JP2006002068A - Stable titanium catalyst solution for polyester production scarcely depositing titanium component - Google Patents
Stable titanium catalyst solution for polyester production scarcely depositing titanium component Download PDFInfo
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- JP2006002068A JP2006002068A JP2004180822A JP2004180822A JP2006002068A JP 2006002068 A JP2006002068 A JP 2006002068A JP 2004180822 A JP2004180822 A JP 2004180822A JP 2004180822 A JP2004180822 A JP 2004180822A JP 2006002068 A JP2006002068 A JP 2006002068A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 229920000728 polyester Polymers 0.000 title claims abstract description 26
- 239000010936 titanium Substances 0.000 title claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 238000000151 deposition Methods 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 4
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000002685 polymerization catalyst Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- KTFJPMPXSYUEIP-UHFFFAOYSA-N 3-benzoylphthalic acid Chemical compound OC(=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C(O)=O KTFJPMPXSYUEIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、チタン触媒に関する。さらに詳しくは、重合触媒としてポリエステル製造に有用なチタン触媒溶液に関する。 The present invention relates to a titanium catalyst. More specifically, the present invention relates to a titanium catalyst solution useful for producing a polyester as a polymerization catalyst.
ポリエチレンテレフタレートやポリエチレンナフタレートに代表されるポリエステルは、優れた力学特性、耐熱性、耐候性、耐電気絶縁性及び耐薬品性を有することから、フィルム、繊維又はボトルなどの成形品として広く使用されている。 Polyesters typified by polyethylene terephthalate and polyethylene naphthalate have excellent mechanical properties, heat resistance, weather resistance, electrical insulation resistance and chemical resistance, so they are widely used as molded products such as films, fibers or bottles. ing.
このポリエステルはその製造過程において、重合反応を円滑に進行させるために重合触媒を用いる。この重合触媒として、例えばテトラアルコキシチタンなどのチタン化合物を用いることは広く知られている。 This polyester uses a polymerization catalyst in the production process in order to make the polymerization reaction proceed smoothly. As this polymerization catalyst, it is widely known to use a titanium compound such as tetraalkoxytitanium.
このチタン触媒は、分散媒としてポリエステルの製造原料のひとつであるエチレングリコールなどに希釈保存し、ポリエステルの反応系に投入する方法が一般的である。しかしながら、こうして調製されたチタン触媒溶液は、保存中経時的に析出物を生じ容器・装置底部に沈殿して目標の触媒投入量とずれが生じたり、析出物を生じた触媒溶液を用いて重合を行った場合には、得られるポリエステル中に黒色の異物が混入したりするという問題点があった。 In general, the titanium catalyst is diluted and stored in ethylene glycol or the like, which is one of polyester production raw materials, as a dispersion medium, and charged into a polyester reaction system. However, the titanium catalyst solution prepared in this manner produces precipitates over time during storage and precipitates at the bottom of the container / equipment, resulting in a deviation from the target catalyst input amount or polymerization using the catalyst solution that produced the precipitates. In the case of performing the above, there is a problem that black foreign matters are mixed in the obtained polyester.
この問題を解決するために、テトラアルコキシチタンのエチレングリコール溶液にアルカリ金属水酸化物を含有させることが提案されている（例えば特許文献１参照。）。しかしながら、この方法では、本来触媒機能としては無用のアルカリ金属水酸化物をポリエステルに存在させることになる上に、このアルカリ金属水酸化物が劇物であり、特に飲料や食料品の包装容器材料向けのポリエステルにおいては、含有するアルカリ金属が内容物に極微量しみだし、安全衛生上問題視されるという欠点があった。
本発明の目的は、上記従来技術が有していた問題点を解消し、チタン化合物のエチレングリコール溶液を長期保存したときの析出物の生成を防止する技術を提供することにある。 An object of the present invention is to provide a technique for solving the problems of the prior art and preventing the formation of precipitates when an ethylene glycol solution of a titanium compound is stored for a long period of time.
本発明者らは、上記目的を達成するべく鋭意検討を行った結果、チタン化合物エチレングリコール溶液に酸成分を添加すれば、析出を生ずることなく安定で取り扱い容易なポリエステル重合触媒が得られる事を見出し、本発明を完成するに到った。 As a result of intensive studies to achieve the above object, the present inventors have found that a stable and easy-to-handle polyester polymerization catalyst can be obtained without causing precipitation if an acid component is added to the titanium compound ethylene glycol solution. The headline and the present invention have been completed.
