JPH04117421A - polyester copolymer - Google Patents
polyester copolymerInfo
- Publication number
- JPH04117421A JPH04117421A JP1302357A JP30235789A JPH04117421A JP H04117421 A JPH04117421 A JP H04117421A JP 1302357 A JP1302357 A JP 1302357A JP 30235789 A JP30235789 A JP 30235789A JP H04117421 A JPH04117421 A JP H04117421A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- component
- glycol
- polyester copolymer
- terephthalic acid
- 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
- 229920000728 polyester Polymers 0.000 title claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 22
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 6
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 2
- 229920001634 Copolyester Polymers 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- -1 butyl ethyl diol Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- VFRRWVCMOFUSPN-UHFFFAOYSA-N 4-methylhexane-3,3-diol Chemical compound CCC(C)C(O)(O)CC VFRRWVCMOFUSPN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001123 polycyclohexylenedimethylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は優れた耐熱性を有する成形品を作ることができ
、かつ結晶化速度が遅いポリエステル共重合体に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyester copolymer that can be used to form molded articles having excellent heat resistance and that has a slow crystallization rate.
［従来の技術及び発明が解決しようとする課題］テレフ
タル酸と１．４−シクロヘキサンジメタノールから得ら
れるポリシクロヘキシレンジメチレンテレフタレートは
融点が高く、そのために該び耐加水分解性を有するポリ
エステルである。[Prior art and problems to be solved by the invention] Polycyclohexylene dimethylene terephthalate obtained from terephthalic acid and 1,4-cyclohexanedimethanol has a high melting point and is therefore a polyester with hydrolysis resistance. .
該ポリエステルはこの特性を利用して、フィルムやボト
ルとして利用することが試みられているが、結晶化しや
すいため、成形条件範囲が狭くなるという問題を有して
いる。Attempts have been made to take advantage of this property and use the polyester to make films and bottles, but since it tends to crystallize, it has the problem of narrowing the range of molding conditions.
［課題を解決するための手段］
本発明者らはかかる現状に鑑み、鋭意研究を重ねた結果
、特定量比の特定量以上のトランス体を含む１．４−シ
クロヘキサンジメタノールと特定の脂肪族ジオールから
なるジオールとテレフタル酸またはその誘導体から得ら
れるポリエステル共重合体が、優れた耐熱性を有し、か
つ結晶化速度の遅いことを見出し、本発明に到達した。[Means for Solving the Problems] In view of the current situation, the present inventors have conducted intensive research and found that 1,4-cyclohexanedimethanol containing a trans isomer in a specific amount or more and a specific aliphatic The present invention was achieved based on the discovery that a polyester copolymer obtained from a diol and terephthalic acid or a derivative thereof has excellent heat resistance and a slow crystallization rate.
すなわち、本発明はテレフタル酸またはその誘導体を主
とするジカルボン酸成分（Ａ）と炭素数２〜１６の脂肪
族ジオール（Ｂ−１）、１５〜８５モル％と８０モル％
以上がトランス体である１、４−シクロへ牛サンジメタ
ツール（Ｂ−２）８５〜１５モル％とからなるグリコー
ル成分（Ｂ）を反応して得られるポリエステル共重合体
である。That is, the present invention uses a dicarboxylic acid component (A) mainly consisting of terephthalic acid or a derivative thereof, and an aliphatic diol having 2 to 16 carbon atoms (B-1), 15 to 85 mol% and 80 mol%.
The above is a polyester copolymer obtained by reacting a glycol component (B) consisting of 85 to 15 mol% of 1,4-cyclohexane dimetatool (B-2), which is a trans form.
本発明で使用するジカルボン酸又はその誘導体（Ａ）は
少なくとも９０モル％がテレフタル酸又はその誘導体か
ら構成されていることが好ましい。It is preferred that at least 90 mol% of the dicarboxylic acid or its derivative (A) used in the present invention is composed of terephthalic acid or its derivative.
テレフタル酸誘導体としてはテレフタル酸のジアルキル
エステル、シアツールエステル等が挙ケられる。ジカル
ボン酸成分として１０モル％以下の範囲で用いることが
できるテレフタル酸またはその誘導体と併用し得る他の
ジカルボン酸としては、フタル酸、イソフタル酸、アジ
ピン酸、セバシン酸、ナフタレン−１，４−もしくは−
２，６−ジカルボン酸等が挙げられる。Examples of terephthalic acid derivatives include dialkyl esters and siatool esters of terephthalic acid. Other dicarboxylic acids that can be used in combination with terephthalic acid or its derivatives, which can be used in an amount of 10 mol% or less as a dicarboxylic acid component, include phthalic acid, isophthalic acid, adipic acid, sebacic acid, naphthalene-1,4- or −
Examples include 2,6-dicarboxylic acid.
