JP2000319432A - Pet material having modified surface and its production - Google Patents
Pet material having modified surface and its productionInfo
- Publication number
- JP2000319432A JP2000319432A JP11125089A JP12508999A JP2000319432A JP 2000319432 A JP2000319432 A JP 2000319432A JP 11125089 A JP11125089 A JP 11125089A JP 12508999 A JP12508999 A JP 12508999A JP 2000319432 A JP2000319432 A JP 2000319432A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- spraying
- pet
- thermal
- base material
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエチレンテレ
フタレートからなる基材表面が溶射皮膜によって改質さ
れたＰＥＴ材とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a PET material in which the surface of a substrate made of polyethylene terephthalate is modified by a thermal spray coating and a method for producing the same.
【０００２】[0002]
【従来技術とその課題】近年、深刻化しつつある地球環
境の保全のために資源リサイクルの必要性が高まってお
り、特に大量に発生するプラスチック製品の廃材につい
ては再生利用技術の進展が急務とされている。例えば、
清涼飲料用を中心に広く使用されているＰＥＴボトルに
関しては、使用済みボトルの回収率が高まり、既にポリ
エステル繊維として再生して衣料品等に利用することも
行われているが、まだ再生品としての用途が限られてお
り、この点がリサイクルシステムを整える上でのネック
になっている。しかして、再生用途を拡大するには、例
えば耐熱性や耐摩耗性等のＰＥＴ（ポリエチレンテレフ
タレート）素材に不足している特性、あるいは熱伝導性
や電気伝導性等の新たな特性を、表面改質等によって付
与することが有望である。2. Description of the Related Art In recent years, the need for resource recycling has been increasing for the preservation of the global environment, which is becoming increasingly serious. ing. For example,
As for PET bottles, which are widely used mainly for soft drinks, the collection rate of used bottles has increased, and polyester bottles have already been recycled as polyester fibers and used for clothing, etc., but they are still recycled. This is a bottleneck in setting up a recycling system. Therefore, in order to expand the use for recycling, it is necessary to improve the properties of the PET (polyethylene terephthalate) material, such as heat resistance and abrasion resistance, which are lacking, or new characteristics such as thermal conductivity and electrical conductivity. Promising depending on the quality and the like is promising.
【０００３】一方、材料表面の改質手段として、塗装や
メッキ等の旧来の技術に加え、真空蒸着法、スパッタリ
ング法、ＰＶＤ法、ＣＶＤ法、溶射法等の新しい技術が
開発されている。これらの中でも溶射法は、改質材の粉
末や線材をプラズマや燃焼ガス等の熱源によって溶融な
いしそれに近い状態に加熱し、高速で基材表面に噴射し
て所望の特性を有する皮膜を形成するものであり、基材
の材質及び溶射材料の種類共に選択肢が広い上、基材の
形状や寸法に制約がなく、広面積の施工にも適し、且つ
皮膜の形成速度が大きいといった利点がある。On the other hand, new techniques such as vacuum deposition, sputtering, PVD, CVD, and thermal spraying have been developed as means for modifying the material surface, in addition to conventional techniques such as painting and plating. Among these, the thermal spraying method is a method in which a powder or a wire of a modifying material is melted or heated to a state close to or molten by a heat source such as a plasma or a combustion gas, and is sprayed at a high speed onto a substrate surface to form a film having desired characteristics. The material has a wide range of choices for both the material of the base material and the type of the sprayed material, and has the advantages that there is no restriction on the shape and size of the base material, that it is suitable for wide area construction, and that the film forming speed is high.
【０００４】しかるに、溶射法は、基材がポリエチレン
等の通常の熱可塑性樹脂である場合、軟化や変形を生じ
て皮膜形成が困難になるとされている。また、溶射法に
よる一般的な皮膜は、断面組織の顕微鏡写真によれば、
溶射粒子が溶けて偏平になった状態で積み重なった積層
構造となっており、基材に対する密着性が充分とは言え
ず、用途によっては耐剥離強度面で不適合になることが
ある。[0004] However, in the thermal spraying method, when the base material is an ordinary thermoplastic resin such as polyethylene, it is said that softening or deformation occurs, and it becomes difficult to form a film. In addition, the general coating by the thermal spraying method, according to the micrograph of the cross-sectional structure,
It has a laminated structure in which the sprayed particles are stacked in a melted and flattened state, and the adhesion to the base material cannot be said to be sufficient.
【０００５】[0005]
【課題を解決するための手段】本発明者は、使用済みＰ
ＥＴボトルの回収等によるリサイクルの目処がつきつつ
あるＰＥＴ（ポリエチレンテレフタレート）材につい
て、その再生用途を拡充すべく様々な観点より検討を重
ねる過程で、溶射法による表面改質を試みたところ、熱
可塑性樹脂であるにも拘わらず、これを基材として軟化
や変形の問題をきたすことなく種々の溶射材料による皮
膜形成が可能である上、溶射粒子が基材中に打ち込まれ
る形で、溶射皮膜と基材との間に界面が形成されない特
異な状態の改質表面を有するＰＥＴ材を得ることに成功
し、本発明をなすに至った。SUMMARY OF THE INVENTION The inventor of the present invention has proposed a
In the process of repeatedly examining the PET (polyethylene terephthalate) material, which is about to be recycled by collecting ET bottles, from various viewpoints in order to expand its recycling applications, we attempted to modify the surface by thermal spraying. Despite being a plastic resin, it can be used as a base material to form films with various thermal spraying materials without causing problems of softening and deformation.In addition, thermal spray coatings are formed by spraying spray particles into the substrate. The present invention succeeded in obtaining a PET material having a modified surface in a peculiar state in which no interface is formed between the substrate and the base material, and accomplished the present invention.
