JPH061835A - Production of aromatic polyester - Google Patents
Production of aromatic polyesterInfo
- Publication number
- JPH061835A JPH061835A JP4162860A JP16286092A JPH061835A JP H061835 A JPH061835 A JP H061835A JP 4162860 A JP4162860 A JP 4162860A JP 16286092 A JP16286092 A JP 16286092A JP H061835 A JPH061835 A JP H061835A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polymer
- ester
- hydroquinone
- aromatic polyester
- 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.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は非晶性芳香族ポリエステ
ルの製造方法に関し、更に詳しくは、溶融成形により優
れた耐熱性、機械特性、耐溶剤性を有する成形品を与え
る非晶性芳香族ポリエステルの製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an amorphous aromatic polyester, more specifically, an amorphous aromatic polyester which gives a molded article having excellent heat resistance, mechanical properties and solvent resistance by melt molding. The present invention relates to a method for producing polyester.
【０００２】[0002]
【従来の技術】芳香族ポリエステルは、その構成成分の
組合せあるいは組成により非晶性ポリマー、結晶性ポリ
マーまたは液晶性ポリマーと種々の特性のものが得られ
る。これらのうち、非晶性ポリマーは、寸法安定性、透
明性、機械特性、耐熱性に優れており、いわゆる非晶性
エンプラとして種々検討されている。特に酸成分として
テレフタル酸とイソフタル酸を用いジオール成分とし
て、２，２―ビス（４―ヒドロキシフェニル）プロパン
（以下ビスフェノールＡという）を用いたポリマーは比
較的バランスのとれた物性を有しておりこれを生かして
開発が進められているが、このポリマーは通常の非晶性
ポリマーと同様、耐溶剤性が不十分であり、各種有機溶
剤に溶解乃至膨潤しやすく、その用途が制限されてい
る。2. Description of the Related Art Aromatic polyesters having various characteristics such as an amorphous polymer, a crystalline polymer or a liquid crystalline polymer can be obtained depending on the combination or composition of its constituent components. Among these, amorphous polymers are excellent in dimensional stability, transparency, mechanical properties, and heat resistance, and have been variously studied as so-called amorphous engineering plastics. Particularly, a polymer using terephthalic acid and isophthalic acid as an acid component and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) as a diol component has a relatively balanced physical property. Development is being carried out by making use of this, but this polymer, like ordinary amorphous polymers, has insufficient solvent resistance, is easily dissolved or swelled in various organic solvents, and its use is limited. .
【０００３】この耐溶剤性を改良する目的でジオール成
分としてハイドロキノンを一部使用したものが提案され
ている（特開昭５２―７８９９９号）。ハイドロキノン
成分の導入されたポリマーは、ジオール成分としてビス
フェノールＡだけを用いたものに比べ確かに耐溶剤性、
耐ストレスクラック性は改良される。しかしながら、そ
の製造方法としてはハイドロキノン成分が、極めて酸化
を受けやすいことあるいはポリマーの溶解性が不十分で
あること等のために、ビスフェノールＡ単独系の製造方
法として用いられている溶液重合法乃至界面重合法を採
用することはできない。For the purpose of improving the solvent resistance, there has been proposed one in which hydroquinone is partially used as a diol component (JP-A-52-78999). The polymer containing the hydroquinone component is certainly more solvent resistant than the polymer using bisphenol A as the diol component,
Stress crack resistance is improved. However, as the production method thereof, the hydroquinone component is extremely susceptible to oxidation, the solubility of the polymer is insufficient, and the like. Therefore, the solution polymerization method or the interface used as the production method of bisphenol A alone is used. The polymerization method cannot be adopted.
