JPH0555540B2 - - Google Patents
Info
- Publication number
- JPH0555540B2 JPH0555540B2 JP1028417A JP2841789A JPH0555540B2 JP H0555540 B2 JPH0555540 B2 JP H0555540B2 JP 1028417 A JP1028417 A JP 1028417A JP 2841789 A JP2841789 A JP 2841789A JP H0555540 B2 JPH0555540 B2 JP H0555540B2
- Authority
- JP
- Japan
- Prior art keywords
- isopropylacrylamide
- solution
- polyn
- hydrophilic
- flat plate
- 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 - Lifetime
Links
- 229920003023 plastic Polymers 0.000 claims description 15
- 239000004033 plastic Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、低い表面エネルギーをもつプラスチ
ツク成形体の表面の親水化方法、さらに詳しくい
えば、本発明は、低い表面エネルギーをもつため
臨界表面張力が低く、水または水性溶媒なような
比較的高い表面張力をもつ液体に濡れにくい性質
を有するポリフルオロカーボンやポリオレフイン
のような固体表面を親水化するための新規な製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for making the surface of a plastic molded article having a low surface energy hydrophilic. The present invention relates to a new manufacturing method for making the surface of a solid such as polyfluorocarbon or polyolefin hydrophilic, which has a property of being difficult to wet with a liquid having a relatively high surface tension such as water or an aqueous solvent.
従来の技術
ポリフルオロカーボンやポリオレフインのよう
なプラスチツクは、表面エネルギーが低いため、
水や水性溶媒との親和性を欠き、これらを含む液
状組成物による表面被覆、印刷、接着などの際に
十分な効果が得られないという欠点がある。Conventional Technology Plastics such as polyfluorocarbons and polyolefins have low surface energies;
It lacks affinity with water and aqueous solvents, and has the disadvantage that sufficient effects cannot be obtained when surface coating, printing, adhesion, etc. are performed using liquid compositions containing these.
これまで、このようなプラスチツクを素材とし
た成形体の表面の親水化する方法としては、グロ
ー放電、プラズマジエツトのような高エネルギー
活性線の照射により、表面の水素引き抜きやフツ
素引き抜きを行い活性化する方法、ポリオレフイ
ンの成形体をクラム硫酸液に浸せきする方法、ポ
リフルオロカーボンの成形体を、ナトリウムナフ
タレンのテトラヒドロフラン溶液やアルカリ金属
の水銀アマルガムで処理する方法などが知られて
いる。 Up until now, methods for making the surface of molded objects made from plastics hydrophilic have been to draw out hydrogen or fluorine from the surface by irradiation with high-energy actinic rays such as glow discharge or plasma jet. A method of activating the polyolefin, a method of immersing a molded polyolefin in a crumb sulfuric acid solution, and a method of treating a molded polyfluorocarbon with a solution of sodium naphthalene in tetrahydrofuran or an alkali metal mercury amalgam are known.
しかしながら、高エネルギー活性線を照射する
方法は、特殊な設備や装置を必要とするために、
工業的方法としては不適当であるし、クロム硫酸
液、ナトリウムナフタレン、アルカリ金属などの
処理剤を用いる方法は、これらが金属に対し腐食
性を示すために、取り扱いにくい上に、作業にも
危険を伴うという欠点がある。 However, the method of irradiating with high-energy active rays requires special equipment and equipment, so
It is unsuitable as an industrial method, and methods using processing agents such as chromium sulfuric acid solution, sodium naphthalene, and alkali metals are corrosive to metals, making them difficult to handle and dangerous for work. It has the disadvantage of being accompanied by
発明が解決しようとする課題
本発明は、従来方法の欠点を克服し、簡単な操
作で、しかも装置の腐食、人体への危険を伴うこ
となく、各種プラスチツク成形体の表面を親水化
するための処理方法を提供することを目的として
なされたものである。Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional methods and provides a method for making the surfaces of various plastic moldings hydrophilic with simple operation and without corrosion of the equipment or danger to the human body. This was done for the purpose of providing a processing method.
