JPH07268020A - Production of vinyl chloride resin for paste technique - Google Patents
Production of vinyl chloride resin for paste techniqueInfo
- Publication number
- JPH07268020A JPH07268020A JP8596094A JP8596094A JPH07268020A JP H07268020 A JPH07268020 A JP H07268020A JP 8596094 A JP8596094 A JP 8596094A JP 8596094 A JP8596094 A JP 8596094A JP H07268020 A JPH07268020 A JP H07268020A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- organic liquid
- aqueous dispersion
- resin
- 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.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ペースト加工用塩化ビ
ニル樹脂の製造方法に関するものである。さらに詳しく
は、本発明は、塩化ビニル樹脂の水性分散液から、粉末
粒子にほぐれやすく、分散性の良好なペースト加工用塩
化ビニル樹脂粉体を、微分散されている特定粘度の有機
液体を用いて製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride resin for paste processing. More specifically, the present invention uses a vinyl chloride resin powder for paste processing, which easily disintegrates into powder particles from an aqueous dispersion of a vinyl chloride resin and has good dispersibility, using an organic liquid having a specific viscosity that is finely dispersed. Manufacturing method.
【０００２】[0002]
【従来の技術】塩化ビニル樹脂の重要な加工法の一つに
ペースト加工がある。塩化ビニル樹脂のペースト加工
は、ペースト加工用に製造された塩化ビニル樹脂を、可
塑剤、安定剤のほか、必要に応じて顔料、充填剤などの
配合剤とともに混合して液状のプラスチゾルとし、この
液状のプラスチゾルを注型、コーティング、浸漬などの
手段で賦型し、加熱溶融固化させることによって成形品
を得るものである。したがって、ペースト加工用塩化ビ
ニル樹脂には、粒径が非常に微細で可塑剤中に分散して
自由にブラウン運動を行い沈降しないこと、適切な粒度
分布を有すること、表面が平滑で内部が緻密な球形粒子
であること、可塑剤と混合するとき凝集することなく容
易に分散して安定なゾルを形成すること、常温では可塑
剤に膨潤されがたく熟成粘度変化が小さく、高温で溶融
する際には容易に迅速に均一にゲル化することなど、さ
まざまな性能が要求される。これらの要求性能の中でも
ゾル分散特性は特に重要である。ペースト加工用塩化ビ
ニル樹脂は、通常単一粒子が多数凝集して樹脂粒子粉体
を形成しているが、プラスチゾル中において、この集合
体が単一粒子にほぐれる必要があり、もしそのまま粗大
粒子として残存していると、プラスチゾルの流動性に影
響を与えるばかりでなく、プラスチゾルの輸送時の目づ
まり、コーティング加工時の筋引きなどのトラブルや、
成形品にした場合に、成形品表面の肌の荒れ及び光沢低
下、さらには成形品の強度低下などの不都合を引き起こ
す。ペースト加工用塩化ビニル樹脂のゾル分散特性は、
通常Ｎｏｒｔｈ Ｆｉｎｅｓｓ Ｇａｕｇｅによって評価
される。この評価法は、調製したプラスチゾルを、溝の
深さが直線的に変わる鋼製ゲージの基線上にのせ、スク
レーパーでゾルを浅い方に向かって引き、粗大凝集粒子
が点として多く現れる位置を読む方法であり、評価は０
〜８のＮＦ値として表される。ＮＦ値が大きいほど、粒
子が細かく、よく分散しているが、従来の技術では４以
上のＮＦ値を得ることは容易ではなかった。このような
ペースト加工上の問題点を改善するために、これに用い
る樹脂粉体を、通常Ｔｙｌｅｒふるい３２５メッシュ全
通のような微細な粉体として供給する方法が提案されて
いる。このための樹脂の製造方法としては、塩化ビニル
又は塩化ビニルを主体とする単量体混合物をラジカル発
生型重合開始剤と乳化剤の存在下に、乳化重合あるいは
微細懸濁重合することによって粒径０.０５〜５μｍの
球形樹脂の水性分散液を得、この水性分散液をスプレー
乾燥する方法が採られているが、水分を蒸発乾燥するに
は多量のエネルギーを必要とする欠点がある。また、こ
うした方法で得られた従来の樹脂は微細な粉体であるた
め、製品の袋詰め時、並びにプラスチゾル製造に際して
の開袋投入及び混合時の粉体飛散など、作業環境の悪化
を引き起こすばかりでなく、粉体流動性が悪いため、自
動計量、自動輸送が困難となっている。かかるペースト
加工用樹脂の現状の問題点を解決するために、ペースト
加工用塩化ビニル樹脂の水性分散液から塩化ビニル樹脂
を、水に難溶であって、かつ塩化ビニル樹脂を溶解又は
膨潤させない有機液体を、水性分散液に添加することに
より、塩化ビニル樹脂を集合体として水相より分離せし
め、これをそのままあるいは造粒させたのち乾燥するこ
とによって塩化ビニル樹脂を回収する方法が特公平１−
４２２８２号公報に提案されている。しかしながら、こ
の方法によって種々の問題点は一応改善されているが、
脱水後の湿潤樹脂集合体のまとまりが強く、乾燥工程で
のブロッキングの発生、乾燥の不均一、分散性の不良や
粗大粒子の存在による成形品の表面の粒状突起の発生な
どの欠点が依然として存在する。また、有機液体の使用
量を低減すると樹脂集合体の収率が低下するという欠点
があり、少ない量の有機液体でペースト加工用塩化ビニ
ル樹脂集合体を形成しうる方法の開発が望まれていた。2. Description of the Related Art Paste processing is one of the important processing methods for vinyl chloride resin. For the paste processing of vinyl chloride resin, the vinyl chloride resin produced for paste processing is mixed with a plasticizer, a stabilizer, and, if necessary, a compounding agent such as a pigment and a filler to form a liquid plastisol. A molded product is obtained by shaping a liquid plastisol by means such as casting, coating, and dipping and heating and melting and solidifying it. Therefore, the vinyl chloride resin for paste processing has a very fine particle size, disperses in the plasticizer, does not freely perform Brownian motion, and does not settle, has an appropriate particle size distribution, has a smooth surface and is dense inside. Spherical particles, that when dispersed with a plasticizer, it can be easily dispersed without agglomeration to form a stable sol, that it does not swell in the plasticizer at room temperature, its aging viscosity change is small, and it melts at high temperatures. Requires various performances such as easy and rapid gelation. Among these performance requirements, the sol dispersion property is particularly important. Vinyl chloride resin for paste processing usually has a large number of single particles agglomerated to form a resin particle powder, but in plastisol, this aggregate needs to be loosened into single particles, and if it remains as coarse particles, If it remains, it not only affects the fluidity of plastisol, but also causes troubles such as clogging during transport of plastisol and scoring during coating.