【０００４】そこで上述の特開昭５２―７８９９９号に
よればハイドロキノン成分の導入されたポリマーの製造
方法として溶融重合法による製造が試みられている。し
かしこの方法は、その実施例に記載されている如く、溶
融重合過程においてポリマーを固化乃至結晶化せしめた
後、引き続きこれを固相重合せしめることによって目的
とする芳香族ポリエステルを製造している。これは３０
０℃以下程度の比較的低い溶融重合温度ではポリマーの
溶融粘度が高いため、十分な靭性を発現しうる高重合度
ポリマーを得ることが、困難であること、更にハイドロ
キノン成分により得られるポリマーが結晶化し得る特性
となるためと考えられる。しかしながら、この固相重合
を併用する方法は、製造プロセスが複雑となり、かつ生
産性が悪く、コスト高であるという問題がある。Therefore, according to the above-mentioned Japanese Patent Laid-Open No. 52-78999, production by a melt polymerization method is tried as a production method of a polymer having a hydroquinone component introduced therein. However, in this method, as described in the example, after solidifying or crystallizing the polymer in the melt polymerization process, the solid-state polymerization of the polymer is subsequently carried out to produce the target aromatic polyester. This is 30
Since the melt viscosity of the polymer is high at a relatively low melt polymerization temperature of about 0 ° C. or less, it is difficult to obtain a polymer having a high degree of polymerization capable of expressing sufficient toughness, and further, the polymer obtained by the hydroquinone component is crystallized. It is considered that this is because the characteristics can be changed. However, this method of using solid-phase polymerization in combination has a problem that the manufacturing process is complicated, the productivity is low, and the cost is high.
【０００５】またこのハイドロキノン成分を導入したポ
リマーは前述の特開昭５２―７８９９９号によれば熱変
形温度が１６５〜１７０℃であり、前述の酸成分として
テレフタル酸とイソフタル酸を用いジオール成分として
ビスフェノールＡを用いたポリマーが１７２℃に比較し
てやや耐熱性に劣るという問題点がある。According to the above-mentioned JP-A-52-78999, the polymer into which the hydroquinone component is introduced has a heat distortion temperature of 165 to 170 ° C., and terephthalic acid and isophthalic acid are used as the above-mentioned acid component, and as a diol component. There is a problem that the polymer using bisphenol A is slightly inferior in heat resistance as compared with 172 ° C.
【０００６】[0006]
【発明の目的】そこで、本発明者らは、耐熱性、耐溶剤
性、耐ストレスクラック性に優れた非晶性芳香族ポリエ
ステルを固相重合を併用することなく溶融重合法によ
り、工業的に安価に製造する方法を提供しようとするも
のである。SUMMARY OF THE INVENTION Therefore, the present inventors have found that an amorphous aromatic polyester excellent in heat resistance, solvent resistance and stress crack resistance can be industrially produced by a melt polymerization method without using solid phase polymerization in combination. It is intended to provide a method of manufacturing at low cost.
【０００７】[0007]
【発明の構成】すなわち、本発明は、（Ａ）イソフタル
酸及び／またはそのエステル形成性誘導体、（Ｂ）ハイ
ドロキノン及び／またはそのエステル形成性誘導体及び
（Ｃ）下記式（Ｉ）That is, the present invention provides (A) isophthalic acid and / or its ester-forming derivative, (B) hydroquinone and / or its ester-forming derivative, and (C) the following formula (I).
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】で表される化合物及び／またはそのエステ
ル形成性誘導体を、成分（Ｂ）と成分（Ｃ）のモル比
（Ｂ／Ｃ）が５０／５０〜８０／２０、成分（Ｂ）と成
分（Ｃ）の合計量が成分（Ａ）に対して９５〜１２０モ
ル％範囲とし、これらを触媒の存在下重合温度３００〜
４００℃で加熱溶融重縮合せしめ、固有粘度（フェノー
ル／テトラクロルエタン混合溶媒（重量比６０／４０）
中、３５℃）０．３〜１．０のポリマーを得ることを特
徴とする非晶性全芳香族ポリエステルの製造方法であ
る。The compound represented by the following formula and / or its ester-forming derivative have a molar ratio (B / C) of component (B) to component (C) of 50/50 to 80/20, and component (B) and component The total amount of (C) is in the range of 95 to 120 mol% with respect to the component (A), and these are added in the presence of a catalyst at a polymerization temperature of 300 to
Intrinsic viscosity (phenol / tetrachloroethane mixed solvent (weight ratio 60/40))
Medium, 35 ° C.) 0.3-1.0 polymer is obtained.
【００１０】本発明はイソフタル酸及び／またはそのエ
ステル形成性誘導体を成分（Ａ）とする。ここでエステ
ル形成性誘導体としては、アルキルエステル、アリール
エステル、酸クロライドを例示できる。成分（Ａ）とし
てはイソフタル酸ジアリールエステルが好ましく、イソ
フタル酸ジフェニルが特に好ましい。The present invention comprises isophthalic acid and / or its ester-forming derivative as component (A). Examples of the ester-forming derivative include alkyl ester, aryl ester, and acid chloride. As the component (A), isophthalic acid diaryl ester is preferable, and diphenyl isophthalate is particularly preferable.
