JP2935084B2 - Hydrophilic fluorinated resin molded product - 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 fluororesin molded article obtained by modifying a fluororesin molded article to be hydrophilic.

[0002]

2. Description of the Related Art Conventionally, the surface of a molded article made of a fluororesin has been modified by a method of treating in an alkali metal solution, a method by plasma, a B (CH ₃ ) ₃ gas or a B ₂ H
F by excimer laser irradiation ₆ and NH ₃ and the surface of the fluorine-based film or the like which is placed in an atmosphere of mixed gas of
A method of modifying a group by substituting the group with a CH ₃ group or an NH ₂ group (JP-A-2-196834) and the like have been known.

[0003]

However, in the above-mentioned various reforming methods, it is difficult to control the reforming due to the structural change of the fluororesin surface. For example, the method of treating in an alkali metal solution has a problem that there is a danger of ignition and instability of the treatment solution, and that the modified portion is vulnerable to sunlight and high heat. In the plasma method,
There is a problem that the surface modification effect is significantly lower than that of a resin containing no fluorine such as polyethylene. Also, B
In the method of irradiating an excimer laser under an atmosphere of (CH ₃ ) ₃ or a mixed gas of B ₂ H ₆ and NH ₃ , not only is it costly to commercialize the apparatus used in the method, but also the toxicity is high. However, there is a problem that an operation requiring skill such as the use of a special gas having a high pressure and a decompression operation is required.

[0004]

The present inventors have conducted various studies to solve the above problems, and as a result, by using an excimer laser under specific conditions, a hydrophilic fluororesin molded article can be easily obtained. We have found what we can achieve and have finally completed the present invention.

That is, the present invention provides a compound having a metal element belonging to Group II of the periodic table, formic acid, acetic acid , a water-soluble polymer compound, carbon monoxide and carbon dioxide in at least a part of a fluororesin molded article. By irradiating an excimer laser beam in a state of being brought into contact with an aqueous solution containing at least one compound selected from the group consisting of, a surface of at least a part of the fluororesin molded article is modified to be hydrophilic. The present invention relates to a hydrophilic fluorine resin molded product.

The excimer laser used in the present invention is not particularly limited as long as it can oscillate an ultraviolet pulse laser. Specifically, an ArF excimer laser (oscillation wavelength 193 nm, photon energy 147 kc
al / mol), KrF excimer laser (oscillation wavelength 2
48 nm, photon energy 115 kcal / mol) and the like.

In order to modify the surface of a fluororesin molded article to be hydrophilic, for example, a C—F bond, a C—C bond, a C—O bond, etc. derived from the fluororesin on the surface of the molded article. ,
Preferably, it is necessary to cleave the CF bond at least partially. As the conditions, the absorption of the oscillation wavelength of the excimer laser used for cutting is within the range of the ultraviolet absorption spectrum of the fluororesin, and the photon energy of the excimer laser light is larger than the binding energy of the above-mentioned bond of the fluororesin. It is necessary, but sure
It is unknown .

When the above conditions are satisfied and the above-mentioned bond of the fluororesin is cut, the part thereof is caused by an H group, an OH group, a COOH group resulting from an aqueous solution containing the specific compound according to the present invention.
It is presumed that the group is substituted with a group, CO group or the like to be modified to be hydrophilic. However, it is unclear what is certain.

The F which has been cleaved and released is removed by binding to an aqueous solution containing the above-mentioned specific compound, for example, Ca, Be, etc. resulting from an aqueous solution containing a compound having a metal element belonging to Group II of the periodic table. Presumed. At this time, as a reason for the binding, for example, the Be-F binding energy is 152 kcal / mol, the binding energy of Ca-F is 133 kcal / mol, and the binding energy of CF is larger than 129 kcal / mol. F,
Ca-F and the like are more easily bound than CF, and Be-F, Ca-
It is presumed that F and the like become CaF ₂ , BeF _{2 and the} like and stabilize, and do not release F again. But what is certain is
It is clear. All of the above have been estimated, but future research
It seems to be elucidated.

