JPS63265951A - Aromatic polyester resin composition - Google Patents
Aromatic polyester resin compositionInfo
- Publication number
- JPS63265951A JPS63265951A JP10058087A JP10058087A JPS63265951A JP S63265951 A JPS63265951 A JP S63265951A JP 10058087 A JP10058087 A JP 10058087A JP 10058087 A JP10058087 A JP 10058087A JP S63265951 A JPS63265951 A JP S63265951A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- aromatic polyester
- resin composition
- present
- group
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title abstract description 14
- 229920001225 polyester resin Polymers 0.000 title description 9
- 239000004645 polyester resin Substances 0.000 title description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 40
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- -1 amine compound Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 125000001118 alkylidene group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- 239000000126 substance Substances 0.000 claims 2
- 238000000465 moulding Methods 0.000 abstract description 7
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000011342 resin composition Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000006076 specific stabilizer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013306 transparent fiber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は成形加工時の安定性に優れた耐熱性の芳香族ポ
リエステル樹脂組成物番こ関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-resistant aromatic polyester resin composition having excellent stability during molding.
〈従来の技術〉
芳香族ポリエステル、特に主鎖の主要部分が芳香族化合
物に由来する構造からなる芳香族ポリエステルは耐熱性
に優れ、電気・電子部品、自動車用部品や一般工業部品
１ζ広く用いられている。<Prior art> Aromatic polyester, especially aromatic polyester whose main chain is derived from an aromatic compound, has excellent heat resistance and is widely used in electrical and electronic parts, automobile parts, and general industrial parts. ing.
〈発明が解決しようとする問題点〉
しかしながら、かかる芳香族ポリエステルは耐熱性を持
つがゆえに高い成形加工温度を必要とし、成形加工時に
酸化・分解・重合・架橋といった反応が起こるため、成
形加工性や成形品の品質上の問題点を有することが多く
認められている。例えば、芳香族ポリエステルを溶融成
形する時に認められる溶融粘度の低下もしくは上昇、成
形品の熱安定性の低下、着色、機械的強度の低下、成形
品中の空孔の発生などの問題点である。<Problems to be solved by the invention> However, because such aromatic polyesters have heat resistance, they require high molding temperatures, and reactions such as oxidation, decomposition, polymerization, and crosslinking occur during molding, resulting in poor moldability. It is recognized that there are many problems with the quality of molded products. For example, problems such as a decrease or increase in melt viscosity that is observed when melt molding aromatic polyester, a decrease in thermal stability of molded products, discoloration, a decrease in mechanical strength, and the occurrence of pores in molded products. .
過去において極めて数多くの芳香族ポリエステルが報告
されてはいるが、かかる問題点の解決について取組まれ
た検討は非常化少なく、安定な成形加工性を有し、且つ
、良好な品質の成形品を得るという観点からの実用的な
解決について報告されていなかった。Although a large number of aromatic polyesters have been reported in the past, very few studies have been carried out to solve these problems, and it is difficult to obtain molded products with stable moldability and good quality. No practical solutions have been reported from this perspective.
本発明の目的は、成形加工時に前述した好ましくない反
応を起こさず、つまり安定な成形加工性を有し、且つ、
良好な品質の成形品を与える耐熱性の芳香族ポリエステ
ル樹脂組成物を提供することにある。The object of the present invention is to not cause the above-mentioned unfavorable reactions during molding, that is, to have stable moldability, and
The object of the present invention is to provide a heat-resistant aromatic polyester resin composition that gives molded products of good quality.
〈問題点を解決するための手段〉
本発明者らは主鎖の主要部分が芳香族化合物に由来する
構造からなる耐熱性芳香族ポリエステルの成形加工性と
成形品の物性について研究を続けてきた。その結果、特
定の安定剤を特定量用いることにより該芳香族ポリエス
テルの成形加工性と成形品の物性が顕著に改良されるこ
とを知見し、本発明を完成させるに至った。<Means for solving the problem> The present inventors have continued research on the moldability and physical properties of molded products of heat-resistant aromatic polyester, which has a structure in which the main part of the main chain is derived from an aromatic compound. . As a result, it was discovered that the moldability of the aromatic polyester and the physical properties of molded articles were significantly improved by using a specific amount of a specific stabilizer, and the present invention was completed.