課題を解決するための手段
本発明者らは、低い表面エネルギーをもつプラ
スチツク成形体の表面を親水化する簡単で安全性
の高い方法を開発するために鋭意研究を重ねた結
果、ポリＮ−イソプロピルアクリルアミド溶液を
用いて表面処理を行うことにより、前記の目的を
達成しうることを見出し、この知見に基づいて本
発明を完成するに至つた。Means for Solving the Problems As a result of intensive research to develop a simple and highly safe method for making the surface of a plastic molded object with low surface energy hydrophilic, the present inventors discovered that polyN-isopropyl It has been discovered that the above object can be achieved by surface treatment using an acrylamide solution, and based on this knowledge, the present invention has been completed.
すなわち、本発明は低い表面エネルギーをもつ
プラスチツク成形体をポリＮ−イソプロピルアク
リルアミド溶液により表面処理することを特徴と
するプラスチツク成形体表面の親水化方法を提供
するものである。 That is, the present invention provides a method for making the surface of a plastic molded article hydrophilic, which comprises treating the surface of a plastic molded article having a low surface energy with a poly-N-isopropylacrylamide solution.
以下、本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明における低いエネルギーをもつプラスチ
ツクとしての代表的な例としては、ポリフルオロ
カーボン、ポリオレフインを挙げることができ
る。 Typical examples of plastics with low energy in the present invention include polyfluorocarbons and polyolefins.
また、本発明方法に用いられるポリＮ−イソプ
ロピルアクリルアミドは、重量平均分子量５万〜
600万の範囲のものが適当である。このものは、
通常濃度0.1〜５％の溶液として用いられる。こ
の溶液の溶媒としては水又は親水性溶媒あるいは
これらの混合物が好ましい。 Furthermore, the poly N-isopropylacrylamide used in the method of the present invention has a weight average molecular weight of 50,000 to 50,000.
Something in the range of 6 million is appropriate. This thing is
It is usually used as a solution with a concentration of 0.1 to 5%. The solvent for this solution is preferably water, a hydrophilic solvent, or a mixture thereof.
なお、ポリＮ−イソプロピルアクリルアミドと
類似の化学構造をもつポリアクリルアミドやポリ
Ｎ，N′−ジメチルアクリルアミドなどを用いた
場合には、所望の親水化が得られないことから、
これはポリＮ−イソプロピルアクリルアミドに特
有の性質に由来するものと推測される。 Note that if polyacrylamide or polyN,N'-dimethylacrylamide, which has a chemical structure similar to polyN-isopropylacrylamide, is used, the desired hydrophilization cannot be obtained.
This is presumed to be due to properties specific to polyN-isopropylacrylamide.
本発明方法は、プラスチツク成形体の表面にポ
リＮ−イソプロピルアクリルアミド溶液を塗布す
るか、あるいはプラスチツク成形体をポリＮ−イ
ソプロピルアミド溶液中に浸せきすることによつ
て行われる。その際のプラスチツク表面における
反応は次の如く進行する。 The method of the invention is carried out by applying a poly-N-isopropylacrylamide solution to the surface of a plastic molded body or by immersing the plastic molded body in a poly-N-isopropylacrylamide solution. The reaction on the plastic surface proceeds as follows.
