JP2007262534A - Apparatus for improving surface of resin base material and method for improving surface of resin base material by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for improving the surface of a resin base material, which can improve the surface of the resin base material at a sufficient treating speed under atmospheric pressure; and to provide a method for improving the surface of the resin base material by using the apparatus. <P>SOLUTION: The apparatus for improving the surface of the resin base material is equipped with: a laser-beam generator 1 generating a laser beam L; a processing vessel 3 into which the laser beam L is introduced; a target 5 for generating scattering particles by the laser beam L with which its surface is irradiated; a gas supplying means 6 for supplying a shield gas to a space between the resin base material 8 whose surface is improved by deposition of the scattering particles scattered from an emission port 3A of the processing vessel 3 and the target 5; and a shield gas atmosphere holding cover 7 composed of a tubular body having a first opening edge and a second opening edge, wherein the first opening edge is joined to the emission port and the second opening edge has a size larger than that of the first opening edge and is arranged close to the surface of the resin base material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin substrate surface modification apparatus and a resin substrate surface modification method using the same, and more particularly, vacuum ultraviolet light exposure and scattering generated by irradiating a target surface with laser light. The present invention relates to a resin substrate surface modifying apparatus used for modifying particles by attaching particles to the substrate surface, and a resin substrate surface modifying method using the resin substrate surface modifying apparatus.

  In recent years, various techniques for activating a substrate surface by irradiating the surface of the substrate made of resin, metal, or the like with X-rays, ultraviolet rays, or vacuum ultraviolet rays have been developed. Among them, as a method that can be modified by adhering scattered particles immediately after activating the substrate surface, Japanese Patent Application Laid-Open No. 2004-2962 (Patent Document 1) uses laser light on the surface of a target. There is a method for surface modification of a substrate using so-called laser ablation, in which vacuum ultraviolet light is generated together with scattered particles and the scattered particles are adhered to the surface of the substrate while being irradiated with the vacuum ultraviolet light. It is disclosed. In the substrate surface modification method described in Patent Document 1, the surface of the substrate is modified in a vacuum state or in a shield gas atmosphere.

However, in the conventional method for modifying the surface of a substrate as described in Patent Document 1, when the surface of the substrate is modified in a vacuum state, evacuation is required and batch processing is performed. Therefore, it is not always sufficient from the viewpoint of processing speed. Furthermore, in the conventional surface modification method for a substrate as described in Patent Document 1, even when the surface of a substrate is modified in a shield gas atmosphere such as helium gas, it is long to replace with helium gas. Since time is required, it is not always sufficient from the viewpoint of processing speed.
JP 2004-2962 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and it is not necessary to perform a surface modification treatment of the resin base material in a batch system, and the surface of the resin base material at a sufficient treatment speed under atmospheric pressure. Resin substrate surface modification device that can modify resin, and resin that can efficiently and reliably modify the surface of resin substrate using the resin substrate surface modification device It aims at providing the surface modification method of a base material.

  As a result of earnest research to achieve the above object, the present inventors, as a result, a laser light generator that generates laser light, a processing vessel into which the laser light is introduced, and the laser light irradiated on the surface A target for generating scattered particles and a shield gas for supplying a shield gas to a space between the target and the resin base material whose surface is modified by attaching the scattered particles scattered from the launch port of the processing container A gas supply means and a cylindrical body having a first opening edge and a second opening edge having a size equal to or larger than the first opening edge at both ends, the first opening edge being joined to the launch port In addition, a surface modification device for a resin substrate in a batch mode is provided by a surface modification device for a resin substrate comprising a shield gas atmosphere holding cover in which a second opening edge is disposed close to the surface of the substrate. Need to process Ku, found that it is possible to modify the surface of the resin substrate at a sufficient processing rate under atmospheric pressure, thereby completing the present invention.

That is, the resin substrate surface modification device of the present invention includes a laser beam generator for generating laser beam,
A processing container into which the laser beam is introduced;
A target for generating scattered particles by the laser light irradiated on the surface;
A gas supply means for supplying a shielding gas to a space between the resin base material whose surface is modified by attaching the scattered particles scattered from the launch port of the processing container and the target;
A cylindrical body having a first opening edge and a second opening edge having a size equal to or larger than the first opening edge at both ends, the first opening edge being joined to the launch port, and a second opening edge A shield gas atmosphere holding cover in which an opening edge is disposed close to the surface of the resin substrate;
It is characterized by providing.

  In the resin substrate surface reforming apparatus of the present invention, a distance between the second opening edge of the shield gas atmosphere holding cover and the surface of the substrate is preferably 30 mm or less.

  Further, in the resin substrate surface modification device of the present invention, a filter is provided which is connected to the second opening edge of the shield gas atmosphere holding cover and whose tip is in contact with the surface of the substrate. It is preferable to further provide.

  The resin substrate surface modification method of the present invention uses the resin substrate surface modification device of the present invention, and irradiates the target surface with laser light to produce vacuum ultraviolet light and scattered particles having a wavelength of 50 nm to 100 nm. The scattering particles are adhered to the surface of the resin substrate while irradiating the vacuum ultraviolet light on the surface of the resin substrate.