すなわち、本発明は、一般式千Ｇｏ−Ａｒ−ＣＯ±、＋
Ｏ−λｒ’−０）及び＋、Ｃ０−Ａ“ｒ −０９−（式
中、Ａｒ、 Ａｒ及びＭは２価の芳香族基を表わす。）
で表わされる構造単位からなる群から選ばれた１種また
は２種以上の構造単位を主たる繰返し構造単位として含
む芳香族ポリエステル１００重量部と下記一般式（Ｉ）
及び／又は（ＩＩ）で表わされる安定剤０．０３〜３重
量部とからなる芳香族ポリエステル樹脂組成物である。That is, the present invention provides general formula 1,000 Go-Ar-CO±, +
O-λr'-0) and +, C0-A"r-09- (wherein Ar, Ar and M represent a divalent aromatic group.)
100 parts by weight of an aromatic polyester containing as a main repeating structural unit one or more structural units selected from the group consisting of structural units represented by the following general formula (I)
and/or 0.03 to 3 parts by weight of a stabilizer represented by (II).
本発明における芳香族ポリエステルは芳香族ジカルボン
酸、芳香族ジフェノール及び芳香族ヒドロキシカルボン
酸からなる群から選ばれた化合物を主たる単量体として
重縮合反応によって得られる芳香族ポリエステルであり
、これららの化合物の組合せに対応して８つのタイプの
芳香族ポリエステルが得られる。すなわち、芳香族ヒド
ロキシカルボン酸及び／又はそのエステル形成性誘導体
を重縮合反応させてなる芳香族ポリエステル、芳香族ジ
カルボン酸及び／又はそのエステル形成性誘導体と芳香
族ジフェノール及び／又はそのエステル形成性誘導体と
を重縮合反応させてなる芳香族ポリエステル、ならびに
芳香族ジカルボン酸及び／又はそのエステル形成性誘導
体、芳香族ジフェノール及び／又はそのエステル形成性
誘導体および芳香族ヒドロキシカルボン酸及び／又はそ
のエステル形成性誘導体を重縮合反応させてなる芳香族
ポリエステルの８つのタイプである。これらのタイプの
芳香族ポリエステルの繰返し構造単位は、上述した組合
せの順に−ｆＣＯ−Ａｒ−０士を含むポリ：Ｌ スｆ
／Ｌ／、（Ｃｏ−Ａｒ−Ｃｏ＋と−Ｉｌ：０−Ａｒ−０
ヂとを含むポリエステル、並びにイＣ０−Ａｒ−Ｃ０−
１−、イ〇−λｒ−〇＋及び（ＣＯ−Ａ″ｒ−ＣＯ〕−
、−〔Ｏ−Ａ′ｒ−Ｏ〕−を含むポリエステルである。The aromatic polyester in the present invention is an aromatic polyester obtained by polycondensation reaction using as a main monomer a compound selected from the group consisting of aromatic dicarboxylic acid, aromatic diphenol, and aromatic hydroxycarboxylic acid. Eight types of aromatic polyesters are obtained corresponding to the combination of compounds. That is, an aromatic polyester obtained by polycondensation reaction of an aromatic hydroxycarboxylic acid and/or an ester-forming derivative thereof, an aromatic dicarboxylic acid and/or an ester-forming derivative thereof, and an aromatic diphenol and/or an ester-forming derivative thereof. Aromatic polyester obtained by polycondensation reaction with derivatives, aromatic dicarboxylic acids and/or ester-forming derivatives thereof, aromatic diphenols and/or ester-forming derivatives thereof, and aromatic hydroxycarboxylic acids and/or esters thereof. These are eight types of aromatic polyesters produced by polycondensation reaction of forming derivatives. The repeating structural units of these types of aromatic polyesters are poly:L-sf containing -fCO-Ar-0 in the order of the above-mentioned combinations.
/L/, (Co-Ar-Co+ and -Il:0-Ar-0
Polyester containing 。 and 。C0-Ar-C0-
1−, i〇−λr−〇+ and (CO−A″r−CO〕−
, -[O-A'r-O]-.
ルエタン基（７＠）−ＣＨ，ＣＨ，べ’Ｄ）、ジフェニ
ルプロ核置換体等を挙げることができる。好ましい芳で
ある。Examples thereof include ethane group (7@)-CH, CH, be'D), diphenyl pro-nuclear substituted product, and the like. It has a favorable aroma.
本発明における芳香族ポリエステルの繰返し構造単位の
好ましい含有割合は、本発明の芳香族ポリエステル樹脂
組成物の成形加工性、品質等の点から＋Ｃｏ−Ｎ’ｒ
−０：）−／壬０−Ａｒ−ＣＯ〕−、−〔Ｏ−Ａ′ｒ−
Ｏ〕−なる比（モル）が０．５〜４．０である。なお、
＋Ｃｏ−Ａｒ−Ｃｏ−）／−１−０−Ａ：ｒ−０４なる
比（モル）は本質的に１である。The preferred content ratio of the repeating structural units of the aromatic polyester in the present invention is +Co-N'r from the viewpoint of moldability, quality, etc. of the aromatic polyester resin composition of the present invention.
