JPH06145398A - Method of fixing organic compound onto surface of polymer molding or solid substrate using ultraviolet laser - Google Patents

Abstract

PURPOSE:To provide a surface treating method comprising fixing selectively an organic azide compound onto the surface of a polymer molding or that of a solid substrate on which polymer decomposition fragments have been built up. CONSTITUTION:An organic azide compound is reacted on the surface of a polymer molding irradiated by ultraviolet laser beams or on the surface of a solid substrate on which the polymer decomposition fragments formed by the irradiation have been built up, so that the azide compound is fixed onto the surface of the molding or the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface processing method for polymer molded articles. More specifically, the present invention improves the structural characteristics and functionality of the surface of the polymer by irradiating it with ultraviolet laser light without leaving impurities such as residues on the surface of the polymer, and then selectively irradiating the laser-irradiated surface with an organic azide. The present invention relates to a novel surface treatment method for immobilizing a compound. In addition, the present invention deposits a polymer decomposition fragment generated by irradiation of a polymer molded article with an ultraviolet laser beam on a solid substrate surface in a vacuum atmosphere, and fixes an organic azide compound on the substrate surface on which the polymer decomposition fragment is deposited. About how to turn.

[0002]

2. Description of the Related Art Ablation (direct etching) using an excimer laser that oscillates high-intensity pulsed light in the ultraviolet region has been actively studied as a precise microfabrication method for polymers from both basic and application points of view. . The present inventors have so far developed (1) formation of a fine structure on a polymer surface by ablation (H. Niino, A. Yabe, et al., Jpn. J. Appl. Phy).
s., 28 , L2225 (1989); Appl. Phys. Lett., 55 , 510 (19
89); ibid., 54 , 2159 (1989); ibid., 57 , 2368 (1990);
J. Photochem. Photobiol. A. Chem., 65 , 303 (1992),
And (2) Irradiation position selective electroless plating can be performed by using the change of surface potential (H. Niino, A. Yabe,
Appl. Phys. Lett., 60 , 2697 (1992)). These are based on periodic surface shape changes and generation of ionic species.

S. Lazare et al. (S. Lazare and R. Srinivas
an, Journal of Physical Chemistry, Vol.90, p.2124
(1986).), When the surface of a polymer film was irradiated with a high-intensity ultraviolet laser such as an excimer laser, the surface of the irradiated portion was easily modified immediately after irradiation, and a new functional group was generated. is doing. Also, S. Lazareth et al. Say that the optical processing of the polymer surface by this ultraviolet laser is a quick and simple method for observing the surface state.
Thus, the processing of the polymer surface using the ultraviolet laser can be processed with high accuracy and at high speed. Furthermore, by controlling the irradiation conditions, it is possible to improve the structural characteristics, chemical properties and functionality of the surface of the irradiated resin, so that it is possible to carry out various surface reactions with good controllability. However, they have not examined the presence or absence of the formation of reaction intermediates on the laser-irradiated surface, and have not proposed any industrial utility or utilization measures for surface treatment. For depositing a polymer decomposition fragment generated by irradiating a polymer molded article with an ultraviolet laser beam on a solid substrate such as glass in a vacuum atmosphere, see S. There is a report from Hansen (SGHan
sen and TERobitaille, AppliedPhysics Letters, vo
l.52, p.81 (1988).). However, they have not examined the chemical reaction characteristics of the deposit, and have not proposed any industrial utility or utilization of the deposit surface. Furthermore, as a method of depositing an organic compound on the surface of a solid substrate using an ultraviolet laser, a chemical vapor deposition method (Che
mical Vapor Deposition (CVD)) (for example, Takase Hirotaka, Applied Physics, vol.57, p.1895 (1988).). This laser CVD method is a completely different method from the present invention described below, because the introduction of the organic compound and the laser irradiation are performed simultaneously, or the introduction of the organic compound is performed first.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an optical surface processing method for a polymer molded article or a solid substrate without irradiating an ultraviolet laser to reduce the excellent characteristics of the optical processing method. It is an object of the present invention to provide a method for regioselectively immobilizing an organic azide compound on the surface of a molded article or a solid substrate or for producing a thin film made of an organic azide compound. An object of the present invention is to provide a more effective surface treatment method for a synthetic resin molded product or a solid substrate.

[0005]

[Means for Solving the Problems] As a result of intensive studies on the polymer processing method using an ultraviolet laser, the present inventors have found that a reaction having a high chemical reactivity such as a radical species on the polymer surface is caused by ultraviolet laser irradiation. It is possible to immobilize an organic azide compound on the laser-irradiated surface by producing a large amount of intermediates and by introducing an organic compound having a functional group that reacts with a radical species such as an azido group. I found a thing. In addition, a radical species having the same high chemical reactivity as described above is also present on the solid substrate on which the polymer decomposition fragments generated by irradiating the polymer molded article with the ultraviolet laser light, and that It was found that it is possible to immobilize the organic azide compound on the surface of the deposition substrate in the same manner as described above.
The present invention has been accomplished based on these findings.

That is, the present invention comprises (1) irradiating the surface of a polymer molded article with an ultraviolet laser beam and then reacting the surface with an organic azide compound. Immobilization method, (2) Method according to item (1), wherein the organic azide compound is an aryl azide compound, (3) Degradation of the polymer produced by irradiating the surface of the polymer molded article with ultraviolet laser light. A method for immobilizing an organic azide compound on a surface of a solid substrate, which comprises depositing fragments on a solid substrate, and then reacting the organic azide compound on the surface of the deposited substrate, and (4) the organic azide compound is an aryl azide compound. The method according to (3) above is provided.

Next, the present invention will be described in detail. The term “polymer molded product” as used herein refers to a film, a sheet, a fiber, a fiber reinforced resin, a resin molded product, or the like. By UV laser irradiation, radical species are generated on the surface of the polymer molded product or the surface of the solid substrate on which the polymer decomposition fragments are deposited, and with it,
It has a high chemical reactivity. Normally, this reactivity is gradually lost with the passage of time after laser irradiation when left in the atmosphere. However, the laser-irradiated surface and the polymer decomposition fragment deposition surface may be exposed to a vacuum atmosphere, an inert atmosphere,
Alternatively, it is possible to maintain the high chemical reactivity of the radical species by maintaining the temperature at a low temperature and extending the life of the free radical that is a reaction intermediate. Therefore,
After laser irradiation, an organic compound having a functional group that reacts with radical species such as an azido group is introduced into the reaction system to immobilize the organic azide compound on the surface of a molded polymer product or a solid substrate in a position-selective manner. It is possible to In the method of the present invention, the surface of the polymer or the surface on which the polymer decomposition fragments are deposited after the irradiation with the ultraviolet laser light is maintained in a vacuum atmosphere of 10 ⁻³ Torr or less, an inert atmosphere of helium, argon, nitrogen or the like, or a low temperature state of 100 K or less. It is preferable. The fact that an organic azide compound is immobilized on the surface of a polymer molded product irradiated with ultraviolet laser light or the surface of a substrate on which polymer decomposition fragments are deposited shows that the F _1S peak of X-ray photoelectron spectroscopy (XPS) is It was confirmed by appearance (FIGS. 1 and 2). In FIGS. 1 and 2, a polyethylene naphthalate (PEN) film was used as a polymer molded product, and pentafluorophenyl azide was used as an aryl azide compound to introduce an azide compound on the polymer surface, and XPS spectra before and after immobilization were performed. Changes are shown. In the XPS spectrum (FIG. 1) after the immobilization, a peak based on fluorine of pentafluorophenyl azide appears. The reason why pentafluorophenyl azide is used here is to easily confirm the immobilization of the azide compound on the polymer by immobilizing the azide compound having an element (fluorine) that does not exist in the polymer.