  In the resin substrate surface modification method of the present invention, it is preferable that the space between the target and the resin substrate has a shielding gas atmosphere with an oxygen amount of 6% by volume or less.

  Moreover, in the resin substrate surface modification method of the present invention, the positional relationship between the target and the resin substrate can be moved relatively, and the moving speed is preferably 400 mm / min or more. Furthermore, it is more preferable to move the resin base material.

  The present inventors infer the reason why the above object is achieved by the resin substrate surface modification apparatus and the resin substrate surface modification method of the present invention as follows. That is, when the laser ablation treatment is performed under atmospheric pressure conditions of a pressure of about 450 to 1060 Torr, the exposure amount of vacuum ultraviolet light and the amount of scattered particles attached to the resin base material are not only irradiated with laser light but also irradiated with laser light. Greatly affected by the type and concentration of the gas in the space through which the vacuum ultraviolet light and scattered particles pass between the target and the resin substrate. For example, since vacuum ultraviolet light having a wavelength of 50 nm to 100 nm radiated from high-temperature plasma on the target surface is absorbed by oxygen and nitrogen in the atmospheric gas, if the atmospheric gas contains oxygen and nitrogen, The amount of exposure to vacuum ultraviolet light is drastically reduced. In addition, since the scattered particles from the target collide with the atmospheric gas molecules before reaching the surface of the resin base material, if the atmospheric gas molecules are heavy, the speed of the collision is increased and the scattered particles become the resin. The probability of not reaching the surface of the substrate increases. Therefore, in order to sufficiently suppress the decrease in the scattering speed of the scattered particles, it is necessary to sufficiently suppress the influence caused by the collision between the scattered particles and the atmospheric gas molecules. Therefore, in order to ensure sufficient vacuum ultraviolet light and scattered particles necessary for surface modification of the resin base material in a shorter time, oxygen in the atmospheric gas in the space between the target and the resin base material, etc. It is necessary to reduce the concentration of hydrogen and to increase the concentration of shield gas such as helium as much as possible.

  Therefore, in the present invention, the specific shielding gas atmosphere holding cover as described above prevents the entry of oxygen and the like from the outside, so that the atmosphere in the space between the target and the resin substrate has a concentration of oxygen and the like. A sufficiently low shielding gas atmosphere is provided, and the exposure amount of vacuum ultraviolet light and the adhesion amount of scattered particles to the resin base material can be set to a sufficient amount in a shorter time. That is, in the present invention, first, the specific shield gas atmosphere holding cover as described above sufficiently prevents air from entering the space between the target and the resin base material, even under atmospheric pressure. The amount of oxygen in the space between the target and the resin substrate can be efficiently reduced to 6% by volume or less (more preferably 4% by volume or less), and the shielding gas atmosphere can be easily maintained. A method or apparatus is provided. In a shielding gas atmosphere with an oxygen amount of 6% by volume or less, the surface of the resin base material is improved by sufficiently improving the transmittance of vacuum ultraviolet light while making it possible to more sufficiently suppress the decrease in the scattering speed of the scattered particles. The surface of the resin substrate can be activated more efficiently by irradiating with a sufficient amount of vacuum ultraviolet light. Therefore, the apparatus for modifying the surface of a resin base material of the present invention makes it possible to perform laser ablation processing in a shield gas atmosphere having an oxygen amount of 6% by volume or less even under atmospheric pressure, and the target or resin base material is 400 mm / It is possible to efficiently modify the surface of the resin base material while moving at a very high moving speed of more than a minute. Thus, the resin substrate surface modification apparatus of the present invention can efficiently and reliably modify the surface of the resin substrate at a sufficient processing speed under atmospheric pressure, thereby improving productivity. In addition, since the equipment is simple, equipment costs and production costs can be reduced.

  Further, if the distance between the second opening edge of the shield gas atmosphere holding cover and the surface of the base material exceeds 30 mm, it tends to be difficult to sufficiently prevent the entry of oxygen or the like. That is, when the distance between the second opening edge of the shield gas atmosphere holding cover and the surface of the base material is 30 mm (more preferably 5 to 10 mm) or less, oxygen or the like is more sufficiently invaded. Thus, a desired shield gas atmosphere (for example, a shield atmosphere having an oxygen concentration of 6% by volume or less) can be achieved more efficiently. Furthermore, in the case where the filter further includes a filter that is connected to the second opening edge of the cover of the present invention and has a tip that comes into contact with the surface of the resin base material, There is a tendency that air is not sufficiently invaded into the space inside the cover without damaging the portion. In the resin substrate surface modification method of the present invention, the target or the resin substrate is moved at a speed of 400 mm / min or more, so that the scattered particles are more uniformly deposited on the surface of the resin substrate. It tends to be possible to process the resin substrate at a high processing speed. In addition, the speed at which the target or the resin base material is moved is more preferably 400 mm / min to 20000 mm / min in consideration of the output of a currently existing laser apparatus.