-0:)-/壬0-Ar-CO]-,-[O-A'r-
O]- ratio (mol) is 0.5 to 4.0. In addition,
The ratio (mole) of +Co-Ar-Co-)/-1-0-A:r-04 is essentially 1.
本発明で用いる芳香族ポリエステルは既知の塊状重縮合
法、溶液重縮合法、懸濁重縮合法等によって製造するこ
とができ、２０〜４００℃、好ましくは１５０〜８６０
℃の反応温度で常圧下または０．１〜１０ｔｏｒｒの減
圧下に重縮合させる。必要に応じてＳｂ、 Ｔｉ５Ｇｅ
等の化合物を重縮合反応の触媒として用いることができ
、また、種々の安定剤や酸化チタン、炭酸カルシウム、
タルク等を添加して重縮合反応を行うこともできる。反
応混合物に後処理を施すことなくそのままで、又は、該
反応混合物に分離、洗浄、乾燥、熱処理等の後処理を施
すことによって、本発明に用いる芳香族ポリエステルが
得られる。The aromatic polyester used in the present invention can be produced by the known bulk polycondensation method, solution polycondensation method, suspension polycondensation method, etc.
Polycondensation is carried out at a reaction temperature of .degree. C. under normal pressure or under reduced pressure of 0.1 to 10 torr. Sb, Ti5Ge as necessary
Compounds such as compounds can be used as catalysts for polycondensation reactions, and various stabilizers, titanium oxide, calcium carbonate,
The polycondensation reaction can also be carried out by adding talc or the like. The aromatic polyester used in the present invention can be obtained as it is without post-processing the reaction mixture, or by subjecting the reaction mixture to post-processing such as separation, washing, drying, heat treatment, etc.
本発明における芳香族ポリエステルの好ましいフロ一温
度（後述）は、本発明の樹脂組成物の成形加工性と耐熱
性とのバランスの点から２００へ４００℃であり、更に
好ましくは８００〜８８０℃である。The preferred flow temperature (described later) of the aromatic polyester in the present invention is 200 to 400°C, more preferably 800 to 880°C, from the viewpoint of the balance between moldability and heat resistance of the resin composition of the present invention. be.
前記一般式（Ｉ）で表わされる化合物のＲ１としては−
ＣＨ２−１−ＣＨＩＣＨ２−並びに−ＣｓＨａ−１ＱＨ
ａ−及び−ＣＩＩＨＩＯ−の直鎖状および分枝状のもの
を挙げることができ、また、Ｒ２としてはメチル基、エ
チル基等のアルキル基やフェニル基等のアリール基を挙
げることができる。これらの化合物は、例えば、対応す
る８、５−ジーｔｅｒｔ−ブチルー４−ヒドロキシフェ
ニルアルキルリチウム塩とハロゲン化リン化合物とを反
応させた後、場合によりエステル化し、次いでＮｉやＣ
ａの水酸化物と反応させることによって得られる。代表
的な化合物として、チバガイギー（Ｃｉｂａ−Ｇｅｉｇ
ｙ）社製のＩｒｇａＳｔａｂ■２００２である８、５−
ジーｔｅｒｔ−ブチルー４−ヒドロキシベンジルリン酸
モノエチルエステルのニッケル塩
１４２５である８、５−ジーｔｅｒｔ−ブチルー４−ヒ
ドロキシベンジルリン酸モノエチルニス８．５−ジーｔ
ａｒｔ−ブチルー４−ヒドロキシベンジルリン酸七ノー
ｎ−ブチルエステルのカルシウム塩、８．６−シーｔｅ
ｒｔ−ブチル−４−ヒドロキシフェニルエチルリン酸モ
ノエチルエステルのカルシウム塩等を例示することがで
きる。R1 of the compound represented by the general formula (I) is -
CH2-1-CHICH2- and -CsHa-1QH
Examples include linear and branched a- and -CIIHIO-, and examples of R2 include alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl. These compounds are produced by, for example, reacting the corresponding 8,5-di-tert-butyl-4-hydroxyphenylalkyl lithium salt with a halogenated phosphorus compound, optionally esterifying it, and then reacting it with Ni or C.
It is obtained by reacting with the hydroxide of a. Ciba-Geigy (Ciba-Geigy) is a representative compound.
y) IrgaStab■2002 manufactured by 8,5-
8,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethyl varnish which is the nickel salt of di-tert-butyl-4-hydroxybenzyl phosphate monoethyl ester 1425 8,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethyl ester
Calcium salt of art-butyl-4-hydroxybenzyl phosphate heptan-n-butyl ester, 8.6-sheet
Examples include calcium salt of rt-butyl-4-hydroxyphenylethyl phosphate monoethyl ester.
