraded products, various compounding agents, and the like. As a result of intensive studies on a new internal release agent to prevent mold contamination caused by substances adhering to the mold and a decrease in release properties, a specific ethylene-vinyl alcohol copolymer graft was used as the internal release agent. The inventor has found that excellent effects can be achieved, and further completed various studies with the present invention.
【０００９】すなわち、本発明は、エチレン−ビニルア
ルコール共重合体１００重量部に対して、アルキレンオ
キサイドを２０〜１０００重量部グラフトさせてなる化
合物からなることを特徴とする内部離型剤を提供するも
のである。また、本発明は、エチレン−ビニルアルコー
ル共重合体１００重量部に対して、アルキレンオキサイ
ドを２０〜１０００重量部グラフトさせてなる化合物１
００重量部に対して、無機フィラー２５０重量部以下含
有する組成物からなることを特徴とする内部離型剤を提
供するものである。That is, the present invention provides an internal release agent comprising a compound obtained by grafting 20 to 1000 parts by weight of an alkylene oxide to 100 parts by weight of an ethylene-vinyl alcohol copolymer. Things. Further, the present invention relates to a compound 1 obtained by grafting 20 to 1000 parts by weight of an alkylene oxide to 100 parts by weight of an ethylene-vinyl alcohol copolymer.
The present invention provides an internal release agent comprising a composition containing 250 parts by weight or less of an inorganic filler with respect to 00 parts by weight.
【００１０】以下、本発明を詳細に説明する。本発明で
用いるエチレン−ビニルアルコール共重合体は、ビニル
アルコールモノマーが不安定な化合物であるため、エチ
レンと直接共重合することは少なく、一般的にはエチレ
ンと飽和カルボン酸のビニルエステル、例えば酢酸ビニ
ル、プロピオン酸ビニル、酪酸ビニル等との共重合体を
部分的に、または完全にけん化して得られる。Hereinafter, the present invention will be described in detail. Since the ethylene-vinyl alcohol copolymer used in the present invention is a compound in which the vinyl alcohol monomer is unstable, it is rarely copolymerized directly with ethylene, and is generally a vinyl ester of ethylene and a saturated carboxylic acid, for example, acetic acid. It is obtained by partially or completely saponifying a copolymer with vinyl, vinyl propionate, vinyl butyrate and the like.
【００１１】けん化反応は、公知の方法で行うことがで
き、例えば特開平２−５１５０４号公報に記載されてい
るように、アルカリ触媒の存在下でアルコールとともに
加熱する方法が挙げられる。The saponification reaction can be performed by a known method, for example, a method of heating with an alcohol in the presence of an alkali catalyst as described in JP-A-2-51504.
【００１２】本発明で用いるエチレン−ビニルアルコー
ル共重合体は、エチレン含有量が８０モル％以上、数平
均分子量が５０００以下の共重合体がその溶融粘度が小
さいことから、アルキレンオキサイドのグラフト反応を
容易に行えるので好ましい。The ethylene-vinyl alcohol copolymer used in the present invention has a copolymer having an ethylene content of at least 80 mol% and a number average molecular weight of at most 5,000 having a low melt viscosity. It is preferable because it can be easily performed.
【００１３】本発明で用いるアルキレンオキサイドは、
特に制限はないが、例えばエチレンオキサイド、プロピ
レンオキサイド、ブチレンオキサイド等が挙げられる。
中でもエチレンオキサイドが好ましい。The alkylene oxide used in the present invention is
Although there is no particular limitation, examples include ethylene oxide, propylene oxide, and butylene oxide.
Among them, ethylene oxide is preferable.
【００１４】アルキレンオキサイドのグラフト量は、特
に制限されるものではないが、例えばエチレン−ビニル
アルコール共重合体１００重量部に対して、２０〜１０
００重量部、好ましくは５０〜５００重量部である。The amount of the alkylene oxide grafted is not particularly limited, but may be, for example, 20 to 10 parts by weight based on 100 parts by weight of the ethylene-vinyl alcohol copolymer.
00 parts by weight, preferably 50 to 500 parts by weight.