【０００６】すなわち、本発明の請求項１に係る改質表
面を有するＰＥＴ材は、ポリエチレンテレフタレートか
らなる基材表面に溶射皮膜が形成され、この溶射皮膜の
少なくとも下部を構成する溶射粒子が基材表層部に粒子
形態を保って埋入した状態にあるものである。このよう
なＰＥＴ材は、溶射皮膜の下部が基材表層部と一体化し
ており、しかも溶射皮膜側から基材内部へと粒子形態を
保った溶射粒子の密度が次第に減少する形で連続的に遷
移し、溶射皮膜と基材との間に剥離性界面が存在しない
ため、溶射材料の基材に対する密着強度が極めて大きい
ものとなる。That is, in the PET material having a modified surface according to the first aspect of the present invention, a thermal spray coating is formed on the surface of a substrate made of polyethylene terephthalate, and the thermal spray particles constituting at least a lower portion of the thermal spray coating are formed on the substrate. It is in a state of being embedded in the surface layer while maintaining the particle form. In such a PET material, the lower part of the thermal spray coating is integrated with the surface layer of the base material, and the density of the thermal spray particles maintaining the particle form gradually decreases from the thermal spray coating side to the inside of the base material, and is continuously reduced. The transition occurs, and since there is no peelable interface between the thermal spray coating and the substrate, the adhesion strength of the thermal spray material to the substrate becomes extremely large.
【０００７】請求項２の発明は、改質表面を有するＰＥ
Ｔ材の製造方法として、ポリエチレンテレフタレートか
らなる基材表面に、溶射に伴う入熱によって基材の表層
部のみが溶融する溶射条件のもとに、改質材粉末を溶射
して溶射皮膜を形成することを特徴とする構成を採用し
たものである。このような方法によれば、基材の表層部
が溶融した状態で溶射粒子が打ち込まれるため、溶射粒
子が容易に基材の表層部内に達し、更にその一部の粒子
は自らの持つ熱量によって基材を溶融させながらより深
い位置まで侵入することになり、前記請求項１の発明で
規定するようなＰＥＴ材を確実に得ることができる。[0007] The invention of claim 2 provides a PE having a modified surface.
As a method for manufacturing the T material, a sprayed coating of a modifier powder is formed on a polyethylene terephthalate substrate surface under thermal spraying conditions in which only the surface layer of the substrate is melted by heat input during thermal spraying. In this case, a configuration characterized by the following is employed. According to such a method, since the thermal spray particles are driven in a state where the surface layer of the base material is melted, the thermal spray particles easily reach the inside of the surface layer of the base material, and some of the particles further depend on the calorific value of the substrate. The material penetrates to a deeper position while melting the base material, so that the PET material as defined in the first aspect of the present invention can be reliably obtained.
【０００８】請求項３の発明は、上記請求項２の改質表
面を有するＰＥＴ材の製造方法において、溶射をプラズ
マ溶射にて行う構成としている。この場合、前記請求項
１の発明で規定するようなＰＥＴ材をより確実に得るこ
とができる。According to a third aspect of the present invention, in the method of manufacturing a PET material having a modified surface according to the second aspect, the thermal spraying is performed by plasma spraying. In this case, a PET material as defined in the first aspect of the present invention can be obtained more reliably.
【０００９】請求項４の発明は、上記請求項２又は３の
改質表面を有するＰＥＴ材の製造方法において、基材と
してポリエチレンテレフタレート製プラスチック廃材を
原料として含む成形物を用いる構成としている。この場
合、ポリエチレンテレフタレートからなる基材にプラス
チック廃材を利用するから、資源リサイクルを促進し、
地球環境の保全に大きく貢献できる。According to a fourth aspect of the present invention, in the method for producing a PET material having a modified surface according to the second or third aspect, a molded product containing a polyethylene terephthalate plastic waste material as a raw material is used as a base material. In this case, since plastic waste is used for the base material made of polyethylene terephthalate, resource recycling is promoted,
It can greatly contribute to the preservation of the global environment.
【００１０】[0010]
【発明の実施の形態】本発明に係る改質表面を有するＰ
ＥＴ材は、ポリエチレンテレフタレート（以下、ＰＥＴ
と略称する）からなる基材表面に溶射皮膜が形成され、
この溶射皮膜の少なくとも下部を構成する溶射粒子が基
材表層部に粒子形態を保って埋入した状態にあるもので
ある。すなわち、このＰＥＴ材では、溶射皮膜の下部が
基材表層部と一体化し、溶射皮膜と基材との間で明確な
界面が存在せず、溶射皮膜側から基材内部へと粒子形態
を保った溶射粒子の密度が次第に減少する形で連続的に
遷移したものとなっている。従って、溶射材料の基材に
対する密着強度が極めて大きく、苛酷な条件下でも溶射
皮膜の界面剥離を生じる懸念はないから、改質表面の強
度による制約を受けずに広範な用途に用い得る。BEST MODE FOR CARRYING OUT THE INVENTION P having a modified surface according to the present invention
ET material is polyethylene terephthalate (hereinafter, PET)
Thermal spray coating is formed on the surface of the base material
The thermal spray particles constituting at least the lower part of the thermal spray coating are in a state of being embedded in the surface layer portion of the base material while maintaining the particle form. That is, in this PET material, the lower part of the thermal spray coating is integrated with the surface layer of the base material, there is no clear interface between the thermal spray coating and the base material, and the particle morphology is maintained from the thermal spray coating side to the inside of the base material. The transition is continuous with the density of the spray particles gradually decreasing. Therefore, since the adhesion strength of the thermal sprayed material to the base material is extremely high and there is no concern that the thermal sprayed coating will peel off even under severe conditions, it can be used for a wide range of applications without being restricted by the strength of the modified surface.