前記一般式（３）で表わされる化合物の鳥および島はｑ
・八−からＣｔ ｏＨａ １−までの第８級アルキル基
であり、Ｘは第１〜８級アミンのいずれでもよい。これ
らの化合物は、例えば、対応するｐ−ｔｅｒｔ−アルキ
ルフェノールとＳＣ４ｍとを反応させた後、次に塩化ニ
ッケルと反応させ、更に、アミン化合物との錯体とする
ことによって得られる。代表的な化合物として２．２゛
−チオ−ビス（４−ｔｅｒｔ−オクチルフェルレート）
のニッケル塩のアミン錯体（下式）
等を例示することができ、Ｘがｎ−ブチルアミンである
アメリカンシアナミドカンパニー（Ａｍｅｒｉｃａｎ
Ｃｙａｎａｍｉｄ Ｃｏｍｐａｎｙ）社製のＣｙａｓｏ
ｒｂ＠ ＵＶ−１０３４、トリエタノールアミンである
同社製（７） Ｃｙａｓｏｒｂ＠ＵＶ−２４０３、ジェ
タノールアミンである同社製のＣｙａｑｏｒｂ＠ ＵＶ
−２４０９、２−エチルヘキシルアミンであるシブロ化
成株製の３ｅｅｓｏｒｂ■６１２ＮＨ等を挙げることが
できる。Bird and island of the compound represented by the general formula (3) are q
- It is an 8th-class alkyl group from 8- to CtoHa 1-, and X may be any of primary to 8th-class amines. These compounds can be obtained, for example, by reacting the corresponding p-tert-alkylphenol with SC4m, then reacting it with nickel chloride, and then forming a complex with an amine compound. A representative compound is 2.2゛-thio-bis(4-tert-octylferulate).
The amine complex (formula below) of the nickel salt of
Cyanamid Company)
rb@UV-1034, manufactured by the same company, which is triethanolamine (7) Cyasorb@UV-2403, Cyaqorb@UV, manufactured by the same company, which is jetanolamine
-2409, 3eesorb 612NH manufactured by Shibro Kasei Co., Ltd., which is 2-ethylhexylamine, and the like.
本発明で安定剤として用いられる前記一般式（Ｉ）およ
び（９）で表わされる化合物は、本発明の樹脂組成物が
製造、成形加工、使用等の時に受ける温度条件下におい
て、本発明の目的効果を達成する程度の耐熱性を持って
いなければならない。The compounds represented by the general formulas (I) and (9) used as stabilizers in the present invention can be It must have sufficient heat resistance to achieve the desired effect.
本発明の樹脂組成物における芳香族ポリエステルと安定
剤との配合割合は、芳香族ポリエステル１００賞量部に
対して安定剤０．０３〜Ｂｆｆｉ量部、好ましくは０．
０６〜１重量部、より好ましくは０．０６〜０．８ＭＩ
ｋ部である。安定剤の配合割合が０．０３重量部未満の
場合は効果が認められず、また、３重量部を越える場合
は発泡や分解を伴い、成形加工性や成形品の物性に悪影
響を与える。なお、樹脂組成物中の安定剤は、該樹脂組
成物を灰化したあとＰまたはＮｉについて比色分析を行
うことによって定量できる。The blending ratio of the aromatic polyester and the stabilizer in the resin composition of the present invention is 0.03 to Bffi parts, preferably 0.03 to Bffi parts of the stabilizer to 100 parts of the aromatic polyester.
06 to 1 part by weight, more preferably 0.06 to 0.8 MI
This is part k. When the blending ratio of the stabilizer is less than 0.03 parts by weight, no effect is observed, and when it exceeds 3 parts by weight, foaming and decomposition occur, which adversely affects the moldability and physical properties of the molded product. Note that the stabilizer in the resin composition can be quantified by performing colorimetric analysis on P or Ni after incinerating the resin composition.
本発明の組成物は例えば次の方法で製造することができ
る。すなわち、芳香族ポリエステルの重縮合反応系もし
くは該反応後処理系へ安定剤を添加する方法、または、
得られた芳香族ポリエステルの粉末、顆粒、ベレットも
しくは溶液に対して室温もしくは加熱下で、安定剤を単
独もしくは溶液状で添加する方法である。更化また、溶
融加工可能な芳香族ポリエステルの場合は、押出機やニ
ーダ−中で安定剤と溶融混合することもできる。The composition of the present invention can be produced, for example, by the following method. That is, a method of adding a stabilizer to the polycondensation reaction system of aromatic polyester or the post-reaction treatment system, or
This is a method in which a stabilizer is added alone or in the form of a solution to the obtained aromatic polyester powder, granules, pellets, or solution at room temperature or under heating. Further, in the case of melt-processable aromatic polyesters, they can be melt-mixed with stabilizers in an extruder or kneader.