The vacuum ultraviolet light having a wavelength of 50 nm to 100 nm referred to in the present invention means vacuum ultraviolet light having at least a part of wavelengths in a wavelength region of 50 nm to 100 nm, and at least one of the following conditions: Is preferably satisfied.
(i) having at least one peak of light intensity in a wavelength region of 50 nm to 100 nm;
(ii) the total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 100 nm to 150 nm;
(iii) The total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 50 nm or less.
(iv) The energy density of light in the wavelength region of 50 nm to 100 nm is 0.1 μJ / cm on the substrate.
^{2 to} 10 mJ / cm ² (more preferably 1 μJ / cm ^{2 to} 100 μJ / cm ² ).
In addition, when the energy density on the substrate is lower than 0.1 μJ / cm ² , the time required for the treatment tends to be excessively long. On the other hand, when the energy density is higher than 10 mJ / cm ^{2, the} substrate is decomposed. There is a tendency.

  According to the present invention, there is no need to perform a surface modification treatment of a resin substrate in a batch system, and a resin substrate that can modify the surface of a resin substrate at a sufficient treatment speed under atmospheric pressure. It is possible to provide a surface modification method for a resin substrate that can efficiently and reliably modify the surface of the resin substrate using the surface modification device and the surface modification device for the resin substrate. It becomes.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

The resin substrate surface modification device of the present invention includes a laser beam generator for generating laser beam,
A processing container into which the laser beam is introduced;
A target for generating scattered particles by the laser light irradiated on the surface;
A gas supply means for supplying a shielding gas to a space between the resin base material whose surface is modified by attaching the scattered particles scattered from the launch port of the processing container and the target;
A cylindrical body having a first opening edge and a second opening edge having a size equal to or larger than the first opening edge at both ends, the first opening edge being joined to the launch port, and a second A cover for holding a shielding gas atmosphere in which the opening edge is disposed close to the surface of the resin base material,
It is characterized by providing.

  FIG. 1 is a schematic cross-sectional view of a preferred embodiment of a resin substrate surface modification apparatus of the present invention. The resin substrate surface modification apparatus shown in FIG. 1 includes a laser beam generator 1, a reflector 2, a processing vessel 3, an optical system 4, a condensing lens 4A disposed in the optical system 4, and a target. 5, a gas supply means 6 connected to the processing container 3, a shield gas atmosphere holding cover 7 joined to the launching port 3 </ b> A of the processing container 3, and a resin base material 8. In FIG. 1, P indicates plasma generated on the surface of the target 6, and A indicates the gas flow of the shield gas.

  In such a resin base material surface reforming apparatus, the reflecting plate 2 is disposed on the optical path of the laser beam L emitted from the laser beam generator 1, and the laser beam L reflected by the reflecting plate 2 is processed into the processing container. 3 is introduced. The processing container 3 includes a window (for example, a quartz window) for introducing the laser light L onto the surface of the target 5 disposed in the processing container 3. And the condensing lens 4A is arrange | positioned on the optical path of the laser beam L introduce | transduced in the processing container 3, Furthermore, the target 5 is arrange | positioned on the optical path of the laser beam L which passed the condensing lens 4A. Yes. Further, in the resin substrate surface modification apparatus shown in FIG. 1, a shield gas atmosphere holding cover 7 is joined to the discharge port 3 </ b> A of the scattered particles of the processing container 3. Therefore, when the shielding gas is supplied from the gas supply means 6 to the inside of the processing container 3, the space between the target 5 and the resin base material 8 can be efficiently made into a shielding gas atmosphere. Further, in the resin substrate surface modification apparatus shown in FIG. 1, a resin substrate 8 connected to a resin substrate driving apparatus (not shown) is disposed. And by such a resin base material drive device, it is possible to perform laser ablation processing (VALA processing) while moving the resin base material 8.

  Although it does not restrict | limit especially as the laser beam generator 1, The laser beam generator which can irradiate the pulse laser beam whose pulse width is 100 picoseconds-100 nanoseconds can be used suitably, for example, a YAG laser apparatus It is composed of an excimer laser device. Among such laser light generators, it is more preferable to use a YAG laser device. In this embodiment, when the target 5 is irradiated with the laser beam L, a high-temperature plasma P is formed on the surface of the target 5, and vacuum ultraviolet light and scattered particles having a wavelength of 50 nm to 100 nm are generated from the plasma P. appear.

Moreover, it does not restrict | limit especially as the reflecting plate 2, A well-known reflecting plate (for example, mirror etc.) can be used suitably. The processing container 3 is a container (for example, a stainless steel container) for housing at least the optical system 4 (including the condensing lens 4A) and the target 5 therein, and the laser light L is contained in the container 3. A window (for example, a quartz window) is provided for introduction into the surface of the target 5 arranged. Further, the condensing lens 4A is not particularly limited, but is a condensing lens capable of setting the irradiation intensity of the pulsed laser light L applied to the target 5 to 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. It is preferable that a condensing lens that can be set to 10 ⁸ W / cm ² to 10 ¹⁰ W / cm ² is particularly preferable.