すなわち、プラスチツクとポリＮ−イソプロピ
ルアクリルアミドが接触すると、その表面に対し
てポリＮ−イソプロピルアクリルアミドの側鎖構
造単位に含まれる疎水性基が選択的に吸着した超
薄膜層が形成され、かつ同じ側鎖構造単位に含ま
れる親水性基はこのようにして形成される超薄膜
層が疎水結合している面とは反対側に分布する。
その結果、プラスチツク表面がこのようにして形
成されるポリＮ−イソプロピルアクリルアミドか
らなる分子レベルの非対称構造をもつ超薄膜を介
して親水化される。 In other words, when plastic and polyN-isopropylacrylamide come into contact, an ultra-thin film layer is formed on the surface in which hydrophobic groups contained in the side chain structural units of polyN-isopropylacrylamide are selectively adsorbed, and The hydrophilic groups contained in the chain structural units are distributed on the side opposite to the surface where the ultra-thin film layer formed in this way has hydrophobic bonds.
As a result, the plastic surface is made hydrophilic through the ultra-thin film made of polyN-isopropylacrylamide and having an asymmetric structure at the molecular level.
発明の効果
本発明は、表面エネルギーの低いポリフルオロ
カーボンやポリオレフインのようなプラスチツク
成形体の表面を、簡単な操作でかつ高い安全性で
容易に親水化しうるので、コーテイング、印刷、
接着等の技術分野において好適に利用することが
できる。Effects of the Invention The present invention can easily hydrophilize the surface of plastic molded articles such as polyfluorocarbons and polyolefins with low surface energy with simple operations and high safety.
It can be suitably used in technical fields such as adhesion.
実施例
次に、実施例により本発明をさらに詳細に説明
する。Examples Next, the present invention will be explained in more detail with reference to examples.
実施例 １
重量平均分子量が約60万のポリＮ−イソプロピ
ルアクリルアミドを水に溶解して、約0.5％の希
薄水溶液に調製する。この希薄な高分子水溶液の
表面張力は室温付近で約48ダイン／cmである。こ
の希薄溶液中にあらかじめ清浄化してあるポリフ
ルオロカーボン製の平板を浸せきしたところ、約
５秒間でこの平板の表面へのポリＮ−イソプロピ
ルアクリルアミドの側鎖構造に含まれる疎水性基
の選択的吸着が完了した。取り出して風乾したの
ち、この表面の純水に対する接触角を実測すると
平均22度であつた。なお、未処理の状態でのポリ
フルオロカーボンの平板表面の純水に対する接触
角は平均122度であつた。Example 1 Poly N-isopropylacrylamide having a weight average molecular weight of about 600,000 is dissolved in water to prepare a dilute aqueous solution of about 0.5%. The surface tension of this dilute aqueous polymer solution is about 48 dynes/cm near room temperature. When a previously cleaned polyfluorocarbon flat plate was immersed in this dilute solution, hydrophobic groups contained in the side chain structure of polyN-isopropylacrylamide were selectively adsorbed onto the surface of the flat plate in about 5 seconds. Completed. After taking it out and air-drying it, the contact angle of the surface with pure water was actually measured to be 22 degrees on average. The contact angle of the untreated polyfluorocarbon plate surface with pure water was 122 degrees on average.
実施例 ２
ポリＮ−イソプロピルアクリルアミドとして重
量平均分子量が５万のものを用いた以外は、実施
例１と同様に処理し、実施例１と同様の結果を得
た。Example 2 The same process as in Example 1 was carried out, except that poly N-isopropylacrylamide having a weight average molecular weight of 50,000 was used, and the same results as in Example 1 were obtained.
実施例 ３
ポリＮ−イソプロピルアクリルアミドとして重
量平均分子量が600万のものを用いた以外は、実
施例１と同様に処理し、実施例１のそれと同様の
結果を得た。このことよりポリＮ−イソプロピル
アクリルアミドについては、重量平均分子量が５
万から600万までの範囲で効果が同一であり、分
子量依存性はないことが分る。Example 3 The same procedure as in Example 1 was carried out except that poly N-isopropylacrylamide having a weight average molecular weight of 6 million was used, and the same results as in Example 1 were obtained. From this, the weight average molecular weight of polyN-isopropylacrylamide is 5.
It can be seen that the effect is the same in the range from 1,000 to 6,000,000, and there is no dependence on molecular weight.