When it is used as a molded product, it causes inconveniences such as roughening of the surface of the molded product and deterioration of gloss, and further deterioration of strength of the molded product. The sol dispersion characteristics of vinyl chloride resin for paste processing are
Usually evaluated by the North Fines Gauge. In this evaluation method, the prepared plastisol is placed on the baseline of a steel gauge in which the depth of the groove changes linearly, and the sol is pulled toward the shallow side with a scraper, and the position where coarse agglomerated particles often appear is read. It is a method and the evaluation is 0
Expressed as a NF value of ~ 8. The larger the NF value, the finer the particles and the better the dispersion. However, it was not easy to obtain an NF value of 4 or more by the conventional technique. In order to improve such a problem in paste processing, there has been proposed a method in which a resin powder used for the paste is supplied as a fine powder such as a Tyler sieve 325 mesh. As a method for producing the resin for this purpose, a particle size of 0 is obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride or a monomer mixture mainly composed of vinyl chloride in the presence of a radical-generating type polymerization initiator and an emulsifier. A method of obtaining an aqueous dispersion of a spherical resin having a diameter of 0.05 to 5 μm and spray-drying this aqueous dispersion has been adopted, but it has a drawback that a large amount of energy is required to evaporate and dry water. Further, since the conventional resin obtained by such a method is a fine powder, it not only causes a deterioration of the work environment such as powder scattering at the time of bag packaging of the product and bag opening and mixing at the time of plastisol production. In addition, because of poor powder fluidity, automatic weighing and automatic transportation are difficult. In order to solve the current problems of the paste processing resin, a vinyl chloride resin from an aqueous dispersion of the paste processing vinyl chloride resin is an organic solvent that is hardly soluble in water and does not dissolve or swell the vinyl chloride resin. The liquid is added to the aqueous dispersion to separate the vinyl chloride resin as an aggregate from the aqueous phase, and a method of recovering the vinyl chloride resin as it is or after granulating and drying is disclosed in Japanese Patent Publication 1-
It is proposed in Japanese Patent No. 422282. However, although this method has improved various problems,
The wet resin aggregates are strongly united after dehydration, and there are still drawbacks such as blocking in the drying process, uneven drying, poor dispersibility and generation of granular projections on the surface of molded products due to the presence of coarse particles. To do. Further, there is a drawback that the yield of the resin aggregate decreases when the amount of the organic liquid used is reduced, and it has been desired to develop a method capable of forming a vinyl chloride resin aggregate for paste processing with a small amount of the organic liquid. .
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、塩化ビニル樹脂の水性分散液から、粉末
粒子にほぐれやすく、分散性の良好なペースト加工用塩
化ビニル樹脂を、少量の有機液体を用いて製造する方法
を提供することを目的としてなされたものである。Under these circumstances, the present invention provides a vinyl chloride resin for paste processing, which is easily disentangled into powder particles from an aqueous dispersion of vinyl chloride resin and has good dispersibility. The purpose of the present invention is to provide a method for manufacturing using a small amount of organic liquid.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記の目的
を達成するために鋭意研究を重ねた結果、塩化ビニル樹
脂の水性分散液に特定の粘度を有し、水に微分散された
有機液体を添加することにより、良好な性能を有する塩
化ビニル樹脂集合体が得られることを見いだし、その知
見に基づいて本発明を完成した。すなわち、本発明は、
ペースト加工用塩化ビニル樹脂の水性分散液に、水に難
溶であってかつ塩化ビニル樹脂を溶解又は膨潤させない
有機液体を添加することにより塩化ビニル樹脂を集合体
として水相より分離して回収する方法において、該有機
液体が３０℃において１００センチポアズ以上１０００
センチポアズ以下の粘度を有し、かつ水に微分散されて
いるものであることを特徴とするペースト加工用塩化ビ
ニル樹脂の製造方法を提供するものである。Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventor has found that an aqueous dispersion of vinyl chloride resin has a specific viscosity and is finely dispersed in water. It was found that a vinyl chloride resin aggregate having good performance can be obtained by adding an organic liquid, and the present invention was completed based on the findings. That is, the present invention is
By adding an organic liquid that is sparingly soluble in water and does not dissolve or swell the vinyl chloride resin to the aqueous dispersion of the vinyl chloride resin for paste processing, the vinyl chloride resin is collected as an aggregate from the aqueous phase. In the method, the organic liquid is 100 centipoise or more and 1000 at 30 ° C.
It is intended to provide a method for producing a vinyl chloride resin for paste processing, which has a viscosity of not more than centipoise and is finely dispersed in water.