In the method of the present invention, the irradiation of the ultraviolet laser beam is performed only on the surface of the polymer before the introduction of the azide compound. Therefore, an active site having a free radical is generated at this opportunity, and this active site reacts with the organic azide compound. It is thought to have been done. That is, it is considered that the free radicals generated by the irradiation with the ultraviolet laser light attacked the azido group, and the organic azide compound was immobilized via the azido radical. Also, the generation of free radicals on the polymer surface by irradiation with ultraviolet laser light is
Electron spin resonance (ES
R) (Fig. 3). Further, when the low temperature state is used, it is possible to accurately determine the adsorption amount of the introduced molecule by the combined use with the ultraviolet absorption spectrum measurement. It is also possible to perform adsorption, and it can be used for techniques such as fabrication of optical elements and optical waveguides.

The introduced molecule may be any organic compound having an azide group which reacts with radical species. The organic azide compound is preferably an aryl azide compound. Preferred organic azide compounds or aryl azide compounds include phenyl azide, pentafluorophenyl azide, trimethylsilyl azide, azidodecane and the like. These organic azide compounds or aryl azide compounds may have a free azido group in the molecule, and may be further substituted with another substituent. Therefore, by chemically modifying an arbitrary organic compound with an azide group, the organic compound can be immobilized on the surface of a polymer molded product or a deposition substrate. For example, if it is desired to make the treated surface water-repellent and oil-repellent, an organic compound having fluorine in the molecule may be chemically modified with an azide group before use.
Further, if a compound that does not have a sufficient vapor pressure in a vacuum is brought into a solution state, it is possible to carry out a surface immobilization treatment with a target organic azide compound in an inert atmosphere such as nitrogen or helium. Any solvent may be used as long as it is stable to free radicals. In addition, the method of the present invention irradiates a laser beam that has passed through a mask (such as a metal plate pattern) corresponding to a portion of the surface of the polymer molded product to be modified, so that only the desired irradiation portion is subjected to surface treatment. It is possible to do. The excimer laser beam is a helium-neon laser,
Argon or krypton ion laser, or N
Compared to other laser beams such as d ⁺ : YAG laser, the beam shape is large, and by scanning the beam and irradiating the site to be modified in any shape, it is possible to easily cope with increasing the area. . In the present invention, a non-thermal photochemical reaction by an ultraviolet laser causes a polymer compound to react, so that there is no thermal damage to the periphery other than the irradiation site,
The surface treatment can be performed extremely selectively and effectively.

An ultraviolet laser is suitable as the laser in the present invention, and XeF (wavelength:
351 nm), XeCl (308 nm), KrF (24
8 nm), ArF (193 nm) or F ₂ (157
nm) excimer laser and the like. Further, also in Nd ⁺ : YAG, dye laser, Kr ion laser, Ar ion laser, or copper vapor laser, it is possible to use a laser beam in which the fundamental oscillation wavelength light is converted into a laser in the ultraviolet region by a non-linear optical element or the like. The laser fluence depends on the polymer material, but the pulse width is about 0.1 mJ in nanoseconds.
A high-brightness laser of / cm ² / pulse or more is desirable. In the present invention, the material of the target polymer molded article may be any of amorphous, crystalline, aromatic and non-aromatic polymers. Preferred polymers include, for example, polyphenylene sulfide, polyether ether ketone, polyetherimide, polysulfone, polyether sulfone, polyimide, polyester, polyolefin, polyacrylate, polyvinyl chloride, polytetrafluorinated ethylene, polyfluorinated vinylidene, Examples thereof include polytrifluorinated ethylene chloride, an epoxy resin, a copolycondensation product of these, or a synthetic resin composed of a mixture thereof. The substrate for depositing the polymer decomposition fragments may be an organic material, an inorganic material, or a metal material.

[0011]

The present invention will be described in more detail based on the following examples. Example 1 A vacuum atmosphere (1 x 10
^-5 Torr), and a KrF excimer laser (wavelength: 248 nm) was irradiated at 100 K to generate active species on the irradiated surface. After that, pentafluorophenyl azide was introduced into the reaction vessel, and a predetermined amount was adsorbed on the irradiated surface,
Immobilization reaction was performed. The temperature of the reaction chamber was raised to room temperature to remove unreacted materials to obtain a surface-treated film. It was confirmed by X-ray photoelectron spectroscopy (XPS) that pentafluorophenyl azide was immobilized only on the surface portion irradiated with the laser (FIG. 1).

