JPH0353322B2 - - Google Patents
Info
- Publication number
- JPH0353322B2 JPH0353322B2 JP57221998A JP22199882A JPH0353322B2 JP H0353322 B2 JPH0353322 B2 JP H0353322B2 JP 57221998 A JP57221998 A JP 57221998A JP 22199882 A JP22199882 A JP 22199882A JP H0353322 B2 JPH0353322 B2 JP H0353322B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyester
- branching agent
- added
- reaction
- 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 - Lifetime
Links
- 229920000728 polyester Polymers 0.000 claims description 15
- 239000006085 branching agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- -1 polybutylene terephthalate Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 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 2
- 230000000052 comparative effect Effects 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
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
本発明はポリエステル、特にポリブチレンテレ
フタレート型ポリエステルの製造方法に関する。
その目的とするところは、重縮合速度の向上にあ
る。
従来よりテトラメチレングリコール使用のポリ
エステルは、現在汎用のポリエチレンテレフタレ
ートと異なり、テトラメチレングリコールが分解
してテトラヒドロフランになり易く、これをいか
に抑えるかが製造上の大きな問題となつていた。
このため、反応触媒としても比較的低温で活性を
有するチタン化合物や錫化合物が一般的に用いら
れている。
しかし、反応中留去すべきグリコールの沸点は
高いにも拘らず、低温重合するために、分解は抑
えられても、反応速度は遅く、生産性が低いとい
う欠点があつた。
従来より、テトラメチレングリコールを主たる
グリコール成分とするポリエステルの見掛け上の
反応速度を向上させるために、分岐剤を添加する
方法は公知である。例えば特公昭55−29095号公
報、56−38604号公報、57−44691号公報、特開昭
50−160344号公報等にその例が記載されている
が、これはいずれもポリオキシアルキレングリコ
ールを多量に含んだ系で、軟質ポリマーに関する
ものである。
他方、ポリブチレンテレフタレートのような硬
質のポリマーにペンタエリスリトールなどの分岐
剤を添加した場合、予想に反して反応速度向上効
果は全くないばかりか、逆に遅くなるという驚く
べき結果が得られた。これはポリエチレンテレフ
タレートの場合からも全く予期しえなかつたこと
である。
そこで本発明者らは、反応速度を向上させる分
岐剤について鋭意検討した結果、ブテレンテレフ
タレートを主たる繰り返し単位とするポリエステ
ルの製造においては、特定化合物のみが反応速度
向上の効果を有することを見い出し、本発明に到
達した。
即ち本発明は、ブチレンテレフタレートを主た
る繰り返し単位とするポリエステルを製造するに
際し、該ポリエステルの重縮合反応初期以前の任
意の段階で、トリメリツト酸、トリメシン酸、ピ
ロメリツト酸、トリカルバリ酸及びこれらのエス
テル形成誘導体から選ばれる少なくとも１種の分
岐剤を、下記(A)式を満足する割合で添加すること
を特徴とするポリエステルの製造方法である。
0.001≦α≦1.1／（ｆ−２）2/3 …(A)
［但し、α、ｆは夫々分岐剤の添加量（全酸成分
に対するモル％）及び官能基数を示す。］
本発明の対象とするポリエステルは、ブチレン
テレフタレートを主たる繰り返し単位とするもの
である。ここに「主たる」とは、実質的には他の
繰り返し単位を含有しないものである。
かかるポリブチレンテレフタレート系ポリエス
テルを製造する際には、通常、触媒、例えばテト
ラブチルチタネート、テトライソプロピルチタネ
ート、シユウ酸チタン、シユウ酸チタンカリウム
等、あるいはこれらの加水分解物、エステル交換
物等のチタン化合物：ジブチル錫オキサイド、酸
化モノブチル錫、トリ−ｎ−ブチル錫（２−エチ
ルヘキソエート）等の錫化合物等の重縮合触媒
（エステル交換触媒もかねる）が用いられる。
本発明では、分枝剤として、芳香族化合物また
は脂肪族化合物であるトリメリツト酸、トリメシ
ン酸、ピロメリツト酸、トリカルバリ酸及びこれ
らの誘導体（酸無水物、低級アルキルエステル
等）を少なくとも１種用いることが肝要である。
多官能化合物であつても、トリメチロールプロパ
ン、グリセリン、ペンタエリスリトール等の如き
多価ヒドロキシ化合物では効果が少ない。これは
ポリエチレンテレフタレートや、ポリテトラメチ
レングリコールをブロツク共重合したポリブチレ
ンテレフタレートの場合からは全く予想できない
ことである。
分岐剤の添加量は、少なすぎると効果は少な
く、逆に多すぎるとゲル化が起こるため、官能基
数をｆとすると、全酸成分に対する添加量αmol
％は下記範囲とする必要がある。
0.001≦α≦1.1／（ｆ−２）3/2
また、該分岐剤の添加時期は、ポリエステルの
重合反応初期以前が望ましい。中期以降では反応
速度が向上してもそれによつて得られる効果は少
なくなるからである。また、分岐剤が低級アルキ
ルエステル誘導体の場合は、エステル化、エステ
ル交換反応前期に添加することが好ましい。酸又
は無水物の場合でも、重合反応前期以前が好まし
く、エステル化反応、エステル交換反応後期以前
が更に好ましい。
尚、本発明においては、通常のポリエステルを
製造する場合と同様に、本発明の目的を損なわな
い範囲で、リン等の熱安定剤、ヒンダードフエノ
ール等の抗酸化剤、ベンゾトリアゾール、ヒドロ
キシベンゾフエノン、シアノアクリレート等の紫
外線吸収剤、酸化チタン、カーボンブラツク、テ
ラゾールブルー等の顔料、染料、タルク等の核
剤、高級脂肪酸塩等の結晶促進剤、離型剤等々が
添加されていても何らさしつかえない。
以下、実施例によつて本発明を具体的に説明す
る。実施例中「部」は重量部を示す、ポリマーの
固有粘度はオルソクロロフエノール溶液の35℃に
おける溶液粘度から算出したものである。
実施例１〜10、比較例１〜４
ジメチルテレフタレート97.1部、テトラメチレ
ングリコール67.6部、テトラブチルチタネート
0.0715部を仕込み、分岐剤（多価カルボン酸及
び／又はその誘導体）を所定量、所定時間に添加
し、内温170℃でエステル交換反応（EI）を実施
した。所定量のメタノールが留去した後、内温を
245℃に上げ、系を減圧にして30mmHgで30分保持
し、次いで0.5mmHgの高真空にして重合した。重
合高真空反応時間及びポリマー固有粘度は第１表
に示す通りであつた。
The present invention relates to a method for producing polyester, particularly polybutylene terephthalate type polyester.
The aim is to improve the polycondensation rate. Conventionally, polyesters using tetramethylene glycol, unlike the currently widely used polyethylene terephthalate, tend to decompose tetramethylene glycol into tetrahydrofuran, and how to suppress this has been a major problem in production.
For this reason, titanium compounds and tin compounds, which are active at relatively low temperatures, are generally used as reaction catalysts. However, although the glycol to be distilled off during the reaction has a high boiling point, it polymerizes at a low temperature, so even if decomposition is suppressed, the reaction rate is slow and productivity is low. Conventionally, a method of adding a branching agent to improve the apparent reaction rate of polyester containing tetramethylene glycol as the main glycol component has been known. For example, Japanese Patent Publication No. 55-29095, Publication No. 56-38604, Publication No. 57-44691,
Examples are described in Japanese Patent No. 50-160344, etc., but all of these are systems containing a large amount of polyoxyalkylene glycol and are related to soft polymers. On the other hand, when a branching agent such as pentaerythritol was added to a hard polymer such as polybutylene terephthalate, the surprising result was obtained that, contrary to expectations, there was no effect of improving the reaction rate at all, and on the contrary, the reaction rate became slower. This was completely unexpected even in the case of polyethylene terephthalate. As a result of intensive research into branching agents that improve the reaction rate, the present inventors discovered that only specific compounds have the effect of improving the reaction rate in the production of polyesters containing buterene terephthalate as the main repeating unit. We have arrived at the present invention. That is, in the present invention, when producing a polyester having butylene terephthalate as a main repeating unit, trimellitic acid, trimesic acid, pyromellitic acid, tricarbaric acid, and their ester-forming derivatives are added at any stage before the initial stage of the polycondensation reaction of the polyester. This is a method for producing polyester, characterized in that at least one branching agent selected from the following is added in a proportion that satisfies the following formula (A). 0.001≦α≦1.1/(f-2) 2/3 ...(A) [However, α and f respectively indicate the amount of branching agent added (mol% relative to the total acid component) and the number of functional groups. ] The polyester targeted by the present invention has butylene terephthalate as a main repeating unit. Here, "main" means one that does not substantially contain other repeating units. When producing such polybutylene terephthalate polyesters, catalysts such as tetrabutyl titanate, tetraisopropyl titanate, titanium oxalate, potassium titanium oxalate, etc., or titanium compounds such as hydrolysates and transesterified products thereof are usually used. : Polycondensation catalysts (also serve as transesterification catalysts) such as tin compounds such as dibutyltin oxide, monobutyltin oxide, and tri-n-butyltin (2-ethylhexoate) are used. In the present invention, at least one aromatic compound or aliphatic compound such as trimellitic acid, trimesic acid, pyromellitic acid, tricarbalic acid, and derivatives thereof (acid anhydride, lower alkyl ester, etc.) may be used as the branching agent. It is essential.
Even if they are polyfunctional compounds, polyhydric hydroxy compounds such as trimethylolpropane, glycerin, pentaerythritol, etc. have little effect. This is completely unexpected from the case of polyethylene terephthalate or polybutylene terephthalate obtained by block copolymerizing polytetramethylene glycol. If the amount of branching agent added is too small, the effect will be small, and if it is too large, gelation will occur. Therefore, if the number of functional groups is f, the amount added to the total acid component is αmol.
The percentage must be within the following range. 0.001≦α≦1.1/(f-2) 3/2 The branching agent is preferably added before the beginning of the polyester polymerization reaction. This is because after the middle stage, even if the reaction rate improves, the effect obtained thereby becomes smaller. Further, when the branching agent is a lower alkyl ester derivative, it is preferably added in the first half of the esterification and transesterification reactions. Even in the case of an acid or anhydride, it is preferably used before the first half of the polymerization reaction, and more preferably before the last half of the esterification reaction or transesterification reaction. In addition, in the present invention, heat stabilizers such as phosphorus, antioxidants such as hindered phenols, benzotriazole, hydroxybenzophenol, etc. are used as long as the purpose of the present invention is not impaired, as in the case of manufacturing ordinary polyester. Even if UV absorbers such as cyanoacrylates, pigments such as titanium oxide, carbon black, and terrasol blue, nucleating agents such as dyes, talc, crystal accelerators such as higher fatty acid salts, mold release agents, etc. are added. There is nothing wrong with that. Hereinafter, the present invention will be specifically explained with reference to Examples. In the examples, "parts" indicate parts by weight. The intrinsic viscosity of the polymer was calculated from the solution viscosity of the orthochlorophenol solution at 35°C. Examples 1 to 10, Comparative Examples 1 to 4 97.1 parts of dimethyl terephthalate, 67.6 parts of tetramethylene glycol, tetrabutyl titanate
A branching agent (polyhydric carboxylic acid and/or its derivative) was added in a predetermined amount at a predetermined time, and transesterification reaction (EI) was carried out at an internal temperature of 170°C. After a predetermined amount of methanol has been distilled off, the internal temperature is
The temperature was raised to 245°C, the system was evacuated and held at 30 mmHg for 30 minutes, and then high vacuum was applied to 0.5 mmHg for polymerization. The polymerization high vacuum reaction time and polymer intrinsic viscosity were as shown in Table 1.
【表】
第１表からも明らかなように、本発明で規定す
る三官能以上の多価カルボン酸又はその誘導体か
らなる分岐剤を添加した場合は重合速度が向上す
る。これに対して、三官能以上の化合物であつて
も多価ヒドロキシ化合物の場合は、重合速度向上
効果が認められない（比較例２〜４）。[Table] As is clear from Table 1, when a branching agent consisting of a trifunctional or higher-functional polycarboxylic acid or a derivative thereof as defined in the present invention is added, the polymerization rate is improved. On the other hand, in the case of a polyhydric hydroxy compound even if it is a trifunctional or higher functional compound, no effect on improving the polymerization rate is observed (Comparative Examples 2 to 4).
Claims (1)
位とするポリエステルを製造するに際し、該ポリ
エステルの重縮合反応初期以前の任意の段階で、
トリメリツト酸、トリメシン酸、ピロメリツト
酸、トリカルバリ酸及びこれらのエステル形成性
誘導体から選ばれる少なくとも１種の分岐剤を、
下記(A)式を満足する割合で添加することを特徴と
するポリエステルの製造方法。 0.001≦α≦1.1／（ｆ−２）2/3 …(A) ［但し、α、ｆは夫々分岐剤の添加量（全酸成分
に対するモル％）及び官能基数を示す。］[Claims] 1. When producing a polyester containing butylene terephthalate as a main repeating unit, at any stage before the initial stage of the polycondensation reaction of the polyester,
At least one branching agent selected from trimellitic acid, trimesic acid, pyromellitic acid, tricarbalic acid and ester-forming derivatives thereof,
A method for producing polyester, characterized in that it is added in a proportion that satisfies the following formula (A). 0.001≦α≦1.1/(f-2) 2/3 ...(A) [However, α and f respectively indicate the amount of branching agent added (mol% relative to the total acid component) and the number of functional groups. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22199882A JPS59113026A (en) | 1982-12-20 | 1982-12-20 | Production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22199882A JPS59113026A (en) | 1982-12-20 | 1982-12-20 | Production of polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59113026A JPS59113026A (en) | 1984-06-29 |
| JPH0353322B2 true JPH0353322B2 (en) | 1991-08-14 |
Family
ID=16775484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22199882A Granted JPS59113026A (en) | 1982-12-20 | 1982-12-20 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59113026A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPM316193A0 (en) * | 1993-12-24 | 1994-01-27 | Bhp Steel (Jla) Pty Limited | Thermosetting polyester resin |
| JP6854121B2 (en) * | 2016-12-28 | 2021-04-07 | 東洋鋼鈑株式会社 | Polybutylene terephthalate resin for film or laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832435A (en) * | 1971-08-31 | 1973-04-28 | ||
| JPS4837974A (en) * | 1971-09-20 | 1973-06-04 |
-
1982
- 1982-12-20 JP JP22199882A patent/JPS59113026A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832435A (en) * | 1971-08-31 | 1973-04-28 | ||
| JPS4837974A (en) * | 1971-09-20 | 1973-06-04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59113026A (en) | 1984-06-29 |
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