【００１５】アルキレンオキサイドのグラフト反応は、
特に制限されるものではなく、例えば特開平３−２２７
３０７号公報に記載されているように、加熱溶融したエ
チレン−ビニルアルコール共重合体に、必要によりアル
カリ触媒を少量加えてアルキレンオキサイドを導入する
ことができる。[0015] The graft reaction of the alkylene oxide is
There is no particular limitation.
As described in JP-A-307-307, an alkylene oxide can be introduced by adding a small amount of an alkali catalyst to the heat-melted ethylene-vinyl alcohol copolymer, if necessary.
【００１６】本発明は、エチレン−ビニルアルコール共
重合体１００重量部に対して、アルキレンオキサイドを
２０〜１０００重量部グラフトさせてなる化合物が内部
離型剤として優れていることを見出したが、この化合物
に無機フィラーを特定量加えてなる組成物を樹脂やゴム
に添加すると、さらに優れた内部離型剤としての効果を
奏することを見出した。The present invention has found that a compound obtained by grafting 20 to 1000 parts by weight of an alkylene oxide with respect to 100 parts by weight of an ethylene-vinyl alcohol copolymer is excellent as an internal mold release agent. It has been found that when a composition obtained by adding a specific amount of an inorganic filler to a compound is added to a resin or rubber, a more excellent effect as an internal mold release agent is exhibited.
【００１７】本発明で用いる無機フィラーは、一般に樹
脂やゴムに配合される無機物を総称するものであり、例
えばカーボンブラック、ケイ酸とその塩、炭酸マグネシ
ウム、炭酸カルシウム、亜鉛華、アルミナ、シリカ、タ
ルク、クレー等が挙げられる。これらの無機フィラー
は、活性を変化させるための表面処理物であってもよ
く、また混合物でもよい。これらの無機フィラーの中で
も、安全性と吸油量の大きさから非晶形シリカ及びカー
ボンブラックが好ましい。The inorganic filler used in the present invention is a general term for inorganic substances generally blended in resins and rubbers, for example, carbon black, silicic acid and its salts, magnesium carbonate, calcium carbonate, zinc white, alumina, silica, Talc, clay and the like. These inorganic fillers may be surface-treated products for changing the activity, or may be mixtures. Among these inorganic fillers, amorphous silica and carbon black are preferable from the viewpoint of safety and oil absorption.
【００１８】無機フィラーを用いる本発明の内部離型剤
は、エチレン−ビニルアルコール共重合体グラフト物１
００重量部に対して、無機フィラー２５０重量部以下含
有する組成物からなるものであり、無機フィラーが２５
０重量部より多くなると、本発明の効果が乏しくなる。The internal release agent of the present invention using an inorganic filler is an ethylene-vinyl alcohol copolymer graft 1
It is composed of a composition containing 250 parts by weight or less of the inorganic filler with respect to 00 parts by weight.
If the amount is more than 0 parts by weight, the effect of the present invention becomes poor.
【００１９】本発明の内部離型剤は、その形態として粉
体状のものが好ましい。粉体化する方法としては特に制
限はなく、低温下での粉砕や、高速ミキサータイプの混
合機等を用いる方法が挙げられる。The internal release agent of the present invention is preferably in the form of a powder. The method of pulverizing is not particularly limited, and examples thereof include pulverization at a low temperature and a method using a high-speed mixer type mixer.
【００２０】本発明の内部離型剤は、樹脂やゴムに添加
して用いることができるが、樹脂やゴムの種類に特に制
限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、ポリスチレン等に代表される熱可塑性樹脂
や、ポリマーアロイ、プラスチック複合材料、あるいは
エチレン−プロピレン−ジエン共重合ゴム（ＥＰＤ
Ｍ）、スチレン−ブタジエンゴム等のゴム類が挙げられ
る。また、樹脂やゴムに添加する本発明の内部離型剤の
量は特に制限されるものではなく、樹脂等の種類により
適宜決めればよい。The internal release agent of the present invention can be used by adding it to a resin or rubber, but is not particularly limited to the type of the resin or rubber. For example, thermoplastic resin represented by polyethylene, polypropylene, polystyrene, etc., polymer alloy, plastic composite material, or ethylene-propylene-diene copolymer rubber (EPD)
M) and rubbers such as styrene-butadiene rubber. The amount of the internal release agent of the present invention to be added to the resin or rubber is not particularly limited, and may be appropriately determined depending on the type of the resin or the like.
