JP3784561B2 - Method for purifying bishydroxyalkyl terephthalate - Google Patents
Method for purifying bishydroxyalkyl terephthalate Download PDFInfo
- Publication number
- JP3784561B2 JP3784561B2 JP01329499A JP1329499A JP3784561B2 JP 3784561 B2 JP3784561 B2 JP 3784561B2 JP 01329499 A JP01329499 A JP 01329499A JP 1329499 A JP1329499 A JP 1329499A JP 3784561 B2 JP3784561 B2 JP 3784561B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- terephthalate
- pet
- bhet
- passing
- 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
Description
【０００１】
【発明の属する技術分野】
本発明は、ビスヒドロキシアルキルテレフタレートの精製方法およびその装置に関するものである。さらに詳しくは、本発明は再生ポリアルキレンテレフタレートの原料として使用可能な粗ビスヒドロキシアルキルテレフタレートの精製方法およびその装置に関するものである。
【０００２】
【従来の技術】
従来、ポリエチレンテレフタレートやポリブチレンテレフタレート（以下、「ＰＥＴ等」と略称する）は、テレフタル酸ジメチルまたはテレフタル酸とエチレングリコールまたは１，４−ブタンジオールを反応させて、ビスヒドロキシエチルテレフタレートまたはビスヒドロキシブチルテレフタレート（以下、「ＢＨＥＴ等」と略称する）を製造し、次いでＢＨＥＴ等を縮合させて製造されている。
【０００３】
テレフタル酸ジメチルまたはテレフタル酸から得られた粗ＢＨＥＴ等は、副生物のメタノールや水が含まれているため、縮合させる前に、蒸留によりメタノールや水を留去して精製していた。
【０００４】
一方、容器包装リサイクル法が１９９７年４月に施行されてから、ＰＥＴ等のリサイクル需要が高まっている。ＰＥＴ等をリサイクルする方法としては、回収したＰＥＴ等を細断して溶融し、繊維状のＰＥＴ等に加工して、生地に再生する方法と、回収ＰＥＴ等を原料のモノマー（ＢＨＥＴ等）に分解して回収し、回収モノマーから再度ＰＥＴ等を合成するケミカルリサイクル法がある。
【０００５】
ＰＥＴ等のケミカルリサイクル法としては、触媒の存在下にアルコールやグリコール類等の溶媒を用いて加溶媒分解反応によりＰＥＴ等を分解し、モノマー（ＢＨＥＴ等）を回収する方法等が知られている。
【０００６】
【発明が解決しようとする課題】
しかし、ケミカルリサイクル法で回収されたモノマー（ＢＨＥＴ等）には、様々な副分解生成物、着色剤、付着物やリサイクル工程中に用いる水に含まれるイオン等の不純物が含まれている。ＰＥＴ等を合成するためには、高純度のモノマーを用いる必要があり、ケミカルリサイクル法で回収されたモノマーは不純物が多く、そのままではＰＥＴ等の合成に用いることができない。
【０００７】
本発明者等は粗ＢＨＥＴ等を含む溶液中から不純物のイオンを除去するためには、イオン交換樹脂を使用すればよいことを見出し、特許出願（特願平１０−３３３１７９号）をした。特願平１０−３３３１７９号において使用されるイオン交換樹脂は強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂である。脱塩性能を重視する場合、アニオン交換樹脂として強塩基性アニオン交換樹脂を用いることが好ましいが、粗ＢＨＥＴ等の濃度によっては通液温度を６０℃以上にする必要があり、このような高温下での通液処理を行うためにはアニオン交換樹脂として弱塩基性アニオン交換樹脂を用いざるを得ない。
【０００８】
ところが、弱塩基性アニオン交換樹脂を用いる場合、処理を繰り返すにつれて塩類のリーク量が増え、高純度のモノマーを回収できないことが判明した。
【０００９】
本発明が解決しようとする課題は、ＰＥＴ等の合成に使用しうる高純度のモノマーとすることが可能な、粗ビスヒドロキシアルキルテレフタレートの精製方法を提供することである。
【００１０】
【課題を解決するための手段】
本発明者らは上記課題を解決するため、鋭意研究を重ねた結果、本発明を完成するに至った。
【００１１】
すなわち、本発明は、粗ビスヒドロキシアルキルテレフタレートを活性炭とイオン交換樹脂を組み合わせて通液処理して精製するビスヒドロキシアルキルテレフタレートの精製方法において、イオン交換樹脂による処理を、単層の強酸性カチオン交換樹脂に通液した後、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂の混層に通液することを特徴とするビスヒドロキシアルキルテレフタレートの精製方法に関するものである。
【００１２】
【発明の実施の形態】
本発明の処理対象となる粗ビスヒドロキシアルキルテレフタレートとは、不純物を含むビスヒドロキシアルキルテレフタレートであり、ポリエチレンテレフタレートを加水分解もしくは加溶媒分解して得られるビスヒドロキシエチルテレフタレートや、ポリブチレンテレフタレートを加水分解もしくは加溶媒分解して得られるビスヒドロキシブチルテレフタレートである。
【００１３】
本発明の処理対象となる粗ＢＨＥＴ等は、廃ＰＥＴ等のケミカルリサイクル工程で得られる粗ＢＨＥＴ等以外にも、通常のＰＥＴ等の合成の高純度原料であるテレフタル酸ジメチルやテレフタル酸から得られる粗ＢＨＥＴ等であってもよい。
【００１４】
なお、ＰＥＴ等のケミカルリサイクル工程としては、ＰＥＴ等を粗ＢＨＥＴ等に分解処理できる方法であればよく、例えば溶媒を用いたＰＥＴ等の加溶媒分解法や、超臨界溶液を用いた分解法等を挙げることができる。
