JP3495540B2 - Surface modification method for polypropylene resin - Google Patents
Surface modification method for polypropylene resinInfo
- Publication number
- JP3495540B2 JP3495540B2 JP2004697A JP2004697A JP3495540B2 JP 3495540 B2 JP3495540 B2 JP 3495540B2 JP 2004697 A JP2004697 A JP 2004697A JP 2004697 A JP2004697 A JP 2004697A JP 3495540 B2 JP3495540 B2 JP 3495540B2
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene resin
- fluorine
- coating
- adhesion
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Treatments Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明は、ポリプロピレン樹
脂を用いて、押し出し加工や射出成形により所定寸法に
形成した加工品や成形品の表面に塗装工事や接着工事を
行うにあたり、ポリプロピレン表面を親水性化して塗装
後の塗膜密着性を良好にするための、あるいは接着強度
を高めるための表面改質方法に関する。
【０００２】
【従来の技術】ポリプロピレン樹脂は、日常生活用品か
ら産業資材、特に自動車部品や電化製品そしてコンピュ
ータ製品に多く用いられている汎用プラスチック材料で
ある。このポリプロピレン樹脂は表面極性が極めて低
く、水に対する濡れ性が悪く撥水性を示す特徴があるた
め、二次加工としての塗装、めっき及び接着が非常に困
難であった。
【０００３】このため、従来から塗装、めっき及び接着
工事の前処理として、種々の表面処理を行うことによっ
て表面改質が行われている。特に、ポリプロピレン樹脂
は前述のとおり構成用成形品として利用分野が広いた
め、簡単でかつ有効な表面改質方法の開発が求められ、
容易に塗装や接着が行われることが要求されていた。
【０００４】このような要求に対し、塗装や接着分野で
は、ポリプロピレン樹脂そのものの改質、即ち共重合や
ポリマーブレンドなどによって樹脂の性状改質を行った
り、あるいは塗装前処理として紫外線照射処理やプラズ
マ処理、またはプライマーの塗布やオゾン酸化による処
理方法等により塗膜の密着性や接着強度の向上を図って
いる。
【０００５】
【発明が解決しようとする課題】しかしながら、これら
の処理方法は設備費が高価であったり、環境対策特にオ
ゾン層の破壊問題と作業環境でも問題が多く、更には処
理時間がかかりすぎるなどの問題があった。本発明は、
このような事情に鑑みなされたものであって、その目的
とするところは、表面極性が極めて低いポリプロピレン
樹脂表面を簡易な設備を用いて短時間に親水化させ、塗
装や接着を容易ならしめる表面改質方法を提供すること
にある。
【０００６】
【課題を解決するための手段】上記目的は、ポリプロピ
レン樹脂の表面改質方法において、前記ポリプロピレン
樹脂をフッ素濃度が０．５〜２．０パーセントの常温雰
囲気中に１〜１０分間放置することにより、このポリプ
ロピレン樹脂の表面を親水性にすることを特徴とするポ
リプロピレン樹脂の表面改質方法、により達成される。
【０００７】
【作用】本発明によれば、極性力成分が極めて小さいポ
リプロピレン樹脂表面をフッ素化処理することにより、
双極子性や分極性の官能基をポリプロピレン樹脂表面に
形成させることができる。即ちポリプロピレン樹脂表面
に−ＣＦ−ＣＦ−と−Ｃ−ＣＦ−の結合が形成され、ポ
リプロピレン樹脂表面の既存のＲ−基（−ＣＨ３−）の
水素原子と置換されることによって官能基が形成される
ものと考えられる。因みに、フッ素原子は電子吸引を起
こしやすい性質があることから、この−ＣＦ−ＣＦ−と
−Ｃ−ＣＦ−の結合内で、フッ素原子による原子吸引が
生じポリプロピレン樹脂表面を極性化し、濡れ性が向上
するものと思われる。
【０００８】
【発明の実施の形態】本発明になるポリプロピレン樹脂
の表面改質方法の詳細につき、以下に説明する。まず、
純度９９％以上のフッ素ガスを真空にしたステンレス製
のボンベに入れ、その後窒素ガスを圧入してボンベ内の
フッ素濃度を０．５〜２．０Ｖｏｌ％となるようにあら
かじめ濃度調整したフッ素ガスを準備する。次いでポリ
プロピレン樹脂成形品・加工品を耐圧製真空チェンバー
内に入れた後、２００〜３００Ｐａ迄真空にする。その
後、所定濃度０．５〜２．０Ｖｏｌ％に予め調整した前
記フッ素ガスをボンベから導入する。フッ素ガス封入後
１〜１０分間放置処理しポリプロピレン樹脂成形品・加
工品の表面を親水化する。
【０００９】所定の処理時間経過後ただちに窒素ガスを
導入しフッ素ガスをパージングする。排気した後、表面
がフッ素化したポリプロピレン樹脂成形品・加工品を取
り出して塗装を行う。フッ素処理したポリプロピレン樹
脂表面は、通常の塗装工程であるプライマー塗布のよう