本発明の樹脂組成物には、本発明の安定剤の他に酸化防
止剤、光安定化（光吸収）剤等の安定剤を本発明の目的
を損わない範囲で添加することができる。また、石英、
酸化鉄、酸化チタン、炭酸カルシウム、マイカ、チタン
酸カリウム、ガラス繊維、炭素繊維、グラファイト、カ
ーボンブラック、ウオラストナイト、ケイ酸カルシウム
等の充填材を添加することもできる。In addition to the stabilizer of the present invention, stabilizers such as antioxidants and light stabilizing (light absorbing) agents may be added to the resin composition of the present invention within a range that does not impair the object of the present invention. Also, quartz,
Fillers such as iron oxide, titanium oxide, calcium carbonate, mica, potassium titanate, glass fiber, carbon fiber, graphite, carbon black, wollastonite, calcium silicate, etc. can also be added.
〈発明の効果〉
本発明によれば、主鎖の主要部分が芳香族化合物に由来
する構造からなる耐熱性芳香族ポリエステルに特定の安
定剤の特定量を添加することによって、成形加工時に好
ましくない反応を起こさず、つまり安定な成形加工性を
有し、且つ良好な品質の成形品を与える耐熱性の芳香族
ポリエステル樹脂組成物を得ることができる。<Effects of the Invention> According to the present invention, by adding a specific amount of a specific stabilizer to a heat-resistant aromatic polyester having a structure in which the main part of the main chain is derived from an aromatic compound, it is possible to eliminate undesirable properties during molding. It is possible to obtain a heat-resistant aromatic polyester resin composition that does not cause any reaction, that is, has stable moldability and provides molded products of good quality.
後述する比較例で示すように、安定剤の量が本発明で特
定された範囲内の量でないとき、得られた樹脂組成物の
成形加工性や物性は好ましくない。これに対して、本発
明の実施例では安定な成形加工性を有し、且つ、良好な
品質の成形品を与える耐熱性の樹脂組成物が得られてい
る。As shown in the comparative examples described later, when the amount of the stabilizer is not within the range specified in the present invention, the moldability and physical properties of the resulting resin composition are unfavorable. On the other hand, in the examples of the present invention, heat-resistant resin compositions that have stable moldability and give molded products of good quality are obtained.
本発明の芳香族ポリエステル樹脂組成物のうち、溶融成
形加工することのできるものは成形品、繊維、フィルム
、被覆材等に用いることができ、溶融成形加工すること
のできないものは充填材等に用いることができる。Among the aromatic polyester resin compositions of the present invention, those that can be melt-molded can be used for molded products, fibers, films, coating materials, etc., and those that cannot be melt-molded can be used as fillers, etc. Can be used.
〈実施例〉
以下、本発明の実施例を示すが、本発明はこれに限定さ
れるものでない。なお、実施例中の物性は次のようにし
て測定した。<Examples> Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition, the physical properties in Examples were measured as follows.
フロ一温度：本発明の芳香族ポリエステルは、溶解し得
る溶媒が無かったり分子量測定値の精度上の問題がある
ので、分子量の目安としてフロ一温度を採用した。これ
は芳香族ポリエステル樹脂またはその樹脂組成物の溶融
流動性を表わし、その温度が低いものほど溶融流動性が
より大きく、従って分子量がより小さい。フロ一温度は
株島津製作所製のフローテスター■ＣＦＴ−５００で測
定され、４℃／ ｒｎ １ ｎの昇温速度で加熱溶励さ
れたサンプル樹脂等を１００ ！／−の荷重のもと内径
１日、長さ１０調のノズルから押出した時、該溶融樹脂
等の粘匣が４８，０００ポイズを示す点における温度と
して表わされる。Flow temperature: Since the aromatic polyester of the present invention has no solvent in which it can be dissolved and there are problems with the accuracy of molecular weight measurements, the flow temperature was used as a guideline for molecular weight. This represents the melt fluidity of the aromatic polyester resin or its resin composition, and the lower the temperature, the greater the melt fluidity, and therefore the smaller the molecular weight. The flow temperature was measured using a flow tester ■CFT-500 manufactured by Shimadzu Corporation, and sample resin etc. heated and excited at a heating rate of 4℃/rn1n was measured at 100℃. It is expressed as the temperature at the point where the viscous box of the molten resin or the like exhibits 48,000 poise when extruded from a nozzle with an inner diameter of 1 day and a length of 10 under a load of /-.
