JPH1036549A - Foamed molded product having termite-repelling property and its production - Google Patents
Foamed molded product having termite-repelling property and its productionInfo
- Publication number
- JPH1036549A JPH1036549A JP20774196A JP20774196A JPH1036549A JP H1036549 A JPH1036549 A JP H1036549A JP 20774196 A JP20774196 A JP 20774196A JP 20774196 A JP20774196 A JP 20774196A JP H1036549 A JPH1036549 A JP H1036549A
- Authority
- JP
- Japan
- Prior art keywords
- termite
- expanded particles
- particles
- resistant
- molded article
- 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、建築物の断熱材・
保温材等として使用される防蟻性を有する発泡成形体及
びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a heat insulating material for a building.
The present invention relates to a termite-resistant foam molded article used as a heat insulating material and the like and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より上記のような防蟻性を有する発
泡成形体の製造方法としては、発泡成形体の表面に防蟻
性物質を有効成分とする防蟻剤を塗布し、その成形体表
面に防蟻性膜を形成する方法が知られている。しかしな
がら上記方法は、発泡成形体に塗布するに当たって、嵩
張る未塗布発泡成形体を塗布工程に運ぶために多大な輸
送コストを必要とする問題を有し、また刷毛などによる
塗装は作業に長時間かかるという問題を、吹き付け塗装
は歩留まりが悪く経済的ではないという問題を有してい
た。さらに被塗装物が複雑な形状を有する場合、細部ま
で塗布が困難になるという問題も有していた。2. Description of the Related Art Conventionally, as a method for producing a foamed molded article having the above-mentioned termite-controlling properties, a termite-controlling agent containing a termite-controlling substance as an active ingredient is applied to the surface of the foamed molded article, A method of forming a termite-resistant film on the surface is known. However, the above-mentioned method has a problem that a large transportation cost is required to carry a bulky uncoated foamed molded article to an application step in applying the foamed molded article, and painting with a brush or the like takes a long time to work. However, spray coating has a problem that the yield is low and it is not economical. Further, when the object to be coated has a complicated shape, there is also a problem that it is difficult to apply the details to the details.
【０００３】そこで上記のような問題を回避するため
に、発泡成形体を製造する前の段階、すなわち原料樹脂
にクロルピリホス等の防蟻性物質を多量に混練した後、
発泡剤を含浸させる等して発泡性樹脂粒子とし、続いて
予備発泡させて予備発泡粒子とし、さらに発泡成形して
防蟻性を有する発泡成形体とする方法も考えられる。Therefore, in order to avoid the above-mentioned problem, a step before the production of the foamed molded article, that is, after kneading a large amount of termite-resistant substance such as chlorpyrifos to the raw material resin,
A method of impregnating a foaming agent into foamed resin particles, preliminarily foaming to form prefoamed particles, and foam molding to form a foamed article having termite resistance is also conceivable.
【０００４】しかしながら上記方法では、良好な防蟻性
を発揮するためには防蟻性物質の混合割合を多くする必
要があり、その結果混練された防蟻性物質により得られ
た発泡成形体の機械的強度が著しく低下するという問題
を生じていた。However, in the above-mentioned method, it is necessary to increase the mixing ratio of the termite-controlling substance in order to exhibit good termite-controlling properties. As a result, the foamed molded article obtained from the kneaded termite-controlling substance is required. There has been a problem that the mechanical strength is significantly reduced.
【０００５】そこで上記のような各問題を回避するため
に、発泡成形体を製造する前の段階、すなわち予備発泡
粒子に防蟻性を付加し発泡させて防蟻性を有する発泡成
形体を製造する方法が考えられる。Therefore, in order to avoid the above-mentioned problems, a stage before the production of the foamed molded body, that is, the pre-expanded particles are added with termite-proofing and foamed to produce a foamed molded body having the termite-proofing property. There is a way to do it.
【０００６】まず防蟻性物質又は防蟻剤を予備発泡粒子
と混合して付着させる方法は、予備発泡粒子に対する防
蟻性物質又は防蟻剤の付着力が欠け実用にならない。次
に防蟻性物質又は防蟻剤を接着剤（バインダー）と混合
攪拌し、予備発泡粒子に塗布して乾燥させて防蟻性物質
又は防蟻剤を予備発泡粒子に付着させた後、その予備発
泡粒子を金型内で発泡させて成形し防蟻性発泡成形体を
得る方法が開示されている（特公平６−１０２７６号広
報参照）。First, the method of adhering a termite-controlling substance or a termiticide to a pre-expanded particle by mixing it with the pre-expanded particle is not practical because the termite-controlling substance or the termite-controlling agent has insufficient adhesion to the pre-expanded particles. Next, the termite-controlling substance or termite-controlling agent is mixed and stirred with an adhesive (binder), applied to the pre-expanded particles and dried to adhere the termite-controlling substance or the termiticide to the pre-expanded particles. A method is disclosed in which the pre-expanded particles are foamed in a mold to obtain a termite-resistant foam molded article (see Japanese Patent Publication No. 6-10276).
【０００７】[0007]
【発明が解決しようとする課題】ところが上記方法で
は、防蟻性を付加するための防蟻性物質又は防蟻剤と接
着剤とを一度に投入しているため、混合時に予備発泡粒
子がコーティングされながら互いに接着して団子状にな
ってしまうという問題を生じ、そのため団子状の予備発
泡粒子を一たん乾燥して粉砕するという製造上の手間と
いう問題を有している。However, in the above method, since the termite-controlling substance or termite-controlling agent and the adhesive for adding termite-controlling properties are added at once, the pre-expanded particles are coated at the time of mixing. However, there is a problem in that the pre-expanded particles are dried and crushed once, so that there is a problem in production.
【０００８】[0008]
【問題を解決するための手段】上記の問題を解決するた
めに、本発明者らは発泡成形体を製造する前の予備発泡
粒子に着目し種々の方法を検討した結果、予備発泡粒子
に防蟻剤を均一にかつ乾燥させながら塗布して防蟻性を
もった予備発泡粒子を形成し、しかも前記の粉砕の後工
程を必要としない新たな方法を完成した。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have focused on pre-expanded particles before producing a foamed molded article and studied various methods. A new method was completed in which pre-expanded particles having termite resistance were formed by applying an ant agent uniformly and while drying, and which did not require a post-pulverization step.
【０００９】すなわち本発明の防蟻性を有する発泡成形
体の製造方法は、予備発泡粒子を空中に浮遊流動させな
がら、その予備発泡粒子に防蟻剤と接着剤とを噴霧して
防蟻性予備発泡粒子を形成した後、その防蟻性予備発泡
粒子を発泡成形して防蟻性発泡成形体を得ることを特徴
としている。That is, the method for producing a termite-resistant foamed molded article of the present invention comprises spraying a termiticide and an adhesive onto the pre-expanded particles while floating the pre-expanded particles in the air. After forming the pre-expanded particles, the termite-resistant pre-expanded particles are subjected to foam molding to obtain a termite-resistant expanded molded article.
【００１０】また本発明の防蟻性を有する発泡成形体の
製造方法は、ポリスチレン等の樹脂からなる予備発泡粒
子を空中に浮遊流動させながら、その予備発泡粒子に防
蟻剤と特定の特性を有する接着剤とを噴霧して防蟻性予
備発泡粒子を形成した後、その防蟻性予備発泡粒子を前
記予備発泡粒子と混合し、その混合体を発泡成形して防
蟻性発泡成形体を得ることを特徴としている。Further, the method for producing a termite-resistant foamed molded article of the present invention is characterized in that the pre-expanded particles made of a resin such as polystyrene are floated and flown in the air while the pre-expanded particles have a specific property as a termiticide. After spraying an adhesive having the composition, the termite-resistant pre-expanded particles are mixed with the termite-resistant pre-expanded particles, and the mixture is foam-formed to form a termite-resistant expanded molded article. It is characterized by obtaining.
【００１１】本発明の予備発泡粒子としては、発泡性樹
脂であればどのような樹脂でも用いることができ、ポリ
スチレン樹脂、ポリエチレン樹脂、ポリメチルメタクリ
レートなどのメタクリル酸エステル重合体の他、上記ポ
リスチレンおよびメタクリル酸エステルの共重合体の予
備発泡粒子等を用いることができる。また予備発泡粒子
の発泡倍率は何倍でも塗布するに際しての支障はない。As the pre-expanded particles of the present invention, any resin may be used as long as it is an expandable resin. In addition to methacrylic acid ester polymers such as polystyrene resin, polyethylene resin, and polymethyl methacrylate, the above-mentioned polystyrene and Pre-expanded particles or the like of a methacrylate copolymer can be used. Also, there is no problem in applying the pre-expanded particles regardless of the expansion ratio.
【００１２】一方本発明の防蟻剤における接着剤として
は、熱可塑性樹脂系の接着剤が使用され、溶剤型常温乾
燥タイプとして、熱可塑性アクリル樹脂、熱可塑性ポリ
エステル樹脂、塩化ビニル樹脂、ウレタン樹脂、ウレタ
ン変性アクリル樹脂、アクリル変性シリコン樹脂等が、
さらにエマルジョン系樹脂としてアクリルエマルジョ
ン、アクリル／スチレン共重合エマルジョン、アクリル
／酢酸ビニル共重合エマルジョン、エチレン／酢酸ビニ
ル共重合エマルジョン、エポキシエマルジョン、ウレタ
ンエマルジョン等が、一方水溶性常温乾燥タイプとし
て、ポリエステル樹脂、ポリアミド樹脂ポリウレタン樹
脂等が使用できる。なおこの接着剤に求められる特性と
して、常温では相互に接着せず一方発泡成形温度では相
互に接着すること、即ちガラス転移温度（Ｔｇ）が−５
０℃以上、４０℃以下のものが使用され、好ましくは−
３５℃以上、３５℃以下のものが使用される。またポリ
スチレンなどを溶解しないため希釈剤として水又はアル
コール系溶剤を使用したバインダーが望ましい。このよ
うな物性を有するエマルジョンとしてアクロナールＰ−
６９８４、ヨドゾールＡＤ−５１（いずれもアクリル／
スチレン樹脂・水エマルション）等をあげることができ
る。On the other hand, a thermoplastic resin-based adhesive is used as an adhesive in the termiticide of the present invention, and a thermoplastic acrylic resin, a thermoplastic polyester resin, a vinyl chloride resin, a urethane resin is used as a solvent-type room temperature drying type. , Urethane modified acrylic resin, acrylic modified silicone resin, etc.
Further, as emulsion resins, acrylic emulsions, acrylic / styrene copolymerized emulsions, acrylic / vinyl acetate copolymerized emulsions, ethylene / vinyl acetate copolymerized emulsions, epoxy emulsions, urethane emulsions, and the like; on the other hand, polyester resins, Polyamide resin polyurethane resin or the like can be used. The properties required of this adhesive are that it does not adhere to each other at room temperature while it adheres to each other at the foam molding temperature, that is, the glass transition temperature (Tg) is -5.
Those having a temperature of 0 ° C or more and 40 ° C or less are used, preferably-
Those having a temperature of 35 ° C or more and 35 ° C or less are used. Further, a binder using water or an alcohol-based solvent as a diluent is desirable because it does not dissolve polystyrene and the like. As an emulsion having such properties, Acronal P-
6984, Iodosol AD-51 (all acrylic /
Styrene resin, water emulsion) and the like.
【００１３】また本発明の防蟻剤を構成する防蟻性物質
としては、ペルメトリン、ビフェントリン、トラロメス
リン等のピレスロイド系薬剤、クロルピリホス、フェニ
トロチオン、プロペタンホス等の有機リン系薬剤、フェ
ノブカルブ等のカーバメート系薬剤その他が使用できる
が、臭気や安全性などの点からマイクロカプセル化した
材料の使用も考えられる。なお防蟻剤と接着剤との混合
割合をＦ値（固形分、つまり不揮発分中の防蟻性物質の
重量％）で表わすと、Ｆ＝５〜９０％、好ましくはＦ＝
１０〜８０％である。また着色顔料として無機系顔料、
有機系顔料を防蟻剤に微量添加することにより、有彩色
防蟻剤として使用することも可能である。The termite-controlling substances constituting the termite-controlling agent of the present invention include pyrethroids such as permethrin, bifenthrin, and tralomethrin; organic phosphorus-based drugs such as chlorpyrifos, fenitrothion and propetanephos; Can be used, but the use of a microencapsulated material is also conceivable in terms of odor and safety. When the mixing ratio of the termiticide and the adhesive is represented by an F value (solid content, that is, the weight% of the termite-controlling substance in the non-volatile content), F = 5 to 90%, preferably F =
10-80%. In addition, inorganic pigments as coloring pigments,
By adding a small amount of an organic pigment to the termiticide, it can be used as a chromatic termiticide.
【００１４】また防蟻性物質としては、白蟻の行動特性
から考えてとくに白蟻に対する忌避性を有するものが有
用であり、例えばペルメトリン、ビフェントリン等のピ
レスロイド系防蟻剤のやヒノキチオール等の混用が望ま
しい。特に忌避性防蟻剤は防蟻性予備発泡粒子の混用比
率を下げても防蟻効果を発揮し得る点で有用である。As the termite-inhibiting substance, those having a repellency against termites are particularly useful in view of the behavioral characteristics of termites. . In particular, repellent termiticides are useful in that the termite-controlling effect can be exerted even when the mixing ratio of termite-controlling pre-expanded particles is reduced.
【００１５】次に予備発泡粒子に防蟻剤を塗布する方法
には、空間部を有しその下部より上方に向かって空気の
吹き込みが可能で、その空間部に防蟻剤などの液体を噴
霧できる装置、例えば流動層乾燥装置を用いる。なお吹
き込む空気の温度を調節する熱交換器を設けてもよい。Next, a method of applying an anti-termitic agent to the pre-expanded particles is as follows: a space is provided, air can be blown upward from a lower portion thereof, and a liquid such as an anti-termitic agent is sprayed into the space. A device that can be used, for example, a fluidized bed dryer is used. A heat exchanger for adjusting the temperature of the blown air may be provided.
【００１６】上記方法では、まず上記装置内に予め所定
倍率に予備発泡させた予備発泡粒子を投入した後、その
装置の下部より空気を吹き込み、予備発泡粒子を装置内
で流動させて浮遊させる。しかるのち水等の溶剤などで
希釈した防蟻剤及び接着剤混合物を一定の割合づつ装置
内で噴霧させ、予備発泡粒子の表面に防蟻剤及び接着剤
混合物を徐々に塗着させる。このとき装置の下部より吹
き込まれている空気により上記溶剤の蒸発が生じ、防蟻
剤及び接着剤混合物の塗布された予備発泡粒子の表面は
徐々に乾燥される。In the above-mentioned method, first, pre-expanded particles which have been pre-expanded at a predetermined magnification are put into the above-mentioned apparatus, and then air is blown from the lower part of the apparatus to flow and float the pre-expanded particles in the apparatus. Thereafter, a mixture of the termiticide and the adhesive diluted with a solvent such as water is sprayed at a constant rate in the apparatus, and the surface of the pre-expanded particles is gradually coated with the mixture of the termiticide and the adhesive. At this time, the solvent is evaporated by the air blown from the lower part of the apparatus, and the surface of the pre-expanded particles to which the termiticide and the adhesive mixture are applied is gradually dried.
【００１７】予め定められた量の防蟻剤及び接着剤混合
物の供給を終了した後、しばらく空気の吹き込みを続
け、防蟻剤及び接着剤混合物の塗布された予備発泡粒子
の表面を完全に乾燥させた後に、その塗布された予備発
泡粒子を装置から取り出す。After the supply of the predetermined amount of the termite-controlling agent and the adhesive mixture is completed, air blowing is continued for a while to completely dry the surface of the pre-expanded particles coated with the termite-controlling agent and the adhesive mixture. After that, the applied pre-expanded particles are removed from the apparatus.
【００１８】なおこの場合の防蟻剤と接着剤の吹き込み
は、混合物での吹き込みに限定されることなく、別々に
噴霧用装置を用いて吹き込むことも可能である。In this case, the blowing of the termiticide and the adhesive is not limited to the blowing with the mixture, but it is also possible to blow separately using a spraying device.
【００１９】このようにして得られた防蟻性を有する予
備発泡粒子を、所定の金型の型窩内で発泡成形すること
により所望する形状を有する防蟻性発泡成形体とするこ
とができる。この防蟻性発泡成形体は、防蟻剤に含有さ
れる防蟻性物質の作用により良好な防蟻性を有してい
る。さらに上記の防蟻性を有する予備発泡粒子を未塗布
の予備発泡粒子と混合させたものを上記と同様に成形し
ても、良好な防蟻性を有する防蟻性発泡成形体を得るこ
とができる。The termite-resistant foamed molded article having a desired shape can be obtained by subjecting the thus obtained pre-expanded termite-resistant particles to foam molding in a mold cavity of a predetermined mold. . This termite-resistant foamed molded article has good termite-control properties due to the action of the termite-controlling substance contained in the termite-controlling agent. Furthermore, even if the pre-expanded particles having the above-mentioned termite-controlling properties are mixed with uncoated pre-expanded particles in the same manner as described above, it is possible to obtain a termite-resistant foamed molded article having a good termite-proofing property. it can.
【００２０】[0020]
【作用】本発明の方法により、予備発泡粒子を空中に浮
遊流動させながらその予備発泡粒子に防蟻剤及び接着剤
を噴霧するから、予備発泡粒子の表面により均一に防蟻
剤を塗布することができ、かつ予備発泡粒子が塗布され
ながら空中で浮遊して流動しており、吹きつけられる空
気によりその予備発泡粒子が乾燥されていくことから、
各予備発泡粒子が相互に接着して団子状になることも回
避されつつ乾燥される。According to the method of the present invention, a termiticide and an adhesive are sprayed on the pre-expanded particles while floating the pre-expanded particles in the air. And the pre-expanded particles are floating in the air while the pre-expanded particles are applied, and since the pre-expanded particles are dried by the blown air,
The pre-expanded particles are dried while being prevented from adhering to each other to form a dumpling.
【００２１】[0021]
（実施例１）本発明の実施例について図１に基づいて説
明すれば、以下の通りである。図１に示すように、予備
発泡粒子２に防蟻剤及び接着剤混合物３を塗布する装置
として、流動コーティング機１（商品名：ミクスグラー
ド、（株）大川原製作所製）を用いており、この流動コ
ーティング機１は略円筒状に成形され、その下部に設け
られた網板状の流動床８の下側に空気を送り込む送風フ
ァン６が設けられ、その空気の温度を必要に応じて調節
する熱交換器７が設置されている。(Embodiment 1) An embodiment of the present invention will be described below with reference to FIG. As shown in FIG. 1, a fluid coating machine 1 (trade name: Mixgrade, manufactured by Okawara Seisakusho Co., Ltd.) is used as an apparatus for applying a termiticide and an adhesive mixture 3 to the pre-expanded particles 2. The fluid coating machine 1 is formed into a substantially cylindrical shape, and is provided with a blower fan 6 for blowing air below a mesh-shaped fluidized bed 8 provided below the fluid coating machine 1, and adjusts the temperature of the air as necessary. A heat exchanger 7 is provided.
【００２２】また流動コーティング機１の空間部中央に
下方に向かって、防蟻剤及び接着剤混合物３を噴霧する
ノズル４が配設され、そのノズル４には、防蟻剤及び接
着剤混合物３を送液するローラー式等のポンプ５が接続
されている。さらに流動コーティング機１の上部には、
流動床８からの空気を排気する排気口９が設けられてい
る。なおその排気口９に予備発泡粒子２が通過して外部
に排出されるのを防止するバグフィルター等のフィルタ
ー（図示せず）が設けられている。なお図中の矢印は空
気の流れる方向を示す。A nozzle 4 for spraying the termiticide and adhesive mixture 3 is disposed downwardly in the center of the space of the fluidized coating machine 1. Is connected to a pump 5 of a roller type or the like for sending liquid. Furthermore, on the upper part of the fluid coating machine 1,
An exhaust port 9 for exhausting air from the fluidized bed 8 is provided. The exhaust port 9 is provided with a filter (not shown) such as a bag filter for preventing the pre-expanded particles 2 from passing through and being discharged to the outside. The arrows in the figure indicate the direction in which the air flows.
【００２３】次にこのような流動コーティング機１を用
いて防蟻性を有する発泡成形体の製造方法について説明
する。まず約５０倍に予備発泡させたポリスチレンから
なる予備発泡粒子２ ３２０ｇを、流動コーティング機
１に投入し、流動床８より空気を吹き込み各予備発泡粒
子２を流動コーティング機１内で流動させた。Next, a method for producing a foamed article having termite resistance using such a fluid coating machine 1 will be described. First, 320 g of pre-expanded particles 2 of polystyrene pre-expanded about 50 times were put into the fluidized coating machine 1, and air was blown from the fluidized bed 8 to flow each of the pre-expanded particles 2 in the fluidized coating machine 1.
【００２４】続いて防蟻剤としてのペルメトリン乳剤
（商品名：エクスミン乳剤、神東塗料（株）製）３０ｇ
と、接着剤としてのアクリル／スチレン樹脂エマルショ
ン（商品名：アクロナールＰ−６９８４、ガラス転移温
度−２５℃、ＢＡＳＦ（株）製）３０ｇとからなる不揮
発成分として約４０％を有する防蟻剤を、溶剤としての
水：ダイアセトンアルコール＝１９：１（重量比）から
なる希釈剤６０ｇで希釈して防蟻剤及び接着剤混合物３
を調製する。Subsequently, 30 g of a permethrin emulsion (trade name: Exmin Emulsion, manufactured by Shinto Paint Co., Ltd.) as a termiticide
And an acrylic / styrene resin emulsion (trade name: Acronal P-6984, glass transition temperature: -25 ° C., manufactured by BASF Corporation) as an adhesive. Dilute with 60 g of a diluent consisting of water: diacetone alcohol = 19: 1 (weight ratio) as a solvent to mix the termiticide and adhesive mixture 3
Is prepared.
【００２５】その後その防蟻剤及び接着剤混合物３をポ
ンプにて３０ｇ／ｍｉｎの速度で送液してノズル４から
流動コーティング機１内に噴霧し、流動している各予備
発泡粒子２の表面に防蟻剤及び接着剤混合物３を徐々に
塗布した。その際流動床８から吹き込む空気の流入速度
は、各予備発泡粒子２が相互に付着して団子状にならな
いように、０．５〜１．０ｍ／ｓｅｃの範囲で調節し
た。Thereafter, the termiticide and adhesive mixture 3 is fed by a pump at a rate of 30 g / min, sprayed from a nozzle 4 into the fluidized coating machine 1, and the surface of each flowing pre-expanded particle 2 is sprayed. A termiticide and adhesive mixture 3 was gradually applied to the mixture. At that time, the inflow speed of the air blown from the fluidized bed 8 was adjusted in the range of 0.5 to 1.0 m / sec so that the respective pre-expanded particles 2 did not adhere to each other to form a dumpling.
【００２６】上記防蟻剤及び接着剤混合物３の全量の噴
霧が終了した後、流動床８からの空気の吹き込みを５分
続け、防蟻剤及び接着剤混合物３の塗布され、流動して
いる各予備発泡粒子２の表面を完全に乾燥させて防蟻性
予備発泡粒子１０を得た。その後流動床８からの空気の
吹き込みを停止し、上記防蟻性予備発泡粒子１０を流動
コーティング機１から取り出した。この防蟻性予備発泡
粒子中のペルメトリンは、約０．４％（Ｗ／Ｗ）に相当
する。After the spraying of the entire amount of the termiticide and adhesive mixture 3 is completed, the blowing of air from the fluidized bed 8 is continued for 5 minutes, and the termiticide and adhesive mixture 3 is applied and flowing. The surface of each pre-expanded particle 2 was completely dried to obtain termite-resistant pre-expanded particles 10. Thereafter, the blowing of air from the fluidized bed 8 was stopped, and the termite-resistant pre-expanded particles 10 were taken out of the fluidized coating machine 1. Permethrin in the termiticide pre-expanded particles corresponds to about 0.4% (W / W).
【００２７】この防蟻性予備発泡粒子１０と未塗布の約
５０倍に予備発泡させた予備発泡粒子２とを種々の割合
で混合したものを所定の金型の型窩内に充填、成形して
防蟻性発泡成形体（縦４００ｍｍ、横３００ｍｍ、厚さ
３０ｍｍ）を得た。A mixture of the pre-expanded termite-resistant particles 10 and the pre-expanded particles 2 pre-expanded about 50 times that of the uncoated particles in various proportions is filled into a mold cavity of a predetermined mold and molded. Thus, a termite-resistant foam molded article (400 mm long, 300 mm wide, and 30 mm thick) was obtained.
【００２８】（実施例２）別に防蟻剤としてのフェノブ
カルブのマイクロカプセル（商品名：バクトップＭＣ、
神東塗料（株）製）３５ｇと、接着剤としてのアクリル
／スチレン樹脂エマルション（商品名：ヨドゾールＡＤ
−５１、ガラス転移温度３０℃、カネボウ（株）製）３
５ｇとからなる、不揮発成分として約４０％を有する防
蟻剤を、溶剤としての水：ダイアセトンアルコール＝１
９：１（重量比）からなる希釈剤７０ｇで希釈して防蟻
剤及び接着剤混合物３を調製する。Example 2 Separately, microcapsules of fenobcarb as termiticides (trade names: Baktop MC,
35 g of Shinto Paint Co., Ltd. and an acrylic / styrene resin emulsion as an adhesive (trade name: Iodosol AD)
−51, glass transition temperature 30 ° C., manufactured by Kanebo Co., Ltd.) 3
5 g of a termiticide having about 40% as a non-volatile component was added to water: diacetone alcohol = 1 as a solvent.
The mixture 3 is prepared by diluting with 70 g of a 9: 1 (weight ratio) diluent.
【００２９】以下実施例１と同様にして防蟻性予備発泡
粒子１１を作成（フェノブカルブとして約１．５％（Ｗ
／Ｗ）に相当）、さらに予備発泡粒子２と種々の割合に
混合して防蟻性発泡成形体を得た。Thereafter, pre-expanded termite-resistant particles 11 were prepared in the same manner as in Example 1 (about 1.5% (W
/ W)) and mixed with the pre-expanded particles 2 at various ratios to obtain a termite-resistant expanded molded article.
【００３０】以下得られた防蟻性発泡成形体について行
った試験例を示す。Hereinafter, test examples performed on the obtained termite-resistant foamed molded product will be described.
【００３１】（試験例１）強度試験 試験は、ＪＩＳ Ａ ９５１１「ポリスチレンフォーム
保温材」のうち、圧縮強度試験法にもとずいて行った。(Test Example 1) Strength Test The test was performed based on the compression strength test method of JIS A 9511 “polystyrene foam heat insulating material”.
【００３２】その結果を表１に示した。この結果から、
得られる防蟻性発泡成形体の強度を落とすことなく成形
するには、混合できる防蟻性予備発泡粒子１０の混合割
合は７５％以下であることが判った。The results are shown in Table 1. from this result,
It was found that the mixing ratio of the termite-resistant pre-expanded particles 10 that can be mixed was 75% or less in order to form the termite-resistant expanded molded article without reducing the strength.
【００３３】[0033]
【表１】 [Table 1]
【００３４】（試験例２）白ありの穿孔試験 試験は（社）日本白あり対策協会認定薬剤効力試験法の
うち、土壌処理剤の防蟻効力試験方法（ＪＴＣＡＳ−第
７号）にもとづいて行った。(Test Example 2) Perforation test with white The test was carried out based on the method for testing the termite-control efficacy of a soil treatment agent (JTCAS-No. 7) among the chemical efficacy test methods certified by the Japan White Preservation Measures Association. went.
【００３５】試験容器として図２のものを用いた。図の
ガラス円筒21の一方に含水率２５％に調整した砂（農薬
用軽石）２３を約６０ｇを入れる。他方２４に餌木とア
カマツ材をそれぞれ３ｇ入れる。ガラス管には防蟻性発
泡成形体２５を管の内径に合うように切断て充填し、ガ
ラス円筒２１に連結する。そして砂を入れたガラス円筒
２３に供試虫職蟻２００頭と兵蟻２０頭を入れて、２５
℃の恒温室に放置する。以下一定期間毎にガラス管内発
泡成形体への供試虫の穿孔度を記録する。The test container shown in FIG. 2 was used. About 60 g of sand (pesticide for agricultural chemicals) 23 adjusted to a water content of 25% is put into one of the glass cylinders 21 in the figure. On the other hand, 3 g of the bait and the red pine are put into 24 respectively. The glass tube is filled with a termite-resistant foam molded body 25 by cutting to fit the inner diameter of the tube, and connected to the glass cylinder 21. Then, 200 test ants and 20 soldiers were put into a glass cylinder 23 containing sand, and 25
Leave in a constant temperature room at ℃. Hereinafter, the piercing degree of the test insect into the foam molded article in the glass tube is recorded at regular intervals.
【００３６】その結果を表２に示した。この結果から得
られた発泡成形体に良好な防蟻性を期待するには、防蟻
性予備発泡粒子１０の混合割合Ｃは約２５％以上、好ま
しくは約５０％以上、防蟻性予備発泡粒子１１の混合割
合Ｃは約５０％以上、好ましくは約７５％以上必要なこ
とがわかった。The results are shown in Table 2. In order to expect good termite resistance from the foamed molded article obtained from the results, the mixing ratio C of the termite-resistant pre-expanded particles 10 is about 25% or more, preferably about 50% or more. It has been found that the mixing ratio C of the particles 11 needs to be about 50% or more, preferably about 75% or more.
【００３７】[0037]
【表２】 [Table 2]
【００３８】※穿孔度 ０：供試発泡成形体への穿孔が
全く認められない １：供試発泡成形体への穿孔距離１ｃｍ未満 ２：供試発泡成形体への穿孔距離２ｃｍ未満 ３：供試発泡成形体への穿孔距離３ｃｍ未満 ４：供試発泡成形体への穿孔距離４ｃｍ未満 ５：供試発泡成形体への穿孔距離４ｃｍ以上* Degree of piercing 0: No piercing was observed in the test foam molded article 1: Less than 1cm piercing distance to the test foam molded article 2: Less than 2cm piercing distance to the test foam molded article 3: Puncture distance to test foam molded article: less than 3 cm 4: Puncture distance to test foam molded article: less than 4 cm 5: Puncture distance to test foam molded article: 4 cm or more
【００３９】上記で述べた方法を用いると、発泡成形体
製造前の予備発泡粒子に防蟻剤を塗布するため、嵩の高
い発泡成形体を塗布場所に移動させて塗布していた従来
の方法と比べ輸送コストの著しい削減が期待できる。When the above-mentioned method is used, the termite-controlling agent is applied to the pre-expanded particles before the production of the expanded molded article. A significant reduction in transportation costs can be expected.
【００４０】また発泡成形体に防蟻剤を塗布していた従
来では、特に形状の複雑な発泡成形体への防蟻性の付与
において、塗布状態が不均一になったり細部への塗布に
工程数がかかったりして、良品の防蟻性発泡成形体の歩
留まりの著しい低下や塗布コストの上昇を招いていた。Conventionally, when a termite-controlling agent is applied to a foamed molded product, especially in the application of termite-controlling properties to a foamed molded product having a complicated shape, the application state becomes uneven or a process for applying to a small part is required. Due to the increase in number, the yield of non-defective termite-resistant foamed molded products has been remarkably reduced and the application cost has been increased.
【００４１】さらに予備発泡粒子に防蟻剤を塗布する従
来の方法では、その乾燥工程に時間がかかり、その上得
られる防蟻性予備粒子が相互に接着して団子状となるブ
ロッキングを回避するために、常に攪拌しながら乾燥す
るという手間が必要であった。Further, in the conventional method of applying an anti-termitic agent to the pre-expanded particles, the drying step takes a long time, and furthermore, the obtained anti-termite-preventive particles are prevented from adhering to each other to form a dumpling. For this reason, it was necessary to perform the work of drying while stirring constantly.
【００４２】しかしながら上記方法では、流動する予備
発泡粒子に防蟻剤を噴霧して塗布するため、極めて均一
に塗布でき、かつ吹き込む空気量を制御することで各防
蟻性予備発泡粒子が流動し、攪拌されながら乾燥される
ため極めて迅速に乾燥され、その上各防蟻性予備発泡粒
子が常に流動していて、団子状となるブロッキング現象
なども回避することができる。However, in the above method, the termite-controlling agent is sprayed and applied to the flowing pre-expanded particles, so that the application can be performed very uniformly, and the termite-controlling pre-expanded particles flow by controlling the amount of air blown. Since it is dried while being stirred, it is dried very quickly, and furthermore, each termite-preventive pre-expanded particle is constantly flowing, so that a blocking phenomenon that forms a dumpling can be avoided.
【００４３】したがって良好な防蟻性能を有する防蟻性
発泡成形体を容易に安定に得ることができ、さらに歩留
まりの向上、工程数や乾燥時間の削減、そのうえ防蟻性
予備発泡粒子に対して所定量以下の防蟻性を付与してい
ない通常の予備発泡粒子を混合して防蟻性を有する発泡
成形体が得られることなどから、総合的なコスト削減が
可能となり従来より実用性の高い方法となっている。Therefore, a termite-resistant expanded molded article having good termite-control performance can be easily and stably obtained, and further, the yield can be improved, the number of steps and drying time can be reduced, and the termite-resistant pre-expanded particles can be obtained. By mixing ordinary pre-expanded particles not imparting termite-proofing properties of a predetermined amount or less to obtain a foamed article having termite-proofing properties, etc., it is possible to reduce overall cost and to be more practical than before. Has become the way.
【００４４】また防蟻性物質が予備発泡粒子内に練り込
まれて製造された従来の防蟻性予備発泡粒子では、得ら
れた発泡成形体が良好な防蟻性を発揮するためには防蟻
性物質の混合割合をかなり高くする必要があり、このた
め得られた成形体の強度が低下していた。In the conventional pre-expanded termite-preventing particles manufactured by kneading the termite-inhibiting substance into the pre-expanded particles, it is necessary for the obtained expanded molded article to exhibit good termite-inhibiting properties. It was necessary to considerably increase the mixing ratio of the ant substance, and as a result, the strength of the obtained molded body was reduced.
【００４５】しかし本発明の方法では、防蟻剤の防蟻性
物質は防蟻性予備発泡粒子の表面にのみ塗布されてお
り、その防蟻性予備発泡粒子の機械的物性にほとんど影
響することがなく、よって得られた防蟻性発泡成形体の
機械的強度にも著しい低下がなく、良好な機械的強度を
有する防蟻性発泡成形体を得ることができる。However, in the method of the present invention, the termite-controlling substance of the termite-controlling agent is applied only to the surface of the termite-controlling pre-expanded particles, and hardly affects the mechanical properties of the termite-controlling pre-expanded particles. Thus, there is no significant decrease in the mechanical strength of the termite-resistant foam molded article thus obtained, and a termite-resistant foam molded article having good mechanical strength can be obtained.
【００４６】これらの結果、上記の方法で得られた防蟻
性発泡成形体は、建材用断熱材・保温材など白ありの被
害が予想される場所等に好適に使用される。As a result, the termite-resistant foamed molded article obtained by the above method is suitably used in places where whitened damage is expected, such as heat insulating materials and heat insulating materials for building materials.
【００４７】[0047]
【発明の効果】本発明の防蟻性を有する発泡成形体の製
造方法は、以上のように予備発泡粒子を流動させながら
防蟻剤及び接着剤を塗布して防蟻性予備発泡粒子を得る
方法である。According to the process for producing a termite-resistant foamed molded article of the present invention, termite-controlling pre-expanded particles are obtained by applying a termiticide and an adhesive while flowing the pre-expanded particles as described above. Is the way.
【００４８】この方法では予備発泡粒子が空中で流動し
ていることから、予備発泡粒子の表面により均一に防蟻
剤を塗布することができ、かつ防蟻性を有する予備発泡
粒子が迅速に乾燥される。よって良好な防蟻性を有する
発泡成形体を容易かつ迅速に得ることができるという効
果を有する。In this method, since the pre-expanded particles are flowing in the air, the termite-controlling agent can be evenly applied to the surface of the pre-expanded particles, and the pre-expanded particles having the anti-termite-proof property are rapidly dried. Is done. Therefore, there is an effect that a foam molded article having good termite resistance can be easily and quickly obtained.
【図１】本発明の防蟻性を有する、発泡成形体の製造方
法における流動層装置の概略構成図である。FIG. 1 is a schematic configuration diagram of a fluidized bed apparatus in a method for producing a foamed molded article having termite resistance according to the present invention.
【図２】上記発泡成形体における、防蟻性を試験する方
法を示す説明図である。FIG. 2 is an explanatory view showing a method for testing termite resistance in the foam molded article.
１ 流動コーティング機 ２ 予備発泡粒子 ３ 防蟻剤及び接着剤混合物 ４ ノズル ５ ポンプ ６ 送風ファン ７ 熱交換機 ８ 流動床 ９ 排気口 １０ 防蟻性予備発泡粒子 ２１ ガラス円筒 ２２ ガラス管 ２３ 砂 ２４ 餌木 ２５ 防蟻性発泡成形体 REFERENCE SIGNS LIST 1 fluidized coating machine 2 pre-expanded particles 3 termite and adhesive mixture 4 nozzle 5 pump 6 blower fan 7 heat exchanger 8 fluidized bed 9 exhaust port 10 termite-resistant pre-expanded particles 21 glass cylinder 22 glass tube 23 sand 24 bait tree 25 Termite-resistant foam molding
Claims (10)
その予備発泡粒子に防蟻剤と接着剤とを噴霧して、その
表面に防蟻性を付与した防蟻性予備発泡粒子を形成した
後、その防蟻性予備発泡粒子を発泡成形することを特徴
とする防蟻性を有する発泡成形体。1. While flowing the pre-expanded particles into the air,
The termite-controlling agent and the adhesive are sprayed on the pre-expanded particles to form termite-resistant pre-expanded particles on the surface thereof, and then the termite-resistant pre-expanded particles are subjected to foam molding. A molded foam having a characteristic termite resistance.
その予備発泡粒子に防蟻剤と接着剤とを噴霧して、その
表面に防蟻性を付与した防蟻性予備発泡粒子を形成した
後、その防蟻性予備発泡粒子を前記予備発泡粒子と混合
し、その混合体を発泡成形することを特徴とする防蟻性
を有する発泡成形体。2. While flowing the pre-expanded particles into the air,
The termite-controlling agent and the adhesive are sprayed on the pre-expanded particles to form termite-resistant pre-expanded particles having a termite-preventive property on the surface thereof. A foamed article having termite resistance, comprising mixing and foaming the mixture.
℃〜３５℃の範囲の特性を有する樹脂エマルションを使
用することを特徴とする請求項１及び請求項２に記載の
防蟻性を有する発泡成形体。3. The adhesive has a glass transition temperature of -50.
The termite-resistant foamed molded article according to claim 1, wherein a resin emulsion having a property in a range of from 0 ° C. to 35 ° C. is used.
するピレスロイド系防蟻成分を使用することを特徴とす
る、請求項１及び請求項２に記載の防蟻性を有する発泡
成形体。4. The termite-resistant foamed molded article according to claim 1, wherein a pyrethroid-based termitic component having repellency to termites is used as the termite-controlling agent. .
合割合が２５％以上である、請求項２に記載の防蟻性を
有する発泡成形体。5. The termite-resistant foamed molded article according to claim 2, wherein the mixing ratio of the termite-resistant pre-expanded particles in the foamed molded article is 25% or more.
その予備発泡粒子に防蟻剤と接着剤とを噴霧して、その
表面に防蟻性を付与した防蟻性予備発泡粒子を形成した
後、その防蟻性予備発泡粒子を発泡成形することを特徴
とする防蟻性を有する発泡成形体の製造方法。6. While flowing the pre-expanded particles into the air,
The termite-controlling agent and the adhesive are sprayed on the pre-expanded particles to form termite-resistant pre-expanded particles on the surface thereof, and then the termite-resistant pre-expanded particles are subjected to foam molding. A method for producing a foamed molded article having a characteristic termite resistance.
その予備発泡粒子に防蟻剤と接着剤とを噴霧して、その
表面に防蟻性を付与した防蟻性予備発泡粒子を形成した
後、その防蟻性予備発泡粒子を前記予備発泡粒子と混合
し、その混合体を発泡成形することを特徴とする防蟻性
を有する発泡成形体の製造方法。7. While flowing the pre-expanded particles into the air,
The termite-controlling agent and the adhesive are sprayed on the pre-expanded particles to form termite-resistant pre-expanded particles having a termite-preventive property on the surface thereof. A method for producing a termite-resistant foamed molded article, comprising mixing and foaming the mixture.
℃〜３５℃の範囲の特性を有する樹脂エマルションを使
用することを特徴とする請求項６及び請求項７に記載の
防蟻性を有する発泡成形体及びその製造方法。8. An adhesive having a glass transition temperature of -50.
The foamed molded article having termite resistance according to claim 6 or 7, wherein a resin emulsion having a property in the range of -35 ° C is used.
するピレスロイド系防蟻成分を使用することを特徴とす
る、請求項６及び請求項７に記載の防蟻性を有する発泡
成形体の製造方法。9. The fire-resistant foamed molded article according to claim 6, wherein a pyrethroid-based termitic component having repellency to termites is used as the termiticide. Manufacturing method.
混合割合が２５％以上である、請求項７に記載の防蟻性
を有する発泡成形体の製造方法。10. The method for producing a termite-resistant foamed molded article according to claim 7, wherein the mixing ratio of the termite-resistant pre-expanded particles in the foamed molded article is 25% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20774196A JPH1036549A (en) | 1996-07-17 | 1996-07-17 | Foamed molded product having termite-repelling property and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20774196A JPH1036549A (en) | 1996-07-17 | 1996-07-17 | Foamed molded product having termite-repelling property and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1036549A true JPH1036549A (en) | 1998-02-10 |
Family
ID=16544773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20774196A Pending JPH1036549A (en) | 1996-07-17 | 1996-07-17 | Foamed molded product having termite-repelling property and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1036549A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0981956A2 (en) * | 1998-08-19 | 2000-03-01 | Nova Chemicals Inc. | Dissolving insecticide in monomer |
| WO2000044224A1 (en) * | 1999-02-01 | 2000-08-03 | The Dow Chemical Company | Insecticide containing foam sheet |
| EP1159875A1 (en) * | 2000-05-31 | 2001-12-05 | The Dow Chemical Company | Insecticide-containing foam sheet and process for the preparation thereof |
| KR100553970B1 (en) * | 1999-07-20 | 2006-02-22 | 삼성토탈 주식회사 | Resin composition for mulching film with anti-insect and anti-rat ability |
| WO2009080723A1 (en) * | 2007-12-21 | 2009-07-02 | Basf Se | Insecticide-equipped particles made of expandable polystyrene and insecticide-equipped molded parts which can be obtained therefrom |
| US20100286296A1 (en) * | 2007-10-15 | 2010-11-11 | Syngenta Crop Protection, Inc. | Anti-termite styrofoam product and method of manufacturing the same |
| JP2012020967A (en) * | 2010-07-15 | 2012-02-02 | Koichi Nishimoto | Foamed resin molded body with termite-proofing effect and method for producing the same |
| WO2012175628A1 (en) | 2011-06-21 | 2012-12-27 | Lanxess Deutschland Gmbh | Mixtures of polymers containing blowing agent, insecticides, and waxes |
-
1996
- 1996-07-17 JP JP20774196A patent/JPH1036549A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0981956A2 (en) * | 1998-08-19 | 2000-03-01 | Nova Chemicals Inc. | Dissolving insecticide in monomer |
| EP0981956A3 (en) * | 1998-08-19 | 2000-08-30 | Nova Chemicals Inc. | Dissolving insecticide in monomer |
| WO2000044224A1 (en) * | 1999-02-01 | 2000-08-03 | The Dow Chemical Company | Insecticide containing foam sheet |
| US6156328A (en) * | 1999-02-01 | 2000-12-05 | The Dow Chemical Company | Insecticide-containing foam sheet and process for the preparation thereof |
| KR100553970B1 (en) * | 1999-07-20 | 2006-02-22 | 삼성토탈 주식회사 | Resin composition for mulching film with anti-insect and anti-rat ability |
| EP1159875B1 (en) * | 2000-05-31 | 2005-04-20 | Dow Global Technologies Inc. | Insecticide-containing foam sheet and process for the preparation thereof |
| EP1159875A1 (en) * | 2000-05-31 | 2001-12-05 | The Dow Chemical Company | Insecticide-containing foam sheet and process for the preparation thereof |
| US20100286296A1 (en) * | 2007-10-15 | 2010-11-11 | Syngenta Crop Protection, Inc. | Anti-termite styrofoam product and method of manufacturing the same |
| WO2009080723A1 (en) * | 2007-12-21 | 2009-07-02 | Basf Se | Insecticide-equipped particles made of expandable polystyrene and insecticide-equipped molded parts which can be obtained therefrom |
| JP2011506567A (en) * | 2007-12-21 | 2011-03-03 | ビーエーエスエフ ソシエタス・ヨーロピア | Insecticide-modified bead material composed of expandable polystyrene, and insecticide-modified molded article obtained from the bead material |
| JP2012020967A (en) * | 2010-07-15 | 2012-02-02 | Koichi Nishimoto | Foamed resin molded body with termite-proofing effect and method for producing the same |
| WO2012175628A1 (en) | 2011-06-21 | 2012-12-27 | Lanxess Deutschland Gmbh | Mixtures of polymers containing blowing agent, insecticides, and waxes |
| US9222253B2 (en) | 2011-06-21 | 2015-12-29 | Lanxess Deutschland Gmbh | Mixtures of polymers containing blowing agent, insecticides, and waxes |
| EP2580961A1 (en) | 2011-10-11 | 2013-04-17 | LANXESS Deutschland GmbH | Mixtures of polymers, insecticides and waxes containing blowing agents |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1077785A (en) | Entrapment of biological agent in matrix of coupled polyhydroxy polymer xanthate | |
| US4985064A (en) | Microsuspension process for preparing solvent core sequential polymer dispersion | |
| US4272398A (en) | Microencapsulation process | |
| US5225279A (en) | Solvent core encapsulant composition | |
| JPH1036549A (en) | Foamed molded product having termite-repelling property and its production | |
| CZ300099B6 (en) | Microcapsule and process for producing thereof | |
| DE1769194C3 (en) | Coating agent for the formation of an opaque coating | |
| JPH11506464A (en) | Dry water dispersible composition of microencapsulated insecticide | |
| AU770670B2 (en) | Sustained release polymer-based water insoluble beads | |
| JP4527021B2 (en) | Termite control agent | |
| EP2723169B1 (en) | Mixtures of polymers, insecticides and waxes containing blowing agents | |
| JP2002102680A (en) | Microcapsule powder and its production method | |
| RU2724547C1 (en) | Alkyd encapsulated biocide | |
| JP5639806B2 (en) | Foamed resin molding having ant-proofing property and manufacturing method thereof | |
| JPH11314032A (en) | Method for microcapsulation of solid substance and microcapsule composition | |
| KR100470033B1 (en) | Manufacturing method of emulsion containing polymer | |
| JPS6265741A (en) | Cosmetic composition, release of vaporable compound thereof is continued | |
| KR0149699B1 (en) | Dispersion of slow-releasing emulsion polymer and method for preparing thereof | |
| JPS63152648A (en) | Foamed plastic material and production thereof | |
| JP2004135591A (en) | Termite-controlling method | |
| AU2006236009A1 (en) | Surface coating with releasable substance | |
| JPH115703A (en) | Sustained release agrochemical preparation composition and its production | |
| JPH0558804A (en) | Floatable agricultural chemical preparation for applying on water surface | |
| JP2003003003A (en) | Insect-controlling polystyrene foam insulator | |
| JPH0356403A (en) | Controlled release device for active ingredient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040312 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040323 |
|
| A02 | Decision of refusal |
Effective date: 20040720 Free format text: JAPANESE INTERMEDIATE CODE: A02 |