【００１１】次に本発明ではハイドロキノン及び／また
はそのエステル形成性誘導体を成分（Ｂ）とする。ここ
でエステル形成性誘導体としては、低級脂肪族カルボン
酸エステルが挙げられ、特に酢酸エステルを好ましく例
示できる。ここで成分（Ｂ）としてはハイドロキノンが
好ましい。Next, in the present invention, hydroquinone and / or its ester-forming derivative is used as the component (B). Examples of the ester-forming derivative include lower aliphatic carboxylic acid ester, and acetic acid ester is particularly preferable. Here, hydroquinone is preferable as the component (B).
【００１２】次に本発明では下記式（Ｉ）Next, in the present invention, the following formula (I)
【００１３】[0013]
【化３】 [Chemical 3]
【００１４】で表される化合物及び／またはそのエステ
ル形成性誘導体を成分（Ｃ）とする。ここで、Ｘは置換
基を有してもよいメチレン基を表すが、具体的にはメチ
レン基、メチルメチレン基、ハロゲン化メチレン基等を
例示することができ、このちうメチレン基が好ましい。
ｎは置換基を有してもよいメチレン鎖の長さを表すが、
４または５を示す。このうちｎ＝５が好ましい。エステ
ル形成性誘導体としては低級脂肪族カルボン酸エステル
が挙げられ、特に酢酸エステルを好ましく例示できる。
成分（Ｃ）としては、１，１―ビス（４―ヒドロキシフ
ェニル）シクロヘキサン（以下ビスフェノールＺとい
う）が好ましい。The compound represented by and / or its ester-forming derivative is used as the component (C). Here, X represents a methylene group which may have a substituent, and specific examples thereof include a methylene group, a methylmethylene group and a halogenated methylene group, and a methylene group is preferable.
n represents the length of a methylene chain which may have a substituent,
4 or 5 is shown. Of these, n = 5 is preferable. Examples of the ester-forming derivative include lower aliphatic carboxylic acid esters, and acetic acid ester is particularly preferable.
As the component (C), 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as bisphenol Z) is preferable.
【００１５】成分（Ｂ）と成分（Ｃ）の使用割合はモル
比（Ｂ／Ｃ）で５０／５０〜８０／２０とする。成分
（Ｂ）のモル分率が５０％より小さいと本発明の目的と
する耐溶剤性、耐ストレスクラック性が今だ不十分とな
り、また８０モル％より大きいと得られるポリマーが結
晶性となる傾向となり、透明性が不十分となる。成分
（Ｂ）と成分（Ｃ）のモル比（Ｂ／Ｃ）は好ましくは５
５／４５〜７５／２５、特に好ましくは６０／４０〜７
０／３０である。本発明の芳香族ポリエステルの製造方
法においては、成分（Ａ）に対し、成分（Ｂ）と成分
（Ｃ）の合計量が９５〜１２０モル％の範囲とし、これ
を加熱重縮合せしめる。成分（Ｂ）と成分（Ｃ）の合計
量は９７〜１１５モル％の範囲が好ましく、９９〜１１
０モル％の範囲とすることが特に好ましい。The molar ratio (B / C) of the component (B) and the component (C) is 50/50 to 80/20. When the mole fraction of the component (B) is less than 50%, the solvent resistance and stress crack resistance targeted by the present invention are still insufficient, and when it is more than 80 mol%, the obtained polymer becomes crystalline. And the transparency becomes insufficient. The molar ratio (B / C) of component (B) and component (C) is preferably 5
5/45 to 75/25, particularly preferably 60/40 to 7
It is 0/30. In the method for producing an aromatic polyester of the present invention, the total amount of the component (B) and the component (C) is in the range of 95 to 120 mol% with respect to the component (A), and this is subjected to polycondensation by heating. The total amount of the component (B) and the component (C) is preferably 97 to 115 mol%, and 99 to 11
The range of 0 mol% is particularly preferable.