  The target 5 is made of a material that generates scattered particles containing metal atoms and / or carbon atoms suitable for modifying the surface of the resin base material 8 by irradiation with the laser beam L described above. As such a material, at least one material is selected from the group consisting of various metals, metal compounds, and carbon. As such a metal material, various transition element metals, typical element metals, metalloids, or alloys thereof can be used, for example, Cu, Al, Ti, Si, Cr, Pt, Au, Ag, Pd, Zr, Mg, Ni, Fe, Co, Zn, Sn, W, Be, Ge, Mn, Mo, Nb, Ta, Hf, alloys containing them as main components, etc., among others, Cu, Al Ti, Si, and Zn are preferable. The metal material here may be, for example, a semiconductor such as silicon, germanium, silicon carbide, gallium arsenide, InP, or ZnTe. Examples of the metal compound material include various transition element metals, oxides, nitrides, and carbides of typical element metals or metalloids. Among them, zinc oxide, titania, alumina, magnesia, beryllia, aluminum nitride, boron nitride , Carbides of metal elements such as silicon nitride, silicon carbide, Fe, Cr, W, Mo, and V are preferable. In addition, the metal compound material here may contain a plurality of metal elements, and may further contain a non-metal element. Examples of the carbon material include various kinds of amorphous carbon, graphite, diamond, etc. Among them, graphite and amorphous carbon are preferable. Furthermore, the target 5 may be a composite material of such a metal material, a metal compound material, and a carbon material. In the present embodiment, a tape-like target formed by evaporating the target material on a tape is used. The shape or the like of the target 5 is not particularly limited. For example, a bulk material made of the target material formed into a plate shape, a rod shape, or the like, or a tape formed by applying the target material on the tape or the like. A shaped target or the like can be used as appropriate.

  The gas supply means 6 includes a gas cylinder 6A and a gas nozzle 6B, and the gas cylinder 6A is connected to the processing container 3 via the gas nozzle 6B. And by supplying shield gas using the gas supply means 6, the space in the processing container 3 and between the target 5 and the resin base material 8 can be made into predetermined shield gas atmosphere. In this way, when the space between the target 5 and the resin base material 8 is made a shielding gas atmosphere using the gas supply means 6, the vacuum ultraviolet light is absorbed by a vacuum ultraviolet light absorbing substance (oxygen or the like) without being in a reduced pressure state. Since the resin substrate surface is irradiated without being absorbed by the semiconductor substrate surface, the semiconductor substrate surface is more efficiently activated. Further, the shielding gas atmosphere is preferable in terms of simplicity of the apparatus and low cost because it is not necessary to use a vacuum pump or a pressure vessel.

  FIG. 2 is a schematic cross-sectional view of the vicinity of the shield gas atmosphere holding cover of the resin substrate surface modification apparatus shown in FIG. The shield gas atmosphere holding cover 7 is joined to the launch port 3A of the processing device 3 that generates vacuum ultraviolet light and scattered particles, and has a first opening edge and a size larger than the first opening edge. It consists of a cylindrical body which has a 2nd opening edge. As described above, the shield gas atmosphere holding cover 7 has the opening diameter D1 of the first opening edge equal to or larger than the opening diameter D2 of the second opening edge (D2 ≧ D1). When the opening diameter D1 is larger than the opening diameter D2, the air around the cover is entrained, and the air is mixed in the space near the processing surface, making VALA processing difficult.

  Further, the shield gas atmosphere holding cover 7 has a first opening edge joined to the launch port 3 </ b> A and a second opening edge arranged close to the surface of the resin base material 8. The distance X between the second opening edge of the shield gas atmosphere holding cover 7 and the surface of the resin base material 8 is preferably 30 mm (more preferably 5 to 10 mm) or less. The second opening edge of the shield gas atmosphere holding cover 7 and the resin base material 8 may be arranged so as to be in contact with each other. When such a distance exceeds the upper limit, it tends to be difficult to sufficiently prevent the entry of oxygen or the like.

  Moreover, it is preferable that the distance L between the target 5 and the resin base material 8 is 30-100 mm, and it is preferable that it is 30-50 mm. If such a distance is less than the lower limit, the distance between the target 5 and the resin base material 8 is too close, and the scattered particles are uniformly deposited on the surface of the resin base material due to the effect of plasma P due to reablation or the like. On the other hand, when the above upper limit is exceeded, the distance between the target 5 and the resin base material 8 is too long, and it becomes difficult to efficiently deposit scattered particles on the surface of the resin base material. The processing speed tends to decrease.