The specific compound contained in the aqueous solution used in the present invention is selected from a compound having a metal element belonging to Group II of the periodic table, formic acid, acetic acid , a water-soluble polymer compound, carbon monoxide and carbon dioxide. At least one of them. Further, the aqueous solution may be a mixed solution containing at least two of these compounds.

The compound having a metal element belonging to Group II of the periodic table is not particularly limited, and conventionally known compounds can be widely used. For example, Ca (OH) ₂ , Be (OH) ₂ , B
a (OH) ₂ , CaCO ₃ , MgCO ₃ , BaCO ₃ ,
CaSO ₄ , BaSO ₄ , BeO and the like can be mentioned.

[0012]

[0013] be a compound having a periodic table group II metal element and a carboxyl group, those classified into a compound having a metal element belonging to Group II the periodic table, the compounds of the present invention all Of course, complex salts, double salts and the like may be used, and there is no particular limitation.

[0014] Examples of the water-soluble polymer compound include polyvinyl alcohol and polyethylene oxide. In the present invention, all the water-soluble polymer compounds having a Group II metal element of the periodic table and a carboxyl group are classified as water-soluble polymer compounds for convenience.

The aqueous solution used in the present invention may contain any one of the various compounds exemplified above, carbon monoxide and carbon dioxide, or may contain two or more thereof. .

There is no particular limitation on the preparation of the aqueous solution containing such various compounds, and natural water, industrial water, tap water, distilled water, pure water, ion-exchanged water and other suitable water may be produced by an appropriate method. It is desirable to mix or dissolve in water. The compound having Be, which is a Group II metal element of the periodic table, is a so-called amphoteric compound.In preparing an aqueous solution containing the compound, not only the above-mentioned water but also an acid or alkali aqueous solution is used. It does not matter even if dissolved, and the concentration of the acid or alkali aqueous solution is not particularly limited, and such an acid or alkali aqueous solution is also included in the category of the aqueous solution in the present invention.

In preparing an aqueous solution containing carbon monoxide and carbon dioxide, there is no particular limitation.
What is necessary is just to dissolve carbon dioxide gas, dry ice and the like. In addition, the gas such as carbon monoxide and carbon dioxide may be flowed into the aqueous solution even during the irradiation with the excimer laser, so that there is an advantage that the concentration of the aqueous solution hardly changes.

With respect to the above-mentioned water, a slight amount of carbon dioxide or the like is dissolved in ordinary natural water, industrial water, tap water, etc., but this amount is extremely small, and such water is used in the present invention. It does not correspond to the aqueous solution containing carbon dioxide or the like.

The concentration of the various compounds contained in the aqueous solution used in the present invention is not particularly limited, but is usually 0.01% by weight or more, preferably 0.1% by weight or more. Even if such an aqueous solution contains an appropriate third component as long as the effect of the present invention is not impaired, it does not matter at all.

The range of the aqueous solution used in the present invention includes all liquids containing various water as a main component such as aqueous suspensions, aqueous dispersions, and emulsions. In the present invention, these are all expressed as aqueous solutions for convenience. Unified.

The fluororesin molded article is brought into contact with the above aqueous solution without any particular limitation. For example, the molded article is immersed in the aqueous solution, the molded article is placed on the surface of the aqueous solution, or the spray is applied to the surface of the molded article. And spraying an aqueous solution.

The fluororesin molded article according to the present invention is obtained by modifying a part or the whole of the surface to be hydrophilic. In order to modify a part of the molded product surface,
The aqueous solution may be partially brought into contact with the surface of the molded product, or the aqueous solution may be brought into contact with the entire surface of the molded product and partially irradiated with excimer laser light, and there is no particular limitation. In order to modify the entire surface of the molded product to be hydrophilic, for example, as described above, the molded product is immersed in an aqueous solution, the molded product is placed on the surface of the aqueous solution, or the spray is applied to the surface of the molded product. Then, an aqueous solution may be sprayed, and the entire surface may be irradiated with excimer laser light.