【００１５】
ケミカルリサイクル工程で分解した粗ＢＨＥＴ等には、ＰＥＴの重合触媒や無機顔料が不溶性無機不純物として含まれているので、本発明の精製処理を行う前に、セラミックフィルター等により不溶性無機不純物を除去する必要がある。
【００１６】
回収ＰＥＴボトルから得られる粗ＢＨＥＴ中のイオン種は詳しく判明していないが、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂の混層に通液することにより塩類のリークが少なくなることが判った。
【００１７】
また、回収ＰＥＴボトルから得られる粗ＢＨＥＴのイオン濃度は詳しくは判明していないが、アニオン成分に比べカチオン成分が多く溶解していることが判り、その分カチオン成分を除去するために強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂との混層に通液する前に、単層の強酸性カチオン交換樹脂に通液することで、処理液品質を落とすことなく、処理量を増やすことができる。
【００１８】
強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂の混層における、両樹脂の混合割合は、容量で強酸性カチオン交換樹脂：弱塩基性アニオン交換樹脂＝２：１〜１：４、好ましくは１：１〜１：２である。
【００１９】
本発明において粗ＢＨＥＴ等が精製される詳しい除去機構は判明していないが、粗ＢＨＥＴ等に含まれる着色剤はイオン交換樹脂では吸着されにくく、活性炭で吸着されることが分かった。
【００２０】
粗ＢＨＥＴ等は、溶媒に加熱溶解して処理することが好ましく、用いる溶媒としては、メタノールやＰＥＴ等の加溶媒分解に用いられるエチレングリコール等を挙げることができる。
【００２１】
活性炭とイオン交換樹脂による処理は、どちらが先でも問題はないが、活性炭の精製度によっては通液により酸化物の溶出があるので、好ましくは活性炭処理を行った後に、イオン交換樹脂による処理を行うことが好ましい。
【００２２】
【実施例】
実施例および比較例で用いた粗ＢＨＥＴ溶液は、ＰＥＴボトルをケミカルリサイクルする工程で得られる濾過処理後の溶液であり、組成は、ＢＨＥＴ１８重量％、エチレングリコール８１重量％、水１重量％である。
【００２３】
実施例１
粗ＢＨＥＴ溶液を温度６０℃で、通液速度２５０ｍｌ／ｈｒで木質活性炭（二村化学（株）製、「太閤ＳＧＡ」）１００ｍｌを充填した活性炭層に通液後、単床式の強酸性カチオン交換樹脂（ローム・アンド・ハース社製「アンバーライトＩＲ−１２０Ｂ」２４ｍｌ）層に通液した後、混床式のイオン交換樹脂（ローム・アンド・ハース社製「アンバーライト ＩＲＡ９６ＳＢ」１２ｍｌ＋「アンバーライト ＩＲ−１２０Ｂ」１２ｍｌ）層に通液した。粗ＢＨＥＴ溶液を１０００ｍｌ、２０００ｍｌ、３０００ｍｌ通液したときの電気伝導率を表１に示す。
【００２４】
比較例１
粗ＢＨＥＴ溶液を温度６０℃、通液速度２５０ｍｌ／ｈｒで木質活性炭（二村化学（株）製、「太閤ＳＧＡ」）１００ｍｌを充填した活性炭層に通液した後、単床式の強酸性カチオン交換樹脂（「アンバーライト ＩＲ−１２０Ｂ」３６ｍｌ）層に通液した後、単床式の弱塩基性アニオン交換樹脂（「アンバーライト ＩＲＡ９６ＳＢ」１２ｍｌ）層に通液した。
【００２５】
粗ＢＨＥＴ溶液を１０００ｍｌ、２０００ｍｌ、３０００ｍｌ通液したときの電気伝導率を表１に示す。
【００２６】
比較例２
粗ＢＨＥＴ溶液を温度６０℃、通液速度２５０ｍｌ／ｈｒで木質活性炭（二村化学（株）製、「太閤ＳＧＡ」）１００ｍｌを充填した活性炭層に通液した後、混床式のイオン交換樹脂（ローム・アンド・ハース社製「アンバーライト ＩＲＡ９６ＳＢ」１２ｍｌ＋「アンバーライト ＩＲ−１２０Ｂ」３６ｍｌ）層に通液した。粗ＢＨＥＴ溶液を１０００ｍｌ、２０００ｍｌ、３０００ｍｌ通液したときの電気伝導率を表１に示す。
【００２７】
【表１】
表１に示した結果から明らかなように、単床式の強酸性カチオン交換樹脂層と単床式の弱塩基性アニオン交換樹脂層に通液した比較例１の精製法では２０００ｍｌを通液した時点で塩類がリークし始めており、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂との混床式のイオン交換樹脂層に通液した比較例２の精製法では、１０００ｍｌ通液した時点で塩類がリークしてくるのに対し、単床式の強酸性カチオン交換樹脂層を通液した後に混床式のイオン交換樹脂層に通液した実施例１の精製方法は、３０００ｍｌの通液処理をしても塩類のリークが少ないことが判る。
【００２９】
【発明の効果】
粗ＢＨＥＴ等を活性炭とイオン交換樹脂を組み合わせて精製処理する方法において、単床式の強酸性カチオン交換樹脂に通液した後、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂の混床式のイオン交換樹脂層に通液することにより、塩類のリークの少ない粗ＢＨＥＴ等の精製処理を行うことができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for purifying bishydroxyalkyl terephthalate and an apparatus therefor. More particularly, the present invention relates to a purification method and apparatus of the crude bishydroxyalkyl terephthalate can be used as a raw material for reproduction polyalkylene terephthalate.
[0002]
[Prior art]