【００１６】本発明では上述の各成分を触媒の存在下に
加熱溶融重縮合せしめる。ここで用いる触媒としてはポ
リエステルの製造時に用いられる従来公知のものが使用
できるが、例えば、三酸化アンチモン等のアンチモン化
合物、酢酸第１錫等の錫化合物、チタンテトラブトキシ
ド等のチタン化合物、酸化ゲルマニウム等のゲルマニウ
ム化合物等を挙げることができる。また該触媒の使用量
は特に制限はないが、上記成分（Ａ）に対して０．１モ
ル％以下程度の量とすることが好ましい。In the present invention, the above-mentioned components are heated and melt-polycondensed in the presence of a catalyst. As the catalyst used here, conventionally known ones used in the production of polyester can be used. Examples thereof include antimony compounds such as antimony trioxide, tin compounds such as stannous acetate, titanium compounds such as titanium tetrabutoxide, and germanium oxide. And other germanium compounds. The amount of the catalyst used is not particularly limited, but is preferably about 0.1 mol% or less with respect to the above component (A).
【００１７】加熱重縮合する際の重合温度は３００〜４
００℃とすることが必要である。ここで重合温度とは重
合後期あるいはその終了時における温度を意味する。重
合温度が３００℃より低いとポリマーの溶融粘度が高く
なり、またポリマーの結晶化がおこるため、高重合度で
かつ透明なポリマーを得ることはできない。また４００
℃より高いとポリマーの劣化等が生じ易く好ましくな
い。The polymerization temperature during the heat polycondensation is 300 to 4
It is necessary to set the temperature to 00 ° C. Here, the polymerization temperature means the temperature at the latter stage of polymerization or at the end thereof. If the polymerization temperature is lower than 300 ° C., the melt viscosity of the polymer becomes high, and the polymer is crystallized, so that it is not possible to obtain a transparent polymer having a high degree of polymerization. Again 400
If the temperature is higher than ° C, the polymer is likely to deteriorate, which is not preferable.
【００１８】本発明の製造方法では重合反応の初期は比
較的低温とし、これを徐々に昇温して最終的に上記重合
温度とすることが好ましい。この際の初期重合反応の反
応温度は、好ましくは１５０〜２８０℃、より好ましく
は１８０〜２５０℃である。この重合反応は常圧下、ま
たは減圧下で実施されるが、初期重合反応時は常圧下と
し、徐々に減圧とすることが好ましい。また常圧時に
は、窒素、アルゴン等の不活性ガス雰囲気下とすること
が好ましい。重縮合反応時間は特に制限はないが大略１
〜１０時間程度である。In the production method of the present invention, it is preferable that the initial temperature of the polymerization reaction is relatively low, and the temperature is gradually raised to the above-mentioned polymerization temperature finally. The reaction temperature of the initial polymerization reaction at this time is preferably 150 to 280 ° C, more preferably 180 to 250 ° C. This polymerization reaction is carried out under normal pressure or under reduced pressure, but it is preferable that the initial polymerization reaction is carried out under normal pressure and gradually reduced. At atmospheric pressure, it is preferable to use an atmosphere of an inert gas such as nitrogen or argon. The polycondensation reaction time is not particularly limited, but is approximately 1
It is about 10 hours.
【００１９】上述の製造方法により得られる本発明の芳
香族ポリエステルはフェノール／テトラクロルエタン混
合溶媒（重量比６０／４０）中、３５℃にて測定した固
有粘度が、０．３〜１．０となることが必要である。固
有粘度が０．３より低いと得られるポリマーの耐熱性、
靭性が不十分であり、１．０より高いと溶融成形時の流
動性が低下するため好ましくない。固有粘度としては、
０．４〜０．８が好ましい。The aromatic polyester of the present invention obtained by the above-mentioned production method has an intrinsic viscosity of 0.3 to 1.0 measured at 35 ° C. in a phenol / tetrachloroethane mixed solvent (weight ratio 60/40). It is necessary to be Heat resistance of the polymer obtained when the intrinsic viscosity is lower than 0.3,
The toughness is insufficient, and if it is higher than 1.0, the fluidity at the time of melt molding decreases, which is not preferable. The intrinsic viscosity is
0.4 to 0.8 is preferable.
【００２０】本発明の好ましい態様としては、成分
（Ａ）としてイソフタル酸ジフェニル、成分（Ｂ）とし
てハイドロキノン、成分（Ｃ）としてビスフェノールＺ
を用い、これを加熱溶融し、温度を徐々に上げ、また反
応系を常圧から徐々に減圧として、生成するフェノール
を徐々に系外へ留出させて重縮合を進める方法が挙げら
れる。更に本発明により得られる芳香族ポリエステルは
比較的溶融粘度が高いため、高重合度とするためにエク
ストルーダー型の反応装置で重合することも好ましく実
施できる。In a preferred embodiment of the present invention, diphenyl isophthalate is used as the component (A), hydroquinone is used as the component (B), and bisphenol Z is used as the component (C).