There is no particular limitation on the irradiation of the fluororesin molded article with excimer laser light, but it is desirable to wash the molded article with various detergents such as alcohol prior to irradiation. By washing with a detergent, oil and dirt adhered to the surface of the fluororesin molded product during the molding process or the like can be removed, and a product with high commercial value can be obtained. The alcohol or the like is not particularly limited, but is preferably an alcohol having a low boiling point so as not to adversely affect the reforming.

The fluororesin used as the raw material of the fluororesin molded article treated in the present invention is not particularly limited.
Tetrafluoroethylene damper perfluoroalkyl vinyl-et <br/> ether copolymer (PFA), polytetrafluoroethylene (PTFE), tetrafluoroethylene - hexafluoropropylene copolymer (FEP), ethylene - tetrafluoroethylene copolymer Examples thereof include a polymer (ETFE) and a mixture thereof. Such a fluororesin, various synthetic resins within a range that does not significantly modify the properties of the fluororesin,
An appropriate third component such as a filler may be added.

Examples of the fluororesin molded article in the present invention include, but are not limited to, films, sheets, tubes, sleeves, tapes, filaments, knits, woven fabrics, strings and the like made of fluororesin. Without
All fluororesin moldings are included.

When a film is used as a fluororesin molded article, the thickness of the film is not particularly limited. For example, when the film is placed on the above aqueous solution, the thickness is desirably 1 mm or less. There is also an advantage that light transmits through the film (for example, the transmittance is 95% or less, preferably 5 to 50%) and is modified at the contact interface between the aqueous solution and the back surface of the film.

The fluororesin molded article of the present invention is suitable, for example, as a material for various artificial organs. Particularly, when used as an artificial blood vessel, an artificial blood vessel having excellent antithrombotic properties can be obtained. Further, since there is no discoloration due to the modification, it can be used for a material such as a contact lens. Still other materials
Composites by bonding, combining, etc. with molded products made of materials
It can also be used as one of the materials, and can be expected to be used in a wide range of fields in all other fields, and there is no particular limitation on the use.

[0028]

EXAMPLES Next, the present invention will be further clarified with reference to examples, but the present invention is not limited to these examples.
The following embodiment will be described with reference to FIG. 1 showing a schematic view of an excimer laser irradiation apparatus.

Example 1 A stainless steel reaction cell [5] (a petri dish may be used)
, An aqueous solution of carbon monoxide having a concentration of about 2.3 to 3.5% by weight is put in, and a film (thickness: 100 μm, light transmittance: 7%) made of PFA resin is brought into contact with the aqueous solution [6] [7]. Then, the film surface was irradiated with ArF excimer laser (wavelength 193 nm) light [1] perpendicularly to the film surface through a mask [3]. The irradiation conditions at this time were a laser fluence of 13 mJ / cm ² / pulse, 8,000 shots, and a frequency of 50 Hz. The aqueous carbon monoxide solution was prepared by blowing a carbon monoxide gas into distilled water at room temperature for 45 minutes.

The film [7] made of the PFA resin treated as described above had a contact angle with water of 34 °, showing excellent hydrophilicity as compared with a contact angle of 106 ° with an unirradiated film. As a result of analysis using an infrared spectrophotometer (FT-IR), peaks derived from -OH, CH, C = O, and C = C were observed. In XPS analysis,-
OH, CH and C = O were confirmed. In this case, O / C (element ratio of C and O) is compared with the unirradiated film.
Is increased by 4.0 times, and F / C (element ratio between C and F) is 1
/ 3.

Example 2 Instead of the aqueous solution [6] of Example 1, 0.1% by weight of B
e (OH) ₂ using a distilled water aqueous solution, and a film made of PFA resin in the aqueous solution (thickness: 100 μm)
[7] was brought into contact (placed in water 5 mm below the surface of the aqueous solution and brought into contact), and an ArF excimer laser beam [1] was irradiated perpendicularly to the film surface. The irradiation conditions were a laser fluence of 13 mJ / cm ² / pulse, a number of shots of 16,000, and a frequency of 50 Hz. The aqueous solution was a suspension, and Be (OH) ₂ was not dissolved because it was insoluble in water.

The film [7] made of the treated PFA resin had a contact angle with water of 39 ° and exhibited excellent hydrophilicity.

Example 3 Instead of the aqueous solution [6] of Example 1, 0.1% by weight of B
Example 1 Using a mixed solution of e (OH) ₂ aqueous solution and a saturated aqueous solution of carbon monoxide (mixing ratio 1: 1), a film (100 μm thick) made of PFA resin [7] was used in the mixed solution.
And the film surface was irradiated vertically with ArF excimer laser light [1]. The irradiation conditions were a laser fluence of 13 mJ / cm ² / pulse, a number of shots of 16,000, and a frequency of 50 Hz. The carbon monoxide mixed aqueous solution was prepared by blowing carbon monoxide gas into distilled water containing 0.1% by weight of Be (OH) ₂ at room temperature for 45 minutes.

The film [7] made of the treated PFA resin had a contact angle with water of 29 ° and exhibited excellent hydrophilicity.

Example 4 A PFA resin film (thickness: 100 μm) [7] was brought into contact with a 0.1% by weight aqueous solution of formic acid in the same manner as in Example 1, and an ArF excimer laser beam [1] was applied to the film surface. Irradiated vertically. Irradiation conditions were as follows: laser fluence 13 mJ / cm ² / pulse, number of shots 8000
Shot and frequency were 50 Hz.

The film [7] made of the treated PFA resin has a markedly increased hydrophilicity as compared with the untreated film.

Example 5 P in a 0.1% by weight aqueous solution of polyvinyl alcohol
A film made of an FA resin (thickness: 100 μm) [7] was brought into contact in the same manner as in Example 1, and an ArF excimer laser beam [1] was irradiated perpendicularly to the film surface. Irradiation conditions are
The laser fluence was 13 mJ / cm ² / pulse, the number of shots was 16,000, and the frequency was 50 Hz.

The film [7] made of the treated PFA resin had a contact angle with water of 40 ° and exhibited excellent hydrophilicity.

Example 6 A film made of PFA resin (thickness: 100 μm) [7] was brought into contact with an aqueous solution of carbon monoxide in the same manner as in Example 1;
The film surface was irradiated with rF excimer laser light [1] vertically. Irradiation condition is laser fluence 12mJ /
cm ² / pulse, 16,000 shots,
The frequency was 30 Hz. The aqueous carbon monoxide solution was prepared by blowing a carbon monoxide gas into distilled water at room temperature for 60 minutes.

The film [7] made of the treated PFA resin showed a remarkable improvement in wettability, a contact angle with water of 30 °, and excellent hydrophilicity.

Example 7 A film (100 μm thick) made of PFA resin (7) was brought into contact with an aqueous solution of carbon monoxide in the same manner as in Example 1,
The film surface was irradiated with rF excimer laser light [1] vertically. Irradiation condition is laser fluence 30mJ /
cm ² / pulse, the number of shots was 6,400, and the frequency was 50 Hz. The aqueous carbon monoxide solution was prepared by blowing a carbon monoxide gas into distilled water at room temperature for 60 minutes.

The film [7] made of the treated PFA resin showed a remarkable improvement in wettability, a contact angle with water of 50 °, and excellent hydrophilicity.

Example 8 A film (thickness: 100 μm) [7] made of a PFA resin was brought into contact with an aqueous solution of carbon dioxide in the same manner as in Example 1,
The film surface was irradiated with rF excimer laser light [1] vertically. Irradiation condition is laser fluence 22mJ /
cm ² / pulse, the number of shots was 8,000, and the frequency was 50 Hz. The aqueous carbon dioxide solution was prepared by blowing carbon dioxide gas into distilled water at room temperature for 60 minutes.