Conventionally, polyethylene terephthalate and polybutylene terephthalate (hereinafter abbreviated as “PET”) are reacted with dimethyl terephthalate or terephthalic acid and ethylene glycol or 1,4-butanediol to produce bishydroxyethyl terephthalate or bishydroxybutyl. It is manufactured by producing terephthalate (hereinafter abbreviated as “BHET etc.”) and then condensing BHET etc.
[0003]
Since crude BHET obtained from dimethyl terephthalate or terephthalic acid contains methanol and water as by-products, it was purified by distilling off methanol and water by distillation before condensation.
[0004]
On the other hand, since the Containers and Packaging Recycling Law came into effect in April 1997, the demand for recycling PET and the like has increased. As methods for recycling PET, etc., the recovered PET, etc. is shredded and melted, processed into fibrous PET, etc., and regenerated into a fabric, and the recovered PET, etc. is used as a raw material monomer (BHET, etc.) There is a chemical recycling method that decomposes and recovers, and again synthesizes PET and the like from recovered monomers.
[0005]
As a chemical recycling method for PET or the like, a method for decomposing PET or the like by a solvolysis reaction using a solvent such as alcohol or glycol in the presence of a catalyst and recovering a monomer (BHET or the like) is known. .
[0006]
[Problems to be solved by the invention]
However, monomers recovered by the chemical recycling method (BHET and the like) contain impurities such as various side decomposition products, colorants, deposits, and ions contained in water used during the recycling process. In order to synthesize PET or the like, it is necessary to use a high-purity monomer, and the monomer recovered by the chemical recycling method has many impurities and cannot be used for the synthesis of PET or the like as it is.
[0007]
The present inventors have found that an ion exchange resin may be used to remove impurity ions from a solution containing crude BHET and the like, and have filed a patent application (Japanese Patent Application No. 10-333179). The ion exchange resins used in Japanese Patent Application No. 10-333179 are a strongly acidic cation exchange resin and a weakly basic anion exchange resin. When importance is attached to desalting performance, it is preferable to use a strongly basic anion exchange resin as an anion exchange resin. However, depending on the concentration of crude BHET or the like, the liquid passing temperature needs to be 60 ° C. or higher. In order to carry out the liquid-passing treatment in step 1, a weakly basic anion exchange resin must be used as the anion exchange resin.