  Further, as the shield gas atmosphere holding cover 7, a cover (transparent or translucent) in which the state of the target 5 (high temperature plasma on the surface of the target 5) irradiated with the laser light L can be observed from the outside. It is preferable to use it. Examples of the material of the shield gas atmosphere holding cover 7 include transparent or translucent resins such as acrylic resin, polycarbonate resin, polyethylene resin, and polypropylene resin, and glass. The shield gas atmosphere holding cover 7 is preferably made of a material capable of absorbing force so that the resin base material 8 is not damaged even if at least a part of the cover 7 contacts the resin base material 8. Then, by using such a shield gas atmosphere holding cover 7, a shield gas is supplied by the gas supply means 6, and thus a space between the target 5 and the resin base material 8 is efficiently provided in a predetermined shield gas atmosphere. It is possible to.

  Further, as the shielding gas, hydrogen gas, helium gas, neon gas, argon gas or the like can be used as appropriate, and hydrogen or helium is used from the viewpoint that the vacuum ultraviolet light is less absorbed and the specific gravity is smaller than air. More preferred. When hydrogen or helium is used as the shielding gas, the reduction in the scattering speed of scattered particles tends to be more efficiently suppressed. Among such shielding gases, it is particularly preferable to use helium from the viewpoint of safety. By using helium as the shielding gas, it is possible to efficiently suppress a decrease in the scattering rate and to improve the transmittance of vacuum ultraviolet light having a wavelength of 50 nm to 100 nm.

  Further, such a shielding gas atmosphere is preferably a shielding gas atmosphere having an oxygen amount of 6% by volume or less (more preferably 4% by volume or less). In a shield gas atmosphere with an oxygen content of 6% by volume or less, the scattering particles are adhered to the surface of the resin base material, so that the reduction in the scattering speed of the scattering particles can be more sufficiently suppressed and the vacuum ultraviolet is used. There is a tendency that the light transmittance can be sufficiently improved and the processing speed can be further improved.

  It does not restrict | limit especially as the resin base material 8, It determines suitably by the use etc. of the product obtained. Examples of the resin constituting the resin substrate 8 include olefin resins {polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, water. Polyisoprene, ethylene-propylene-diene copolymer, ethylene-butene-diene copolymer, polymethylpentene, etc.}, butyl rubber, polyester, polycarbonate, polyacetal, polyamide, aromatic polyamide, polyamideimide, polyetherimide , Polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone, polyphthalamide, polyether nitrile, polybenzimidazole, polycarbodiimide, acrylic resin {poly Chill (meth) acrylate, poly (meth) acrylamide, etc.}, acrylic rubber, fluororesin {poly-4-fluorinated ethylene, etc.}, fluororubber, liquid crystal polymer, epoxy resin, melamine resin, urea resin, diallyl phthalate resin, phenol resin, Polysilane, silicone resin (polysiloxane, etc.), silicone rubber, urethane resin, styrene resin {polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, etc.], polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, Examples of the resin base material include polymers (homopolymers or copolymers) such as polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, and polyvinyl acetate, and laminates thereof. For higher hardness From the standpoint of focusing mainly on resins used for disk substrates, glass replacement parts, sliding parts, seal parts, skin materials, etc., which have effective scratch resistance and abrasion resistance effects, polycarbonate, acrylic resin, Polyamide, polyphenylene sulfide, polyphenylene ether, polyacetal, fluororesin, various polyimides, phenol resin, fluororubber, ethylene-propylene-diene copolymer, silicone rubber and the like are preferable. In addition, such resin base materials may be dyes, pigments, fibrous reinforcements, particulate reinforcements, plasticizers, flame retardants, heat stabilizers, antioxidants, weather resistance imparting agents, antistatic agents as necessary. An appropriate amount of additives such as a transparency improver may be contained.

  In such a resin substrate surface reforming apparatus of the present invention, the space between the target 5 and the resin substrate 8 is efficiently oxygenated even under atmospheric pressure by the shield gas atmosphere holding cover 7 described above. A shielding gas atmosphere having an amount of 6% by volume or less (more preferably 4% by volume or less) can be used, and the atmosphere can be maintained. Therefore, the surface modification device for the resin base material of the present invention irradiates the surface of the target 5 with laser light L to generate vacuum ultraviolet light and scattered particles having a wavelength of 50 nm to 100 nm, and the surface of the resin base material 8 By applying scattered particles while irradiating vacuum ultraviolet light, there is no need to perform surface modification treatment of the resin substrate 8 in a batch system, and the target 5 or the resin substrate 8 is 400 mm / min or more under atmospheric pressure. The scattered particles can be deposited on the surface of the resin base material 8 while being moved at a very fast moving speed, and the surface of the resin base material 8 can be efficiently and reliably modified at a sufficient processing speed.

  The preferred embodiment of the resin substrate surface modification apparatus of the present invention has been described above. Next, another preferred embodiment of the resin substrate surface modification apparatus of the present invention will be described.

  FIG. 3 is a schematic cross-sectional view of another preferred embodiment of the resin substrate surface modification apparatus of the present invention. The resin substrate surface modification apparatus shown in FIG. 3 includes a laser beam generator 1, a reflector 2, a processing container 3, an optical system 4, a condensing lens 4A disposed in the optical system 4, and a target. A target 5 connected to the driving device 11, a gas supply means 6 connected to the processing container 3, a shield gas atmosphere holding cover 7 joined to the launch port 3A of the processing container 3, and a shield gas atmosphere holding cover 7 and a resin base material 8 are provided.