加熱減量：芳香族ポリエステルおよびその樹脂組成物を
８２メツシユのふるいを通過するように（すなわち０．
５−以下）粉砕して粉砕品を得、精秤されたそれぞれの
粉砕品的１０ｆを一定の温度に保たれた炉内に２４時間
装いたときの重量減少量をもとの重量に対する割合（ｍ
で表わしたものである。Heat Loss: Aromatic polyesters and their resin compositions are passed through an 82 mesh sieve (i.e. 0.
5- or less) Grind to obtain a pulverized product, and calculate the amount of weight loss when placing 10 f of each precisely weighed pulverized product in a furnace kept at a constant temperature for 24 hours, as a percentage of the original weight ( m
It is expressed as
色調：前述の加熱減量を測定した後の試料のうち８２メ
ツシユと６５メツシエのふるいの間に存在する（すなわ
ち０．２〜０．５■）粒子の色調を、日本電色工業株製
のデジタル測色色差計ＮＤ−１０１ＤＰを用いて測定し
た。Ｌの値は明度を表わし、１００は純白、Ｏは純黒に
対応する。Color tone: The color tone of the particles (i.e. 0.2 to 0.5 square meters) present between the sieves of 82 mesh and 65 mesh after measuring the heat loss described above was measured using a digital camera manufactured by Nippon Denshoku Kogyo Co., Ltd. Measurement was performed using a colorimeter ND-101DP. The value of L represents lightness, with 100 corresponding to pure white and O corresponding to pure black.
参考例１
ｐ−アセトキシ安息香酸７．２０ｋ（４０，０モル）、
テレフタル酸８．８２１ｋ （１，０モル）及び４．イ
ージアセトキシジフェニル５．４５４（２０，２モル）
を（し型攪拌翼をもつ重合槽に仕込み、窒素ガス雰囲気
下で攪拌しながら８８０℃まで昇温し、副生する酢酸を
除去しながら強力な攪拌のもと８８０℃で８時間重縮合
させた。その後、徐々に冷却し、２００℃になったとき
に反応生成物である重合体を系外へ取出した。重合体の
収量は１０．８８ｆｔで理論収量に対して９７．８％で
あった。この重合体をハンマーミルで粉砕して１．５−
以下の粒子とした後、ロータリーキルンを用いて窒素〃
ス雰囲気下に８２０℃で５時間処理し、芳香族ポリエス
テルを得た。この芳香族ポリエステルのフロ一温度は８
６２℃であった。Reference example 1 p-acetoxybenzoic acid 7.20k (40.0 mol),
8.821k (1.0 mol) of terephthalic acid and 4. Ediacetoxydiphenyl 5.454 (20.2 mol)
was charged into a polymerization tank with a rectangular stirring blade, heated to 880°C while stirring in a nitrogen gas atmosphere, and polycondensed at 880°C for 8 hours with strong stirring while removing by-product acetic acid. Thereafter, it was gradually cooled, and when the temperature reached 200°C, the reaction product, the polymer, was taken out of the system.The yield of the polymer was 10.88 ft, which was 97.8% of the theoretical yield. This polymer was ground with a hammer mill to give 1.5-
After forming the following particles, nitrogen was added using a rotary kiln.
The mixture was treated at 820° C. for 5 hours in a gas atmosphere to obtain an aromatic polyester. The flow temperature of this aromatic polyester is 8
The temperature was 62°C.
実施例１〜４、比較例１〜２
参考例１で得られた粉末状の芳香族ポリエステル１００
７；１８部に対して、８．５−ジーｔｅｒｔ−ブチルー
４−ヒドロキシベンジルリン酸モノエチルエステルのニ
ッケル塩１”８点１９５ｃ。Examples 1-4, Comparative Examples 1-2 Powdered aromatic polyester 100 obtained in Reference Example 1
7; nickel salt of 8.5-di-tert-butyl-4-hydroxybenzyl phosphoric acid monoethyl ester 1"8 points 195c per 18 parts.
チバガイギー（Ｃｉｂａ−Ｇｅｉｇｙ）社製０） Ｉｒ
ｇａｓｔａｂ■２００２）の０（比較例１）、０．０５
（実施例１）、０．１（実施例２）、０．８（実施例８
）、１．０（実施例４）および５．０（比較例２）重量
部をそれぞれ加えてトライブレンドし、２２０℃で８０
分間混合した後、シリンダ一温度を８６０℃に設定した
８０■径の押出機により滞留時間７〜１２分で溶融押出
しを行った。押出された樹脂組成物をハンマーミルによ
って０．５■以下に粉砕し、得られた粉砕品について加
熱減量と色調を測定した。結果を第１表にまとめた。Ciba-Geigy 0) Ir
gastab■2002) 0 (Comparative Example 1), 0.05
(Example 1), 0.1 (Example 2), 0.8 (Example 8)
), 1.0 (Example 4) and 5.0 (Comparative Example 2) were triblended, and the mixture was heated to 80% at 220°C.