実施例 ４
実施例１に用いたポリＮ−イソプロピルアクリ
ルアミドの希薄水溶液にあらかじめ表面を清浄化
してある高密度ポリエチレン製の平板を浸せきし
たところ、10秒間でこの平板の表面への選択的吸
着が達成された。次にこの平板を取り出して風乾
したのち、この表面の純水に対する接触角を実測
したところ、平均22度であつた。なお、未処理の
状態での高密度ポリエチレンの平板表面の純水に
対する接触角は平均98度であつた。Example 4 When a high-density polyethylene flat plate whose surface had been previously cleaned was immersed in the dilute aqueous solution of polyN-isopropylacrylamide used in Example 1, selective adsorption onto the surface of the flat plate was achieved in 10 seconds. It was done. Next, this flat plate was taken out and air-dried, and the contact angle of the surface with pure water was actually measured, and the average was 22 degrees. In addition, the contact angle of the flat plate surface of high-density polyethylene with pure water in an untreated state was 98 degrees on average.
比較例 １
重量平均分子量が33万のポリＮ，Ｎ−ジメチル
アクリルアミドを純水に溶解して１％希薄溶液を
調製し、ポリフルオロカーボンの平板に実施例１
と同じ条件で表面処理を施したのち、このポリフ
ルオロカーボン製平板表面の純水に対する接触角
を実測したところ平均122度で、表面の性質は不
変であつた。Comparative Example 1 A 1% dilute solution was prepared by dissolving poly N,N-dimethylacrylamide with a weight average molecular weight of 330,000 in pure water, and Example 1 was prepared on a polyfluorocarbon flat plate.
After surface treatment under the same conditions as above, the contact angle of the surface of this polyfluorocarbon flat plate with pure water was actually measured to be 122 degrees on average, and the surface properties remained unchanged.
比較例 ２
重量平均分子量が58万のポリアクリルアミドの
１％希薄水溶液を調製し、ポリフルオロカーボン
の平板に実施例１と同じ条件で表面処理を施した
のち、このポリフルオロカーボン製平板表面の純
水に対する接触角を実測したところ平均122度で、
表面の性質は不変であつた。Comparative Example 2 A 1% dilute aqueous solution of polyacrylamide with a weight average molecular weight of 580,000 was prepared, and a polyfluorocarbon flat plate was subjected to surface treatment under the same conditions as in Example 1. When the contact angle was actually measured, the average was 122 degrees.
The surface properties remained unchanged.
Claims (1)
体をポリＮ−イソプロピルアクリルアミド溶液に
より表面処理することを特徴とするプラスチツク
成形体表面の親水化方法。1. A method for making the surface of a plastic molded object hydrophilic, which comprises treating the surface of a plastic molded object with a low surface energy with a polyN-isopropylacrylamide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028417A JPH02208326A (en) | 1989-02-07 | 1989-02-07 | Rendering surface of plastic molding hydrophilic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028417A JPH02208326A (en) | 1989-02-07 | 1989-02-07 | Rendering surface of plastic molding hydrophilic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208326A JPH02208326A (en) | 1990-08-17 |
| JPH0555540B2 true JPH0555540B2 (en) | 1993-08-17 |
Family
ID=12248081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028417A Granted JPH02208326A (en) | 1989-02-07 | 1989-02-07 | Rendering surface of plastic molding hydrophilic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208326A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI237282B (en) | 2003-01-07 | 2005-08-01 | Pentax Corp | Push button device having an illuminator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250018A (en) * | 1984-05-28 | 1985-12-10 | Mitsui Toatsu Chem Inc | Antifogging resin |
-
1989
- 1989-02-07 JP JP1028417A patent/JPH02208326A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250018A (en) * | 1984-05-28 | 1985-12-10 | Mitsui Toatsu Chem Inc | Antifogging resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02208326A (en) | 1990-08-17 |
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