[0008]
However, when weakly basic anion exchange resins are used, it has been found that as the treatment is repeated, the amount of salt leakage increases and it is not possible to recover a high-purity monomer.
[0009]
The problem to be solved by the present invention is to provide a method for purifying crude bishydroxyalkyl terephthalate, which can be a highly pure monomer that can be used in the synthesis of PET and the like.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, the present invention has been completed.
[0011]
That is, the present invention relates to a bishydroxyalkyl terephthalate purification method in which crude bishydroxyalkyl terephthalate is purified by passing through a combination of activated carbon and an ion exchange resin. The present invention relates to a method for purifying bishydroxyalkyl terephthalate characterized by passing through a resin and then passing through a mixed layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The process subject to crude bishydroxyalkyl terephthalate of the present invention, a bis-hydroxyalkyl terephthalate containing impurities, Po Rie Chi alkylene terephthalate or bis-hydroxyethyl terephthalate obtained by hydrolysis or solvolysis, port ribs Chi terephthalate Is bishydroxybutyl terephthalate obtained by hydrolysis or solvolysis.
[0013]
Processed subject to rough BHET or the like of the present invention, in addition to the crude BHET and the like obtained by the chemical recycling process of waste such as PET is also obtainable from dimethyl terephthalate and terephthalic acid of high purity raw material of conventional synthesis such as PET Coarse BHET or the like may be used.
[0014]
The chemical recycling process for PET or the like may be any method that can decompose PET or the like into crude BHET, for example, a solvolysis method such as PET using a solvent, a decomposition method using a supercritical solution, or the like. Can be mentioned.
[0015]
Since the crude BHET decomposed in the chemical recycling step contains PET polymerization catalyst and inorganic pigment as insoluble inorganic impurities, the insoluble inorganic impurities are removed by a ceramic filter or the like before the purification treatment of the present invention. There is a need.
[0016]
Although the ionic species in the crude BHET obtained from the recovered PET bottle has not been clarified in detail, it has been found that leakage of salts is reduced by passing through a mixed layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin. .
[0017]
Further, although the ion concentration of the crude BHET obtained from the recovered PET bottle has not been clarified in detail, it can be seen that the cation component is more dissolved than the anion component. By passing through a single layer strongly acidic cation exchange resin before passing through the mixed layer of the exchange resin and weakly basic anion exchange resin, the amount of treatment can be increased without degrading the quality of the processing solution.
[0018]
In the mixed layer of the strongly acidic cation exchange resin and the weakly basic anion exchange resin, the mixing ratio of the two resins by volume is strongly acidic cation exchange resin: weakly basic anion exchange resin = 2: 1 to 1: 4, preferably 1: 1-1: 2.
[0019]
Although a detailed removal mechanism for purifying crude BHET or the like is not known in the present invention, it has been found that the colorant contained in the crude BHET or the like is hardly adsorbed by the ion exchange resin and is adsorbed by activated carbon.
[0020]
Crude BHET and the like are preferably processed by dissolving in a solvent by heating, and examples of the solvent to be used include ethylene glycol used for solvolysis of methanol and PET.
[0021]
Either treatment with activated carbon or ion exchange resin has no problem in either case, but depending on the degree of purification of activated carbon, there is an elution of oxides due to the liquid passing through, so treatment with ion exchange resin is preferably performed after activated carbon treatment. It is preferable.
[0022]
【Example】
The crude BHET solution used in the examples and comparative examples is a solution after filtration obtained in the process of chemically recycling the PET bottle, and the composition is 18% by weight of BHET , 81% by weight of ethylene glycol, and 1% by weight of water. is there.
[0023]
Example 1
The crude BHET solution was passed through an activated carbon layer filled with 100 ml of wood activated carbon (manufactured by Nimura Chemical Co., Ltd., “Taiko SGA”) at a temperature of 60 ° C. and a flow rate of 250 ml / hr. After passing through a resin (Rom & Haas "Amberlite IR-120B" 24 ml) layer, mixed bed ion exchange resin (Rohm & Haas "Amberlite IRA96SB" 12 ml + "Amberlite IR" -120B "12 ml). Table 1 shows the electrical conductivity when the crude BHET solution was passed through 1000 ml, 2000 ml, and 3000 ml.
[0024]
Comparative Example 1
The crude BHET solution was passed through an activated carbon layer filled with 100 ml of wood activated carbon (manufactured by Nimura Chemical Co., Ltd., “Dazai SGA”) at a temperature of 60 ° C. and a flow rate of 250 ml / hr. After passing through a resin (“Amberlite IR-120B” 36 ml) layer, it was passed through a single-bed weakly basic anion exchange resin (“Amberlite IRA96SB” 12 ml) layer.