【０００５】本発明方法は、基本的には塩化ビニル樹脂
の水性分散液を調整する第１工程、第１工程で得られた
水性分散液を回分式槽型混合機に導き、３０℃において
１００センチポアズ以上１０００センチポアズ以下の粘
度を有し、かつ水に微分散されている有機液体を添加す
る第２工程、塩化ビニル樹脂集合体の水性分散液から、
塩化ビニル樹脂集合体を分離回収する第３工程、及び回
収した塩化ビニル樹脂集合体を乾燥する第４工程から構
成される。本発明において用いられるペースト加工用塩
化ビニル樹脂の水性分散液は、通常の乳化重合又は微細
懸濁重合により製造された塩化ビニルの単独重合体、又
は塩化ビニルを主体とした（通常は７０重量％以上）共
重合体、例えば、塩化ビニルと酢酸ビニル、塩化ビニリ
デン、エチレン、プロピレン、ブテン、アクリロニトリ
ル、アクリル酸エステル、メタクリル酸エステル又はマ
レイン酸などの単量体との共重合体の水性分散液のこと
であって、通常のペースト加工に供しうるものであれば
特に制限なく使用することができる。本発明において用
いられる塩化ビニル樹脂の水性分散液は、通常塩化ビニ
ル樹脂を１０〜７０重量％程度含有するものである。こ
のような水性分散液としては、重合終了後の塩化ビニル
樹脂の水性分散液をそのまま使用してもよいし、必要な
らば一部脱水し、あるいは水を添加して用いてもよい。
塩化ビニル樹脂の含有量が１０重量％未満では廃水量が
製品量に比べて多くなりすぎ不経済であるし、塩化ビニ
ル樹脂の含有量が７０重量％を超えると、水性分散液と
有機液体との混合液の粘度が著しく上昇し操業が困難と
なる。In the method of the present invention, basically, the first step of preparing an aqueous dispersion of vinyl chloride resin, the aqueous dispersion obtained in the first step are introduced into a batch-type tank mixer, and 100 at 30 ° C. From the second step of adding an organic liquid having a viscosity of not less than 1000 centipoise and not more than 1000 centipoise and finely dispersed in water, an aqueous dispersion of a vinyl chloride resin aggregate,
It comprises a third step of separating and collecting the vinyl chloride resin aggregate, and a fourth step of drying the collected vinyl chloride resin aggregate. The aqueous dispersion of the vinyl chloride resin for paste processing used in the present invention is mainly composed of vinyl chloride homopolymer produced by ordinary emulsion polymerization or fine suspension polymerization, or vinyl chloride (usually 70% by weight). Above) copolymer, for example, an aqueous dispersion of a copolymer of vinyl chloride and vinyl acetate, vinylidene chloride, ethylene, propylene, butene, acrylonitrile, acrylic acid ester, methacrylic acid ester or a monomer such as maleic acid That is, any material that can be used for ordinary paste processing can be used without particular limitation. The aqueous dispersion of vinyl chloride resin used in the present invention usually contains about 10 to 70% by weight of vinyl chloride resin. As such an aqueous dispersion, an aqueous dispersion of a vinyl chloride resin after completion of polymerization may be used as it is, or may be partially dehydrated or water may be added if necessary.
If the content of vinyl chloride resin is less than 10% by weight, the amount of wastewater is too large compared to the product amount and it is uneconomical. If the content of vinyl chloride resin exceeds 70% by weight, the aqueous dispersion and the organic liquid are The viscosity of the mixed solution of (1) remarkably increases, which makes operation difficult.
【０００６】本発明方法においては、水に難溶であっ
て、塩化ビニル樹脂の分離回収時において塩化ビニル樹
脂を溶解又は膨潤させない有機液体であり、かつ３０℃
において１００センチポアズ以上１０００センチポアズ
以下、好ましくは１５０センチポアズ以上５００センチ
ポアズ以下の粘度を有するものが用いられる。３０℃に
おける粘度が１００センチポアズ未満の有機液体を用い
て得た塩化ビニル樹脂集合体は、プラスチゾルとしたと
きほぐれ易さが十分でなく満足すべき分散性を有しない
ので好ましくない。一方、３０℃における粘度が１００
０センチポアズを超える有機液体を使用すると、塩化ビ
ニル樹脂の水性分散液から均一な集合体となった粒状樹
脂を得ることができないので好ましくない。本発明方法
において用いられる有機液体は、３０℃における粘度が
１００センチポアズ以上１０００センチポアズ以下、好
ましくは１５０センチポアズ以上５００センチポアズ以
下であり、かつ水に難溶であって、塩化ビニル樹脂を水
性分散液から分離処理する温度において塩化ビニル樹脂
を溶解又は膨潤させないものであれば特に制限なく使用
することができ、例えば、フタル酸ジトリデシル、トリ
メリット酸トリオクチル、トリメリット酸トリイソデシ
ル、エポキシヘキサヒドロフタル酸ジイソデシルなどを
挙げることができる。さらに、エポキシ系可塑剤、例え
ば、エポキシ化大豆油なども適切な粘度と特性を有し上
記の条件を満足するものは、本発明方法において好適に
使用することができる。In the method of the present invention, it is an organic liquid which is sparingly soluble in water and does not dissolve or swell the vinyl chloride resin during separation and recovery of the vinyl chloride resin, and at 30 ° C.
In the above, a material having a viscosity of 100 to 1,000 centipoise, preferably 150 to 500 centipoise is used. A vinyl chloride resin aggregate obtained by using an organic liquid having a viscosity of less than 100 centipoise at 30 ° C. is not preferable because it does not have sufficient disentangling property when plastisol and does not have satisfactory dispersibility. On the other hand, the viscosity at 30 ° C is 100
The use of an organic liquid exceeding 0 centipoise is not preferable because it is not possible to obtain a granular resin in the form of a uniform aggregate from an aqueous dispersion of a vinyl chloride resin. The organic liquid used in the method of the present invention has a viscosity at 30 ° C. of 100 centipoises or more and 1000 centipoises or less, preferably 150 centipoises or more and 500 centipoises or less, and is sparingly soluble in water, and a vinyl chloride resin from an aqueous dispersion. It can be used without particular limitation as long as it does not dissolve or swell the vinyl chloride resin at the temperature for separation treatment, for example, ditridecyl phthalate, trioctyl trimellitate, triisodecyl trimellitate, diisodecyl epoxyhexahydrophthalate and the like. Can be mentioned. Further, epoxy plasticizers such as epoxidized soybean oil having suitable viscosity and properties and satisfying the above conditions can be suitably used in the method of the present invention.
