JPH0577692B2 - - Google Patents
Info
- Publication number
- JPH0577692B2 JPH0577692B2 JP1596189A JP1596189A JPH0577692B2 JP H0577692 B2 JPH0577692 B2 JP H0577692B2 JP 1596189 A JP1596189 A JP 1596189A JP 1596189 A JP1596189 A JP 1596189A JP H0577692 B2 JPH0577692 B2 JP H0577692B2
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- laser
- compound
- hydrophilic
- lipophilic
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
- B29C59/165—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating of profiled articles, e.g. hollow or tubular articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0838—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using laser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
Landscapes
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フツ素樹脂の表面の改質方法に係
り、特にレーザーによりフツ素樹脂の表面を選択
的に親水性又は親油性に改質する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for modifying the surface of a fluororesin, and particularly to a method for selectively modifying the surface of a fluororesin to make it hydrophilic or lipophilic using a laser. Regarding how to.
フツ素樹脂は、化学的に非常に安定した樹脂で
あるため広範な産業分野で利用されている。 Fluorine resins are chemically very stable resins and are therefore used in a wide range of industrial fields.
一方、フツ素樹脂の特性を備えたまま選択的
（部分的）に表面を親水性又は親油性に改質する
ことができれば、その利用分野が一段と拡張され
る。 On the other hand, if it is possible to selectively (partially) modify the surface to make it hydrophilic or lipophilic while retaining the characteristics of fluororesin, the field of its application will be further expanded.
例えば、部分的に親水性に改質することによ
り、接着性をもたすことができるため、他の物質
との複合体として利用できる。又、フツ素樹脂か
ら成る人工血管の内部のみを細かい間隔をおいて
親水性に改質することにより、血栓を防止する効
果がある。あるいは、親油性に改質することによ
り、水無しオフセツト印刷の原版に利用できる。 For example, by partially modifying it to make it hydrophilic, it can have adhesive properties and can be used as a composite with other substances. Further, by modifying only the inside of the artificial blood vessel made of fluororesin to make it hydrophilic at small intervals, it is effective to prevent blood clots. Alternatively, by modifying it to make it lipophilic, it can be used as an original plate for waterless offset printing.
従来、プラズマ法や金属Naとアンモニア水を
用いて化学的にフツ素樹脂を改質する方法、更に
はアルカリ金属溶液法、アルカリ金属アマルガム
法、電界法、スパツタエツチング処理、放電処
理、コロナ放電処理等が知られている。しかし、
従来の方法では、フツ素樹脂の表面を選択的（必
要とする部分のみ）に親水性又は親油性に改質す
ることができなかつた。
Conventional methods include plasma method, chemical modification of fluororesin using metallic Na and aqueous ammonia, as well as alkali metal solution method, alkali metal amalgam method, electric field method, sputter etching treatment, electric discharge treatment, and corona discharge. Treatments etc. are known. but,
With conventional methods, it has not been possible to selectively (only the necessary portion) modify the surface of a fluororesin to make it hydrophilic or lipophilic.
本発明は、レーザーを用いてフツ素樹脂の表面
を選択的に親水性又は親油性に改質する方法を提
供することを目的とする。
An object of the present invention is to provide a method for selectively modifying the surface of a fluororesin to be hydrophilic or lipophilic using a laser.
上記の目的を達成させるために本発明は、Ｂ又
はAl化合物のガス雰囲気中で、フツ素樹脂表面
にArFレーザーを照射することを特徴とする。
In order to achieve the above object, the present invention is characterized in that the surface of a fluororesin is irradiated with an ArF laser in a B or Al compound gas atmosphere.
又、本発明は、親水基又は親油基を有するＢ又
はAl化合物ガスを用いることによつて達成され
る。 Further, the present invention is achieved by using a B or Al compound gas having a hydrophilic group or a lipophilic group.
更に、本発明は、Ｂ又はAl化合物ガスに、親
水基又は親油基を有する他の化合物ガスを混合し
たガスを用いることによつて達成される。 Furthermore, the present invention can be achieved by using a gas in which B or Al compound gas is mixed with another compound gas having a hydrophilic group or lipophilic group.
上記化合物ガスとしては、フツ素樹脂表面を
ArFレーザーとの光分解反応により親水性或いは
親油性に改質し得るものであれは種々のものが使
用することができ、特に限定されるべきものでは
ない。しかしながら、具体的には（B2H6，
NH3）、（BHNH）3、Ｂ（CH3）3、Ｂ（C2H5）3、Ｂ
（C6H5）3、Al（CH3）3、Al（C2H5）3、Al（C4H9）3を
挙げることができ、これらの内のいずれかを使用
するのが好ましい。 The above compound gas is applied to the fluororesin surface.
Various materials can be used as long as they can be modified to be hydrophilic or lipophilic by a photolysis reaction with an ArF laser, and there are no particular limitations. However, specifically (B 2 H 6 ,
NH 3 ), (BHNH) 3 , B(CH 3 ) 3 , B(C 2 H 5 ) 3 , B
( C6H5 ) 3 , Al( CH3 ) 3 , Al( C2H5 ) 3 , Al ( C4H9 ) 3 , and it is preferable to use any one of these . .
本発明では、光子エネルギーが148Kcalである
ArFレーザーを照射するので、Ｃ−Ｆ結合エネル
ギーが128Kcalであるフツ素樹脂のＣ−Ｆ結合を
切断することができる。しかし、Ｆは結合力が強
くすぐに再結合してしまう。そのため本発明で
は、Ｃよりも結合力が強くしかもArFレーザーで
は切断されることがない、148Kcal以上の結合エ
ネルギーをもつた原子であるＢ又はAlを結合さ
せるようにしている（Ｆ−Ｂ：183Kcal、Ｆ−
Al：158Kcal）。
In the present invention, the photon energy is 148 Kcal
Since the ArF laser is irradiated, the C-F bond of the fluororesin, which has a C-F bond energy of 128 Kcal, can be cut. However, F has a strong binding force and recombines quickly. Therefore, in the present invention, B or Al, which is an atom with a bonding energy of 148 Kcal or more, is bonded (F-B: 183 Kcal), which has a stronger bonding force than C and cannot be cut by ArF laser. ,F-
Al: 158Kcal).
すなわち、ArFレーザーで切れるＢ又はAl化
合物のガス雰囲気中で、フツ素樹脂表面にレーザ
ーを照射するので、レーザーの照射された部分の
み選択的にＦを引き抜くことができる。そしてＢ
又はAl化合物が、−OH、−COOH、−NH2、−CO、
−SO3HあるいはＯ、Ｎ、Ｓなどの原子を含む基
すなわち親水基を有する化合物である場合には、
Ｆが親水基に置換されてフツ素樹脂の表面を親水
性に改質することができる。一方、Ｂ又はAl化
合物が、−CoH2o+1や−C6H5などの炭化水素すな
わち親油基を有する化合物である場合には、Ｆが
親油基に置換されフツ素樹脂の表面を親油性に改
質することができる。 That is, since the surface of the fluororesin is irradiated with a laser in a gas atmosphere of B or Al compounds that can be cut with an ArF laser, F can be selectively extracted from only the portions irradiated with the laser. And B
Or the Al compound is -OH, -COOH, -NH2 , -CO,
- In the case of a compound having a group containing atoms such as -SO 3 H or O, N, or S, that is, a hydrophilic group,
When F is substituted with a hydrophilic group, the surface of the fluororesin can be modified to be hydrophilic. On the other hand, when the B or Al compound is a compound having a hydrocarbon such as -C o H 2o+1 or -C 6 H 5 , that is, a lipophilic group, F is substituted with the lipophilic group and the fluororesin is The surface can be modified to be lipophilic.
本発明によれば、レーザーが照射された部分の
み選択的にフツ素樹脂の表面を親水性又は親油性
に改質することができるので、前述した種々の用
途にフツ素樹脂を利用できる効果がある。
According to the present invention, it is possible to selectively modify the surface of the fluororesin to make it hydrophilic or lipophilic only in the area irradiated with the laser, so that the fluororesin can be used for the various purposes mentioned above. be.
実施例 １
NH3とB2H6のガスを、それぞれ20Torrで封入
したセル内のフツ素樹脂表面に垂直にArFレーザ
ー（193nm）をレーザー光のエネルギー密度を変
え、30、45、60秒間照射した。第１図は、そのと
きのレーザーを照射した部分のフツ素樹脂表面の
水との接触角の関係を示すグラフである。同図か
ら明らかなように、レーザーエネルギー密度を高
くしていくと接触角が小さくあるピーク値をも
ち、強い親水性をもつた表面に改質することがで
きた。Example 1 ArF laser (193 nm) was irradiated perpendicularly to the fluororesin surface in a cell filled with NH 3 and B 2 H 6 gases at 20 Torr for 30, 45, and 60 seconds by changing the energy density of the laser light. did. FIG. 1 is a graph showing the relationship between the contact angle with water on the fluororesin surface of the portion irradiated with the laser at that time. As is clear from the figure, as the laser energy density was increased, the contact angle had a small peak value and the surface could be modified to have strong hydrophilicity.