な処理や溶剤処理を全く必要とせず、エナメル塗料を直
接１回塗装のみで膜厚の薄い密着性の良好な表面を得る
ことができる。またポリプロピレン樹脂表面が親水化し
ていることで塗装のみならず接着においても、あらゆる
種類の接着剤に対して良好な接着強度を得ることができ
る。
【００１０】以下に本発明の実施例を図１を参照して詳
述する。同図において、１は耐圧製真空チェンバーであ
り、２はチェンバー本体、３は該本体２の上部開口に開
閉自在に設けられた蓋、４は図示しない真空ポンプに接
続された排気口、５はフッ素ガスを充填したステンレス
製のボンベ６に配管７で接続された第１吸気口、８は窒
素ガスを充填したステンレス製のボンベ９に配管１０で
接続された第２吸気口であり、各配管７および１０には
管路を開閉するためのバルブ１１および１２が設けられ
ている。
【００１１】チェンバー本体２内には、該本体２の底面
に立設された支柱１３上にテーブル１４が一体に設けら
れており、このテーブル１４上に被処理物たるポリプロ
ピレン樹脂性の箱型ケース２０が載置される。このよう
に構成されたフッ素化処理装置を用いて、ポリプロピレ
ン樹脂表面をフッ素化する方法について説明する。
【００１２】まずフッ素化処理に先立ってボンベ６を真
空にし、その中に純度９９％以上のフッ素ガスを所定圧
入れ、その後窒素ガスを圧入してフッ素濃度を１．０Ｖ
ｏｌ％に調整する。一方、ポリプロピレン樹脂（宇部興
産（株）製ＵＢＥポリプログレードＪ６０９Ｈ）を用い
て箱型の所定形状に射出成形加工したケース２０を耐圧
製真空チェンバー１内に入れテーブル１４上に載置す
る。 その後チェンバー１内を真空度２００〜３００Ｐ
ａになる迄排気口４から排気した後、所定濃度１．０ｖ
ｏｌ％に調整したフッ素ガスをボンベ６から導入する。
フッ素ガス導入後５〜７分間ケース２０をフッ素ガス雰
囲気中に放置し、ポリプロピレン樹脂表面を親水化させ
ることによって表面を改質させる。
【００１３】所定時間経過後は直ちに窒素ガスボンベ９
から窒素ガスを導入し、フッ素ガスを不活性物質にパー
ジすると共にチェンバー１の真空を解除する。その後、
蓋３を開け被処理物のポリプロピレン樹脂製ケース２０
を取り出す。この時ケース２０の塗装を施す面には、指
紋等の汚れが付着しないように注意が必要である。チェ
ンバー１から取り出したケース２０には直ちに塗装す
る。塗装は常法により行うが、塗装前処理例えばプライ
マー塗り、溶剤拭き取り等の前処理は全く必要とせず、
フッ素ガス処理した表面に直接エナメルを塗布する。
【００１４】エナメルは常温乾燥型のアクリル樹脂と特
殊ポリオレフィン系樹脂を主成分とした一液型塗料（大
橋化学（株）製ポリナールＮｏ３５０）を用いて常温に
て処理した。エナメル１００部に対してシンナー６０部
（重量）を加えて、塗料粘度を１２〜１５秒（フォード
カップＮｏ４）に調合し、スプレーガンにて一回塗り
（塗膜約２０μ）し、室温にて２４時間放置した。その
後、ポリプロピレンと塗膜の密着性を確認するため、平
面部の塗装面に１ｍｍ方眼１００ＥＡ（隙間間隔１ｍ
ｍ、ます目１００）を形成し、塗膜の付着を確認した。
その結果、０／１００（欠点碁盤目／碁盤目）の良好な
密着性が得られた（ＪＩＳＫ５４００ ８．５項碁盤目
密着性試験）。
【００１５】更に、最も良好な塗膜との密着性が得られ
るフッ素化処理条件（フッ素濃度と処理時間）を設定す
るため、供試体として縦１００×横１００×厚さ５ｍｍ
のポリプロピレン樹脂（宇部興産（株）製ＵＢＥポリプ
ロ グレード６０９Ｈ）を１条件につき５枚使用し、フ
ッ素濃度と処理時間を変えて上記実施例と同一方法にて
塗装を行ったものの密着性試験をおこなったところ、次
の表に示す結果が得られた。
【表１】
この実験結果から明らかなように、フッ素化処理条件と
してはフッ素濃度０．５〜２．０ＶＯＬ％、処理時間１
〜１０分が最も適当であった。
【００１６】
【発明の効果】本発明によれば、ポリプロピレン樹脂を
用いて、押し出し加工や射出成形により所定寸法に形成
した加工品や成形品のポリプロピレン表面に塗装工事や
接着工事を行うにあたり、ポリプロピレン表面を親水性
化して塗装後の塗膜密着性を良好にするために、常温で
希薄なフッ素濃度ガスにより、ポリプロピレン樹脂表面
をフッ素化処理し該表面を親水性にすることができ、塗
装後の塗膜密着性あるいは接着強度を高めることができ
る。また、所定濃度のフッ素雰囲気に成形品や加工品を
置くだけであるから、形状が複雑なものであっても容易
にフッ素化処理ができる。このため、作業工数が低減さ
れ生産性が向上すると共に、コストダウンを図ることが