【０００７】本発明方法において、有機液体は水中油滴
の状態で水に微分散させて使用する。本発明方法におい
て用いる有機液体は、その粘度が３０℃において１００
センチポアズ以上１０００センチポアズ以下であり、塩
化ビニル樹脂の水性分散液の粘度に比較すると高粘度で
あるので、あらかじめ微分散された状態にしておくこと
により、塩化ビニル樹脂の水性分散液の中での偏在を防
ぎ、均一に分散して塩化ビニル樹脂の集合体の形成に効
果を発揮することができる。有機液体の水中への微分散
を助けるためには、アニオン性界面活性剤又はノニオン
性界面活性剤を添加することができる。これらの界面活
性剤の添加量は有機液体に対して０.５〜１０重量％程
度が適当である。また、有機液体の水中への微分散のた
めに、高速撹拌機、振動撹拌機、超音波撹拌などの手段
を用いることができる。本発明方法においては、有機液
体は平均液滴径１０〜１００μｍの微分散状態で使用す
る。平均液滴径が１００μｍを超えると有機液体が偏在
し、本発明の目的は達せられない。また、平均液滴径を
１０μｍより小さくしても、そのために投入するエネル
ギーに見合う利点は見られない。塩化ビニル樹脂の水性
分散液から塩化ビニル樹脂を集合体として分離するため
に使用する有機液体は、一般には融点が２０℃以下であ
り、常圧における沸点が塩化ビニル樹脂の分離回収時の
温度以上、好ましくは２００℃以上のものが望ましい
が、本発明方法に用いる粘度を有する有機液体は、ほぼ
これらの条件を充足している。In the method of the present invention, the organic liquid is used by being finely dispersed in water in the form of oil drops in water. The organic liquid used in the method of the present invention has a viscosity of 100 at 30 ° C.
Since it is not less than 1000 centipoise and not more than 1000 centipoise, and has a high viscosity as compared with the viscosity of the aqueous dispersion of vinyl chloride resin, it is possible to disperse the vinyl chloride resin in the aqueous dispersion by making it finely dispersed in advance. It is possible to prevent the above, and to disperse evenly, and it is possible to exert an effect in forming an aggregate of the vinyl chloride resin. Anionic or nonionic surfactants can be added to aid the fine dispersion of the organic liquid in water. The amount of these surfactants added is appropriately about 0.5 to 10% by weight with respect to the organic liquid. Further, for finely dispersing the organic liquid in water, a means such as a high-speed stirrer, a vibration stirrer, or an ultrasonic stirrer can be used. In the method of the present invention, the organic liquid is used in a finely dispersed state having an average droplet diameter of 10 to 100 μm. If the average droplet diameter exceeds 100 μm, the organic liquid is unevenly distributed, and the object of the present invention cannot be achieved. Further, even if the average droplet diameter is smaller than 10 μm, there is no advantage corresponding to the energy input for that purpose. The organic liquid used to separate the vinyl chloride resin as an aggregate from the aqueous dispersion of the vinyl chloride resin generally has a melting point of 20 ° C. or lower and a boiling point at atmospheric pressure of the temperature at which the vinyl chloride resin is separated and recovered. The temperature is preferably 200 ° C. or higher, but the organic liquid having a viscosity used in the method of the present invention substantially satisfies these conditions.
【０００８】本発明に用いる有機液体が水に難溶である
ことが要求される理由は以下の２点にある。第１には、
水性分散液との混合のあと、分離すべき水相への同伴量
を減少させて、有機液体の損失を防ぎ、廃水処理費用を
軽減させるためであり、第２には、水に分散した塩化ビ
ニル樹脂粒子を有機液体を介して集合せしめるには、樹
脂粒子と水との間に有機液体が粒子表面に存在すること
が必要であるためである。また、本発明に用いる有機液
体が、本発明における分離回収時の温度において樹脂を
溶解又は膨潤させるものである場合には、樹脂粒子が変
形、変質を起こすため不都合である。なお、本発明で使
用する有機液体は、大部分が製品樹脂に残留するため、
ペースト加工時の操作性、加工性及び成形品の品質に対
し悪影響を与えるものは避けなければならない。以上の
点からすれば、有機液体として通常ペースト加工に用い
られる液状配合剤を使用するのが一番自然で合理的であ
る。本発明方法において用いられる有機液体の使用量
は、塩化ビニル樹脂１００重量部当たり０.１〜５重量
部、好ましくは１〜３重量部である。有機液体の使用量
が０.１重量部未満であると、水性分散液中の塩化ビニ
ル樹脂の集合体の形成が不十分であり、有機液体の使用
量が５重量部を超えると、空搬ダクトに塩化ビニル樹脂
粉体が付着したり、塩化ビニル樹脂集合体が固くなりペ
ースト調製時に分散性が悪くなるので好ましくない。The organic liquid used in the present invention is required to be sparingly soluble in water for the following two reasons. First,
After mixing with the aqueous dispersion, the amount of entrainment in the aqueous phase to be separated is reduced to prevent the loss of organic liquid and reduce the wastewater treatment cost. This is because it is necessary for the organic liquid to exist on the particle surface between the resin particles and water in order to collect the vinyl resin particles via the organic liquid. Further, when the organic liquid used in the present invention dissolves or swells the resin at the temperature at the time of separation and recovery in the present invention, the resin particles are deformed and deteriorated, which is inconvenient. Since most of the organic liquid used in the present invention remains in the product resin,
Items that adversely affect the operability and processability during paste processing and the quality of molded products must be avoided. From the above points, it is most natural and rational to use the liquid compounding agent which is usually used for paste processing as the organic liquid. The amount of the organic liquid used in the method of the present invention is 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin. When the amount of the organic liquid used is less than 0.1 part by weight, the formation of the vinyl chloride resin aggregate in the aqueous dispersion is insufficient, and when the amount of the organic liquid used exceeds 5 parts by weight, it is transported by air. The vinyl chloride resin powder adheres to the duct, and the vinyl chloride resin aggregate becomes hard, so that the dispersibility becomes poor at the time of preparing the paste, which is not preferable.