Example 2 A polyester film was placed in a vacuum atmosphere (1 × 10 ^-5 To
rr), the KrF excimer laser was irradiated at room temperature to deposit the generated polymer decomposition fragments on the glass solid substrate. After that, pentafluorophenyl azide was introduced into the reaction vessel, the immobilization reaction was performed, and the vacuum state (1
The unreacted material was removed by setting to 10 ^-5 Torr) to obtain a surface-treated film. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface of the substrate on which polymer decomposition fragments had been deposited. Example 3 On a polyester film, a helium atmosphere (1 atm),
Irradiation with a KrF excimer laser was performed at room temperature to generate active species on the irradiated surface. Then, the film irradiated with the laser was immersed in a toluene solution of pentafluorophenyl azide for immobilization reaction to obtain a surface-treated film. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface portion irradiated with the laser.

Example 4 A polymethylmethacrylate film was placed in a vacuum atmosphere (1
Irradiation with ArF excimer laser was performed at room temperature for 10 × 10 ⁻⁵ Torr) to deposit the generated polymer decomposition fragments on the glass solid substrate. Then, pentafluorophenyl azide was introduced into the reaction vessel, the immobilization reaction was performed, and the vacuum reaction (1 × 10 ⁻⁵ Torr) was performed again to remove the unreacted material to obtain a surface-treated film. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface of the substrate on which polymer decomposition fragments had been deposited. Example 5 By the same treatment as in Example 4 except that the polymethylmethacrylate film was changed to a polyvinyl chloride film,
A surface-treated film was obtained. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface of the substrate on which polymer decomposition fragments had been deposited.

Example 6 A surface-treated film was obtained in the same manner as in Example 4, except that the polymethylmethacrylate film was changed to a polytetrafluorinated ethylene film. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface of the substrate on which polymer decomposition fragments had been deposited. Example 7 A surface-treated film was obtained by the same treatment as in Example 4 except that the polymethyl methacrylate film was changed to a polyethylene film. As in Example 1, it was confirmed by X-ray photoelectron spectroscopy that pentafluorophenyl azide was immobilized only on the surface of the substrate on which polymer decomposition fragments had been deposited.

[0015]

According to the method of the present invention, the surface processing method of a polymer molded article and a solid substrate using an ultraviolet laser is extremely effective and precise because the laser has excellent energy and position controllability. It is possible to deposit a uniform and thin film of an organic azide compound only on a pattern formation site by laser irradiation. According to the method of the present invention, it is possible to precisely control the adsorption amount of the azide compound as the substrate by monitoring the ultraviolet absorption spectrum. As a result, the reaction can be sufficiently performed even with the adsorption amount of several molecular layers, which suggests that the method of the present invention can be applied not only to the surface modification method but also to the production of a polymer ultra-thin film multilayer structure. .

[Brief description of drawings]

FIG. 1 is an X-ray photoelectron spectroscopy (XPS) spectrum of a polyethylene naphthalate (PEN) film on which pentafluorophenyl azide is immobilized in Example 1.

FIG. 2 is an XPS spectrum of a PEN film before introducing pentafluorophenyl azide in Example 1.

FIG. 3 is an electron spin resonance (ESR) spectrum showing that free radicals were generated on the irradiated surface of the PEN film by irradiation with ultraviolet laser light.

Claims (4)

[Claims] 1. A method for immobilizing an organic azide compound on the surface of a polymer molded article, which comprises irradiating the surface of the polymer molded article with an ultraviolet laser beam and then reacting the surface with an organic azide compound. 2. The method according to claim 1, wherein the organic azide compound is an aryl azide compound. 3. A solid characterized by irradiating the surface of a polymer molded article with an ultraviolet laser beam to deposit the generated polymer decomposition fragments on a solid substrate, and then reacting an organic azide compound on the surface of the deposited substrate. A method for immobilizing an organic azide compound on a substrate surface. 4. The method according to claim 3, wherein the organic azide compound is an aryl azide compound.