できる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating process and an adhesive process on a surface of a processed product or molded product formed to a predetermined size by extrusion or injection molding using a polypropylene resin. The present invention relates to a surface modification method for making a polypropylene surface hydrophilic so as to improve the adhesion of a coated film after coating or for increasing the adhesive strength. 2. Description of the Related Art Polypropylene resin is a general-purpose plastic material widely used in daily necessities and industrial materials, particularly in automobile parts, electric appliances and computer products. This polypropylene resin has extremely low surface polarity, has poor wettability to water, and exhibits water repellency, so that coating, plating and bonding as secondary processing were extremely difficult. [0003] For this reason, surface modification has been conventionally carried out by performing various surface treatments as pretreatments for painting, plating and bonding work. In particular, as described above, polypropylene resin has a wide field of application as a molded article for components, and therefore, the development of a simple and effective surface modification method is required.
It has been demanded that painting and bonding be easily performed. [0004] In response to such demands, in the field of coating and bonding, modification of the polypropylene resin itself, that is, property modification of the resin by copolymerization or polymer blending, etc. The adhesion or the adhesion strength of the coating film is improved by a treatment or a treatment method such as application of a primer or ozone oxidation. [0005] However, these treatment methods are expensive in equipment cost, and have many environmental measures, especially the problem of destruction of the ozone layer and the work environment, and the treatment time is too long. There was such a problem. The present invention
In view of such circumstances, the purpose is to make the surface of a polypropylene resin having a very low surface polarity hydrophilic in a short period of time using simple equipment, thereby facilitating painting and adhesion. It is to provide a reforming method. [0006] The object of the present invention is to provide a polypropylene
In the method for modifying a surface of a lenticular resin, the polypropylene
Resin in a normal temperature atmosphere with a fluorine concentration of 0.5 to 2.0%
This polyp can be left in the atmosphere for 1 to 10 minutes.
The polypropylene resin has a hydrophilic surface.