  In the present embodiment, disk-like carbon is used as the target 5, and the target 5 is connected to the target driving device 11. Such a target drive device 11 allows the laser beam L to be repeatedly irradiated to the same position on the surface of the target 5 and rotated and translated so that the target 5 does not open a hole. Such a target driving device 11 is not particularly limited, and a known device such as a motor can be appropriately used. In the present embodiment, a fresh surface (a laser light non-irradiated surface) of the target 5 is sequentially drawn out to the irradiation position of the laser light L by the target driving device 11.

Further, the target 5 has an irradiation shape of the laser beam L formed on the surface of the target 5 such that the major axis width is approximately ellipse that is 1.5 to 10 times the minor axis width. preferably be placed in an opening angle θ of the perpendicular L ₁ direction of the surface of the incident direction and the target 13 of the laser beam L shown in FIG. 4 so as to be 50 to 85 °, the opening angle θ is 65 to 75 ° It is more preferable to arrange them as follows. In this way, by making the shape of the light irradiated by the laser light L to be substantially elliptical, it is possible to uniformly deposit an appropriate amount of scattered particles by reducing the amount of scattered particles in unnecessary directions, and more efficiently. The resin base material tends to be modified. The substantially elliptical shape mentioned here is a shape including an elliptical shape and a line segment shape in which the width in the major axis direction is 1.5 to 10 times (more preferably 2 to 6 times) the width in the minor axis direction. is there.

  In such a substantially elliptical shape, when the width in the major axis direction is less than 1.5 times the width in the minor axis direction, the angular distribution of scattered particles in the in-plane direction perpendicular to the target surface and including the major axis becomes wide. However, when the processing speed is increased, the concentration varies depending on the location, and it tends to be difficult to attach a sufficient amount of scattered particles to all the areas to be processed. However, the angular distribution of scattered particles in the in-plane direction including the major axis becomes small, but the angular distribution of the scattered particles in the plane perpendicular to the target surface and including the minor axis becomes too wide, and uneven particle concentration in the moving direction Although the number of particles in the vertical direction is reduced, the width in which the vertical particles are distributed becomes too narrow, the longitudinal movement distance becomes extremely short, and the overall processing speed tends to be slow. Further, when the opening angle θ is less than the lower limit, when the laser light is irradiated, the width in the major axis direction of the irradiation light tends to be less than 1.5 times the width in the minor axis direction, while the upper limit is If it exceeds, the width in the major axis direction of the irradiated light shape tends to exceed 10 times the width in the minor axis direction.

  Further, the filter 9 is arranged so as to be connected to the second opening edge of the shield gas atmosphere holding cover 7, and the front end thereof is in contact with the surface of the resin base material 8. By further providing the filter 9 in this way, the shield gas can flow out of the cover 7 while preventing air from entering the space inside the shield gas atmosphere holding cover 7 more efficiently. It becomes. As such a filter 9, it is preferable to use a flexible material so as not to damage the object to be treated. As the material, for example, a nonwoven fabric (polyolefin), a soft foamed urethane, a soft foamed rubber, a PVA foam or the like is used. be able to. In the present embodiment, the shape of the shield gas atmosphere holding cover 7 is cylindrical (D2 = D1).

  As mentioned above, although preferred embodiment of the surface modification apparatus of the resin base material of this invention was described, the surface modification apparatus of the resin base material of this invention is not limited to the said embodiment. For example, in the above embodiment, the shield gas atmosphere holding cover does not include the gas rectifying unit. However, in the present invention, a gas rectifying unit may be further provided on the shield gas atmosphere holding cover. FIG. 5 is a schematic cross-sectional view of the vicinity of the shield gas atmosphere holding cover of the resin substrate surface reforming apparatus in which the shield gas atmosphere holding cover including the gas rectifying unit is arranged. By using the shield gas atmosphere holding cover 7 further including the gas rectifying unit 7A, the gas flow A can be more sufficiently controlled, and a desired shield gas atmosphere can be achieved more efficiently. In addition, such a gas rectification | straightening part 7A can change and use the shape and magnitude | size suitably so that shield gas may flow more efficiently, when performing a laser ablation process.

  Moreover, in the resin substrate surface modification apparatus of the present invention, a vacuum pump may be further connected to the processing vessel 3. By arranging the vacuum pump in this way, the inside of the processing container 3 can be maintained at a predetermined pressure condition. The condition of the pressure inside the processing container 3 is not particularly limited. For example, the pressure is preferably an atmospheric pressure or lower, and more preferably 500 Torr or lower.

  Using the resin substrate surface modification apparatus of the present invention as described above, the surface of the target is irradiated with laser light to generate vacuum ultraviolet light having a wavelength of 50 nm to 100 nm and scattered particles. By applying the scattered particles while irradiating the vacuum ultraviolet light, it is not necessary to perform a surface modification treatment of the resin substrate in a batch system, and the surface of the resin substrate is modified at a sufficient treatment speed under atmospheric pressure. Resin substrate surface modification device that can be modified and resin substrate surface modification device that can efficiently and reliably modify the surface of the resin substrate using the resin substrate surface modification device It is possible to provide a surface modification method.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
A vacuum ultraviolet light assisted laser ablation process (hereinafter referred to as “VALA process”) was performed using the resin substrate surface modification apparatus shown in FIG. In such a treatment, a flat plate test piece of polypropylene (“PC-6” manufactured by Nippon Polypro Co., Ltd., size: 150 mm long, 70 mm wide, 3 mm thick) was used as the resin base material 8. As the shield gas atmosphere holding cover 7, an acrylic resin cover having an opening diameter D1 of 100 mm, an opening diameter D2 of 150 mm, and a length of 30 mm is used, and the target 5 (target surface) irradiated with the laser light L is used. The high temperature plasma) can be observed from the outside. Furthermore, as the target 5, a carbon tape target in which carbon (film thickness: 17 μm) was laminated on a PET tape having a width of 10 mm and a thickness of 50 μm was used. Moreover, the distance between the target 5 and the resin base material 8 was 50 mm. Furthermore, the distance between the second opening edge of the shield gas atmosphere holding cover 7 and the surface of the resin base material 8 was set to 10 mm. Further, helium gas was supplied into the processing device 3 from the gas nozzle 6B of the gas supply means 6, and the space between the target 5 and the resin base material 8 was made a helium gas atmosphere under atmospheric pressure (760 Torr). In addition, the oxygen concentration (vol%) of the space through which the scattered particles between the target 5 and the resin base material 8 in such a helium gas atmosphere pass is measured by a digital oximeter (XPO-318) manufactured by New Cosmos Electric. The results are shown in Table 1.

During the VALA process, a laser beam L of 1064 nm, a pulse width of 7 ns, an energy of 1.84 J, and a repetition rate of 10 Hz from a pulse YAG laser device manufactured by Spectra Physics Co., Ltd. as a laser beam generator 1 is collected at a focal length of 200 mm. It condensed using the optical lens 4A and irradiated to the film side of the target 5, and the vacuum ultraviolet light and scattering particle | grains with a wavelength of 50 nm-100 nm were generated in the advancing direction front side of the laser beam L of the target 5. In such processing, the processing speed was set to 1200 cm ² / min by moving the resin base material 8 connected to a pulse motor. At this time, the laser irradiation intensity was 2.5 GW / cm ² .

(Example 2)
The apparatus shown in FIG. 1 is the same as the apparatus shown in FIG. 1 except that the shield gas atmosphere holding cover 7 having the gas rectifying unit 7A shown in FIG. 5 is used and a filter 9 is further provided at the second opening edge of the shield gas atmosphere holding cover 7. Except for using a resin substrate surface modification device having a configuration, and further installing the resin substrate surface modification device in a treatment chamber (the atmosphere is mainly composed of helium gas) separated from the outside of the air atmosphere. In the same manner as in Example 1, VALA treatment was performed.

  The shield gas atmosphere holding cover 7 used for such a VALA process is a cover provided with a gas rectifying unit made of polycarbonate having a tapered shape. Moreover, the material of the main body of the shielding gas atmosphere holding cover 7 is also made of polycarbonate so that the state of the target irradiated with the laser (high temperature plasma on the target surface) can be observed from the outside. Further, the filter 9 was connected to the second opening edge of the shield gas atmosphere holding cover 7 so as to contact the surface of the resin base material 8. In addition, as such a filter 9, the nonwoven fabric (The air filter "PA / 306" by Japan Vilene Co., Ltd.) was used, and it was made not to damage a to-be-processed object even if it contacts a to-be-processed object. Further, when performing the VALA treatment, helium gas was allowed to flow out of the shield gas atmosphere holding cover 7 through the filter 9. In this way, air is prevented from entering the inside of the shield gas atmosphere holding cover 7 and helium gas is selectively introduced into the main space between the target 5 and the resin base material 8 through which the vacuum ultraviolet light and scattered particles pass. By supplying at a high speed, the helium concentration in the main space through which most of the vacuum ultraviolet light and scattered particles between the target 5 and the resin substrate 8 pass can be increased in a shorter time.