[0025]
Table 1 shows the electrical conductivity when the crude BHET solution was passed through 1000 ml, 2000 ml, and 3000 ml.
[0026]
Comparative Example 2
The crude BHET solution was passed through an activated carbon layer filled with 100 ml of wood activated carbon (manufactured by Nimura Chemical Co., Ltd., “Taiko SGA”) at a temperature of 60 ° C. and a flow rate of 250 ml / hr, and then mixed bed type ion exchange resin ( The solution was passed through a layer of “Amberlite IRA96SB” (12 ml + “Amberlite IR-120B” 36 ml) manufactured by Rohm and Haas. Table 1 shows the electrical conductivity when the crude BHET solution was passed through 1000 ml, 2000 ml, and 3000 ml.
[0027]
[Table 1]
As is apparent from the results shown in Table 1, 2000 ml was passed through the purification method of Comparative Example 1 which was passed through the single bed type strongly acidic cation exchange resin layer and the single bed type weak base anion exchange resin layer. In the purification method of Comparative Example 2 in which salts began to leak at the time and passed through a mixed bed type ion exchange resin layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin, In contrast, the purification method of Example 1 in which the single bed type strongly acidic cation exchange resin layer was passed through and then the mixed bed type ion exchange resin layer was passed through the 3000 ml solution passing treatment. It turns out that there is little leak of salt.
[0029]
【The invention's effect】
In a method of purifying crude BHET or the like by combining activated carbon and ion exchange resin, after passing through a single bed type strongly acidic cation exchange resin, a mixed bed type of strong acid cation exchange resin and weakly basic anion exchange resin is used. By passing the solution through the ion exchange resin layer, it is possible to perform a purification treatment such as crude BHET with little leakage of salts.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01329499A JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01329499A JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000212126A JP2000212126A (en) | 2000-08-02 |
| JP2000212126A5 JP2000212126A5 (en) | 2004-11-25 |
| JP3784561B2 true JP3784561B2 (en) | 2006-06-14 |
Family
ID=11829185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01329499A Expired - Lifetime JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3784561B2 (en) |
-
1999
- 1999-01-21 JP JP01329499A patent/JP3784561B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000212126A (en) | 2000-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2001122825A (en) | Method for purifying crude bishydroxyalkyl terephthalate | |
| JP2769391B2 (en) | Ethylene glycol recovery method | |
| KR20210067555A (en) | Method for chemical recycling waste plastics including crystallization | |
| JP2004181352A (en) | Method for refining non-aqueous liquid material | |
| JP3831775B2 (en) | Method for purifying bishydroxyalkyl terephthalate | |
| JP3784561B2 (en) | Method for purifying bishydroxyalkyl terephthalate | |
| JP2000191593A (en) | Purification of bishydroxyalkyl terephthalate | |
| US7306738B2 (en) | Method of deionizing solution yielded by polyester decomposition with ethylene glycol | |
| JP3243891B2 (en) | Purification method of pyruvate | |
| JP3001097B1 (en) | Method for producing sorbic acid | |
| JP2000239230A (en) | Purification of bishydroxyalkyl terephthalate | |
| JPH01115820A (en) | Production of niobium hydroxide of tantalum hydroxide | |
| JPH07258403A (en) | Purification of polyether | |
| JPH08259728A (en) | Production of aromatic dicarboxylic acid and alkylene glycol | |
| JP2004346229A (en) | Method for refining decomposition product solution obtained by decomposing polyester with ethylene glycol | |
| JPS58203927A (en) | Production of chloromethyl alkyl ether | |
| JPH0328114A (en) | Recycling method for aqueous by-product generated from manufacture of sodium dithionite | |
| JP3113776B2 (en) | Method for producing D-kilo-inositol | |
| JPH0636749B2 (en) | Method for purifying glucose solution or starch syrup | |
| JPH0456814B2 (en) | ||
| JP4280119B2 (en) | Method for producing iopamidol | |
| JP2000212117A (en) | Recovery of highly pure terephthalic acid from recovered polyester bottle | |
| JP3189023B2 (en) | Method for purifying arabinogalactan-containing composition | |
| JPS6081176A (en) | Method for separating inorganic salt formed as by- product in production of epoxy resin | |
| JPH024730A (en) | Purification of 2,2-bis(4-hydroxyphenyl) hexafluoro-propane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20031209 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20031209 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060307 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060315 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090324 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090324 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100324 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110324 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120324 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130324 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130324 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |