JPH07188437A - Apparatus for modifying fluororesin surface - Google Patents

Abstract

PURPOSE:To obtain an apparatus for efficiently and homogeneously modifying a surface of a fluororesin by constituting the apparatus of an ultraviolet laser light irradiation mechanism having a specific constitution and a transfer mechanism for transferring the fluororesin in a controlled manner. CONSTITUTION:This apparatus comprises an ultraviolet laser light irradiation mechanism (a) and a transfer mechanism 6, 7, and 8 for transferring a fluororesin 5 in a controlled manner, the mechanism (a) comprising an ultraviolet laser light generator 1, a focusing lens 2 for focusing the ultraviolet laser light emitted from the generator 1, a deflecting mirror 3 for reflecting and deflecting the focused light, and a driving means 4 for rotating the mirror 3 so that the reflected and deflected light evenly scans a surface of the fluororesin 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for efficiently modifying the surface of a fluororesin by irradiation with ultraviolet laser light such as excimer laser light.

[0002]

2. Description of the Related Art The present inventors have previously mentioned the drawbacks of fluororesins,
That is, due to its chemically inert surface, not only is it difficult to apply adhesives and paints, but it is also difficult to combine it with other materials. It was clarified that it can be effectively eliminated by using irradiation (for example, Japanese Patent Application No. 4-145595).
Japanese Patent Application No. 4-327822, Japanese Patent Application No. 5-03794
No. 3, Japanese Patent Application No. 4-145595 and Japanese Patent Application No. 5-25
See each specification of No. 8087 and JP-A No. 5-125208. However, since such a surface modification method of a fluororesin uses a high-energy laser beam, the laser light is uniformly and efficiently applied to the surface of a fluororesin product, particularly a long film or sheet in a winding form. Good irradiation is extremely difficult. Therefore, there is a demand for development of an apparatus capable of uniformly and efficiently irradiating the surface of the fluororesin with an ultraviolet laser beam at a low cost.

As a laser light irradiation device for processing, there is known a laser light irradiation device used in the SOI forming technology of a three-dimensional circuit element and the laser CVD technology in the field of semiconductors (for example, Kaihei 2-2480
No. 41), this type of laser light irradiation device was developed for irradiating a small object such as polycrystalline silicon or a semiconductor substrate with laser light. From a practical point of view, it cannot be used as it is for surface modification of a standard film or sheet.

[0004]

In view of such circumstances in the art, the present invention provides a low-cost and uniform modification of a fluororesin surface by uniformly and efficiently irradiating the surface with an ultraviolet laser beam. It was made to provide an enabling device.

[0005]

That is, the present invention is directed to an ultraviolet laser light generator, a focusing lens for focusing the ultraviolet laser light emitted from the ultraviolet laser light generator, and a deflector for reflecting and deflecting the focused ultraviolet laser light. An ultraviolet laser light irradiation mechanism comprising a mirror and a driving means for rotating the deflection mirror so that the reflected and deflected ultraviolet laser light uniformly scans the surface of the treated fluororesin, and the fluororesin is conveyed under control. The present invention relates to a fluororesin surface reforming apparatus having a transport mechanism for

An apparatus for modifying the surface of a fluororesin according to the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a schematic configuration diagram showing the basic structure of an apparatus for surface modification of fluororesin according to the present invention. The ultraviolet laser light emitted from the ultraviolet laser light generator (1) is focused by a focusing lens (2), guided to a deflecting mirror (3), and reflected and deflected by the deflecting mirror. In this case, the angle of the deflection mirror (3) with respect to the focused ultraviolet laser light is such that the reflected and deflected ultraviolet laser light uniformly scans the surface of the fluororesin (5) to be processed in the X-axis direction in the figure. In addition, it is appropriately adjusted by the driving means (4). On the other hand, the fluororesin (5) is the transport mechanism drive motor.
Take-up roller from supply roller (7) by (6)
Toward (8), it is conveyed in the Y-axis direction in the figure. in this case,
The transportation speed of the fluororesin (5) is adjusted in consideration of the irradiation width and scanning speed of the reflected and deflected ultraviolet laser light so that the scanning area on the surface of the fluororesin to be processed is uniformly irradiated with the ultraviolet laser light. It

As the ultraviolet laser light, ultraviolet laser light having a wavelength of 400 nm or less is suitable. In particular, KrF excimer laser light (wavelength: 248 nm) and ArF excimer laser light (wavelength: 193 nm), which can stably obtain a high output for a long time, are preferable.

As the focusing lens (2), a lens known in the art, such as a plano-convex lens, may be used as appropriate.
By appropriately selecting the focal length of the focusing lens (2) and the relative position on the optical path of the focusing lens with respect to the ultraviolet laser generator (1) and the surface of the fluororesin to be treated, an ultraviolet laser beam having a desired light intensity is obtained. Is obtained. By interposing a homogenizer between the ultraviolet laser generator (1) and the focusing lens (2), it becomes possible to irradiate a more uniform ultraviolet laser beam, which results in a more uniform surface modification effect of the fluororesin. can get.

As the deflecting mirror (3), a commercially available mirror for high-energy beams, such as a dielectric multilayer mirror and a metal vapor deposition mirror, may be used as appropriate, but the former is preferable in terms of reflectance. Is preferred. However, in the case of a dielectric multi-layer film mirror, the angle dependence of its reflectance differs depending on the manufactured mirror, so in order to use it within the optimum angle range, an ultraviolet laser generator (1)
It is desirable that the relative position of the mirror with respect to the surface of the fluororesin to be treated be variable and that position be set appropriately. The incident angle of the focused laser light on the deflecting mirror (3) is adjusted by the driving means (4). In other words, the deflection mirror
(3) is adjusted by the operation of the driving means (4) so that its rotation is repeatedly reversed at every required rotation angle (reciprocating rotation). The incident angle is the length in the lateral direction with respect to the transport direction of the fluororesin to be treated, and the fluororesin to be treated from the deflection mirror (3)
It is appropriately selected according to the distance to (5), the relative positional relationship between the deflecting mirror and the fluororesin to be treated, and the like. As the driving means (4), for example, a stepping motor, a servo motor or the like is used. In addition, in order to perform the ultraviolet laser irradiation without considering the angular dependence of the reflectance due to the rotation of the deflecting mirror (3), for example, another deflecting mirror is used to direct the ultraviolet laser light to the direction of conveyance of the fluororesin to be treated. On the fluororesin surface by projecting the reflected light on the fluororesin surface by the deflecting mirror (3) and rotating the deflecting mirror (3) while maintaining the reflection angle. The ultraviolet laser beam may be scanned with. In the case of such a scanning mode, both of the deflecting mirrors can be fixed and used at an appropriate reflection angle according to their reflection characteristics.

Irradiation with ultraviolet laser light is usually carried out in the atmosphere, but it may be carried out under reduced pressure or in an oxygen atmosphere. The irradiation temperature is usually room temperature, but it may be heating temperature or cooling temperature. Further, the irradiation conditions of the ultraviolet laser light depends on the type and form of the treated fluororesin and the desired degree of surface modification, but generally,
The fluence is about 10 mJ / cm ² / pulse or more and the number of shots is about 5000 or less.

The scanning width and scanning speed of the surface of the fluororesin with the ultraviolet laser light are not particularly limited, but they are usually 20 to 100 cm and 5 to 20 cm / sec, respectively. Also,
The ultraviolet laser light may be unidirectionally scanned in the X-axis direction in the figure, but it is efficient to alternately reverse the scanning direction.

Examples of the mechanism for conveying the fluororesin to be treated (5) include a conveyer and a conveyer which are composed of a drive motor (6), a winding roller (8) and a supply roller (7). The former is useful for treating a long sheet or film, and the latter is used for treating a fluororesin molding having a relatively small size. The transport speed of the fluororesin depends on the irradiation width and scanning speed of the ultraviolet laser light and is not particularly limited, but it should be selected so that the ultraviolet laser light is evenly irradiated on the surface to be treated. Thus, the surface of the fluororesin to be treated is uniformly and two-dimensionally irradiated with the ultraviolet laser light, and the fluororesin can be uniformly and efficiently surface-modified. In this case, the ultraviolet laser generation pulse interval of the ultraviolet laser light generator (1), the conveying speed of the fluororesin to be treated (5) and the reciprocating rotation speed of the deflecting mirror (3) are appropriately selected and linked to each other. It is possible to modify the entire surface of the fluororesin molded product having a shape or a desired part.

The fluororesin treated according to the present invention is
Fluorine-containing polymers, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoro Alkoxy ethylene terpolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene
(PCTFE), trifluorochloroethylene-ethylene copolymer (ECTFE), polyvinylidene fluoride (PV
DF) and polyvinyl fluoride (PVF) and the like or any mixture thereof. Alternatively, a resin obtained by kneading a light absorbing substance with these fluororesins may be used.

Although the specific shape of the fluororesin treated by the apparatus according to the present invention is not particularly limited, a sheet,
Examples include films, porous membranes, and other shaped bodies.

The present inventors have found that various modifying aids such as
By irradiating the surface of the fluororesin with an ultraviolet laser beam in the presence of an aromatic carboxylate or the like, it has been clarified that the effect of modifying the surface of the fluororesin is promoted (see the specification of the aforementioned patent application). ). Therefore, by incorporating a means for applying this type of modification aid liquid to the fluororesin to be treated in the above-mentioned device, the additional value of the device can be increased. Examples of the modifying aid liquid application means include:
Examples thereof include a coating roller, a sprayer, a dipping bath, and a coating brush.

Further, in the surface modification treatment of the fluororesin with a high-energy ultraviolet laser beam such as an excimer laser beam, fine reaction products and the like are scattered around by ablation and the like, and the focusing lens (2) and the deflecting mirror ( 3) Not only pollutes etc., but also deteriorates the working environment. As a solution to such a problem, it is preferable to dispose clean air spraying means for the focusing lens, deflecting mirror, etc. and exhausting means for contaminated air after spraying. In this case, a shielding box having an ultraviolet laser beam passage window and an exhaust port may be provided together in order to effectively exhaust the gas and prevent the ultraviolet laser beam from scattering in the work environment.

[0017]

EXAMPLES The present invention will be described below with reference to examples. FIG. 2 is a schematic side view showing an embodiment of the apparatus for surface modification of fluororesin according to the present invention. In the figure, (3) to (5), (7) and (8) have the same meaning as in FIG. 1, and (5 ′) is PTF.
E-long film, (9) a coating roller, (10) a heater, (11) a heat shield plate, and (12) a saucer. The ultraviolet laser light generator (1), focusing lens (2) and drive motor (6) shown in FIG.
Not shown in.

PTFE with a thickness of 0.3 mm and a width of 30 cm
While transporting the long film (5 ') from the supply roller (7) to the winding roller (8) (transport speed: 16 cm / min),
It is reciprocally rotated by the operation of drive process (4) (rotation angle: 12
The surface of the film (5 ′) was irradiated with KrF excimer laser light (wavelength: 248 nm) that was reflected and deflected by the deflecting mirror (3). In this case, prior to the KrF excimer laser light irradiation treatment, a 10% aqueous solution of sodium benzoate was applied to the PTFE film (5 ') using a coating roller (9), and the film (5 coated with the aqueous sodium benzoate solution was applied. ')
Was dried using a heater (10) arranged separately from the coating system by a heat shield plate (11). In addition, Kr
The irradiation conditions of the F excimer laser light are as follows. Fluence: 260mJ / cm ² / pulse Running width: 30cm Running speed: 17cm / sec

The peel strength of the irradiated film was measured as follows. That is, width 25mm, length 150
mm, 300 μm thick stainless steel plate, and 30 mm wide, 150 mm long, 300 μm thick sample piece coated with epoxy resin adhesive (“Bond E Set Cleaner” manufactured by Konishi Co., Ltd.). The doshis were piled up, a weight (bottom surface 6 cm x 6 cm, 3 kg) was placed on it, and left for 12 hours or more to bond them. Then, using a tensile tester (manufactured by Shimadzu Corporation Autograph P-100), the sample piece was pulled at a speed of 10 mm / min and the 180 ° peel strength was measured. As a result, a value of 1.04 kg / cm was obtained. Was given. This value is
The value was significantly higher than the value of 0.01 kg / cm for the sample not irradiated with laser light, which means that the adhesiveness was also significantly improved.

[0020]

According to the present invention, a chemically inert fluororesin surface can be efficiently and uniformly modified without impairing the heat resistance and chemical resistance which are the characteristics of the fluororesin. This makes it possible to provide a modified fluororesin having significantly improved added value with significantly improved wettability, adhesiveness, printability, paintability, etc. at low cost.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing a basic structure of a fluororesin surface modification apparatus according to the present invention.

FIG. 2 is a schematic side view showing one embodiment of the apparatus for surface modification of fluororesin according to the present invention.

[Explanation of symbols]

 1 UV Laser Light Generator 2 Focusing Lens 3 Deflection Mirror 4 Driving Means 5 Fluororesin 6 Drive Motor 7 Supply Roller 8 Winding Roller 9 Coating Roller 10 Heating Heater 11 Heat Cutoff Plate 12 Receiving Plate

Claims (5)

[Claims] 1. An ultraviolet laser light generator (1), a focusing lens (2) for focusing the ultraviolet laser light emitted from the ultraviolet laser light generator (1), and a deflection for reflecting and deflecting the focused ultraviolet laser light. Driving means (4) for rotating the deflecting mirror (3) so that the mirror (3) and the reflected and deflected ultraviolet laser light uniformly scans the surface of the treated fluororesin (5).
An apparatus for modifying the surface of a fluororesin, which comprises an ultraviolet laser light irradiation mechanism comprising and a transport mechanism (6, 7, 8) for transporting the fluororesin under control. 2. The apparatus according to claim 1, wherein the ultraviolet laser light generator (1) is an excimer laser light generator. 3. Device according to claim 1, wherein the deflecting mirror (3) is a dielectric multilayer mirror. 4. A homogenizer is provided between the ultraviolet laser light generator (1) and the focusing lens (2).
The apparatus according to 2 or 3. 5. The apparatus according to claim 1, further comprising a modifying auxiliary agent liquid applying means (9).