JPH07110904B2 - Hydrophilic fluorine film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic fluorine-based film which is modified to be hydrophilic by bringing a film made of a fluorine-based resin into contact with water and irradiating it with an excimer laser.

[0002]

2. Description of the Related Art Conventionally, in order to modify the surface of a film made of a fluororesin, a method carried out in an alkali metal solution, a method using plasma, B (CH ₃ ) ₃ , B ₆ H ₆ and NH ₃ gas, etc. The surface of a fluorine-based film or the like placed in the atmosphere of CH ₃ is irradiated with an excimer laser to change the F group
Group, and a method of substituting with a NH ₂ group for modification and the like have been known.

[0003]

However, with the method using an alkali metal solution or plasma, it is difficult to miniaturize the modified region to the micron order due to the structural change of the surface of the fluororesin, and selective modification is performed. I couldn't. On the other hand, in the method of irradiating the excimer laser in the atmosphere of B (CH ₃ ) ₃ , B ₆ H ₆ and NH ₃ gas, the device is complicated and the operation is difficult, and the cost is expensive.

[0004]

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of continuing various investigations in order to easily obtain a hydrophilic fluorine-based film by a method or apparatus simplified by using an excimer laser. .

In the present invention, a film made of a fluororesin is brought into contact with water (for example, a film is placed in water or on the surface of water), and the surface of the film is irradiated with an excimer laser. , C—C bond, C—O bond are cleaved, and the part is caused by water —H
The present invention relates to the provision of a hydrophilic fluorine-based film which is substituted with a group and an —OH group to be hydrophilically modified.

The excimer laser according to the present invention is capable of oscillating an ultraviolet pulse laser, and examples thereof include ArF excimer laser (oscillation wavelength 193 mm, photon energy 147 kcal) and KrF excimer laser (oscillation wavelength 248 mm, photon energy 115 kcal). it can.

The modification by the excimer laser irradiation according to the present invention means the C--F bond, the C--C bond, the C--C bond, which is the main structure of the fluororesin, by the light of an excimer laser having high photon energy, for example, ArF excimer laser. This means cutting off the -O bond and substituting it with another functional group for modification.
U

In order to make the surface of the fluororesin hydrophilic by the irradiation of such excimer laser, the excimer laser oscillation wavelength is slightly absorbed within the ultraviolet absorption spectrum of the fluororesin , and the fluororesin is also used. Resin C
When the bond energy of —F bond, C—C bond, and C—O bond is smaller than the excimer laser photon energy, the C—F bond, C—C bond, and C—O bond of the fluororesin are cleaved, and the portion , --H group, --OH resulting from water etc.
By being substituted group are believed to be reformed to be hydrophilic.

The film according to the present invention can be brought into contact with water by a method such as placing the film in water or on the surface of water, or spraying water on the surface of the film by spraying or the like, but there is no particular limitation. Of course. The water according to the present invention is not particularly limited as long as it is colorless and transparent and does not contain impurities that are insoluble in water, and examples thereof include distilled water, pure water and ion exchange water. At this time, hydrogen peroxide (H ₂ O ₂ ) water having a concentration of 0.1 to 50% is also in the category of water according to the present invention, although not particularly limited, in addition to those exemplified above.

The fluororesin according to the present invention includes PF
A (tetrafluoroethylene-perfluoro Arukirubi
Nyl ether copolymer), PTFE (polytetrafluoroethylene), FEP (tetrafluoroethylene / hexafluoropropylene copolymer), ETFE (ethylene / tetrafluoroethylene copolymer), and the like, but particularly preferred fluorine-based resin For this, PFA is desirable. The reason is that the P—A C—O bond energy (8
5 kcal / mol) is, C-F bond (bond energy 128kcal / mol), for less than the binding energy of C-C bond (bond energy 104kcal / mol), liable to be cleaved from the C-C bonds and C-F bond Na
It is considered that that portion is easily replaced by —H group, —OH group, etc. and selectively hydrophilized.

A fill made of a fluororesin according to the present invention
The thickness of the frame is not particularly limited, but the excimer laser
Transmission through the film (for example, the transmittance is 95% or less,
1 to 50%, more preferably 10 to 50%), and water
As long as it is thick enough to be modified at the interface with
Is preferably 1 mm or less.

The film made of a fluororesin according to the present invention includes a sheet, a tube, a sleeve, etc. made of a fluororesin, and the present invention is a molded product made of a fluororesin instead of the film. Needless to say, it can be applied to, for example, filaments, tubes, knits, woven fabrics, strings, etc., and there is no particular limitation.