A method for modifying the surface of a propylene resin. According to the present invention, the surface of a polypropylene resin having a very small polar force component is fluorinated,
Dipolar or polarizable functional groups can be formed on the surface of the polypropylene resin. That is, a bond between -CF-CF- and -C-CF- is formed on the surface of the polypropylene resin, and a functional group is formed by replacing a hydrogen atom of an existing R-group (-CH3-) on the surface of the polypropylene resin. It is considered to be. Incidentally, since fluorine atoms have a property of easily attracting electrons, in the bond between -CF-CF- and -C-CF-, atoms are attracted by fluorine atoms to polarize the surface of the polypropylene resin, and the wettability is reduced. It seems to improve. [0008] The details of the method for modifying the surface of a polypropylene resin according to the present invention will be described below. First,
A fluorine gas having a purity of 99% or more is put into a vacuum-made stainless steel cylinder, and then a nitrogen gas is press-fitted thereinto, and a fluorine gas whose concentration has been adjusted in advance so that the fluorine concentration in the cylinder becomes 0.5 to 2.0 Vol% is obtained. prepare. Next, the polypropylene resin molded product / processed product is placed in a pressure-resistant vacuum chamber, and the pressure is reduced to 200 to 300 Pa. Thereafter, the fluorine gas previously adjusted to a predetermined concentration of 0.5 to 2.0 Vol% is introduced from a cylinder. After sealing the fluorine gas, it is left standing for 1 to 10 minutes to hydrophilize the surface of the molded or processed polypropylene resin product. Immediately after the elapse of a predetermined processing time, nitrogen gas is introduced and fluorine gas is purged. After evacuating, the fluorinated polypropylene resin molded product / processed product is taken out and painted. The fluorine-treated polypropylene resin surface does not require any treatment such as primer coating, which is a usual coating process, or any solvent treatment, and a thin film with good adhesion can be obtained by directly applying the enamel paint only once. be able to. In addition, since the surface of the polypropylene resin is made hydrophilic, good adhesive strength can be obtained for all kinds of adhesives not only in painting but also in bonding. An embodiment of the present invention will be described below in detail with reference to FIG. In the figure, 1 is a pressure-resistant vacuum chamber, 2 is a chamber main body, 3 is a lid provided at the upper opening of the main body 2 so as to be openable and closable, 4 is an exhaust port connected to a vacuum pump (not shown), 5 is A first intake port connected to a stainless steel cylinder 6 filled with fluorine gas through a pipe 7, and a second intake port 8 connected to a stainless steel cylinder 9 filled with nitrogen gas through a pipe 10. 7 and 10 are provided with valves 11 and 12 for opening and closing the pipeline. In the chamber main body 2, a table 14 is integrally provided on a column 13 standing upright on the bottom surface of the main body 2, and a box-shaped case made of polypropylene resin as an object to be processed is provided on the table 14. 20 is placed. A method for fluorinating the surface of the polypropylene resin using the fluorination apparatus configured as described above will be described. Prior to the fluorination treatment, the cylinder 6 is evacuated, and a fluorine gas having a purity of 99% or more is injected thereinto at a predetermined pressure.
ol%. On the other hand, a case 20 injection-molded into a box-shaped predetermined shape using a polypropylene resin (UBE Polypro Grade J609H manufactured by Ube Industries, Ltd.) is placed in the pressure-resistant vacuum chamber 1 and placed on the table 14. Thereafter, the inside of the chamber 1 is vacuumed to 200 to 300P.
After exhausting from the exhaust port 4 until a
The fluorine gas adjusted to ol% is introduced from the cylinder 6.
The case 20 is left in a fluorine gas atmosphere for 5 to 7 minutes after the introduction of the fluorine gas, and the surface is modified by hydrophilizing the surface of the polypropylene resin. After a lapse of a predetermined time, the nitrogen gas cylinder 9 is immediately turned on.
, A fluorine gas is purged to an inert substance, and the vacuum of the chamber 1 is released. afterwards,
Open the lid 3 and use the polypropylene resin case 20 to be treated.
Take out. At this time, care must be taken so that dirt such as fingerprints does not adhere to the surface of the case 20 to be coated. The case 20 taken out of the chamber 1 is immediately painted. Coating is performed by a usual method, but no pre-treatment such as primer pre-treatment such as primer coating or solvent wiping is required.