The film [7] made of the treated PFA resin showed a remarkable improvement in wettability, a contact angle with water of 37 °, and excellent hydrophilicity.

Example 9 A film made of a PFA resin having excellent hydrophilicity was obtained by treating in the same manner as in Example 8 except that the film was placed on the surface of the aqueous solution.

The film [7] made of the treated PFA resin showed excellent hydrophilicity.

Comparative Example A film made of PFA resin in air (100 μm thick)
m) [7] was placed, and the film surface was irradiated with ArF excimer laser light [1] vertically. The irradiation conditions were a laser fluence of 22 mJ / cm ² / pulse, 8,000 shots, and a frequency of 50 Hz.

The film [7] made of the treated PFA resin had a wavy surface and an impaired appearance as compared with the untreated film. There was no difference in the contact angle with water between the film and the untreated film, and the hydrophilicity was not modified.

[0049]

According to the present invention, it is possible to use a simple apparatus by using an easy-to-handle aqueous solution without using a complicated apparatus or a highly toxic B ₂ H ₆ gas or NH ₃ gas as in the prior art. Moreover, a fluororesin molded article having excellent hydrophilicity can be obtained by a simple operation. The hydrophilicity imparted in the present invention is extremely excellent, and the hydrophilicity is not likely to be altered by sunlight or heat. The hydrophilic fluorine-based resin molded product of the present invention is, for example, an artificial blood vessel having excellent antithrombotic properties, various artificial organs, and is also suitable as a material for contact lenses and the like because there is no discoloration due to modification. Utilizing this functionality, it can be expected to be used in various fields in the future.

[Brief description of the drawings]

FIG. 1 is a drawing showing an example of a schematic diagram of an excimer laser irradiation device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Excimer laser beam 2 Mirror 3 Mask 4 Lens 5 Reaction cell 6 Aqueous solution 7 Fluorine resin molding (film) 8 XY-stage 9 Excimer laser oscillation device

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Shimizu 25-1 Mitsumi-machi, Neyagawa-shi, Osaka Japan Atomic Energy Research Institute, Takasaki Research Laboratory Osaka Branch (72) Inventor Shunichi Kawanishi 25-1, Mitsumi-cho, Neyagawa-shi, Osaka No. Japan Atomic Energy Research Institute Takasaki Research Institute Osaka Branch (72) Inventor Masanobu Nishi 25-1 Mitsui Minamimachi, Neyagawa City, Osaka Prefecture Japan Atomic Energy Research Institute Takasaki Research Institute Osaka Branch (72) Inventor Shunichi Sugimoto Mitsui, Neyagawa City, Osaka Prefecture 25-1 Minamimachi Japan Atomic Energy Research Institute Takasaki Research Institute Osaka Branch Office Radiation Irradiation Promotion Association (56) References JP-A-4-370123 (JP, A) JP-A-3-281544 (JP, A) (58) Surveyed field (Int.Cl. ⁶ , DB name) C08J 7/00-7/18

Claims (4)

(57) [Claims] 1. A compound having a metal element belonging to Group II of the periodic table in at least a part of a fluororesin molded article,
The fluororesin molding is performed by irradiating an excimer laser beam in contact with an aqueous solution containing at least one compound selected from formic acid, acetic acid, a water-soluble polymer compound, carbon monoxide and carbon dioxide. A molded article of a hydrophilic fluororesin, wherein at least a part of the surface of the article is modified to be hydrophilic. 2. The molded article of claim 1, wherein the aqueous solution is a mixed solution containing at least two compounds. 3. A fluorine over the entire surface of the resin molding in a state in which contacted the aqueous solution, obtained by irradiating the excimer laser beam according to claim 1 or claim 2 hydrophilic fluororesin molded article according to. 4. The hydrophilic fluororesin molded article according to claim 1 , wherein the entire surface of the fluororesin molded article is modified to be hydrophilic.