After mixing for a minute, melt extrusion was carried out using an 80 mm diameter extruder with a cylinder temperature set at 860 DEG C. for a residence time of 7 to 12 minutes. The extruded resin composition was pulverized to 0.5 square centimeters or less using a hammer mill, and the heat loss and color tone of the resulting pulverized product were measured. The results are summarized in Table 1.
実施例６〜８、比較例８
参考例１で得られた芳香族ポリエステルに対して、８．
５−ジーｔｅｒｔ−ブチルー４−ヒドロキシベンジルリ
ン酸モノエチルエステルのカルシウム塩〔融点ＳＯＳ℃
、チバガイギー（Ｃｉ ｂａ−Ｇｅ ｉｇ）ｒ）社製の
Ｉｒｇａｎｏ嫂１４２５ ）を安定剤として用い、前述
の実施例および比較例と同様に行った。結果を第２表に
まとめた。Examples 6 to 8, Comparative Example 8 Compared to the aromatic polyester obtained in Reference Example 1, 8.
Calcium salt of 5-di-tert-butyl-4-hydroxybenzyl phosphate monoethyl ester [melting point SOS°C
, Irgano 1425 (manufactured by Ciba-Geigy) was used as a stabilizer, and the same procedure as in the above-mentioned Examples and Comparative Examples was carried out. The results are summarized in Table 2.
参考例２
ｐ−７セトキシ安息香酸１．０３ Ｋｐ （ＩＩ，０モ
ル）と２−７セトキシー６−ナフトエ酸０．９２Ｋｐ（
４，０モル）を攪拌翼付きの重合槽に仕込み、窒素ガス
雰囲気下で攪拌しながら２８０℃まで昇温し、副生する
酢酸を除去しながらこの温度で１時間重縮合させた。更
に、８２０℃まで昇温しこの温度で１時間重縮合させた
後、系をｇ ｔｏｒｒの減圧にして８２０℃で８０分間
重縮合させた。溶であった。また、この重合体組成物中
の安定剤の量は約０．１８ ＰＨＲであった。粉砕され
た粒子状の重合体組成物を、ロータリーキルンを用いて
減圧下８８０℃で８時間処理し、芳香族ポリエステル樹
脂組成物を得た。この樹脂組成物は５００℃以下では溶
融しなかった。結果を第４表に示した。Reference example 2 p-7 setoxybenzoic acid 1.03 Kp (II, 0 mol) and 2-7 setoxy6-naphthoic acid 0.92 Kp (II, 0 mol)
4.0 mol) was placed in a polymerization tank equipped with a stirring blade, the temperature was raised to 280° C. while stirring under a nitrogen gas atmosphere, and polycondensation was carried out at this temperature for 1 hour while removing by-produced acetic acid. Further, the temperature was raised to 820°C and polycondensation was carried out at this temperature for 1 hour, and then the system was reduced to g torr and polycondensation was carried out at 820°C for 80 minutes. It was melting. Also, the amount of stabilizer in this polymer composition was about 0.18 PHR. The pulverized particulate polymer composition was treated under reduced pressure at 880° C. for 8 hours using a rotary kiln to obtain an aromatic polyester resin composition. This resin composition did not melt at temperatures below 500°C. The results are shown in Table 4.
比較例６
安定剤を添加しなかったこと以外は実施例１２と同様に
行ない、比較用の芳香族ポリエステルを得た。結果を第
４表に示した。Comparative Example 6 A comparative aromatic polyester was obtained in the same manner as in Example 12, except that no stabilizer was added. The results are shown in Table 4.
第 ４ 表
参考例８
２．５−ジアセトキシビフェニル２１７Ｏｆ（８，０４
モル）とテレフタル酸１８２８Ｆ（８，００モル）とか
ら参考例２と同様にして芳香族ポリエステル２４４７９
（理論数示に対して９６．８％）を得た。このポリエ
ステルのフロ一温度は８１８℃であった。Table 4 Reference Example 8 2.5-Diacetoxybiphenyl 217Of(8,04
mol) and terephthalic acid 1828F (8,00 mol) in the same manner as in Reference Example 2 to prepare aromatic polyester 24479.
(96.8% of the theoretical value) was obtained. The flow temperature of this polyester was 818°C.