実施例 ２
（BHNH）3ガスを用いて実施例１と同じ条件
で実施した結果、同様にレーザーが照射された部
分のみ親水性をもつた表面に改質することができ
た。Example 2 As a result of carrying out the experiment under the same conditions as in Example 1 using (BHNH) 3 gas, it was possible to modify the surface to have hydrophilicity only in the portion irradiated with the laser.
実施例 ３
Ｂ（CH3）3のガスを40Torr封入したセル内で、
フツ素樹脂表面に垂直にArFレーザーを、レーザ
ー光のエネルギー密度を変え、10、20、30秒間照
射した。第２図は、そのときのレーザーを照射し
た部分のフツ素樹脂表面の油の接触角の変化を示
すグラフである。同図から、明らかなように、レ
ーザーのエネルギー密度を高くしていくと接触角
が小さくなり、あるピーク値をもち、親油性が増
大することが判つた。この親油性の増大は、フツ
素樹脂のＣ−Ｆ結合が切断され、手をなくしたＣ
がCH3基と結合したＦとCH3が置換された結果生
じたものである。Example 3 In a cell filled with 40 Torr of B(CH 3 ) 3 gas,
The ArF laser was irradiated perpendicularly to the fluororesin surface for 10, 20, and 30 seconds while changing the energy density of the laser light. FIG. 2 is a graph showing the change in the contact angle of oil on the fluororesin surface in the area irradiated with the laser at that time. As is clear from the figure, as the energy density of the laser increases, the contact angle decreases and reaches a certain peak value, indicating that the lipophilicity increases. This increase in lipophilicity is due to the cleavage of the C-F bond in the fluororesin, resulting in the loss of the C-F bond.
is a result of substitution of CH 3 with F bonded to CH 3 group.
実施例 ４
実施例３において、Ｂ（CH3）3ガスに代えて、
Ｂ（C2H5）3、Ｂ（C6H5）3、Al（CH3）3、Al
（C2H5）3、Al（C4H9）3、Al（C6H5）3の各ガスを用
いて同一条件で実施した結果、いずれも実施例３
とほぼ同様な親油性の改質が得られた。Example 4 In Example 3, instead of B(CH 3 ) 3 gas,
B(C 2 H 5 ) 3 , B(C 6 H 5 ) 3 , Al(CH 3 ) 3 , Al
(C 2 H 5 ) 3 , Al (C 4 H 9 ) 3 , and Al (C 6 H 5 ) 3 under the same conditions, all of which were Example 3.
Almost the same lipophilic modification was obtained.
実施例 ５
透明テフロンチユーブ１の中に、B2H6
（20Torr）とNH3（20Torr）の混合ガスを流し、
チユーブの外側から格子状のスリツトを通した
ArFレーザー光２（30mj／cm2）をインターバル
をおいて（10pps）入射する。その際チユーブを
回転させる（矢印Ａ）。次のインターバルに移る
前に、チユーブ１を矢印Ｂ方向に引つ張り再度レ
ーザー光２を照射する。この操作を繰り返すと、
チユーブ内部のみが、リング状の親水性部分３と
疏水性部分４が列状になつた人工血管が形成され
る。Example 5 In the transparent Teflon tube 1, B 2 H 6
(20Torr) and NH 3 (20Torr),
passed through a grid-like slit from the outside of the tube.
ArF laser light 2 (30 mj/cm 2 ) is incident at intervals (10 pps). At this time, rotate the tube (arrow A). Before moving on to the next interval, the tube 1 is pulled in the direction of arrow B and the laser beam 2 is irradiated again. If you repeat this operation,
An artificial blood vessel is formed in which ring-shaped hydrophilic portions 3 and hydrophobic portions 4 are arranged in rows only inside the tube.
なお、チユーブの回転と移動を同時に行うと親
水性部分と疏水性部分とがらせん状になつて得ら
れる。 Note that when the tube is rotated and moved at the same time, a hydrophilic portion and a hydrophobic portion are formed in a spiral shape.