即ち、本発明によれば、下記一般式（１）
により表されるチタン化合物を０．１〜２０重量％及び芳香族ジカルボン酸を０．１〜３重量％含むエチレングリコール溶液とすることにより、アルカリ金属塩の添加などを行わなくても、析出物を生じることなく長期保存可能なポリエステル製造用チタン触媒溶液が提供される。
That is, according to the present invention, the following general formula (1)
By using an ethylene glycol solution containing 0.1 to 20% by weight of a titanium compound represented by the formula (1) and 0.1 to 3% by weight of an aromatic dicarboxylic acid, a precipitate can be formed without adding an alkali metal salt or the like. A titanium catalyst solution for producing a polyester that can be stored for a long period of time without causing odor is provided.
本発明によれば、長期保存してもチタン成分を析出せず、安定した状態でポリエステル製造用のチタン触媒溶液として保存及び使用し安全衛生上問題の無いポリエステルを得ることが出来る。 According to the present invention, a titanium component does not precipitate even after long-term storage, and can be stored and used as a titanium catalyst solution for polyester production in a stable state.
以下、本発明について詳細に説明する。
本発明で用いるチタン化合物は下記式（１）で表される。
The titanium compound used in the present invention is represented by the following formula (1).
他のチタン化合物ではポリエステル製造用触媒として好ましくなかったり、安定化の効果が見出せないことがある。より詳細にはテトラアルコキシチタンのモノマー、テトラアルコキシチタンのオリゴマー、又は両化合物の混合物である。テトラアルコキシチタンのオリゴマーとは、具体的にはヘキサアルコキシジチタン、オクタアルコキシトリチタンを挙げることができる。しかしより好ましくはテトラアルコキシチタンである。また、テトラアルコキシチタンとしては、テトラブトキシチタン、テトラプロポキシチタンその他のテトラアルコキシチタンが好ましく、なかでもテトラブトキシチタンがより好ましい。チタン化合物は単一種の化合物であっても複数の種類の混合物であっても良い。このチタン化合物をエチレングリコール溶液とする場合、該溶液中のテトラアルコキシチタン含有量は、０．１〜２０重量％とする必要がある。含有量が０．１重量％未満であると、溶媒が多すぎるために所定量の触媒を投入するのに、多量の溶液が必要となり生産効率が悪くなる。一方、２０重量％を超えると溶液粘度が上昇する、又は触媒溶液の安定性を損なうなどの問題があるので好ましくない。 Other titanium compounds are not preferable as a catalyst for polyester production, and the stabilizing effect may not be found. More specifically, it is a tetraalkoxytitanium monomer, a tetraalkoxytitanium oligomer, or a mixture of both compounds. Specific examples of tetraalkoxytitanium oligomers include hexaalkoxydititanium and octaalkoxytrititanium. However, tetraalkoxy titanium is more preferable. Moreover, as tetraalkoxy titanium, tetrabutoxy titanium, tetrapropoxy titanium, and other tetraalkoxy titanium are preferable, and tetrabutoxy titanium is more preferable. The titanium compound may be a single type of compound or a mixture of a plurality of types. When this titanium compound is an ethylene glycol solution, the tetraalkoxytitanium content in the solution needs to be 0.1 to 20% by weight. If the content is less than 0.1% by weight, the solvent is too much, so that a large amount of solution is required to introduce a predetermined amount of catalyst, and the production efficiency is deteriorated. On the other hand, if it exceeds 20% by weight, there is a problem in that the solution viscosity increases or the stability of the catalyst solution is impaired.