【００１１】しかして、ＰＥＴからなる基材としては、
板材、棒材、様々な形状の部材、シート、フィルム、箔
等、用途に応じた様々な形態のものを使用できるが、特
に資源リサイクルによる地球環境の保全に貢献し、また
原料コストを抑える意味からも、使用済みＰＥＴボトル
等の廃ＰＥＴ材より得られる再生ＰＥＴ成分が原料の全
量もしくは一部として含まれた成形物を用いることが好
適である。一方、溶射材料としては、特に制約はなく、
金属やセラミックを始めとする種々の材料を改質目的に
応じて適宜選択して用いればよい。However, as a substrate made of PET,
Sheets, bars, members of various shapes, sheets, films, foils, etc. can be used in various forms depending on the application, but in particular, it contributes to the preservation of the global environment through resource recycling and also reduces raw material costs. For this reason, it is preferable to use a molded product in which a recycled PET component obtained from a waste PET material such as a used PET bottle is included as a whole or a part of a raw material. On the other hand, there are no particular restrictions on the thermal spray material,
Various materials such as metals and ceramics may be appropriately selected and used according to the purpose of modification.
【００１２】このような改質表面を有するＰＥＴ材は、
ＰＥＴからなる基材表面に、溶射に伴う入熱によって基
材の表層部のみが溶融する溶射条件のもとに、改質材粉
末を溶射して溶射皮膜を形成する、という本発明に係る
製造方法によって容易に得ることができる。すなわち、
この方法によれば、図１（イ）に示すようにＰＥＴから
なる基材１の表層部１ａが溶融した状態で溶射粒子２が
打ち込まれるため、同図（ロ）に示すように該溶射粒子
２が容易に基材１の表層部１ａ内に達し、更に同図
（ハ）に示すように一部の粒子２が自らの持つ熱量によ
って基材１を溶融させながらより深い位置まで侵入する
結果、前記のように粒子形態を保った溶射粒子が溶射皮
膜側から基材内部へと密度を次第に減じる形で連続的に
遷移した状態となったＰＥＴ材が確実に得られることに
なる。いっぽう、自らの持つ熱量によって基材の深い位
置まで侵入する粒子が増加するとＰＥＴ材自体の溶融軟
化が懸念されるが、ある程度の粒子の埋め込みによって
皮膜が基材表面をカバーするようになると積層される粒
子の熱量は形成された皮膜を伝わって放散されるために
問題は生じない。なお、図１における基材１の梨地部分
は溶融領域を示し、溶射フレーム（炎）に晒されている
同図（イ）の状態からフレーム通過後の冷却に伴って同
図（ロ）から（ハ）へと縮小している。A PET material having such a modified surface is
The manufacturing method according to the present invention, in which the surface of a substrate made of PET is sprayed with a modifier powder under a spraying condition in which only the surface layer portion of the substrate is melted by heat input accompanying the spraying to form a sprayed film. It can be easily obtained by the method. That is,
According to this method, as shown in FIG. 1A, the thermal spray particles 2 are driven in a state where the surface layer 1a of the base material 1 made of PET is molten, and therefore, as shown in FIG. 2 easily reaches the surface layer 1a of the substrate 1, and furthermore, as shown in FIG. 3C, some particles 2 penetrate to a deeper position while melting the substrate 1 by its own heat. As a result, a PET material in which the thermal spray particles maintaining the particle form as described above are continuously transitioned from the thermal spray coating side to the inside of the base material in a state where the density gradually decreases can be reliably obtained. On the other hand, if the number of particles that penetrate deep into the substrate increases due to its own heat, the PET material itself may be melted and softened. The calorific value of the particles is transmitted through the formed film and dissipated, so that no problem occurs. The satin portion of the base material 1 in FIG. 1 indicates a molten region, and from the state of FIG. 1A exposed to the thermal spraying frame (flame), as shown in FIG. C) has been reduced.
【００１３】ここで、溶射に伴う入熱によって上述のよ
うに基材の表層部のみが溶融する溶射条件を採択できる
のは、基材を構成するＰＥＴ自体の持つ特性に依拠して
いる。すなわち、ＰＥＴの基材では、溶射フレームによ
って溶融させ得る適度の融点（５３３°Ｋ）を有し、且
つ熱伝導率が低いため、溶射フレームに晒された表層部
だけを高温化して溶融状態とすることが可能である。ま
た、ＰＥＴ材は通常ＳｉＯ2 によってガラス強化されて
おり、ポリエチレンなどに比べて熱に対する軟化抵抗は
大きいと考えられる。The reason why the thermal spraying condition in which only the surface layer of the base material is melted by the heat input accompanying the thermal spraying as described above can be adopted depends on the characteristics of PET itself constituting the base material. That is, since the PET base material has an appropriate melting point (533 ° K) that can be melted by the thermal spraying frame and has a low thermal conductivity, only the surface layer exposed to the thermal spraying frame is heated to a molten state. It is possible to Further, the PET material is usually glass-reinforced by SiO 2 , and is considered to have a higher softening resistance to heat than polyethylene or the like.
【００１４】これに対し、ＰＥＴに近い融点を持つ金
属、例えば錫（融点５０５°Ｋ）等を基材に用いて同様
の条件で溶射を行っても、金属の熱伝導率が高いため、
溶射フレームに晒された表層部が融点に達する前に、基
材全体に熱が拡散してしまうため、表層部は溶融状態に
ならない。また、一般的なセラミックの基材では、熱伝
導率は低くても極めて高融点であるため、通常の溶射条
件から外れた極端に大きい入熱量でない限りは表層部が
溶融状態になることはない。従って、金属やセラミック
の基材では、形成される溶射皮膜は溶射粒子が溶けて偏
平になった状態で基材の表面上に積み重なった積層構造
となり、溶射粒子が基材表層部に粒子形態を保って埋入
した状態の改質品は得られない。一方、ポリエチレン等
の通常の熱可塑性樹脂を基材とした場合は、既述のよう
に溶射時の入熱によって軟化や変形を生じるため、溶射
皮膜の形成が困難である。On the other hand, even if thermal spraying is performed under the same conditions using a metal having a melting point close to that of PET, for example, tin (melting point: 505 ° K) as a base material, the thermal conductivity of the metal is high.
Before the surface layer exposed to the thermal spray frame reaches the melting point, heat is diffused throughout the substrate, so that the surface layer does not become molten. In addition, a general ceramic base material has a very high melting point even if the thermal conductivity is low, so that the surface layer portion does not become a molten state unless an extremely large heat input amount deviates from normal thermal spraying conditions. . Therefore, in the case of a metal or ceramic substrate, the formed thermal spray coating has a laminated structure in which the thermal spray particles are melted and flattened on the surface of the substrate, and the thermal spray particles have a particle form on the surface layer of the substrate. A modified product that is kept and embedded cannot be obtained. On the other hand, when a normal thermoplastic resin such as polyethylene is used as a base material, as described above, the heat input during the thermal spraying causes softening and deformation, so that it is difficult to form a thermal spray coating.
【００１５】本発明に係る改質表面を有するＰＥＴ材の
製造方法には、プラズマ溶射や高速ガスフレーム溶射の
ような高速溶射法を始めとする種々の溶射法を採用でき
るが、中でもプラズマ溶射法はＰＥＴからなる基材の表
層部のみを溶融状態とするための条件設定が容易である
ことから特に推奨される。しかして、各溶射法におい
て、基材への入熱量に関与する各条件、例えば溶射距
離、溶射ガン又は／及び基材の移動速度、アーク出力
（プラズマ溶射）、作動ガス圧（流量）等を経験的に選
択することにより、ＰＥＴからなる基材の表層部のみを
溶融状態とするための溶射条件を設定すればよい。In the method of manufacturing a PET material having a modified surface according to the present invention, various thermal spraying methods such as high-speed thermal spraying such as plasma thermal spraying and high-speed gas flame thermal spraying can be employed. Is particularly recommended because it is easy to set conditions for melting only the surface layer of the PET base material. Thus, in each thermal spraying method, various conditions relating to the amount of heat input to the substrate, such as the spraying distance, the moving speed of the thermal spray gun or / and the substrate, arc output (plasma thermal spraying), working gas pressure (flow rate), etc. By making an empirical selection, thermal spraying conditions for bringing only the surface portion of the PET base material into a molten state may be set.
【００１６】[0016]
【実施例】以下、本発明の実施例を比較例と対比して具
体的に説明する。なお、使用した溶射装置とその溶射条
件、溶射用基材Ａ，Ｂ，Ｃは次のとおりである。EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. In addition, the thermal spraying apparatus used, its thermal spraying conditions, and the thermal spray base materials A, B, and C are as follows.
【００１７】〔溶射装置〕図２に示すプラズマ溶射装置
（スルーザーメテコ社製９ＭＢ）…砲弾状の陰極３がタ
ングステンを主体とする合金、この陰極３を取り囲むノ
ズル状の陽極４が銅からなり、陽極４のノズル口である
プラズマ噴出口５の外側に溶射粉末供給口６を有すると
共に、両極３，４を冷却するための冷却水循環路７を備
える。なお、図中の７ａは冷却水入口、７ｂは冷却水出
口、８は作動ガス入口である。[Thermal Spraying Apparatus] Plasma spraying apparatus shown in FIG. 2 (9 MB manufactured by Sulzer Metco Co.): shell-shaped cathode 3 is made of an alloy mainly composed of tungsten, and nozzle-shaped anode 4 surrounding cathode 3 is made of copper. A spraying powder supply port 6 outside a plasma jetting port 5 which is a nozzle port of the anode 4, and a cooling water circulation path 7 for cooling the electrodes 3 and 4. In the figure, 7a is a cooling water inlet, 7b is a cooling water outlet, and 8 is a working gas inlet.
【００１８】 〔溶射条件〕 溶射雰囲気・・・・・・・・・・・・・・空気 一次プラズマガス・・・・・・・・・・・アルゴン 二次プラズマガス・・・・・・・・・・・水素 溶射距離・・・・・・・・・・・・・・・１５０〜２００ｍｍ アーク電流・・・・・・・・・・・・・・５００Ａ アーク電圧・・・・・・・・・・・・・・５５Ｖ又は６０Ｖ 溶射ガン移動速度・・・・・・・・・・・５．５又は１０ｍ／分 溶射ガン走査・・・・・・・・・・・・・１パス ステップ幅・・・・・・・・・・・・・・５ｍｍ又は６ｍｍ[Spraying conditions] Spraying atmosphere: air Primary plasma gas: argon Secondary plasma gas:・ ・ Hydrogen Spraying distance ・ ・ ・ ・ ・ 150-200mm Arc current ・ ・ ・ ・ ・ ・ 500A Arc voltage ・ ・ ・ ・ ・ ・······ 55V or 60V Spray gun moving speed 5.5 or 10m / min Spray gun scanning 1 Pass step width: 5mm or 6mm
【００１９】〔溶射用基材Ａ〕…使用済みＰＥＴボトル
を用い、カッターにてボトル上下の硬質部分を切除した
残部を短冊状に切断し、更にシュレッダーにかけて細か
く裁断し、この裁断片をエチルアルコールにて３分間超
音波洗浄して乾燥させたものを電気炉内で３２５℃に加
熱して溶融させ、この溶融物を予め２５０〜２６０℃に
温めておいた金型内に流し込み、放冷によって固化後に
金型から外し、８０番のエメリー紙で表面を研磨したも
ので、５０×５０×４ｍｍの板状をなす。 〔溶射用基材Ｂ〕…５０×５０×４ｍｍの軟鋼板を脱脂
処理後、サンドブラスト処理を施したもの。 〔溶射用基材Ｃ〕…５０×５０×４ｍｍの錫（Ｓｎ）板
を脱脂処理後、サンドブラスト処理を施したもの。[Substrate for thermal spraying A]: Using a used PET bottle, the remaining portion of the upper and lower hard portions cut off with a cutter is cut into strips, further shredded and cut into small pieces. Is heated at 325 ° C. in an electric furnace to be melted, poured into a mold preheated to 250 to 260 ° C., and allowed to cool. After solidification, it is removed from the mold and the surface is polished with No. 80 emery paper to form a 50 × 50 × 4 mm plate. [Substrate for thermal spraying B]: A soft steel sheet of 50 × 50 × 4 mm is subjected to a degreasing treatment and then subjected to a sandblasting treatment. [Substrate C for thermal spraying]: A tin (Sn) plate of 50 × 50 × 4 mm that has been subjected to degreasing and then sandblasting.
【００２０】実施例１ 溶射材料として粒径４５〜９５μｍのＣｕ（銅）粉末
（スルザーメテコ社製の製品名５５）を用い、アーク電
圧を５５Ｖ、溶射距離を２００ｍｍ、溶射ガン移動速度
を５．５ｍ／分、ステップ幅を６ｍｍに設定して、ＰＥ
Ｔの溶射用基材Ａの表面にプラズマ溶射した。Example 1 Cu (copper) powder having a particle size of 45 to 95 μm (product name 55 manufactured by Sulzer Metco Co., Ltd.) was used as a spray material, an arc voltage was 55 V, a spray distance was 200 mm, and a spray gun moving speed was 5.5 m. / Min, step width is set to 6mm, PE
Plasma spraying was performed on the surface of the substrate A for thermal spraying of T.
【００２１】比較例１ 溶射ガン移動速度を１０ｍ／分に変更した以外は、実施
例１と同様にして溶射用基材Ａ（ＰＥＴ）の表面にＣｕ
粉末をプラズマ溶射した。Comparative Example 1 The same procedure as in Example 1 was carried out except that the moving speed of the spray gun was changed to 10 m / min.
The powder was plasma sprayed.
【００２２】比較例２ 溶射ガン移動速度を１０ｍ／分に変更し、溶射用基材Ｂ
（軟鋼）の表面に実施例１と同様にしてＣｕ粉末をプラ
ズマ溶射した。COMPARATIVE EXAMPLE 2 Thermal spray gun moving speed was changed to 10 m / min,
Cu powder was plasma-sprayed on the surface of (mild steel) in the same manner as in Example 1.
【００２３】上記の実施例１及び比較例１，２で得られ
た各表面改質板について、断面のミクロ組織を調べるた
めに、エメリー紙で１５００番まで研磨したのち、アル
ミナバフ研磨（粒径０．０５μｍ）によって鏡面仕上げ
し、走査型電子顕微鏡によって断面組織を観察した。図
３（イ）に実施例１の、同（ロ）に比較例１の、同
（ハ）に比較例２の、それぞれ表面改質板における表層
部断面の電子顕微鏡写真を示す。なお、これら写真中の
白色部分はＥＤＸ（エネルギー分散型Ｘ線）分析によっ
てＣｕ成分であることが確かめられている。Each of the surface-modified plates obtained in Example 1 and Comparative Examples 1 and 2 was polished with emery paper up to No. 1500 in order to examine the microstructure of the cross section. .05 μm), and the cross-sectional structure was observed with a scanning electron microscope. FIG. 3 (a) shows electron micrographs of the surface layer section of the surface-modified plate of Example 1, FIG. 3 (b) of Comparative Example 1, and FIG. 3 (c) of Comparative Example 2 respectively. It is confirmed by EDX (energy dispersive X-ray) analysis that the white portions in these photographs are Cu components.
【００２４】図３（イ）より、実施例１にて得られた表
面改質板では、基材内部まで多くのＣｕ粒子が球状に近
い状態で埋入しており、溶射皮膜の下部が基材表層部に
一体化し、溶射皮膜と基材との間で明確な界面が存在し
ていないことが判る。これに対し、比較例２にて得られ
た表面改質板では、図３（ハ）に示すように、溶射皮膜
はＣｕ粒子が溶けて偏平になった状態で基板表面上に積
み重なった典型的な積層構造となっており、溶射皮膜と
基材との間で明確な界面を生じている。また、比較例１
にて得られた表面改質板では、図３（ロ）に示すよう
に、基材表面に部分的にＣｕ粒子が存在するだけで、Ｃ
ｕが皮膜化していない。しかして、比較例１の結果は、
ＰＥＴの基材であっても、溶射ガンの移動速度が速過
ぎ、基材表層部が溶融していない状態では、皮膜形成が
困難になることを示唆している。FIG. 3 (a) shows that in the surface-modified plate obtained in Example 1, many Cu particles were buried in a nearly spherical state to the inside of the base material, and the lower part of the thermal spray coating was the base. It can be seen that there is no clear interface between the thermal spray coating and the base material integrated with the material surface layer. On the other hand, in the surface-modified plate obtained in Comparative Example 2, as shown in FIG. 3 (c), a typical sprayed coating was formed on a substrate surface in a state where Cu particles were melted and flattened. And a clear interface between the thermal spray coating and the substrate. Comparative Example 1
As shown in FIG. 3B, in the surface-modified plate obtained in the above, only Cu particles are partially present on the surface of the base material.
u is not formed into a film. Thus, the result of Comparative Example 1 is
Even with a PET substrate, it is suggested that the film formation becomes difficult when the moving speed of the thermal spray gun is too fast and the surface layer of the substrate is not melted.
【００２５】実施例２，比較例３ 溶射材料として実施例１及び比較例２，３で用いたＣｕ
粉末を分級して得られた粒径４５〜６５μｍのＣｕ粉末
を用い、溶射距離を２００ｍｍ、溶射ガン移動速度を
５．５ｍ／分に設定して、溶射用基材Ａ（ＰＥＴ）と溶
射用基材Ｃ（錫）の表面に同時にプラズマ溶射した。か
くして得られた各表面改質板の前記同様の電子顕微鏡写
真を、基材Ａを用いた実施例２は図４（イ）に、基材Ｃ
を用いた比較例３は同図（ロ）に、それぞれ示す。Example 2 and Comparative Example 3 Cu used in Example 1 and Comparative Examples 2 and 3 as a thermal spray material was used.