【０００９】本発明方法において、ペースト加工用塩化
ビニル樹脂の水性分散液と有機液体の混合には、回分式
槽型混合機を好適に使用することができる。回分式槽型
混合機としては、撹拌機や邪魔板を有する公知の混合機
が用いられる。混合の程度は、塩化ビニル樹脂の有機液
体による集合能率に大きな影響を与えるため、好ましく
は混合機の単位容積当たりの混合動力が１ｋＷ／ｍ3以
上であって、混合時間との積が４ｋＷ・Ｈｒ／ｍ3以上
であることが望ましい。本発明方法においては、回分式
槽型混合機において、塩化ビニル樹脂の水性分散液と有
機液体との混合液を、通常２０〜７０℃、かつ使用する
有機液体が塩化ビニル樹脂を溶解又は膨潤させない温度
で撹拌するが、高温になるほど有機液体により塩化ビニ
ル樹脂が膨潤されやすくなるので、５０℃以下で撹拌混
合することが有利である。この温度が７０℃を超えると
有機液体の塩化ビニル樹脂への吸収が速まるばかりか、
塩化ビニル樹脂が軟化し合体化して最終製品がもはやペ
ースト加工に適合しなくなるおそれがある。かかる操作
により、粒子径５０〜５００μｍ、平均１００〜３００
μｍの粒状の集合体を形成させることができる。次に、
有機液体を介して集合した塩化ビニル樹脂集合体を水相
から分離回収するには、集合体の形状に応じて公知の方
法、例えば、粒子径差を利用してろ布、金網などを用い
る真空脱水法や遠心脱水法、あるいは比重差を利用した
遠心沈降分離法などを用いることができる。In the method of the present invention, a batch type tank mixer can be preferably used for mixing the aqueous dispersion of the vinyl chloride resin for paste processing and the organic liquid. As the batch type tank mixer, a known mixer having a stirrer or a baffle plate is used. Since the degree of mixing has a great influence on the collection efficiency of the vinyl chloride resin with the organic liquid, the mixing power per unit volume of the mixer is preferably 1 kW / m 3 or more, and the product with the mixing time is 4 kW. It is preferably Hr / m 3 or more. In the method of the present invention, in a batch tank mixer, a mixed liquid of an aqueous dispersion of vinyl chloride resin and an organic liquid is usually 20 to 70 ° C., and the organic liquid used does not dissolve or swell the vinyl chloride resin. Stirring is carried out at a temperature, but the vinyl chloride resin is more likely to be swollen by the organic liquid as the temperature rises, so stirring and mixing at 50 ° C. or lower is advantageous. If this temperature exceeds 70 ° C, not only the absorption of the organic liquid into the vinyl chloride resin is accelerated,
The vinyl chloride resin may soften and coalesce and the final product may no longer be compatible with paste processing. By such an operation, the particle diameter is 50 to 500 μm, the average is 100 to 300.
It is possible to form a granular aggregate of μm. next,
In order to separate and collect the vinyl chloride resin aggregate aggregated through the organic liquid from the aqueous phase, a known method according to the shape of the aggregate, for example, vacuum dehydration using a filter cloth, a wire net, etc. by utilizing the difference in particle size. Method, centrifugal dehydration method, or centrifugal sedimentation separation method utilizing difference in specific gravity can be used.
【００１０】以下に、本発明の態様を列挙する。 （１）ペースト加工用塩化ビニル樹脂の水性分散液に、
水に難溶であってかつ塩化ビニル樹脂を溶解又は膨潤さ
せない有機液体を添加することにより塩化ビニル樹脂を
集合体として水相より分離して回収する方法において、
該有機液体が３０℃において１００センチポアズ以上１
０００センチポアズ以下の粘度を有し、かつ水に微分散
されているものであることを特徴とするペースト加工用
塩化ビニル樹脂の製造方法。 （２）有機液体の３０℃における粘度が１５０センチポ
アズ以上５００センチポアズ以下である上記(１)記載の
ペースト加工用塩化ビニル樹脂の製造方法。 （３）有機液体の液滴径が平均１０〜１００μｍである
上記(１)又は(２)記載のペースト加工用塩化ビニル樹脂
の製造方法。 （４）アニオン性界面活性剤又はノニオン性界面活性剤
を該有機液体に対し０.５〜１０重量％さらに添加した
上記(１)、(２)又は(３)記載のペースト加工用塩化ビニ
ル樹脂の製造方法。 分離工程において分離された塩化ビニル樹脂集合体は、
次に乾燥工程に送られ、付着水分が除去される。この乾
燥工程においては、ペースト加工時の分散性を損なわな
いような条件を設定することが必要である。すなわち乾
燥工程中の塩化ビニル樹脂の温度は、通常７０℃以下、
好ましくは５０℃以下となるようにする。すなわち、形
成された塩化ビニル樹脂集合体の粒子径分布に近い状態
の粒状を再現するように条件を選ぶ。乾燥装置として
は、被乾燥物の温度を低く維持するためには減圧の撹拌
乾燥機の使用が好ましく、また、樹脂の粒度が比較的揃
っていれば低温乾燥、操業能率向上の点から、流動床式
乾燥機が適当であるが、広く公知の乾燥装置が使用可能
である。乾燥工程においては装置を適当に選ぶことによ
って不定形の、あるいは粒度分布の広い樹脂を製品とし
て得ることも可能であるが、押出型造粒機などのペレッ
ト形成機を工程中に組み込むことによって粒子形状を均
質化することも可能である。この場合も、造粒時に熱や
圧力により樹脂が溶融したり有機液体を吸収したりし
て、ペースト混練時の分散性を損なうようなことがあっ
てはならない。The aspects of the present invention will be listed below. (1) To an aqueous dispersion of vinyl chloride resin for paste processing,
In a method of recovering the vinyl chloride resin as an aggregate by separating from the aqueous phase by adding an organic liquid that is poorly soluble in water and does not dissolve or swell the vinyl chloride resin,
The organic liquid is 100 centipoise or more at 30 ° C. 1
A method for producing a vinyl chloride resin for paste processing, which has a viscosity of 000 centipoise or less and is finely dispersed in water. (2) The method for producing a vinyl chloride resin for paste processing according to the above (1), wherein the viscosity of the organic liquid at 30 ° C. is 150 centipoise or more and 500 centipoise or less. (3) The method for producing a vinyl chloride resin for paste processing according to the above (1) or (2), wherein the droplet size of the organic liquid is 10 to 100 μm on average. (4) The vinyl chloride resin for paste processing according to the above (1), (2) or (3), wherein an anionic surfactant or a nonionic surfactant is further added to the organic liquid in an amount of 0.5 to 10% by weight. Manufacturing method. The vinyl chloride resin aggregate separated in the separation step is
Next, it is sent to a drying process to remove the attached water. In this drying step, it is necessary to set conditions that do not impair the dispersibility during paste processing. That is, the temperature of the vinyl chloride resin during the drying step is usually 70 ° C. or lower,
The temperature is preferably 50 ° C or lower. That is, the conditions are selected so that the granularity in a state close to the particle size distribution of the formed vinyl chloride resin aggregate is reproduced. As a drying device, it is preferable to use a reduced pressure stirring dryer in order to keep the temperature of the material to be dried low.Moreover, if the particle size of the resin is relatively uniform, low temperature drying, in order to improve the operating efficiency, flow A floor dryer is suitable, but widely known dryers can be used. In the drying process, it is possible to obtain a resin with an indeterminate shape or a wide particle size distribution as a product by selecting an appropriate device, but by incorporating a pellet forming machine such as an extrusion-type granulator in the process, particles can be obtained. It is also possible to homogenize the shape. Also in this case, the resin should not be melted or absorb the organic liquid due to heat or pressure during granulation, and the dispersibility during paste kneading should not be impaired.