さらに本発明においては芳香族ジカルボン酸をエチレングリコール溶液としたときに０．１〜３重量％含む必要がある。芳香族ジカルボン酸としては、具体的にはテレフタル酸、イソフタル酸、フタル酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェニルスルホンジカルボン酸又はベンゾフェノンジカルボン酸などを挙げることができる。好ましくはポリエステルを製造する際に、ポリエステル中に共重合されうる芳香族ジカルボン酸である。より好ましくはポリエステル製造の際に主原料として用いる芳香族ジカルボン酸又は芳香族ジカルボン酸誘導体に由来する芳香族ジカルボン酸である。このような芳香族ジカルボン酸を上述の量の範囲でエチレングリコール中に含ませておくことで、テトラアルコキシチタンのエチレングリコール溶液中での安定性が増大し、析出物の生成を抑制することができる。一方芳香族ジカルボン酸の含有量が０．１重量％未満であると析出物を生じやすくなり、本発明の効果をそうすることができない。また３重量％を超える場合には、効果は定常化するので、それ以上含ませておくことは経済的に不利となる。 Further, in the present invention, it is necessary that the aromatic dicarboxylic acid is contained in an amount of 0.1 to 3% by weight when the ethylene glycol solution is used. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Examples thereof include acids, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, and benzophenone dicarboxylic acid. Preferably, it is an aromatic dicarboxylic acid that can be copolymerized in the polyester when the polyester is produced. More preferred is an aromatic dicarboxylic acid derived from an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative used as a main raw material in the production of polyester. By including such an aromatic dicarboxylic acid in the above-mentioned amount in ethylene glycol, the stability of tetraalkoxytitanium in an ethylene glycol solution is increased, and the formation of precipitates can be suppressed. it can. On the other hand, when the content of the aromatic dicarboxylic acid is less than 0.1% by weight, precipitates are likely to be generated, and the effect of the present invention cannot be achieved. If it exceeds 3% by weight, the effect becomes steady, so it is economically disadvantageous to contain more than 3% by weight.
本発明では、テトラアルコキシチタンをエチレングリコール溶液として用いる。本発明に用いるエチレングリコールはわざわざ加熱処理する必要は無い。しかしエチレングリコール中の含水率が高い場合は、水分を除去するため１００℃以上に加熱して水分を除去しておくことが好ましい。触媒溶液の保存温度は特に限定されないが、通常１０〜９０℃、好ましくは２０〜５０℃である。また、保存期間も限定されないが、少なくとも１ヶ月以上は安定に保存することができる。 In the present invention, tetraalkoxytitanium is used as the ethylene glycol solution. The ethylene glycol used in the present invention does not need to be heat-treated. However, when the water content in ethylene glycol is high, it is preferable to remove the water by heating to 100 ° C. or higher in order to remove the water. Although the preservation | save temperature of a catalyst solution is not specifically limited, Usually, it is 10-90 degreeC, Preferably it is 20-50 degreeC. In addition, although the storage period is not limited, it can be stably stored for at least one month.
以上の触媒溶液は、ポリエステル製造時の触媒として使用することができ、そのポリエステルの製造方法は本発明の一態様でもある。例えば、ポリエチレンテレフタレート及び／又はポリエチレンナフタレート製造の触媒として用いる場合には、重合触媒として用いることもできるし、またエステル交換反応を経由してポリエチレンテレフタレート又はポリエチレンナフタレートを得る場合には、エステル交換反応触媒として兼用してもよい。ポリエステル製造時の条件としては、本発明の触媒をチタン元素の仕込み量が従来のチタン触媒と同量になるように使用することでポリエステル製造用チタン触媒溶液として好適に作用する。またポリエステル製造時の条件は、公知の方法を採用すればよい。 The above catalyst solution can be used as a catalyst during the production of polyester, and the method for producing the polyester is also an embodiment of the present invention. For example, when used as a catalyst for the production of polyethylene terephthalate and / or polyethylene naphthalate, it can also be used as a polymerization catalyst. When obtaining polyethylene terephthalate or polyethylene naphthalate via a transesterification reaction, transesterification is possible. It may also be used as a reaction catalyst. As the conditions for producing the polyester, the catalyst of the present invention is preferably used as a titanium catalyst solution for producing polyester by using the titanium element so that the amount of the titanium element is the same as that of the conventional titanium catalyst. Moreover, what is necessary is just to employ | adopt a well-known method for the conditions at the time of polyester manufacture.
以下、本発明を実施例によりさらに具体的に説明する。なお、本実施例中において、エチレングリコール中の水分率の測定は平沼産業株式会社製ＡＱ−３Ｃ型微量水分測定器を用いて測定した。触媒液中のチタン濃度は、液体サンプルを適宜希釈して、蛍光Ｘ線装置（理学電機工業３２７０Ｅ型）にて、定量分析を実施した。なお実施例、比較例中「部」とは重量部を表す。 Hereinafter, the present invention will be described more specifically with reference to examples. In this example, the moisture content in ethylene glycol was measured using an AQ-3C type trace moisture meter manufactured by Hiranuma Sangyo Co., Ltd. The titanium concentration in the catalyst solution was quantitatively analyzed with a fluorescent X-ray apparatus (Rigaku Corporation 3270E type) after appropriately diluting the liquid sample. In the examples and comparative examples, “parts” represents parts by weight.