本発明で使用するグリコールは炭素数２〜１６の脂肪族
ジオール（Ｂ−１）１５〜８５モル％と、８０モル％以
上がトランス体である１、４−７クロヘキサンジメタノ
ール（Ｂ−２）１１５〜１５モル％とからなるものであ
る。The glycol used in the present invention contains 15 to 85 mol% of an aliphatic diol (B-1) having 2 to 16 carbon atoms, and 1,4-7 chlorohexanedimethanol (B-2) of which 80 mol% or more is trans isomer. ) 115 to 15 mol%.
炭素数２〜１６の脂肪族ジオール（Ｂ−１）としては、
エチレングリコール、プロピレングリコール、テトラメ
チレングリコール、ヘキサメチレングリコール、ネオペ
ンチルグリコール、オクタメチレングリコール、ブチル
エチルフロア ＸＨンジオール、ジエチルプロパンジオ
ール、３．９−ビス（１１−ジメチル−２ヒドロキンエ
チル）−２，４８、１０−テトラオキサスピロ［５，５
］ ウンデカン等が挙げられるが、エチレングリコール
、フロピレンゲリコール、テトラメチレングリコール、
ヘキサメチレングリコールが特に好ましい。脂肪族ジオ
ールとして炭素数が１６を超えた脂肪族ジオールを用い
て得られるポリエステル共重合体は該共重合体から得ら
れる成形品が充分な耐熱性を有していないので好ましく
ない。As the aliphatic diol (B-1) having 2 to 16 carbon atoms,
Ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, octamethylene glycol, butyl ethyl diol, diethylpropanediol, 3.9-bis(11-dimethyl-2hydroquinethyl)-2, 48,10-tetraoxaspiro[5,5
] Undecane etc. are mentioned, but ethylene glycol, furopylene gelicol, tetramethylene glycol,
Particularly preferred is hexamethylene glycol. Polyester copolymers obtained using aliphatic diols having more than 16 carbon atoms are not preferred because molded articles obtained from the copolymers do not have sufficient heat resistance.
本発明で使用する炭素数２〜１６の脂肪族ジオール（Ｂ
−１）はグリコール成分（Ｂ）中１５〜８５モル％の範
囲とするのが好ましく、さらには３０〜７０モル％の範
囲とするのが好ましい。 （Ｂ−１）成分が（Ｂ）成分
中１５モル％未満であるポリエステル共重合体は結晶化
速度が大きいために好ましくない。また、 （Ｂ−１＞
成分が（Ｂ）成分中８５モル％を超えたポリエステル共
重合体は結晶化速度が大きくなったり、ガラス転移温度
が低くなりすぎるために好ましくない。C2-16 aliphatic diol (B
-1) is preferably in the range of 15 to 85 mol%, more preferably 30 to 70 mol% in the glycol component (B). A polyester copolymer in which component (B-1) accounts for less than 15 mol% of component (B) is not preferred because of its high crystallization rate. Also, (B-1>
A polyester copolymer containing more than 85 mol% of the component (B) is not preferable because the crystallization rate becomes high or the glass transition temperature becomes too low.
本発明で使用する１、４−７クロヘ牛サンジメタツール
のトランス体の量は８０モル％以上であることが好まし
く、トランス体の量が８０モル％未満の１．４−／クロ
へ牛サンジメタツールを用いて作られるポリエステル共
重合体からの成形品は充分な耐熱性を有していない。The amount of trans isomer in the 1,4-7 Kurohebyusanjimetatool used in the present invention is preferably 80 mol% or more; Molded articles made from polyester copolymers using MetaTool do not have sufficient heat resistance.
本発明のポリエステル共重合体はテレフタル酸またはテ
レフタル酸ジメチルと、エチレングリコール及ヒ１，４
−シクロヘキサンジメタノールとを主たる出発原料とし
て、エステル化反応、エステル交換反応を行ない、引き
続き重縮合反応を行なうことによって得られる。The polyester copolymer of the present invention contains terephthalic acid or dimethyl terephthalate, ethylene glycol and
- It is obtained by carrying out an esterification reaction and a transesterification reaction using cyclohexanedimethanol as the main starting material, followed by a polycondensation reaction.
このエステル化、又はエステル交換反応および重縮合反
応には通常のポリエステルに用いられる触媒を使用する
ことができる。For this esterification, transesterification reaction, and polycondensation reaction, catalysts commonly used for polyesters can be used.
なお、本発明のポリエステル共重合体には難燃剤、繊維
状強化材、充填剤、酸化安定剤、熱安定剤、着色剤、紫
外線吸収剤などを必要に応じて添加してもよい。Incidentally, flame retardants, fibrous reinforcing materials, fillers, oxidation stabilizers, heat stabilizers, colorants, ultraviolet absorbers, etc. may be added to the polyester copolymer of the present invention, if necessary.
以下実施例を挙げて本発明を具体的に説明する。The present invention will be specifically explained below with reference to Examples.