実施例１８
参考例８で得られた芳香族ポリエステル１００重量部と
実施例１〜４で用いた安定剤０．２重ｆｉｔ部とから芳
香族ポリエステル樹脂組成物を得た。Example 18 An aromatic polyester resin composition was obtained from 100 parts by weight of the aromatic polyester obtained in Reference Example 8 and 0.2 parts by weight of the stabilizer used in Examples 1 to 4.
この樹脂組成物を、孔径Ｑ、Ｑ７ｍ、孔長０．１４■、
孔数８０６の紡糸口金を付けたスクリュー型押出機によ
り８６０℃で紡糸したところ、単糸切れがなく安定に紡
糸することができ、繊維中の気泡数の少ない（４，８個
／ｍ）、淡黄色の透明な繊維が得られた。この繊維を綜
研化学株製の熱媒Ｎｅｏ−５Ｋ−Ｏｉｊ１４００■中に
おいて８２０℃で８時間処理したものについて第５表に
示した。This resin composition has a pore diameter Q of 7 m, a pore length of 0.14 cm,
When the fibers were spun at 860°C using a screw extruder equipped with a spinneret with 806 holes, the fibers could be stably spun without any breakage, and the number of bubbles in the fibers was small (4.8/m). A light yellow transparent fiber was obtained. Table 5 shows the fibers treated at 820° C. for 8 hours in a heating medium Neo-5K-Oij1400 manufactured by Soken Kagaku Co., Ltd.
比較例７
安定剤を用いないこと以外は実施例１８と同様にして芳
香族ポリエステルの繊維を得た。この繊維について第５
表に示した。なお、紡糸口金の出口においてガスの発生
が見られ単糸切れも多く、安定に紡糸することができた
時間は短かく、得られた繊維は細いものであった。Comparative Example 7 Aromatic polyester fibers were obtained in the same manner as in Example 18 except that no stabilizer was used. About this fiber
Shown in the table. In addition, gas generation was observed at the exit of the spinneret, there were many single fiber breakages, the time during which stable spinning was possible was short, and the obtained fibers were thin.
■６表■Table 6
Claims (1)
〕−及び−〔ＣＯ−Ａ″ｒ−Ｏ〕−（式中、Ａｒ、Ａ′
ｒ及びＡ″ｒは２価の芳香族基を表わす。）で表わされ
る構造単位からなる群から選ばれた１種または２種以上
の構造単位を主たる繰返し構造単位として含む芳香族ポ
リエステル１００重量部と下記一般式（ I ）及び／又
は（II）で表わされる安定剤０．０３〜３重量部とから
なる芳香族ポリエステル樹脂組成物。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は炭素数１〜５のアルキレン基またはア
ルキリデン基を、Ｒ＿２は炭素数１〜６のアルキル基ま
たは炭素数６〜８のアリール基を、そしてＭはＮｉまた
はＣａをそれぞれ表わす。）▲数式、化学式、表等があ
ります▼（II） （式中、Ｒ＿３およびＲ＿４は炭素数４〜１０アルキル
基を、そしてＸはアミン化合物をそれぞれ表わす。）[Claims] General formula -[CO-Ar-CO]-, -[O-A'r-O
]-and-[CO-A″r-O]-(wherein Ar, A′
100 parts by weight of an aromatic polyester containing as a main repeating structural unit one or more structural units selected from the group consisting of the structural units represented by r and A″r represent a divalent aromatic group. and 0.03 to 3 parts by weight of a stabilizer represented by the following general formula (I) and/or (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 represents an alkylene group or alkylidene group having 1 to 5 carbon atoms, R_2 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and M represents Ni or Ca.) There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_3 and R_4 represent an alkyl group with 4 to 10 carbon atoms, and X represents an amine compound.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10058087A JPS63265951A (en) | 1987-04-22 | 1987-04-22 | Aromatic polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10058087A JPS63265951A (en) | 1987-04-22 | 1987-04-22 | Aromatic polyester resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63265951A true JPS63265951A (en) | 1988-11-02 |
Family
ID=14277827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10058087A Pending JPS63265951A (en) | 1987-04-22 | 1987-04-22 | Aromatic polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63265951A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1327648A1 (en) * | 2000-09-12 | 2003-07-16 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| EP1400549A4 (en) * | 2001-02-23 | 2005-02-09 | Toyo Boseki | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
-
1987
- 1987-04-22 JP JP10058087A patent/JPS63265951A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1327648A1 (en) * | 2000-09-12 | 2003-07-16 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| EP1327648A4 (en) * | 2000-09-12 | 2005-01-19 | Toyo Boseki | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| EP1400549A4 (en) * | 2001-02-23 | 2005-02-09 | Toyo Boseki | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
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