［実施例１］
ガラス製容器に水分率０．５％のエチレングリコール８９部にテトラブトキシチタン１０部を混合攪拌して得た均一溶液にテレフタル酸１部、（いずれも和光純薬工業株式会社製試薬）を加え撹拌してチタン触媒液を得た（理論チタン濃度１．４１重量％）。この溶液を室温にて保存したが３０日間経過した時点で、液中のチタン濃度は１．４３重量％とほぼ理論量どおりだった。
[Example 1]
Add 1 part of terephthalic acid (reagents manufactured by Wako Pure Chemical Industries, Ltd.) to a homogeneous solution obtained by mixing and stirring 10 parts of tetrabutoxy titanium in 89 parts of ethylene glycol with a water content of 0.5% in a glass container. The mixture was stirred to obtain a titanium catalyst solution (theoretical titanium concentration 1.41% by weight). This solution was stored at room temperature, but after 30 days, the titanium concentration in the liquid was 1.43% by weight, which was almost the theoretical amount.
［比較例１］
ガラス製容器に水分率０．３％のエチレングリコール９０部にテトラブトキシチタン１０部（和光純薬工業株式会社製試薬）を加え均一撹拌することにより、透明な溶液を得た（理論チタン濃度１．４１重量％）。この溶液を常温にて保存したところ３６時間後に析出が生じた。溶液中のチタン濃度を測定すると１．３４重量％と理論チタン濃度より低下していた。
[Comparative Example 1]
A transparent solution was obtained by adding 10 parts of tetrabutoxytitanium (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) to 90 parts of ethylene glycol having a moisture content of 0.3% in a glass container to obtain a transparent solution (theoretical titanium concentration 1). .41 wt%). When this solution was stored at room temperature, precipitation occurred after 36 hours. When the titanium concentration in the solution was measured, it was 1.34% by weight, which was lower than the theoretical titanium concentration.
本発明によれば、長期保存してもチタン成分を析出せず、安定した状態でポリエステル製造用のチタン触媒溶液として保存することができる。またこのチタン触媒触媒溶液を使用し、透明で異物がなく安全衛生上問題の無いポリエステルを得ることが出来る。従って飲料用途のペットボトルなど衛生面での要求があるポリエステルを製造するの好適であり、工業的意義は大きい。 According to the present invention, the titanium component does not precipitate even after long-term storage, and can be stored in a stable state as a titanium catalyst solution for polyester production. Further, by using this titanium catalyst catalyst solution, it is possible to obtain a polyester which is transparent and free from foreign matters and has no safety and health problems. Therefore, it is suitable to produce polyester having sanitary requirements such as PET bottles for beverage use, and has great industrial significance.
Claims (1)
により表されるチタン化合物を０．１〜２０重量％及び芳香族ジカルボン酸を０．１〜３重量％含むエチレングリコール溶液であるポリエステル製造用チタン触媒溶液。 The following general formula (1)
A titanium catalyst solution for producing a polyester, which is an ethylene glycol solution containing 0.1 to 20% by weight of a titanium compound represented by the formula (1) and 0.1 to 3% by weight of an aromatic dicarboxylic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004180822A JP2006002068A (en) | 2004-06-18 | 2004-06-18 | Stable titanium catalyst solution for polyester production scarcely depositing titanium component |
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| JP2004180822A JP2006002068A (en) | 2004-06-18 | 2004-06-18 | Stable titanium catalyst solution for polyester production scarcely depositing titanium component |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006121121A1 (en) * | 2005-05-12 | 2006-11-16 | Asahi Kasei Fibers Corporation | Titanium oxide sol and process for producing polyalkylene terephthalate therewith |
| WO2012157258A1 (en) * | 2011-05-18 | 2012-11-22 | 東レ株式会社 | Catalyst solution for use in production of polyester, and method for producing polyester resin using same |
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2004
- 2004-06-18 JP JP2004180822A patent/JP2006002068A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006121121A1 (en) * | 2005-05-12 | 2006-11-16 | Asahi Kasei Fibers Corporation | Titanium oxide sol and process for producing polyalkylene terephthalate therewith |
| US7759270B2 (en) | 2005-05-12 | 2010-07-20 | Fuji Titanium Industry Co., Ltd. | Titanium oxide sol and process for producing polyalkylene terephthalate therewith |
| WO2012157258A1 (en) * | 2011-05-18 | 2012-11-22 | 東レ株式会社 | Catalyst solution for use in production of polyester, and method for producing polyester resin using same |
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