【００１１】[0011]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。なお、実施例及び比較例における各特
性は下記の方法により判定した。 （１）ゾル分散特性 樹脂５０ｇとジ−２−エチルヘキシルフタレート３０ｇ
を擂潰機で混合して調製したものにより、ゾル中の樹脂
粒子の粒度ＮＦ（Ｎｏｒｔｈ Ｆｉｎｅｓｓ Ｇａｕｇ
ｅ）を測定した。溝の深さが直線的に変わる０.５イン
チ幅の鋼製ゲージの、深さ最大位置にある基線上にゾル
をのせ、スクレーパーでゾルを浅い方に向かって引き、
粗大凝集粒子が点として多く現れる位置を読む。０が最
も粗く、８が最も細かい。この数値の８は粒径０に相当
し、４は粒径５１μｍであり、０は粒径１０２μｍであ
る。ＮＦ値が大きいほど、粒子が細かく、よく分散して
いることを示す。 （２）回収率The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The properties in the examples and comparative examples were determined by the following methods. (1) Sol dispersion property 50 g resin and 30 g di-2-ethylhexyl phthalate
The particle size NF (North Fine Gauging) of the resin particles in the sol can be adjusted by mixing them with a crusher.
e) was measured. Place the sol on the base line at the maximum depth position of a 0.5 inch wide steel gauge where the groove depth changes linearly, and pull the sol toward the shallow side with a scraper,
Read the locations where large numbers of coarse particles appear as dots. 0 is the coarsest and 8 is the finest. This numerical value 8 corresponds to a particle size of 0, 4 is a particle size of 51 μm, and 0 is a particle size of 102 μm. The larger the NF value, the finer the particles and the better the dispersion. (2) Recovery rate
【数１】 [Equation 1]
【００１２】実施例１ ペースト加工用塩化ビニル樹脂の水性分散液を、あらか
じめ目開き２５０μｍの金網を張ったスクリーンに通
し、通過した水性分散液に水を加えて固形分含有量３５
重量％に調整した。次に調整した水性分散液１１kgを直
径２０cm、内容量１２リットルの槽型混合装置に入れ、
１１００rpmで撹拌を開始すると同時に混合装置底部よ
り、別途、容量５００mlのステンレス製ビーカーにトリ
メリット酸トリオクチル［新日本理化(株)社製、３０℃
における粘度１６２センチポアズ］１５０ｇ及び水１５
０ｇを入れ、高速撹拌機を用いて１１００rpmで１０分
間撹拌しトリメリット酸トリオクチルを微分散せしめた
ものを、撹拌を継続しつつ毎分７ｇの速度で４０分間注
入した。その後１１００rpmでさらに撹拌混合を９０分
継続したところ、粒状樹脂の水分散液が得られた。この
分散液を通気量８０ml／sec・cm2のろ布を用いて真空ろ
過し、粒状樹脂を分離したところ６７００ｇの湿潤粒状
樹脂が得られた。これを小型流動乾燥機で乾燥したとこ
ろ３９００ｇの粒状塩化ビニル樹脂が得られた。この粒
状塩化ビニル樹脂についてゾル分散特性を求めた。 実施例２ 容量５００mlのステンレス製ビーカーにトリメリット酸
トリイソデシル［新日本理化(株)社製、３０℃における
粘度２８７センチポアズ］１５０ｇ、水１５０ｇ及びポ
リオキシエチレンソルビタンモノラウレート１.５ｇを
入れ、高速撹拌機を用い１１００rpmで１０分間撹拌し
トリメリット酸トリイソデシルを微分散せしめた。ペー
スト加工用塩化ビニル樹脂の水性分散液を、あらかじめ
目開き２５０μｍの金網を張ったスクリーンに通し、通
過した水性分散液に水を加えて固形分含有量３５重量％
に調整した。次に調整した水性分散液１１kgを直径２０
cm、内容量１２リットルの槽型混合装置に入れ、１２５
０rpmで撹拌を開始すると同時に混合装置底部より上記
のトリメリット酸トリイソデシルの微分散液を毎分７ｇ
の速度で４０分間注入した。その後１１００rpmでさら
に撹拌混合を９０分継続したところ、粒状樹脂の水分散
液が得られた。この分散液を通気量８０ml／sec・cm2の
ろ布を用いて真空ろ過し粒状樹脂を分離したところ７０
１０ｇの湿潤粒状樹脂が得られた。これを小型流動乾燥
機で乾燥したところ３９６０ｇの粒状塩化ビニル樹脂が
得られた。この粒状塩化ビニル樹脂についてゾル分散特
性を求めた。Example 1 An aqueous dispersion of a vinyl chloride resin for paste processing was passed through a screen preliminarily covered with a wire mesh having openings of 250 μm, and water was added to the aqueous dispersion that had passed through to obtain a solid content of 35.