Using a Cu powder having a particle size of 45 to 65 μm obtained by classifying the powder, the spraying distance is set to 200 mm, and the spraying gun moving speed is set to 5.5 m / min. Plasma spraying was simultaneously performed on the surface of the substrate C (tin). The electron micrographs of the respective surface-modified plates thus obtained are shown in FIG.
(B) of Comparative Example 3 using the above.
【００２６】図４（イ）で示すようにＰＥＴからなる基
材Ａを用いた実施例２の場合は基材内部まで多くのＣｕ
粒子が埋入しているのに対し、錫からなる基材Ｃを用い
た比較例３の場合は図４（ロ）で示すように前記比較例
２の軟鋼からなる基材Ｂを用いた場合と同様の積層構造
の溶射皮膜が形成されている。このようにＰＥＴ（融点
５３３°Ｋ）と錫（同５０５°Ｋ）とは近い融点で、し
かも錫の方が僅かに低融点であるにも関わらず、同一条
件で形成される溶射皮膜の形態に大きな差が現れるの
は、ＰＥＴの場合は低い熱伝導率のためにプラズマフレ
ームからの入熱によって表層部のみが高温化して溶融す
るのに対し、錫の場合は高い熱伝導率のためにプラズマ
フレームからの入熱が速やかに基材全体に拡散する結
果、表層部が溶融するほど高温化しないものと想定され
る。なお、この基材表層部の溶融の有無については、両
基材Ａ，Ｃの表面に切り傷を付け、これら両基材Ａ，Ｃ
の表面に上記溶射時と同じ条件で且つＣｕ粉末を供給せ
ずにプラズマフレームを照射した際、基材Ｃの表面の切
り傷には変化がない一方、基材Ａの表面の切り傷に変形
を生じたことからも確認されている。As shown in FIG. 4A, in the case of Example 2 using the base material A made of PET, a large amount of Cu
In the case of Comparative Example 3 using the substrate C made of tin while the particles are embedded, the case of using the substrate B made of the mild steel of Comparative Example 2 as shown in FIG. A sprayed coating having the same laminated structure as that described above is formed. As described above, although the melting points of PET (melting point 533 ° K) and tin (505 ° K) are close to each other, and tin has a slightly lower melting point, the form of the thermal spray coating formed under the same conditions The large difference appears in the case of PET because only the surface layer is heated and melted by heat input from the plasma frame due to the low thermal conductivity in the case of PET, whereas the high thermal conductivity is used in the case of tin. It is assumed that as a result of the heat input from the plasma frame rapidly diffusing throughout the base material, the temperature does not become so high as to melt the surface layer. In addition, regarding the presence or absence of melting of the surface layer of the base material, a cut is made on the surface of both base materials A and C, and the base materials A and C are cut.
When the plasma flame was irradiated to the surface of the substrate under the same conditions as in the above thermal spraying and without supplying the Cu powder, the cut on the surface of the base material C did not change, but the cut on the surface of the base material A was deformed. It is confirmed from that.
【００２７】実施例３〜５ 実施例３では溶射距離を１５０ｍｍとし、実施例４では
溶射距離を２５０ｍｍとし、実施例５では溶射材料とし
て前記同様の分級による粒径７５〜９０μｍのＣｕ粉末
を用い、それ以外の条件は各々実施例１と同様にして溶
射用基材Ａの表面にＣｕ粉末をプラズマ溶射した。得ら
れた各表面改質板の前記同様の電子顕微鏡写真を、実施
例３は図５（イ）に、実施例４は同図（ロ）に、実施例
５は同図（ハ）に、それぞれ示す。Examples 3 to 5 In Example 3, the spraying distance was 150 mm, in Example 4, the spraying distance was 250 mm, and in Example 5, Cu powder having a particle size of 75 to 90 μm was used as the spraying material in the same manner as described above. The Cu powder was plasma-sprayed on the surface of the thermal spraying substrate A in the same manner as in Example 1 except for the above conditions. The same electron micrographs of the obtained surface modified plates as in the above are shown in FIG. 5A for Example 3, FIG. 5B for Example 4, and FIG. Shown respectively.
【００２８】図５（ハ）と図３（イ）との対比から、溶
射時の基材表層部の溶融程度を決定するパラメーター
は、プラズマフレームの照射による入熱量と溶射粒子が
保有する熱量による入熱量との合計であり、溶射材料の
粒径が大きいほど、その粒子自体が保有する熱量も大き
くなる結果、溶射粒子の基材中への埋入（打ち込み）深
さが大きくなることが判る。また、図５（イ）（ロ）と
図３（イ）との対比から、溶射距離が短くなるほど、プ
ラズマフレームによる入熱量が大きくなると共に、Ｃｕ
粒子の保有熱量も飛翔距離が短くなって溶射面に到達す
るまでに失われにくくなるから、基材の溶融する表層部
の深さが増し、これに対応して溶射粒子の基材中への埋
入（打ち込み）深さも大きくなることが判る。From the comparison between FIG. 5 (c) and FIG. 3 (a), the parameters for determining the degree of melting of the substrate surface layer during thermal spraying depend on the amount of heat input by irradiation of the plasma flame and the amount of heat held by the spray particles. It is understood that the larger the particle size of the thermal spray material, the larger the amount of heat possessed by the particles itself, and as a result, the deeper the embedment (implantation) of the thermal spray particles into the base material. . Also, from the comparison between FIGS. 5A and 5B and FIG. 3A, the shorter the spraying distance, the larger the heat input by the plasma frame and the higher the Cu input.
Since the amount of retained heat of the particles is also difficult to be lost before reaching the sprayed surface as the flight distance becomes shorter, the depth of the surface layer where the base material melts increases, and correspondingly, the sprayed particles into the base material It can be seen that the embedding (implantation) depth also increases.
【００２９】実施例６，比較例４ 溶射材料として平均粒径２５．７μｍのＴｉＯ2 （二酸
化チタン）粉末（昭和電工社製のＫ−３０Ｍ）を用い、
アーク電圧を６０Ｖ、溶射距離を２００ｍｍ、溶射ガン
移動速度を５．５ｍ／分、ステップ幅を５ｍｍに設定し
て、溶射用基材Ａ（ＰＥＴ）及び溶射用基材Ｃ（錫）の
表面に同時にプラズマ溶射した。得られた各表面改質板
の前記同様の電子顕微鏡写真を、基材Ａを用いた実施例
６は図６（イ）に、基材Ｃを用いた比較例４は同図
（ロ）に、それぞれ示す。Example 6 and Comparative Example 4 TiO 2 (titanium dioxide) powder (K-30M manufactured by Showa Denko KK) having an average particle size of 25.7 μm was used as a spray material.
The arc voltage is set to 60 V, the spraying distance is set to 200 mm, the spraying gun moving speed is set to 5.5 m / min, and the step width is set to 5 mm, and the surface of the base material for thermal spraying A (PET) and the base material for thermal spraying C (tin) are set. At the same time, plasma spraying was performed. Electron micrographs of the obtained surface-modified plates, which are similar to those described above, are shown in FIG. 6A for Example 6 using the base material A, and in FIG. 6B for Comparative Example 4 using the base material C. , Respectively.
【００３０】図６（イ）より、溶射材料としてＴｉＯ2
粉末を用いた場合でも、ＰＥＴの基材Ａでは、基材内部
まで多くのＴｉＯ2 粒子が粒状形態を保って埋入してお
り、溶射皮膜の下部が基材表層部に一体化し、溶射皮膜
と基材との間で明確な界面が存在していないことが判
る。これに対し、同図（ロ）に示すように、錫の基材Ｃ
では、溶射皮膜はＴｉＯ2 粒子が溶けて偏平になった状
態で基板表面上に積み重なった典型的な積層構造となっ
ており、溶射皮膜と基材との間で明確な界面を生じてい
る。なお、これら写真中の白色部分はＥＤＸ分析によっ
てＴｉＯ2 成分であることが確かめられている。また、
このＴｉＯ2 粉末を用いた場合でも、ＰＥＴよりなる基
材Ａに対する溶射距離の長短による打ち込み深さは、前
記Ｃｕ粒子を用いた場合と同様の傾向を示した。FIG. 6A shows that TiO 2 is used as a thermal spray material.
Even when the powder is used, in the PET base material A, many TiO 2 particles are embedded in the base material while maintaining the granular form, and the lower part of the thermal spray coating is integrated with the surface layer of the base material, and the thermal spray coating is formed. It can be seen that there is no clear interface between the substrate and the substrate. On the other hand, as shown in FIG.
In, the thermal spray coating has a typical laminated structure in which the TiO 2 particles are melted and flattened on the substrate surface, and a clear interface is generated between the thermal spray coating and the substrate. It is confirmed by EDX analysis that the white portions in these photographs are TiO 2 components. Also,
Even when this TiO 2 powder was used, the implantation depth due to the length of the sprayed distance to the substrate A made of PET showed the same tendency as that when the Cu particles were used.
【００３１】[0031]
【発明の効果】請求項１の発明によれば、改質表面を有
するＰＥＴ材として、ポリエチレンテレフタレートから
なる基材表面に溶射皮膜が形成された構造であって、溶
射皮膜と基材との間に剥離性界面が存在しないため、溶
射材料の基材に対する密着強度が極めて大きく、苛酷な
条件下でも溶射皮膜の界面剥離を生じる懸念がなく、も
って改質表面の強度による制約を受けずに広範な用途に
用い得るものが提供される。According to the first aspect of the present invention, a PET material having a modified surface has a structure in which a sprayed film is formed on the surface of a substrate made of polyethylene terephthalate. Because there is no peelable interface, the adhesion strength of the sprayed material to the substrate is extremely large, and there is no concern that the sprayed coating will peel off even under severe conditions. What can be used for various applications is provided.
【００３２】請求項２の発明によれば、上記の改質表面
を有するＰＥＴ材を確実に且つ容易に製造する方法が提
供される。According to the second aspect of the present invention, there is provided a method for reliably and easily manufacturing a PET material having the above-mentioned modified surface.
【００３３】請求項３の発明によれば、上記の製造方法
において、改質表面を有する優れたＰＥＴ材をより確実
に製造できるという利点がある。According to the third aspect of the present invention, there is an advantage in the above manufacturing method that an excellent PET material having a modified surface can be manufactured more reliably.
【００３４】請求項４の発明によれば、上記の製造方法
において、基材として使用済みＰＥＴボトル等のポリエ
チレンテレフタレート製プラスチック廃材を原料として
含む成形物を用いることから、資源リサイクルを促進
し、地球環境の保全に大きく貢献できるという利点があ
る。According to the fourth aspect of the present invention, in the above-mentioned manufacturing method, since a molded product containing a waste plastic material made of polyethylene terephthalate such as a used PET bottle as a base material is used as a base material, resource recycling is promoted, There is an advantage that it can greatly contribute to environmental conservation.
【図１】 本発明に係る改質表面を有するＰＥＴ材の製
造方法における、溶射時の溶射粒子の挙動を模式的に示
すものであって、（イ）は溶射フレームの照射により基
材表層部が溶融した状態の縦断面図、（ロ）は溶射フレ
ームの通過後の溶射粒子が打ち込まれた状態の縦断面
図、（ハ）は打ち込まれた溶射粒子が更に沈み込む状態
を示す縦断面図である。FIG. 1 schematically shows the behavior of spray particles during thermal spraying in a method for producing a PET material having a modified surface according to the present invention. (B) is a longitudinal sectional view showing a state in which the sprayed particles have been injected after passing through the spraying frame, and (c) is a longitudinal sectional view showing a state in which the injected sprayed particles are further submerged. It is.