第１図は、本発明の実施例で得られたグラフで
あり、レーザーが照射された部分のフツ素樹脂表
面の水との接触角の変化を示す。第２図は、本発
明の実施例で得られたグラフであり、レーザーが
照射された部分のフツ素樹脂表面の油との接触角
の変化を示す。第３図は、本発明の具体的な実施
方法を説明する概略図、第４図は、第３図に示さ
れる方法により内面の表面処理が施された人工血
管の透視図。
１……透明テフロンチユーブ、２……レーザー
光、３……親水性部分、４……疏水性部分。
FIG. 1 is a graph obtained in an example of the present invention, showing the change in the contact angle with water on the fluororesin surface of the portion irradiated with the laser. FIG. 2 is a graph obtained in an example of the present invention, showing changes in the contact angle with oil on the surface of the fluororesin in the portion irradiated with the laser. FIG. 3 is a schematic diagram illustrating a specific implementation method of the present invention, and FIG. 4 is a perspective view of an artificial blood vessel whose inner surface has been surface-treated by the method shown in FIG. 3. 1... Transparent Teflon tube, 2... Laser light, 3... Hydrophilic part, 4... Hydrophobic part.
Claims (1)
ArFレーザーを照射することにより、フツ素樹脂
の表面を選択的に改質することを特徴とするレー
ザーによるフツ素樹脂の表面改質方法。 ２ Ｂ又はAl化合物が親水基又は親油基を有す
る化合物である請求項１記載のレーザーによるフ
ツ素樹脂の表面改質方法。 ３ Ｂ又はAl化合物ガスに、親水基又は親油基
を有する化合物ガスを混合する請求項１記載のレ
ーザーによるフツ素樹脂の表面改質方法。 ４ Ｂ又はAl化合物が、（B2H6＋NH3）、
（BHNH）3、Ｂ（CH3）3、Ｂ（C2H5）3、Ｂ（C6H5）3、
Al（CH3）3、Al（C2H5）3、Al（C4H9）3の中から選
択されたいずれか１つの化合物である請求項２記
載のレーザーによるフツ素樹脂の表面改質方法。[Claims] 1. In a B or Al compound atmosphere, fluororesin
A method for modifying the surface of a fluororesin using a laser, which method comprises selectively modifying the surface of the fluororesin by irradiating it with an ArF laser. 2. The method for surface modification of a fluororesin using a laser according to claim 1, wherein the B or Al compound is a compound having a hydrophilic group or a lipophilic group. 3. The method of surface modification of a fluororesin using a laser according to claim 1, wherein a compound gas having a hydrophilic group or a lipophilic group is mixed with the B or Al compound gas. 4 B or Al compound is (B 2 H 6 +NH 3 ),
(BHNH) 3 , B(CH 3 ) 3 , B(C 2 H 5 ) 3 , B(C 6 H 5 ) 3 ,
The surface modification of the fluororesin by the laser according to claim 2 is a compound selected from Al(CH 3 ) 3 , Al(C 2 H 5 ) 3 and Al(C 4 H 9 ) 3 . quality method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1596189A JPH02196834A (en) | 1989-01-25 | 1989-01-25 | Surface modification method of fluororesin using laser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1596189A JPH02196834A (en) | 1989-01-25 | 1989-01-25 | Surface modification method of fluororesin using laser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02196834A JPH02196834A (en) | 1990-08-03 |
| JPH0577692B2 true JPH0577692B2 (en) | 1993-10-27 |
Family
ID=11903324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1596189A Granted JPH02196834A (en) | 1989-01-25 | 1989-01-25 | Surface modification method of fluororesin using laser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02196834A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2740764B2 (en) * | 1990-11-19 | 1998-04-15 | 工業技術院長 | Selective electroless plating method for polymer molded product surface |
| JP3176740B2 (en) * | 1992-12-08 | 2001-06-18 | 倉敷紡績株式会社 | Surface modification method of fluororesin using ultraviolet laser light |
| US5419968A (en) * | 1993-02-16 | 1995-05-30 | Gunze Limited | Surface-hydrophilized fluororesin moldings and method of producing same |
| MY120404A (en) * | 1993-10-15 | 2005-10-31 | Kuraishiki Boseki Kabushiki Kaisha | Process for modifying the surfaces of the molded materials made of fluorine resins |
| JP2999365B2 (en) * | 1994-05-10 | 2000-01-17 | 倉敷紡績株式会社 | Method for hydrophilizing porous body made of fluororesin |
| JP3206310B2 (en) * | 1994-07-01 | 2001-09-10 | ダイキン工業株式会社 | Surface-modified fluororesin molded product |
| MY113227A (en) * | 1995-01-18 | 2001-12-31 | Kurashiki Boseki Kk | Tube-shaped film having its inner peripheral surface treated, method for treating inner peripheral surface of tube-shaped film and apparatus therefor |
| CN100405120C (en) * | 2003-05-22 | 2008-07-23 | 利奎阿维斯塔股份有限公司 | display device |
-
1989
- 1989-01-25 JP JP1596189A patent/JPH02196834A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02196834A (en) | 1990-08-03 |
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