Adjusted to wt%. Next, 11 kg of the prepared aqueous dispersion was put into a tank type mixing device having a diameter of 20 cm and an internal volume of 12 liters,
Trioctyl trimellitate [manufactured by Shin Nippon Rika Co., Ltd., 30 ° C.] was added to a stainless steel beaker with a capacity of 500 ml separately from the bottom of the mixing device at the same time when stirring was started at 1100 rpm.
Viscosity of 162 centipoise] 150 g and water 15
0 g was added and the mixture was stirred at 1100 rpm for 10 minutes using a high-speed stirrer, and trioctyl trimellitate was finely dispersed, and the mixture was injected at a rate of 7 g / min for 40 minutes while continuing stirring. Then, the mixture was further stirred and mixed at 1100 rpm for 90 minutes to obtain an aqueous dispersion of granular resin. This dispersion was vacuum filtered using a filter cloth having an air flow rate of 80 ml / sec · cm 2 to separate the granular resin, and 6700 g of wet granular resin was obtained. When this was dried with a small fluid dryer, 3900 g of granular vinyl chloride resin was obtained. The sol dispersion characteristics of this granular vinyl chloride resin were determined. Example 2 Triisodecyl trimellitate [manufactured by Shin Nippon Rika Co., Ltd., viscosity 287 centipoise at 30 ° C.] 150 g, water 150 g and polyoxyethylene sorbitan monolaurate 1.5 g were put into a stainless steel beaker having a capacity of 500 ml, and high speed was applied. Using a stirrer, the mixture was stirred at 1100 rpm for 10 minutes to finely disperse triisodecyl trimellitate. The aqueous dispersion of vinyl chloride resin for paste processing was passed through a screen with a mesh of 250 μm in advance, and water was added to the aqueous dispersion that had passed through to obtain a solid content of 35% by weight.
Adjusted to. Next, 11 kg of the prepared aqueous dispersion is used to obtain a diameter of 20
cm, the volume of 12 liters, put into a tank type mixing device, 125
Start stirring at 0 rpm, and at the same time, from the bottom of the mixing device, 7 g of the above triisodecyl trimellitate fine dispersion liquid per minute.
For 40 minutes. Then, the mixture was further stirred and mixed at 1100 rpm for 90 minutes to obtain an aqueous dispersion of granular resin. The dispersion liquid was vacuum filtered using a filter cloth having an air flow rate of 80 ml / sec · cm 2 to separate the granular resin.
10 g of wet granular resin was obtained. When this was dried with a small fluid dryer, 3960 g of granular vinyl chloride resin was obtained. The sol dispersion characteristics of this granular vinyl chloride resin were determined.
【００１３】比較例１ 容量５００mlのステンレス製ビーカーにジイソノニルフ
タレート［３０℃における粘度４１センチポアズ］１５
０ｇ、水１５０ｇ及びポリオキシエチレンソルビタンモ
ノラウレート１.５ｇを入れ、高速撹拌機を用い１１０
０rpmで１０分間撹拌しジイソノニルフタレートを微分
散せしめた。ペースト加工用塩化ビニル樹脂の水性分散
液を、あらかじめ目開き２５０μｍの金網を張ったスク
リーンに通し、通過した水性分散液に水を加えて固形分
含有量３５重量％に調整した。次に調整した水性分散液
１１kgを直径２０cm、内容量１２リットルの槽型混合装
置に入れ、１１００rpmで撹拌を開始すると同時に混合
装置底部より上記のジイソノニルフタレートの微分散液
を毎分７ｇの速度で４０分間注入した。その後１１００
rpmでさらに撹拌混合を９０分継続したところ、粒状樹
脂の水分散液が得られた。その分散液を通気量８０ml／
sec・cm2のろ布を用いて真空ろ過し粒状樹脂を分離した
ところ６３９０ｇの湿潤粒状樹脂が得られた。これを小
型流動乾燥機で乾燥したところ３８８０ｇの粒状塩化ビ
ニル樹脂が得られた。この粒状塩化ビニル樹脂について
ゾル分散特性を求めた。実施例１、実施例２及び比較例
１の結果を第１表に示す。Comparative Example 1 Diisononyl phthalate [viscosity 41 centipoise at 30 ° C.] 15 was added to a stainless beaker having a capacity of 500 ml.
0 g, 150 g of water and 1.5 g of polyoxyethylene sorbitan monolaurate were added, and a high speed stirrer was used.
The mixture was stirred at 0 rpm for 10 minutes to finely disperse the diisononyl phthalate. The aqueous dispersion of vinyl chloride resin for paste processing was passed through a screen having a wire mesh of 250 μm open beforehand, and water was added to the aqueous dispersion that had passed through to adjust the solid content to 35% by weight. Next, 11 kg of the prepared aqueous dispersion was put into a tank-type mixing device having a diameter of 20 cm and an internal volume of 12 liters, and stirring was started at 1100 rpm. At the same time, the fine dispersion of diisononyl phthalate described above was mixed from the bottom of the mixing device at a rate of 7 g / min. Infused for 40 minutes. Then 1100
When stirring and mixing were further continued for 90 minutes at rpm, an aqueous dispersion of granular resin was obtained. Aeration volume of 80 ml /
6390g wet granulation resin was separated granular resin was vacuum filtered with a sec · cm 2 of filtrate fabric was obtained. When this was dried with a small fluid dryer, 3880 g of granular vinyl chloride resin was obtained. The sol dispersion characteristics of this granular vinyl chloride resin were determined. The results of Example 1, Example 2 and Comparative Example 1 are shown in Table 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】比較例１の塩化ビニル樹脂から得られたプ
ラスチゾルのＮＦ値が４.０であるのに対して、実施例
１のＮＦ値は５.０、実施例２のＮＦ値は５.５であり、
本発明方法により得られた塩化ビニル樹脂はプラスチゾ
ルにおいて良好な分散性を有していることが分かる。The plastisol obtained from the vinyl chloride resin of Comparative Example 1 has an NF value of 4.0, while the NF value of Example 1 is 5.0 and the NF value of Example 2 is 5.5. And
It can be seen that the vinyl chloride resin obtained by the method of the present invention has good dispersibility in plastisol.