The use of the present invention is suitable, for example, as a material for various artificial organs, and particularly when used as an artificial blood vessel, an artificial blood vessel having an excellent antithrombosis can be obtained. Further, since there is no discoloration due to the modification, it can be used as a material such as a contact lens. In addition to these, a wide range of applications can be expected in each field.

Next, the present invention will be explained based on examples, but it is needless to say that this is only one embodiment and not limited to this.

[0015]

【Example】

Example 1 A reaction cell 5 made of stainless steel having an entrance window made of synthetic quartz.
Put water in a petri dish (may be a petri dish) and put PFA on 6 water surfaces.
Film made of resin (thickness 50μ, light transmittance 20
%) 7 and then ArF excimer laser (oscillation wavelength 193 mm) 1 was irradiated vertically to the film surface through the mask 3. The irradiation conditions at this time were a laser energy density of 100 mJ / cm ² , 5000 shots, and a pulse repetition rate of 50 PPS. Processed P
The film 7 made of FA resin has a contact angle with water of 34 degrees and exhibits excellent hydrophilicity. Infrared spectrophotometer (FT-I
As a result of analysis by the ATR method (total reflection method) of R), C-OH
Expansion and contraction and C-H lateral shake expansion / contraction mode were recognized. Also, X
According to CIS and OIS in PS analysis, in the surface layer, -OH group is a carbonyl group (= C = O) and ether bond (C-O-
More than C).

Example 2 The water 6 of Example 1 was replaced with a 1% aqueous hydrogen peroxide solution, a film (50 μ) 7 made of PFA resin was placed on the aqueous solution, and the film surface was irradiated with ArF excimer laser 1 vertically. did. Irradiation conditions are laser energy density 50m
J / cm ² , shot number was 3000 shots, and pulse repetition was 50 PPS. The film made of the treated fluororesin had a contact angle with water of 30 °, and an excellent hydrophilic fluororesin film was obtained.

Comparative Example 1 Instead of the water 6 of Example 1, NH ₃ and B were used as reaction gases.
_The film (50 μ) 7 made of FEP was treated in the same manner as in Example 1 except that the mixed gas with ₃ H ₆ was sealed in the reaction cell at 15 Torr. The contact angle of the treated film with water is 52 degrees, and the result of IR analysis is 1200 cm ^−1.
C-F absorption in the vicinity decreased, and -NH in the vicinity of 3300 ^-1.
The absorption of _two groups was observed, and the presence of N derived from the —NH ₂ group was recognized by XPS analysis. Comparison from the above results
Example 1 uses gas and is troublesome to handle.
Certain NH ₃ gas and toxicity are very strong, and there is a danger of explosion.
There are problems such as using B ₃ H ₆ gas,
I don't like it. In this respect, the present application
Since I use, I say that such a problem can not occur,
It also has a special effect .

As is apparent from the above results, the present invention uses only simplified water 6 which does not use B ₂ H ₆ gas and NH ₃ gas as in the prior art, and uses the surface of a film made of a fluororesin. Even if the excimer laser 1 is irradiated on the above, the hydrophilic fluorine-based film 7 having excellent hydrophilicity can be obtained.

[0020]

EFFECTS OF THE INVENTION The present invention is as described above. According to the present invention, a film made of a fluororesin or the like can be modified to be hydrophilic by using only water, and can be produced by a very simplified process. Is. The hydrophilic fluorine-based film or the like of the present invention is suitable as a material for various artificial organs including artificial blood vessels having excellent antithrombosis and contact lenses that do not discolor at all, and will be widely used in the future due to their superior functionality. It can be expected to be used in various fields.

[Brief description of drawings]

FIG. 1 shows an example of a schematic view of an excimer laser irradiation device.

[Explanation of symbols]

 1. Excimer laser. 2. mirror. 3. mask. 4. Lens 5. Reaction cell. 6. water. 7. A film made of fluorine resin. 8. XY-stage. 9. Excimer laser generator.

Claims (2)

[Claims] 1. A hydrophilic film, characterized in that a film made of a fluororesin is brought into contact with water, and the film surface is irradiated with an excimer laser so that all or part of the surface of the fluorofilm is modified to be hydrophilic. Fluorine film. 2. The hydrophilic fluorine-based film according to claim 1, which is similar to claim 1, except that a molded product made of a fluorine-based resin is used instead of the film made of the fluorine-based resin.