A method of advancing polycondensation by gradually melting the temperature of the reaction system from normal pressure to gradually reducing it by gradually heating the reaction system to a reduced pressure is used. Furthermore, since the aromatic polyester obtained by the present invention has a relatively high melt viscosity, it can be preferably polymerized in an extruder type reaction apparatus in order to obtain a high degree of polymerization.
【００２１】上述の製造法により得られる本発明の芳香
族ポリエステルは、非晶性ポリマーであり、これを例え
ば射出成形等の溶融成形法により透明な成形品を得るこ
とができる。また本発明のポリマーが非晶性であること
は例えばＤＳＣによりその融点が観測されないことなど
から確認することができる。The aromatic polyester of the present invention obtained by the above-mentioned production method is an amorphous polymer, and a transparent molded article can be obtained by a melt molding method such as injection molding. Further, the fact that the polymer of the present invention is amorphous can be confirmed, for example, by its melting point not being observed by DSC.
【００２２】本発明の芳香族ポリエステルはその製造
時、必要に応じて酸化安定剤、着色防止剤などの各種安
定剤、着色剤、顔料、滑剤等の各種添加剤を添加しても
差し支えない。During the production of the aromatic polyester of the present invention, various stabilizers such as oxidation stabilizers and anti-coloring agents, and various additives such as colorants, pigments and lubricants may be added if necessary.
【００２３】[0023]
【発明の効果】本発明の製造方法によれば、耐熱性、靭
性、耐要溶剤性、及び耐ストレスクラック性の良好な非
晶性全芳香族ポリエステルが、安価な溶融重合プロセス
により製造することができる。According to the production method of the present invention, an amorphous wholly aromatic polyester having good heat resistance, toughness, solvent resistance, and stress crack resistance can be produced by an inexpensive melt polymerization process. You can
【００２４】[0024]
【実施例】以下実施例を挙げて本発明を詳述するが、実
施例中「部」は「重量部」を意味する。固有粘度は、フ
ェノール／テトラクロルエタン混合溶媒（重量比６０／
４０）中、濃度１．２ｇ／ｄｌ、温度３５℃にて測定し
た。ポリマーの熱特性は荷重たわみ温度測定機を用い２
℃／分の昇温速度にて測定した。EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, “parts” means “parts by weight”. The intrinsic viscosity is phenol / tetrachloroethane mixed solvent (weight ratio 60 /
40), the concentration was 1.2 g / dl, and the temperature was 35 ° C. For the thermal properties of polymers, use a deflection temperature measuring device under load.
It was measured at a temperature rising rate of ° C / min.
【００２５】[0025]
【実施例１〜３及び比較例１】イソフタル酸ジフェニル
３１８部、ハイドロキノン及びビスフェノールＺの所定
量、三酸化アンチモン０．０９部（触媒）及びリン酸ト
リフェニル０．３３部（安定剤）を撹拌装置及び窒素導
入口を備えた真空留出系を有する反応容器に入れ、常圧
下窒素気流中２４０℃で３０分間反応後、１．５時間か
けて３４０℃まで昇温した。次いで同温度にて徐々に減
圧とし、３０分後に約１ｍｍＨｇとした。Examples 1 to 3 and Comparative Example 1 318 parts of diphenyl isophthalate, a predetermined amount of hydroquinone and bisphenol Z, 0.09 part of antimony trioxide (catalyst) and 0.33 part of triphenyl phosphate (stabilizer) were stirred. The reactor was placed in a reaction vessel having a vacuum distillation system equipped with an apparatus and a nitrogen inlet, reacted at 240 ° C. for 30 minutes in a nitrogen stream under normal pressure, and then heated to 340 ° C. over 1.5 hours. Next, the pressure was gradually reduced at the same temperature, and after 30 minutes, the pressure was adjusted to about 1 mmHg.
【００２６】この間フェノールが発生留去した。同条件
下にて約９０分間重合を行ないポリマーを得た。得られ
たポリマーは淡茶色透明であった。During this period, phenol was generated and distilled off. Polymerization was performed for about 90 minutes under the same conditions to obtain a polymer. The obtained polymer was light brown and transparent.