Apply enamel directly to the surface that has been treated with fluorine gas. The enamel was treated at room temperature using a one-pack type paint (Polynal No. 350, manufactured by Ohashi Chemical Co., Ltd.) containing acrylic resin and special polyolefin resin as main components at room temperature. Add 60 parts (weight) of thinner to 100 parts of enamel, adjust the coating viscosity to 12 to 15 seconds (Ford Cup No. 4), apply once with a spray gun (approximately 20μ of coating), and at room temperature. It was left for 24 hours. Then, in order to check the adhesion between the polypropylene and the coating film, a 1 mm square 100EA (gap interval 1 m
m, squares 100) were formed, and adhesion of the coating film was confirmed.
As a result, good adhesion of 0/100 (defect cross-cut / cross-cut) was obtained (JISK5400 8.5 cross-cut adhesion test). Furthermore, in order to set the fluorination treatment conditions (fluorine concentration and treatment time) that provide the best adhesion to the coating film, the specimen was 100 × 100 × 5 mm in thickness.
Adhesion test was carried out using a polypropylene resin (UBE PolyPro Grade 609H manufactured by Ube Industries, Ltd.) per condition, using 5 sheets per condition, changing the fluorine concentration and the treatment time, and applying the same method as in the above example. As a result, the results shown in the following table were obtained. [Table 1] As is clear from the experimental results, the fluorination treatment conditions were a fluorine concentration of 0.5 to 2.0 VOL%, a treatment time of 1
-10 minutes was most appropriate. According to the present invention, when a coating work or a bonding work is performed on a polypropylene surface of a processed product or a molded product formed to a predetermined size by extrusion or injection molding using a polypropylene resin, In order to make the surface hydrophilic and improve the adhesion of the coated film after coating, the surface of the polypropylene resin can be fluorinated with a dilute fluorine-concentration gas at room temperature to make the surface hydrophilic. Can improve the adhesion of the coating film or the adhesive strength. Further, since a molded product or a processed product is simply placed in a fluorine atmosphere of a predetermined concentration, fluorination treatment can be easily performed even if the shape is complicated. Therefore, the number of work steps is reduced, the productivity is improved, and the cost can be reduced.
【図面の簡単な説明】
【図１】本発明のポリプロピレン樹脂の表面改質方法に
用いる装置の模式図である。
【符号の説明】
１ チェンバー
２ 本体
３ 蓋
４ 排気口
５ 第１の吸気口
６ フッ素ガスボンベ
７・１０ 配管
８ 第２の吸気口
９ 窒素ガスボンベ
１１・１２ バルブ
１４ テーブル
２０ 被処理物たるケースBRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an apparatus used for a method for modifying the surface of a polypropylene resin according to the present invention. [Description of Signs] 1 Chamber 2 Main body 3 Lid 4 Exhaust port 5 First intake port 6 Fluorine gas cylinder 7.10 Piping 8 Second intake port 9 Nitrogen gas cylinder 11 ・ 12 Valve 14 Table 20 Case to be treated
Claims (1)
いて、 前記ポリプロピレン樹脂をフッ素濃度が０．５〜２．０
パーセントの常温雰囲気中に１〜１０分間放置すること
により、このポリプロピレン樹脂の表面を親水性にする
ことを特徴とするポリプロピレン樹脂の表面改質方法。 (57) [Claims] [Claim 1] A method for modifying the surface of a polypropylene resin.
And the fluorine concentration of the polypropylene resin is 0.5 to 2.0.
Leave for 1 to 10 minutes in a normal temperature atmosphere
Makes the surface of this polypropylene resin hydrophilic
A method for modifying the surface of a polypropylene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004697A JP3495540B2 (en) | 1997-01-17 | 1997-01-17 | Surface modification method for polypropylene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004697A JP3495540B2 (en) | 1997-01-17 | 1997-01-17 | Surface modification method for polypropylene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10204195A JPH10204195A (en) | 1998-08-04 |
| JP3495540B2 true JP3495540B2 (en) | 2004-02-09 |
Family
ID=12016126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004697A Expired - Fee Related JP3495540B2 (en) | 1997-01-17 | 1997-01-17 | Surface modification method for polypropylene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3495540B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020006479A (en) | 2000-07-12 | 2002-01-19 | 아끼모토 유미 | Protective film for fpd, vapor deposited material for protective film and its production method, fpd, and manufacturing device for fpd protective film |
-
1997
- 1997-01-17 JP JP2004697A patent/JP3495540B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10204195A (en) | 1998-08-04 |
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