【００１６】[0016]
【発明の効果】ペースト加工用塩化ビニル樹脂の水性分
散液に３０℃における粘度が１００センチポアズ以上１
０００センチポアズ以下の有機液体を微分散状態で添加
することにより、プラスチゾル中で容易に単一粒子にほ
ぐれ、良好な分散状態を与える塩化ビニル樹脂粒子集合
体を得ることができる。EFFECTS OF THE INVENTION Aqueous dispersions of vinyl chloride resin for paste processing have a viscosity of 100 centipoise or more at 30 ° C.
By adding an organic liquid of not more than 000 centipoise in a finely dispersed state, it is possible to easily loosen into single particles in plastisol to obtain a vinyl chloride resin particle aggregate which gives a good dispersed state.
Claims (1)
液に、水に難溶であってかつ塩化ビニル樹脂を溶解又は
膨潤させない有機液体を添加することにより塩化ビニル
樹脂を集合体として水相より分離して回収する方法にお
いて、該有機液体が３０℃において１００センチポアズ
以上１０００センチポアズ以下の粘度を有し、かつ水に
微分散されているものであることを特徴とするペースト
加工用塩化ビニル樹脂の製造方法。1. A vinyl chloride resin as an aggregate is added to an aqueous dispersion of a vinyl chloride resin for paste processing by adding an organic liquid that is hardly soluble in water and does not dissolve or swell the vinyl chloride resin from an aqueous phase. A method for separating and recovering, wherein the organic liquid has a viscosity of 100 centipoise or more and 1000 centipoise or less at 30 ° C. and is finely dispersed in water. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08596094A JP3947234B2 (en) | 1994-03-31 | 1994-03-31 | Manufacturing method of vinyl chloride resin for paste processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08596094A JP3947234B2 (en) | 1994-03-31 | 1994-03-31 | Manufacturing method of vinyl chloride resin for paste processing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07268020A true JPH07268020A (en) | 1995-10-17 |
| JP3947234B2 JP3947234B2 (en) | 2007-07-18 |
Family
ID=13873319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08596094A Expired - Fee Related JP3947234B2 (en) | 1994-03-31 | 1994-03-31 | Manufacturing method of vinyl chloride resin for paste processing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3947234B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002572A1 (en) * | 1997-07-07 | 1999-01-21 | Shin Dai-Ichi Vinyl Corporation | Vinyl chloride resin granules for paste processing and process for producing the same |
| GB2344345A (en) * | 1998-12-02 | 2000-06-07 | Solvay | Halogen-containing vinyl polymer resins |
-
1994
- 1994-03-31 JP JP08596094A patent/JP3947234B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002572A1 (en) * | 1997-07-07 | 1999-01-21 | Shin Dai-Ichi Vinyl Corporation | Vinyl chloride resin granules for paste processing and process for producing the same |
| JP4059929B2 (en) * | 1997-07-07 | 2008-03-12 | 新第一塩ビ株式会社 | Vinyl chloride resin granules for paste processing and manufacturing method thereof |
| GB2344345A (en) * | 1998-12-02 | 2000-06-07 | Solvay | Halogen-containing vinyl polymer resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3947234B2 (en) | 2007-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3432483A (en) | Continuous process for preparing finely divided polymers | |
| US4581444A (en) | Flocculation of latex particles and production of thermoplastic resin | |
| JPH03255133A (en) | Manufacture of agglomerated molding powder consisting of polytetrafluoroethylene and hydrophobic filler | |
| JP2005520928A (en) | Production method of sub-micron polytetrafluoroethylene powder and their products | |
| JP2581322B2 (en) | Method for producing vinyl chloride resin for paste processing | |
| JP3947234B2 (en) | Manufacturing method of vinyl chloride resin for paste processing | |
| US4604454A (en) | Method of recovering vinyl chloride resin | |
| JPH054976B2 (en) | ||
| JPH0240086B2 (en) | NETSUKASOSEIJUSHINOSEIZOHOHO | |
| JP4059929B2 (en) | Vinyl chloride resin granules for paste processing and manufacturing method thereof | |
| WO1989002905A1 (en) | Process for continuously producing granular polymer and process for controlling particle size of said polymer | |
| JPH0873519A (en) | Production of vinyl chloride resin for paste processing | |
| JPH0378413B2 (en) | ||
| JPH0247482B2 (en) | NETSUKASOSEIJUSHINOSEIZOHOHO | |
| JPS61176615A (en) | Method for recovering vinyl chloride resin | |
| GB1590097A (en) | Process for the manufacture of a powder based on a vinyl chloride polymer and suitable for the preparation of a plastisol | |
| US4171428A (en) | Method for manufacturing plastisol resins using spray-drying | |
| JPH07268021A (en) | Production of vinyl chloride resin for paste technique | |
| TW200533595A (en) | Process for the manufacture of a composite material, composite material and use thereof | |
| JP3532376B2 (en) | Method for producing vinyl chloride resin granules for paste foam molding | |
| JPH0134259B2 (en) | ||
| JPH07102076A (en) | Production of vinyl chloride resin powder for paste processing | |
| JP3257078B2 (en) | Recovery method for vinyl chloride resin | |
| CN214327614U (en) | Polyvinyl chloride resin pasting device based on micro-suspension method | |
| JP3956169B2 (en) | Vinyl chloride resin granules for paste processing and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Effective date: 20040225 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040426 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050623 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050823 |
|
| A61 | First payment of annual fees (during grant procedure) |
Effective date: 20070413 Free format text: JAPANESE INTERMEDIATE CODE: A61 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |