JP2930376B2 - Method and apparatus for continuous surface modification of sheet of plastic material - Google Patents
Method and apparatus for continuous surface modification of sheet of plastic materialInfo
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- JP2930376B2 JP2930376B2 JP17238490A JP17238490A JP2930376B2 JP 2930376 B2 JP2930376 B2 JP 2930376B2 JP 17238490 A JP17238490 A JP 17238490A JP 17238490 A JP17238490 A JP 17238490A JP 2930376 B2 JP2930376 B2 JP 2930376B2
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- gas
- sheet
- chamber
- plastic material
- containing gas
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はプラスチック材料のシート表面改質法とその
装置に関する。本明細書においてプラスチックとはいわ
ゆる合成樹脂を意味する。プラスチック材料のシートと
はプラスチックのフィルムとプラスチックの繊維の布は
くの両方を含む。Description: TECHNICAL FIELD The present invention relates to a method and an apparatus for modifying a sheet surface of a plastic material. In this specification, plastic means a so-called synthetic resin. Sheets of plastic material include both plastic films and plastic fiber fabric foils.
プラスチックは一般に疎水性であり、また接着性、染
色性、印刷性が劣るため使用目的に応じ表面改質が行な
われている。表面改質の方法には例えば （１）酸、アルカリ、酸化剤等の化学薬品による湿式処
理 （２）コロナ放電法、プラズマ法、紫外線法、火炎法等
の乾式処理 がある。Plastics are generally hydrophobic and have poor adhesion, dyeability, and printability, so that surface modification is performed according to the intended use. Examples of the surface modification method include (1) wet treatment with a chemical such as acid, alkali, and oxidizing agent, and (2) dry treatment such as corona discharge method, plasma method, ultraviolet method, and flame method.
湿式処理は連続的に表面改質を行なう場合、薬品の濃
度管理が困難であり、また水洗、脱水、乾燥等の工程が
必要である。乾式法は上記の問題はないが、それぞれ次
の欠点がある。コロナ放電は改質効果が小さく、長期的
な効果の持続性が小さい。プラズマ法は周波数によって
は分子構造が破壊され、蒸発、気化が起る。また装置の
大型化が困難である。紫外線法は特定の高分子にしか適
用でず、また火炎法はシート状の成型品、例えば、フィ
ルム、多孔質膜、織布、不織布等には適用しにくいなど
の欠点がある。In the case of performing the surface modification continuously in the wet treatment, it is difficult to control the concentration of the chemical, and steps such as water washing, dehydration, and drying are required. The dry method does not have the above problems, but has the following disadvantages. Corona discharge has a small reforming effect and a long-lasting effect. In the plasma method, the molecular structure is destroyed depending on the frequency, and evaporation and vaporization occur. Also, it is difficult to increase the size of the device. The ultraviolet method is applicable only to specific polymers, and the flame method is disadvantageous in that it is difficult to apply to a sheet-like molded product, for example, a film, a porous film, a woven fabric, a nonwoven fabric, and the like.
上記の欠点を解決する方法としてF2ガスの特異な反応
性を利用した表面改質方法がある（特公昭59−5601）。There is a surface modification method using the specific reactivity of the F 2 gas as a method of solving the above drawbacks (Japanese 59-5601).
F2ガスは反応性に富むため、ほとんどすべてのプラス
チックに適用可能であり、短時間の処理で改質効果は著
しい。Since F 2 gas is highly reactive, it is applicable to almost all plastics, modification effect in a short time of processing significant.
親水性、接着性、印刷性、染色性等の改質には、ポリ
エステル樹脂のような酸素含有プラスチックを除き、通
常、不活性ガス（N2ガス、Arガスなど）で希釈したF2ガ
スにO2ガス、CO2ガス、SO2ガス等を添加、混合したガス
によって改質処理が行なわれている。しかしこの方法に
おいても添加ガスがF2ガスと反応し易く、流量と混合す
る割合は制限を受ける。特にSO2ガスの場合顕著であ
り、混合の際F2ガスとSO2ガスとの反応により、熱発生
によってプラスチックが劣化し改質作用を示さない。SO
F2ガス、SO2F2ガスを生成するために、所望の表面改質
効果を得るには適正な処理条件の範囲は狭い。Hydrophilicity, adhesion, printability, the modification of such staining, except oxygen-containing plastics such as polyester resin, typically, an inert gas (N 2 gas, Ar gas, etc.) to F 2 gas diluted with The reforming process is performed by a gas obtained by adding and mixing O 2 gas, CO 2 gas, SO 2 gas, and the like. However, also in this method, the additive gas easily reacts with the F 2 gas, and the mixing ratio with the flow rate is limited. In particular, this is remarkable in the case of SO 2 gas. During the mixing, the reaction between the F 2 gas and the SO 2 gas causes the plastic to deteriorate due to heat generation, and does not exhibit a reforming action. SO
In order to generate F 2 gas and SO 2 F 2 gas, the range of appropriate processing conditions for obtaining a desired surface modification effect is narrow.
本発明者は帯状のプラスチック材料のシートを予め添
加ガス（SO2ガス）で充たした前処理室を通し、添加ガ
ス（SO2ガス）を前記シートの表面に付着（吸着）させ
た後、F2ガス（添加ガスを少量添加してもよい）で充た
した反応室で処理する連続表面改質方法によって改質の
効果は著しく向上し、高速処理化が可能である事を見出
した。The inventor of the present invention passed through a pretreatment chamber previously filled with a band-shaped sheet of plastic material with an additive gas (SO 2 gas), and allowed the additive gas (SO 2 gas) to adhere (adsorb) to the surface of the sheet. It has been found that the effect of the reforming is remarkably improved by a continuous surface reforming method in which the treatment is performed in a reaction chamber filled with two gases (additional gas may be added in a small amount), and high-speed treatment can be performed.
本発明は、プラスチック材料のシートに、予めSO2ガ
スを付着させた後、F2ガスと接触させることからなる連
続表面改質処理方法を提供する。The present invention provides a continuous surface modification treatment method comprising attaching a SO 2 gas to a sheet of a plastic material in advance and then contacting the sheet with a F 2 gas.
また、本発明は、プラスチック材料のシートを連続的
に表面改質処理する装置であって、ロール状シートの保
持および繰り出し手段を備えた第１室（シート保持室）
と、第１室から繰り出されたシートにSO2含有ガスを接
触させる第２室（第１ガス処理室）と、SO2含有ガスと
接触したシートにF2含有ガスを接触させる第３室（第２
ガス処理室）と、第３室から引き出されたシートの巻取
りおよび保持手段を備えた第４室（シート巻取り室）を
含み、該第２室と該第３室が少なくとも２種類のガスを
定量的に混合して該室に供給する手段と排気口を備えて
いる装置を提供する。Further, the present invention is an apparatus for continuously surface-modifying a sheet of a plastic material, and a first chamber (sheet holding chamber) provided with a roll-shaped sheet holding and feeding means.
And a second chamber (first gas processing chamber) for bringing the SO 2 -containing gas into contact with the sheet fed from the first chamber, and a third chamber (for bringing the F 2 -containing gas into contact with the sheet in contact with the SO 2 -containing gas). Second
A gas processing chamber) and a fourth chamber (sheet winding chamber) provided with a means for winding and holding the sheet drawn from the third chamber, wherein the second chamber and the third chamber are at least two types of gas. Provided with means for quantitatively mixing and supplying the mixture to the chamber and an exhaust port.
本発明の方法が適用されるプラスチックの種類は特に
限定されず、ポリエチレン、ポリプロピレン等のポリオ
レフィン、ポリエステル、ポリアミド、ポリイミド、ポ
リフェニレンスルフィド、シリコン樹脂、含フッ素樹脂
等である。The type of plastic to which the method of the present invention is applied is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyimides, polyphenylene sulfides, silicone resins, and fluorine-containing resins.
本発明方法において、SO2による予備処理の際に、SO2
ガスは反応速度調整のために25容量％まで希釈されても
よい。25％未満では活性が低下し非実用的な反応時間を
要する。In the method of the present invention, when the pretreatment with SO 2, SO 2
The gas may be diluted to 25% by volume to adjust the reaction rate. If it is less than 25%, the activity is reduced and an impractical reaction time is required.
本発明の方法においてF2による処理の際にF2ガスは反
応速度調整のために25容量％までは希釈されてもよい。
25％未満では活性が失われる。F 2 gas during the treatment with F 2 in the method of the present invention may be diluted to 25% by volume in order to adjust the reaction rate.
If it is less than 25%, the activity is lost.
プラスチックのシートは上記のガス濃度範囲で、0.5m
/分〜50m/分の速度で処理される。0.5m/分未満の速度で
表面処理を施しても特性の向上は見られない。また50m/
分を越えると改質効果が認められなくなる。0.5 m for plastic sheet in the above gas concentration range
Processed at speeds from 50m / min to 50m / min. Even if the surface treatment is performed at a speed of less than 0.5 m / min, no improvement in characteristics is observed. Also 50m /
If the amount exceeds the limit, the reforming effect is not recognized.
上記のガス濃度と処理速度はプラスチックのシートの
温度が50℃を越えないように制御される。50℃を越える
とプラスチックスの劣化を惹起する。The above gas concentrations and processing rates are controlled so that the temperature of the plastic sheet does not exceed 50 ° C. Exceeding 50 ° C causes plastics to deteriorate.
本発明の方法によりF2ガス、SO2ガスを用いて表面を
改質したプラスチックのシートはその表面の吸水性また
は保水性等が格段に改良され、接着性、染色性、印刷性
に優れた材料となる。具体的には電池のセパレーター
材、ろ過材あるいは被覆用基材として極めて有用であ
る。By the method of the present invention, a plastic sheet whose surface has been modified using F 2 gas and SO 2 gas has remarkably improved surface water absorption or water retention, and has excellent adhesiveness, dyeability, and printability. Material. Specifically, it is extremely useful as a battery separator material, a filter material or a coating substrate.
次に本発明を図面を参照して具体的に説明する。 Next, the present invention will be specifically described with reference to the drawings.
第１図は本発明の方法を実施するための装置の概念図
である。次に好適実施態様としての装置について記載す
る。FIG. 1 is a conceptual diagram of an apparatus for performing the method of the present invention. Next, an apparatus as a preferred embodiment will be described.
装置はSUS304系ステンレス鋼で造られた。この装置は
巻かれたプラスチック材料のシートＳの保持室10、第１
ガス処理室30、第２ガス処理室40、巻き取り室20からな
る。保持室10と巻き取り室20は実質的に同じ形状のもの
であるが、密閉できる巻かれた（巻かれる）プラスチッ
ク材料のシートを軸支できて、N2ガスの導入口を有し、
気体を遮断しつつプラスチック材料のシートの繰り出す
ための（受け入れるための）スリットと接続のために出
口にフランジを有する容器である。スリットは独立の板
に設けて接続部のフランジ間に狭持してもよい。The device was made of SUS304 stainless steel. The device comprises a holding chamber 10 for a rolled sheet S of plastic material,
It comprises a gas processing chamber 30, a second gas processing chamber 40, and a winding chamber 20. The holding chamber 10 and the winding chamber 20 are of substantially the same shape, but can support a sheet of a plastic material that can be hermetically sealed (wound) and have an inlet for N 2 gas,
A container with a slit for feeding out (receiving) a sheet of plastic material and a flange at the outlet for connection while blocking gas. The slit may be provided in a separate plate and held between the flanges of the connection portion.
第１ガス処理室30は実質的にプラスチック材料のシー
トが通過する筒状容器であって、両端にそれぞれ、前記
保持室10および第２ガス処理室40への接続のためのフラ
ンジを有する。第１ガス処理室30にはN2ガスおよびSO2
ガスの導入口とガス排出口が設けられている。SO2とN2
は流量計FMで計測されて混合器Ｍに入り、ここで混合さ
れて第１ガス処理室に導入される。N2ガスはSO2と混合
されることなく単独でも第１処理室に導入できることに
なっている。The first gas processing chamber 30 is a substantially cylindrical container through which a sheet of plastic material passes, and has a flange at each end for connection to the holding chamber 10 and the second gas processing chamber 40, respectively. The first gas processing chamber 30 contains N 2 gas and SO 2
A gas inlet and a gas outlet are provided. SO 2 and N 2
Is measured by the flow meter FM and enters the mixer M, where it is mixed and introduced into the first gas processing chamber. The N 2 gas is to be introduced into the first processing chamber by itself without being mixed with SO 2 .
この第１処理室30に接続する第２処理室40は実質的に
前者と同じものであり、SO2のかわりにF2ガスが導入さ
れる。前記と同じように気体を遮断しつつプラスチック
スのシートを通過させるためのスリット板が設けられ
る。これは前記のようにフランジ間に挟持される独立の
板であってもよい。The second processing chamber 40 connected to the first processing chamber 30 is substantially the same as the former, and F 2 gas is introduced instead of SO 2 . As described above, a slit plate for passing a sheet of plastics while blocking gas is provided. This may be a separate plate sandwiched between the flanges as described above.
巻き取り室20については既に説明したが、第２ガス処
理室40と取り室20の間には、洗浄室と乾燥室を挿入して
もよい。これは当業者が適宜に設計することのできるも
のであるから詳細に説明する必要はなかろう。Although the winding chamber 20 has already been described, a cleaning chamber and a drying chamber may be inserted between the second gas processing chamber 40 and the winding chamber 20. This can be appropriately designed by those skilled in the art and need not be described in detail.
二つのガス処理室はスペース節約のために屈曲させて
あるが、それは必須ではない。巻き取りのために軸を回
転駆動させるためのモーターが設けてあることも言を要
しないであろう。The two gas treatment chambers are bent to save space, but this is not required. It will not be necessary to say that a motor for rotating the shaft for winding is provided.
本発明者らが試作した装置は、保持部および巻き取り
部の直径70cm、巾100cmであり、ガス処理室は巾、高さ1
00cm、直線としての長さ2mであった。The apparatus prototyped by the present inventors has a holding section and a winding section with a diameter of 70 cm and a width of 100 cm, and the gas processing chamber has a width and height of 1 cm.
It was 00 cm long and 2 m long as a straight line.
実施例１ ポリプロピレン繊維の不織布（巾35cm、厚さ0.21mm、
嵩密度78g/m2、ロール状に巻き取られているもの）を第
１図の連続処理装置の保持室10に装填し第１処理室、第
２ガス処理室をN2で置換を行なって、不活性雰囲気とし
た後、SO2濃度50容量％、F2濃度30容量％になるように
各ガスとN2を流した。次に、処理速度が2m/分になるよ
うに不織布を移動させた。処理は室温で行なった。処理
した不織布は洗浄部で温水で洗浄し、100℃で乾燥し
た。親水性の評価は、水滴による吸水時間で評価した。
0.30秒であった。（非処理物は吸収されなかった。） 水滴法は、水平に固定した不織布に落下させた水滴が
不織布に吸収されるのに要する時間を測定することから
なる。Example 1 Nonwoven fabric of polypropylene fiber (width 35 cm, thickness 0.21 mm,
The bulk density of 78 g / m 2 , which has been wound up in a roll, is loaded into the holding chamber 10 of the continuous processing apparatus shown in FIG. 1, and the first processing chamber and the second gas processing chamber are replaced with N 2. After making the atmosphere inert, each gas and N 2 were flowed so that the SO 2 concentration was 50% by volume and the F 2 concentration was 30% by volume. Next, the nonwoven fabric was moved so that the processing speed was 2 m / min. The treatment was performed at room temperature. The treated nonwoven fabric was washed with warm water in a washing section and dried at 100 ° C. The hydrophilicity was evaluated based on the time of water absorption by water droplets.
0.30 seconds. (Non-processed material was not absorbed.) The water drop method consists of measuring the time required for water drops dropped on a horizontally fixed nonwoven fabric to be absorbed by the nonwoven fabric.
実施例２〜８ SO2濃度、F2濃度、処理速度、反応温度を変更する以
外は実施例１と同様な操作を行ない、ポリプロピレンと
ポリエチレンの繊維からなる不織布の処理物を得た。吸
水時間を表１に示す。Examples 2 to 8 The same operation as in Example 1 was performed except that the concentration of SO 2, the concentration of F 2 , the processing speed, and the reaction temperature were changed to obtain a processed nonwoven fabric made of polypropylene and polyethylene fibers. Table 1 shows the water absorption time.
実施例９、10 実施例２においてポリプロピレンとポリエチレンの繊
維からなる不織布をポリプロピレンの繊維の不織布及び
ポリフェニレンスルフィド繊維の不織布に変更して処理
物を得た。吸水時間は表１に示す。Examples 9 and 10 In Example 2, a nonwoven fabric made of polypropylene and polyethylene fibers was changed to a nonwoven fabric made of polypropylene fibers and a nonwoven fabric made of polyphenylene sulfide fibers to obtain treated products. The water absorption time is shown in Table 1.
比較例１ 実施例１において、SO2前処理室でSO250容量％、F230
重量％の混合ガスで処理した以外は、同様な操作を行な
ったところ、急激に反応速度が上昇し、ポリプロピレン
とポリエチレンの繊維からなる不織布が焼けてしまっ
た。Comparative Example 1 In Example 1, SO 2 50% by volume SO 2 pretreatment chamber, F 2 30
When the same operation was performed except that the treatment was performed with a mixed gas of weight%, the reaction speed increased rapidly, and the nonwoven fabric composed of polypropylene and polyethylene fibers was burned.
比較例２ 実施例１において、SO2濃度20容量％、F2濃度15容量
％に変更した以外は同様な操作を行ない、処理物を得
た。吸水時間は181秒であった。Comparative Example 2 A processed product was obtained in the same manner as in Example 1, except that the SO 2 concentration was changed to 20% by volume and the F 2 concentration was changed to 15% by volume. The water absorption time was 181 seconds.
以上の実施例と比較例の結果を第１表にまとめて示
す。Table 1 summarizes the results of the above Examples and Comparative Examples.
実施例11 実施例１において不織布を厚さ10μｍ、巾35cmのポリ
エステルフィルムに変更した以外は同様の操作を行な
い、処理物を得た。処理前のフィルム上の水滴の接触角
は63゜であったが、処理後は23゜となり、親水性が著し
く向上した。 Example 11 A treated product was obtained in the same manner as in Example 1, except that the nonwoven fabric was changed to a polyester film having a thickness of 10 µm and a width of 35 cm. The contact angle of the water droplet on the film before the treatment was 63 °, but it was 23 ° after the treatment, and the hydrophilicity was remarkably improved.
添付図面は本発明の装置の構造を示す概念図である。 10……シート保持室、20……巻き取り室、 30……第１ガス処理室、40……第２ガス処理室、 Ｓ……シート、Ｍ……混合器、FM……流量計。 The accompanying drawings are conceptual diagrams showing the structure of the device of the present invention. 10: Sheet holding chamber, 20: Winding chamber, 30: First gas processing chamber, 40: Second gas processing chamber, S: Sheet, M: Mixer, FM: Flow meter.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久下 光一 埼玉県大宮市北袋町１丁目297番地 三 菱金属株式会社化成品開発センター内 (72)発明者 竹貫 伸也 東京都千代田区岩本町３丁目８番16号 株式会社トーケムプロダクツ内 (72)発明者 廣岡 正紀 茨城県猿島郡総和町駒羽根1399 (72)発明者 徳武 信利 茨城県猿島郡総和町駒羽根1399 (56)参考文献 特開 昭60−88044（ＪＰ，Ａ) 特開 昭50−107088（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08J 7/00 - 7/18 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Kushita 1-297 Kitabukuro-cho, Omiya-shi, Saitama, Japan Mitsui Kinzoku Co., Ltd. Chemical Development Center (72) Inventor Shinya Takeuki 3-chome Iwamotocho, Chiyoda-ku, Tokyo No. 8-16 Inside Tochem Products Co., Ltd. (72) Inventor Masaki Hirooka 1399 Komahane, Sawa-machi, Sarushima-gun, Ibaraki Prefecture (72) Inventor Nobutoshi Tokutake 1399, Komahane, Sawa-machi, Sarushima-gun, Ibaraki (56) References JP 60-88044 (JP, A) JP-A-50-107088 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08J 7/00-7/18
Claims (6)
度が25容量％以上のSO2含有ガスと接触させた後、次にF
2濃度が25容量％以上のF2含有ガスと接触させることか
らなる、プラスチック材料のシートの連続表面改質処理
方法。1. A sheet of a plastic material is first contacted with an SO 2 -containing gas having an SO 2 concentration of at least 25% by volume,
2 concentration consists of contacting with 25 volume percent or more of F 2 containing gas, a continuous surface modification method of a sheet of plastic material.
の混合ガスであり、F2含有ガスがF2とN2および／または
Arとの混合ガスである、請求項１記載の方法。2. The SO 2 -containing gas is a mixed gas of SO 2 and N 2 and / or Ar, and the F 2 -containing gas is F 2 and N 2 and / or
The method according to claim 1, wherein the gas is a mixed gas with Ar.
ガスとの接触を、該シートを0.5〜50m/分の速度で移動
させながら50℃以下の温度で行う、請求項１または２記
載の方法。3. The method according to claim 1, wherein the contact of the sheet with the SO 2 -containing gas and the subsequent F 2 -containing gas is performed at a temperature of 50 ° C. or less while moving the sheet at a speed of 0.5 to 50 m / min. The described method.
もしくはアルカリ水で洗浄し、中和し、150℃以下で乾
燥することをさらに含む、請求項１ないし３のいずれか
１項に記載の方法。4. The method according to claim 1, further comprising washing the sheet having been brought into contact with the F 2 -containing gas with water or alkaline water, neutralizing the sheet, and drying it at 150 ° C. or lower. The method described in.
改質処理する装置であって、ロール状シートの保持およ
び繰り出し手段を備えた第１室と、第１室から繰り出さ
れたシートにSO2含有ガスを接触させる第２室と、SO2含
有ガスと接触したシートにF2含有ガスを接触させる第３
室と、第３室から引き出されたシートの巻取りおよび保
持手段を備えた第４室を含み、該第２室と該第３室が少
なくとも２種類のガスを定量的に混合して該室に供給す
る手段と排気口を備えている装置。5. A continuous surface modification to apparatus a sheet of plastic material, a first chamber provided with a holding and feeding means of the roll sheet, SO 2 to the sheet fed from the first chamber A second chamber for contacting the gas containing gas and a third chamber for contacting the gas containing F 2 gas with the sheet contacted with the gas containing SO 2 gas
And a fourth chamber provided with means for winding and holding the sheet drawn out of the third chamber, wherein the second chamber and the third chamber quantitatively mix at least two types of gases. A device provided with a means for supplying air to an air outlet.
けられている請求項５記載の装置。6. The apparatus according to claim 5, wherein a washing room and a drying room are provided between the third room and the fourth room.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17238490A JP2930376B2 (en) | 1990-06-29 | 1990-06-29 | Method and apparatus for continuous surface modification of sheet of plastic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17238490A JP2930376B2 (en) | 1990-06-29 | 1990-06-29 | Method and apparatus for continuous surface modification of sheet of plastic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0459838A JPH0459838A (en) | 1992-02-26 |
| JP2930376B2 true JP2930376B2 (en) | 1999-08-03 |
Family
ID=15940919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17238490A Expired - Lifetime JP2930376B2 (en) | 1990-06-29 | 1990-06-29 | Method and apparatus for continuous surface modification of sheet of plastic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2930376B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977314A (en) * | 2017-05-16 | 2017-07-25 | 山东瀚民生物科技有限公司 | A kind of moisture-retention sustained release and release control fertilizer of agricultural crop straw water-loss reducer coating and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837323A (en) * | 1994-09-01 | 1998-11-17 | Hashimoto Chemical Co., Ltd. | Surface improving method of polypropylene products for plating, joining or coating |
| JP4638995B2 (en) * | 2001-03-30 | 2011-02-23 | 株式会社クラレ | Molded body and method for producing the same |
| CN102290323A (en) * | 2011-05-12 | 2011-12-21 | 秦皇岛嘉隆高科实业有限公司 | Line voltage halogen lamp illuminating directionally |
-
1990
- 1990-06-29 JP JP17238490A patent/JP2930376B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977314A (en) * | 2017-05-16 | 2017-07-25 | 山东瀚民生物科技有限公司 | A kind of moisture-retention sustained release and release control fertilizer of agricultural crop straw water-loss reducer coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0459838A (en) | 1992-02-26 |
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