【図２】 本発明の実施例に用いるプラズマ溶射装置の
縦断面図である。FIG. 2 is a longitudinal sectional view of a plasma spraying apparatus used in an embodiment of the present invention.
【図３】 本発明の実施例及び比較例で得られた表面改
質板の表層部の断面組織を示す電子顕微鏡写真図であ
り、（イ）は実施例１、（ロ）は比較例１、（ハ）は比
較例２にそれぞれ対応する。FIGS. 3A and 3B are electron micrographs showing the cross-sectional structures of the surface layer portions of the surface-modified plates obtained in Examples and Comparative Examples of the present invention, wherein FIG. 3A is Example 1, and FIG. , (C) correspond to Comparative Example 2, respectively.
【図４】 上記同様の電子顕微鏡写真図であり、（イ）
は実施例２、（ロ）は比較例３にそれぞれ対応する。FIG. 4 is an electron micrograph similar to the above,
Corresponds to Example 2 and (b) corresponds to Comparative Example 3, respectively.
【図５】 上記同様の電子顕微鏡写真図であり、（イ）
は実施例３、（ロ）は実施例４、（ハ）は実施例５にそ
れぞれ対応する。FIG. 5 is an electron micrograph similar to the above, (a)
Corresponds to the third embodiment, (b) corresponds to the fourth embodiment, and (c) corresponds to the fifth embodiment.
【図６】 上記同様の電子顕微鏡写真図であり、（イ）
は実施例６、（ロ）は比較例４にそれぞれ対応する。FIG. 6 is an electron micrograph similar to the above, (a)
Corresponds to Example 6, and (b) corresponds to Comparative Example 4, respectively.
１ 基材 １ａ 表層部 ２ 溶射粒子 DESCRIPTION OF SYMBOLS 1 Substrate 1a Surface part 2 Sprayed particles
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年８月５日（１９９９．８．５）[Submission date] August 5, 1999 (1999.8.5)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図３[Correction target item name] Figure 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図３】 FIG. 3
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図４[Correction target item name] Fig. 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図４】 FIG. 4
【手続補正３】[Procedure amendment 3]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図５[Correction target item name] Fig. 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図５】 FIG. 5
【手続補正４】[Procedure amendment 4]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図６[Correction target item name] Fig. 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図６】 FIG. 6
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F006 AA35 AB35 BA02 DA01 4F100 AB17 AK42A BA02 DE01B EC03B EC032 EH112 EH56B EH562 EJ61B EJ612 GB72 GB90 JK06 JL00 JL00A JL11 JM02B 4K031 AA08 AB07 AB08 CB18 CB39 CB42 DA04 EA10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AA35 AB35 BA02 DA01 4F100 AB17 AK42A BA02 DE01B EC03B EC032 EH112 EH56B EH562 EJ61B EJ612 GB72 GB90 JK06 JL00 JL00A JL11 JM02B 4K031 AA08 AB07 CB18 CB18
Claims (4)
材表面に溶射皮膜が形成され、この溶射皮膜の少なくと
も下部を構成する溶射粒子が基材表層部に粒子形態を保
って埋入した状態にある改質表面を有するＰＥＴ材。1. A modified surface in which a thermal spray coating is formed on the surface of a substrate made of polyethylene terephthalate, and thermal spray particles constituting at least a lower portion of the thermal spray coating are embedded in the surface layer of the substrate while maintaining the particle form. PET material having
材表面に、溶射に伴う入熱によって基材の表層部のみが
溶融する溶射条件のもとに、改質材粉末を溶射して溶射
皮膜を形成することを特徴とする改質表面を有するＰＥ
Ｔ材の製造方法。2. A thermal spray coating of a modifier powder on a polyethylene terephthalate substrate surface under thermal spraying conditions in which only the surface layer of the substrate is melted by heat input during thermal spraying. Having a modified surface characterized by the following:
Manufacturing method of T material.
載のＰＥＴ材の製造方法。3. The method according to claim 1, wherein the thermal spraying is performed by plasma spraying.
製プラスチック廃材を原料として含む成形物を用いる請
求項２又は３に記載のＰＥＴ材の製造方法。4. The method for producing a PET material according to claim 2, wherein a molded product containing polyethylene terephthalate plastic waste material as a raw material is used as a base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11125089A JP2000319432A (en) | 1999-04-30 | 1999-04-30 | Pet material having modified surface and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11125089A JP2000319432A (en) | 1999-04-30 | 1999-04-30 | Pet material having modified surface and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000319432A true JP2000319432A (en) | 2000-11-21 |
Family
ID=14901579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11125089A Pending JP2000319432A (en) | 1999-04-30 | 1999-04-30 | Pet material having modified surface and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000319432A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330550A (en) * | 2004-05-20 | 2005-12-02 | Snecma Moteurs | Method for providing thermal barrier having bending flexibility |
| WO2016064858A1 (en) * | 2014-10-21 | 2016-04-28 | Oreltech Ltd. | A method and system for forming a patterned metal film on a substrate |
-
1999
- 1999-04-30 JP JP11125089A patent/JP2000319432A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330550A (en) * | 2004-05-20 | 2005-12-02 | Snecma Moteurs | Method for providing thermal barrier having bending flexibility |
| WO2016064858A1 (en) * | 2014-10-21 | 2016-04-28 | Oreltech Ltd. | A method and system for forming a patterned metal film on a substrate |
| CN107002218A (en) * | 2014-10-21 | 2017-08-01 | 奥雷尔科技有限公司 | A kind of method and system that pattern metal film is formed in substrate |
| US11661527B2 (en) | 2014-10-21 | 2023-05-30 | Oreltech Ltd. | Composition for forming a patterned metal film on a substrate |
| US11912883B2 (en) | 2014-10-21 | 2024-02-27 | Oreltech Ltd. | Method and system for forming a patterned metal film on a substrate |
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