【００２７】次にこのポリマーを射出成形機（日本製
鋼、Ｎ４０Ａ型）を用いてシリンダー温度３４０℃、金
型温度１００℃、成形サイクル約８０秒の条件下で射出
成形した。得られた成形品の物性を表１に示す。Next, this polymer was injection molded using an injection molding machine (Nippon Steel Co., N40A type) under the conditions of a cylinder temperature of 340 ° C., a mold temperature of 100 ° C. and a molding cycle of about 80 seconds. Table 1 shows the physical properties of the obtained molded product.
【００２８】表１には比較として非晶性芳香族ポリエス
テル樹脂（ユニチカ（株）製、ＵポリマーＵ―１００）
についても併記したが、本発明の芳香族ポリエステル
は、耐熱性が良好で、かつ耐溶剤性が極めて優れている
ことがわかる。In Table 1, for comparison, an amorphous aromatic polyester resin (U Polymer U-100 manufactured by Unitika Ltd.)
As described above, it is understood that the aromatic polyester of the present invention has good heat resistance and extremely excellent solvent resistance.
【００２９】[0029]
【表１】 [Table 1]
Claims (1)
ステル形成性誘導体、（Ｂ）ハイドロキノン及び／また
はそのエステル形成性誘導体及び（Ｃ）下記式（Ｉ） 【化１】 で表される化合物及び／またはそのエステル形成性誘導
体を、成分（Ｂ）と成分（Ｃ）のモル比（Ｂ／Ｃ）が５
０／５０〜８０／２０、成分（Ｂ）と成分（Ｃ）の合計
量が成分（Ａ）に対して９５〜１２０モル％の範囲と
し、これらを触媒の存在下重合温度３００〜４００℃で
加熱溶融重縮合せしめ、固有粘度（フェノール／テトラ
クロルエタン混合溶媒（重量比６０／４０）中、３５
℃）０．３〜１．０のポリマーを得ることを特徴とする
非晶性全芳香族ポリエステルの製造方法。1. (A) isophthalic acid and / or its ester-forming derivative, (B) hydroquinone and / or its ester-forming derivative, and (C) the following formula (I): The compound represented by and / or its ester-forming derivative has a molar ratio (B / C) of component (B) and component (C) of 5
0/50 to 80/20, the total amount of the component (B) and the component (C) is set to 95 to 120 mol% with respect to the component (A), and these are added in the presence of a catalyst at a polymerization temperature of 300 to 400 ° C. Heat melt polycondensation, intrinsic viscosity (phenol / tetrachloroethane mixed solvent (weight ratio 60/40), 35
C.) 0.3 to 1.0 polymer is obtained, and a method for producing an amorphous wholly aromatic polyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16286092A JP3164889B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing aromatic polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16286092A JP3164889B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing aromatic polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH061835A true JPH061835A (en) | 1994-01-11 |
| JP3164889B2 JP3164889B2 (en) | 2001-05-14 |
Family
ID=15762632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16286092A Expired - Fee Related JP3164889B2 (en) | 1992-06-22 | 1992-06-22 | Method for producing aromatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3164889B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112007002599T5 (en) | 2006-11-07 | 2010-01-14 | Ntn Corp. | Wheel bearing device for a vehicle |
| DE112008000830T5 (en) | 2007-04-04 | 2010-02-18 | Ntn Corporation | Wheel bearing and wheel bearing device with the wheel bearing |
| JP2021191866A (en) * | 2016-07-28 | 2021-12-16 | Jsr株式会社 | Composition, cured product, and laminate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3067584B1 (en) * | 2017-06-14 | 2019-08-09 | Seb S.A. | BOTTLE WITH BRAKE ELEMENT AND HOLDING OF THE COVER |
-
1992
- 1992-06-22 JP JP16286092A patent/JP3164889B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112007002599T5 (en) | 2006-11-07 | 2010-01-14 | Ntn Corp. | Wheel bearing device for a vehicle |
| US8047722B2 (en) | 2006-11-07 | 2011-11-01 | Ntn Corporation | Wheel bearing apparatus for a vehicle |
| DE112008000830T5 (en) | 2007-04-04 | 2010-02-18 | Ntn Corporation | Wheel bearing and wheel bearing device with the wheel bearing |
| US9200669B2 (en) | 2007-04-04 | 2015-12-01 | Ntn Corporation | Wheel bearing and a wheel bearing apparatus having the wheel bearing |
| JP2021191866A (en) * | 2016-07-28 | 2021-12-16 | Jsr株式会社 | Composition, cured product, and laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3164889B2 (en) | 2001-05-14 |
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