【００２１】内部離型剤と、樹脂やゴムとの混合は特に
制限されるものではなく、例えばドライブレンド、バン
バリーミキサー、ロールスクリュー型混練押出機等が挙
げられる。Mixing of the internal release agent with the resin or rubber is not particularly limited, and examples thereof include a dry blend, a Banbury mixer, and a roll screw kneading extruder.
【００２２】また、本発明の内部離型剤は、樹脂やゴム
に一般的に添加される帯電防止剤、滑剤、熱安定剤、酸
化防止剤、光安定剤、蛍光剤、加工助剤、架橋剤、分散
剤、発泡剤、難燃剤、消泡剤、補強剤、顔料、加硫促進
剤、加硫剤、無滴剤などと併用してもよい。The internal release agent of the present invention includes antistatic agents, lubricants, heat stabilizers, antioxidants, light stabilizers, fluorescent agents, processing aids, crosslinking agents generally added to resins and rubbers. It may be used in combination with an agent, a dispersant, a foaming agent, a flame retardant, an antifoaming agent, a reinforcing agent, a pigment, a vulcanization accelerator, a vulcanizing agent, and a dripless agent.
【００２３】本発明の内部離型剤は、射出成形、プレス
成形、ブロー成形などの成形装置や成形金型などの汚染
防止、離型性の向上に利用できるが、本発明はこれらの
装置、金型に限定されるものではない。The internal release agent of the present invention can be used to prevent contamination of molding equipment such as injection molding, press molding, blow molding, etc., and to prevent contamination of molding dies, and to improve mold releasability. It is not limited to a mold.
【００２４】[0024]
【発明の効果】以上、詳述したとおり本発明の内部離型
剤は、容易に成形装置や金型などの汚染を防止し、離型
性にも優れ、しかも成形製品の光沢の低下を抑制するこ
とができる。As described in detail above, the internal release agent of the present invention easily prevents contamination of molding equipment and molds, has excellent mold release properties, and suppresses a decrease in gloss of molded products. can do.
【００２５】[0025]
【実施例】以下、本発明を実施例、参考例及び比較参考
例によって説明するが、本発明はこれらに限定されるも
のではない。EXAMPLES The present invention will be described below with reference to examples, reference examples and comparative reference examples, but the present invention is not limited to these examples.
【００２６】実施例１ エチレン含有量３１重量％、数平均分子量１９００のエ
チレン−酢酸ビニル共重合体１２０kgを２５０klのメタ
ノール中、６５℃で水酸化カリウム１．０kgを触媒とし
て２時間反応し、続いて反応液を１５０℃まで上昇させ
てメタノールを留去し、９０％けん化率の反応物１００
kgを得た。続いて、けん化物１００kgを１８０℃にして
２００kgのエチレンオキサイドを２時間かけて導入し、
３００kgの化合物を得た（内部離型剤（Ａ））。EXAMPLE 1 120 kg of an ethylene-vinyl acetate copolymer having an ethylene content of 31% by weight and a number average molecular weight of 1900 were reacted in 250 kl of methanol at 65 ° C. for 2 hours using 1.0 kg of potassium hydroxide as a catalyst. The temperature of the reaction solution was raised to 150 ° C. to distill off methanol, and the reaction product 100 having a 90% saponification rate was removed.
kg gained. Subsequently, 100 kg of saponified product was brought to 180 ° C., and 200 kg of ethylene oxide was introduced over 2 hours.
300 kg of compound were obtained (internal release agent (A)).
【００２７】実施例２ ７０℃に加熱溶融した、実施例１で得られた内部離型剤
（Ａ）１２kgと非晶形シリカ（塩野義製薬製、カープレ
ックス１１２０）８kgとを８０リットルのヘンシェルミ
キサー（三池製作所製）にいれ、５分間高速攪拌して５
メッシュ篩１００％パスの微粉状組成物を得た（内部離
型剤（Ｂ））。 参考例１及び比較参考例１ 実施例２で得られた内部離型剤（Ｂ）の離型性等の効果
を確認するために、表１のゴム配合組成物をバンバリー
ミキサー及び熱ロール混合によって調整し、未加硫生地
を得た。Example 2 An 80-liter Henschel mixer containing 12 kg of the internal release agent (A) obtained in Example 1 and 8 kg of amorphous silica (Carplex 1120, manufactured by Shionogi & Co., Ltd.), which was heated and melted at 70 ° C., was used. (Manufactured by Miike Seisakusho) and mix for 5 minutes at high speed.
A fine powder composition having a 100% pass of a mesh sieve was obtained (internal release agent (B)). Reference Example 1 and Comparative Reference Example 1 In order to confirm the effects such as the releasability of the internal release agent (B) obtained in Example 2, the rubber compounded composition of Table 1 was mixed with a Banbury mixer and a hot roll. After adjustment, an unvulcanized dough was obtained.
【００２８】[0028]
【表１】 [Table 1]
【００２９】前記未加硫生地を圧縮加硫装置によって１
８０℃で５分間加熱圧縮した。この加硫操作は、連続８
０回の圧縮加硫成形を行って、金型の汚染状況を観察し
た。その結果、内部離型剤（Ｂ）を添加しない比較参考
例１では、加硫金型全面が白い付着物で汚染され、また
ゴム表面の光沢が著しく低下した。一方、内部離型剤
（Ｂ）を添加した参考例１では、付着物が金型中央部に
わずかに残るだけであり、またゴム表面の光沢も良好で
あった。The unvulcanized dough is compressed by a compression vulcanizer to obtain
Heat compression was performed at 80 ° C. for 5 minutes. This vulcanization operation is continuous 8
The compression vulcanization molding was performed 0 times, and the contamination status of the mold was observed. As a result, in Comparative Reference Example 1 in which the internal release agent (B) was not added, the entire surface of the vulcanization mold was contaminated with white deposits, and the gloss of the rubber surface was significantly reduced. On the other hand, in Reference Example 1 in which the internal release agent (B) was added, only a small amount of the deposit remained at the center of the mold, and the gloss of the rubber surface was good.
【００３０】実施例３ 実施例１で得られた内部離型剤（Ａ）１．２kgと、カー
ボンブラック（東海電極製シーストＳＯ）０．９kgを、
３リットルのバンバリーミキサーで８０℃で１０分間混
合して黒色微粉体の組成物を得た（内部離型剤
（Ｃ））。 参考例２、３ 実施例３で得られた内部離型剤（Ｃ）または実施例１で
得られた内部離型剤（Ａ）のそれぞれ３重量部を参考例
１と同様のゴム組成物に配合し、参考例１と同様に連続
成形を行って金型の汚染状況をそれぞれ観察した。その
結果、内部離型剤（Ｃ）を用いた参考例２では、参考例
１と同様に汚染は極めて少なく、内部離型剤（Ａ）を用
いた参考例３では、参考例２より少し汚染を示したが、
比較参考例１の場合よりも明らかに汚染は少なかった。
また、いずれもゴム表面の光沢は良好であった。Example 3 1.2 kg of the internal mold release agent (A) obtained in Example 1 and 0.9 kg of carbon black (Toshikai electrode Seat SO) were used.
The mixture was mixed with a 3-liter Banbury mixer at 80 ° C. for 10 minutes to obtain a black fine powder composition (internal mold release agent (C)). Reference Examples 2 and 3 3 parts by weight of each of the internal release agent (C) obtained in Example 3 and the internal release agent (A) obtained in Example 1 were added to the same rubber composition as in Reference Example 1. The mixture was mixed and continuously molded in the same manner as in Reference Example 1 to observe the contamination status of the mold. As a result, in Reference Example 2 using the internal release agent (C), the contamination was extremely low as in Reference Example 1, and in Reference Example 3 using the internal release agent (A), the contamination was slightly smaller than in Reference Example 2. Was shown,
The contamination was clearly lower than in the case of Comparative Reference Example 1.
In all cases, the gloss on the rubber surface was good.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｆ 216/06 Ｃ０８Ｆ 216/06 (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 65/00 - 65/48 C08L 71/00 - 71/04 B29C 33/58 - 33/66 C08F 8/00,210/02,210/06 Continuation of the front page (51) Int.Cl. 7 identification code FI C08F 216/06 C08F 216/06 (58) Field surveyed (Int. Cl. 7 , DB name) C08G 65/00-65/48 C08L 71 / 00-71/04 B29C 33/58-33/66 C08F 8 / 00,210 / 02,210 / 06
Claims (5)
０重量部に対して、アルキレンオキサイドを２０〜１０
００重量部グラフトさせてなる化合物からなることを特
徴とする内部離型剤。1. An ethylene-vinyl alcohol copolymer 10.
20 to 10 parts by weight of alkylene oxide
An internal release agent comprising a compound obtained by grafting 00 parts by weight.
０重量部に対して、アルキレンオキサイドを２０〜１０
００重量部グラフトさせてなる化合物１００重量部に対
して、無機フィラー２５０重量部以下含有する組成物か
らなることを特徴とする内部離型剤。2. An ethylene-vinyl alcohol copolymer 10.
20 to 10 parts by weight of alkylene oxide
An internal mold release agent comprising a composition containing 250 parts by weight or less of an inorganic filler with respect to 100 parts by weight of a compound obtained by grafting 00 parts by weight.
エチレンと飽和カルボン酸のビニルエステルとの共重合
体の部分もしくは完全けん化物であって、エチレン含有
量が８０モル％以上、数平均分子量が５０００以下の共
重合体である請求項１または２記載の内部離型剤。3. An ethylene-vinyl alcohol copolymer,
3. A partially or completely saponified copolymer of ethylene and a vinyl ester of a saturated carboxylic acid, wherein the copolymer has an ethylene content of 80 mol% or more and a number average molecular weight of 5000 or less. Internal release agent.
イドである請求項１または２記載の内部離型剤。4. The internal release agent according to claim 1, wherein the alkylene oxide is ethylene oxide.
ボンブラックである請求項２記載の内部離型剤。5. The internal release agent according to claim 2, wherein the inorganic filler is amorphous silica or carbon black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04134860A JP3094656B2 (en) | 1992-05-27 | 1992-05-27 | Internal release agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04134860A JP3094656B2 (en) | 1992-05-27 | 1992-05-27 | Internal release agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320330A JPH05320330A (en) | 1993-12-03 |
| JP3094656B2 true JP3094656B2 (en) | 2000-10-03 |
Family
ID=15138169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04134860A Expired - Fee Related JP3094656B2 (en) | 1992-05-27 | 1992-05-27 | Internal release agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3094656B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056780A1 (en) * | 1999-03-23 | 2000-09-28 | Nisshinbo Industries, Inc. | Polymer, binder resin, composition for ionically conductive polymer electrolyte, and secondary battery |
| JP4343420B2 (en) * | 2000-11-29 | 2009-10-14 | 三井化学株式会社 | Polar group-containing branched olefin copolymer and thermoplastic resin composition containing the copolymer |
| DE60124829T2 (en) | 2000-09-07 | 2007-06-28 | Mitsui Chemicals, Inc. | A polar group-containing olefin copolymer, a process for the production thereof, a thermoplastic resin composition containing this copolymer and their use |
| US7811646B2 (en) | 2001-05-14 | 2010-10-12 | Kuraray Co., Ltd. | Modified ethylene-vinyl alcohol copolymer and method for the production thereof |
| EP1479725B1 (en) | 2002-02-26 | 2014-05-14 | Kuraray Co., Ltd. | Resin composition and multi-layer structures |
| JP3751903B2 (en) * | 2002-05-14 | 2006-03-08 | 株式会社クラレ | Process for producing modified ethylene-vinyl alcohol copolymer |
| EP1419903B1 (en) | 2002-11-13 | 2008-05-28 | Bridgestone Corporation | Innerliner for pneumatic tires and pneumatic tire |
-
1992
- 1992-05-27 JP JP04134860A patent/JP3094656B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05320330A (en) | 1993-12-03 |
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