実施例１〜９および比較例１〜４
テレフタル酸を酸成分とし、第１表に示す成分比の１．
４−シクロヘキサンジメタノールとエチレングリコール
、１４−ブタンジオールおよび１６−ヘキサンジオール
をグリフール成分として、エステル化触媒としてテトラ
ブチルチタネートを仕上りポリマーの重量に対して０．
１％を添加して、２６０℃でエステル化反応を行なっ
た後、重縮合触媒として三酸化アンチモンと亜燐酸を仕
上りポリマーの重量に対してそれぞれ０．０３％と０．
０４％添加して、減圧下２８５℃〜３２０°Ｃで重縮合
を行ない、種々のポリエステル共重合体を製造した。得
られたポリエステル共重合体はストランド状にポリマー
を取り出し、水冷してカッターでペレット状にした。Examples 1 to 9 and Comparative Examples 1 to 4 Terephthalic acid was used as the acid component, and the component ratios shown in Table 1 were 1.
4-cyclohexanedimethanol, ethylene glycol, 14-butanediol, and 16-hexanediol are used as glyfur components, and tetrabutyl titanate is used as an esterification catalyst to give 0.0% by weight based on the weight of the polymer.
After adding 1% and carrying out the esterification reaction at 260°C, antimony trioxide and phosphorous acid were added as polycondensation catalysts to give 0.03% and 0.03%, respectively, based on the weight of the polymer.
04% was added and polycondensation was carried out at 285°C to 320°C under reduced pressure to produce various polyester copolymers. The obtained polyester copolymer was taken out in the form of a strand, cooled with water, and made into pellets using a cutter.
得られたポリエステル共重合体はヒドラジン水溶液で分
解し、ガスクロでグリコール成分の分析を行った。結果
を第１表に示す。The obtained polyester copolymer was decomposed with an aqueous hydrazine solution, and the glycol component was analyzed by gas chromatography. The results are shown in Table 1.
得られたポリエステル共重合体をフェノール／テトラク
ロルエタン（１： １重量比）に溶解してＱ、５ｇ／ｄ
ｌの濃度てηｓｐ／ ｃを測定した。結果を第１表に示
す。The obtained polyester copolymer was dissolved in phenol/tetrachloroethane (1:1 weight ratio) to give Q, 5 g/d.
ηsp/c was measured at the concentration of l. The results are shown in Table 1.
得られたペレットを用い、１オンスの小型射出成形機に
てシリンダー温度３１０〜３２０℃、金型温度７０℃に
て厚さ６．４ｍｍＸ長さ１２７ｍｍ×幅１２．６ｍｍの
成形品を得た。Using the obtained pellets, a molded product having a thickness of 6.4 mm, a length of 127 mm, and a width of 12.6 mm was obtained using a 1-ounce small injection molding machine at a cylinder temperature of 310 to 320°C and a mold temperature of 70°C.
これらはいずれも透明な試片てあった。これをシートあ
るいはボトルなどの成形加工温度範囲にあたる１４０°
Ｃにて１５分間加熱し、結晶化による白化の程度をみた
。結果を第１表に示す。All of these specimens were transparent specimens. This is 140°, which is the temperature range for forming sheets or bottles.
C for 15 minutes, and the degree of whitening due to crystallization was observed. The results are shown in Table 1.
く白化の程度〉
Ａ；透明（変化なし）
Ｂ：若干白くヘーズがかかる
Ｃ：すりガラス状の透明性
Ｄ： 白く濁り不透明
［発明の効果］
本発明によって得られるポリエステル共重合体は小さい
結晶化速度を有し、かつ該共重合体から得られる成形品
は優れた耐熱性を有するために、ポリエステル樹脂の利
用分野を拡大するものである。Degree of whitening> A: Transparent (no change) B: Slightly white with haze C: Frosted glass-like transparency D: White, cloudy and opaque [Effects of the invention] The polyester copolymer obtained by the present invention has a low crystallization rate and molded articles obtained from the copolymer have excellent heat resistance, expanding the field of use of polyester resins.
Claims (1)
成分（Ａ）と炭素数２〜１６の脂肪族ジオール（Ｂ−１
）１５〜８５モル％と８０モル％以上がトランス体であ
る１，４−シクロヘキサンジメタノール（Ｂ−２）８５
〜１５モル％とからなるグリコール成分（Ｂ）を反応し
て得られるポリエステル共重合体。A dicarboxylic acid component (A) mainly consisting of terephthalic acid or its derivative and an aliphatic diol having 2 to 16 carbon atoms (B-1
) 15 to 85 mol% and 1,4-cyclohexanedimethanol (B-2) 85 in which 80 mol% or more is trans isomer
A polyester copolymer obtained by reacting a glycol component (B) consisting of ~15 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1302357A JPH04117421A (en) | 1988-12-28 | 1989-11-21 | polyester copolymer |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-334862 | 1988-08-28 | ||
| JP63-334861 | 1988-08-28 | ||
| JP33486188 | 1988-12-28 | ||
| JP1302357A JPH04117421A (en) | 1988-12-28 | 1989-11-21 | polyester copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04117421A true JPH04117421A (en) | 1992-04-17 |
Family
ID=26563079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1302357A Pending JPH04117421A (en) | 1988-12-28 | 1989-11-21 | polyester copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04117421A (en) |
-
1989
- 1989-11-21 JP JP1302357A patent/JPH04117421A/en active Pending
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