(Example 3)
VALA treatment was performed in the same manner as in Example 1 except that the resin substrate surface modification apparatus shown in FIG. 3 was used. That is, as the shielding gas atmosphere holding cover 7, a cylindrical tempered glass cover having an opening diameter D1 and D2 of 100 mm and a length of 30 mm is used, and a target 5 (high temperature plasma on the target surface) irradiated with a laser is used. ) Can be observed from the outside. Further, as the filter 9, a filter made of soft foamed urethane rubber was used, so that the object to be treated was not damaged even if it contacted the object to be treated. Further, the laser beam L having a wavelength of 1064 nm, a pulse width of 7 ns, an energy of 1.84 J, and a repetition rate of 10 Hz from a pulse YAG laser device manufactured by SpectraPhysics Co., Ltd. is condensed using a condenser lens 11 having a focal length of 200 mm. The surface was irradiated so that the shape of the irradiation light formed on the surface of the target 5 was an ellipse (5.0 × 2.5 mm). Note that the irradiation intensity of the laser at this time was 2.8 GW / cm ² . The incident angle of the laser beam was set to 18 ° (θ shown in FIG. 4 is 72 °) with respect to the target 5. Further, as the target 5, disc-shaped carbon was used. Further, a pulse motor was used as the resin base material driving device 11 and rotated at a speed of about 1 rpm so that the laser irradiation part of the target was as fresh as possible.

(Comparative Example 1)
VALA treatment was performed in the same manner as in Example 1 except that the shield gas atmosphere holding cover 7 was not used.

(Comparative Example 2)
VALA treatment was performed in the same manner as in Example 2 except that the shield gas atmosphere holding cover 7 and the filter 9 were not used.

(Comparative Example 3)
VALA treatment was performed in the same manner as in Example 3 except that the shield gas atmosphere holding cover 7 and the filter 9 were not used.

<Evaluation of adhesion (A)>
The resin base material after VALA treatment obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was left indoors for 1 day, and then a water-based metallic base paint for body (trade name “WBC713T” manufactured by Kansai Paint Co., Ltd.). And a solvent-type clear paint for bumpers (trade name “SOFLEX 7172” manufactured by Kansai Paint Co., Ltd.) are applied so that the respective coating films become 15 μm and 25 μm, and laminated for 20 minutes at 120 ° C. (holding) Baking was done to obtain a painted plate.

  Next, after the obtained coated plate was left indoors for 1 day, a cross-cut tape peeling test was performed, and the initial adhesion was evaluated according to the following evaluation criteria. Moreover, after immersing the obtained coated board in 40 degreeC warm water for 10 days, the cross-cut tape peeling test was done and the water-resistant adhesion was evaluated according to the following evaluation criteria. The cross-cut peel test was performed according to JIS K5400. The results are shown in Table 1.

[Evaluation criteria for adhesion]
◯: The number of peeled is 0. Δ: The number of peeled is in the range of 1/100 to 9/100. X: The number of peeled is 10/100 or more.

<Evaluation of adhesion (B)>
The resin base material after VALA treatment obtained in Example 3 and Comparative Example 3 was left indoors for 1 day, and then a solvent-type metallic base paint for bumpers (trade name “SOFLEX 420T” manufactured by Kansai Paint Co., Ltd.) and a bumper were used. Solvent-type clear paint (trade name “SOFLEX 500TL” manufactured by Kansai Paint Co., Ltd.) was applied so that the respective coatings were 15 μm and 25 μm, laminated and baked at 90 ° C. for 20 minutes (retained). Initial adhesion and water-resistant adhesion were evaluated in the same manner as in the above adhesion test except that the obtained coated plate was used. The results are shown in Table 1.

As is clear from the results in Table 1, the resin substrate after VALA treatment obtained in Examples 1 to 3 has sufficiently high initial adhesion and water-resistant adhesion even when the treatment speed is 1200 cm ² / min or more. It was confirmed that it shows sex. From such a result, even if the processing speed is 1200 cm ² / min by using the shield gas atmosphere holding cover 7 and setting the oxygen concentration to 6 vol% (Examples 1 and 3), the resin substrate It was confirmed that can be sufficiently modified. Further, it was confirmed that the resin base material can be sufficiently modified even when the treatment speed is 1400 cm ² / min in the case where the oxygen concentration is 4 vol% (Example 2).

On the other hand, the resin substrate after VALA treatment obtained in Comparative Examples 1 and 3 was insufficient in initial adhesion and water-resistant adhesion even under the condition of a treatment rate of 100 cm ² / min. This is because the oxygen concentration became 10 vol% because the shield gas atmosphere holding cover 7 was not used. Further, the resin substrate after VALA treatment obtained in Comparative Example 2 had sufficient initial adhesion and water-resistant adhesion at a treatment speed of 100 cm ² / min, but initial adhesion at a treatment speed of 400 cm ² / min. The water resistance and water adhesion were not sufficient. This is because the oxygen concentration became 8 vol% because the shield gas atmosphere holding cover 7 was not used.

  From these results, by using the resin substrate surface reforming apparatus of the present invention, it is possible to efficiently perform VALA treatment under a shielding gas atmosphere, and efficiently perform the resin base at a sufficient treatment speed under atmospheric pressure. It was confirmed that the surface of the material can be modified.

  As described above, according to the present invention, it is not necessary to perform the surface modification treatment of the resin base material in a batch manner, and the surface of the resin base material can be modified at a sufficient treatment speed under atmospheric pressure. Resin substrate surface modification device, and resin substrate surface modification method capable of efficiently and reliably modifying the resin substrate surface using the resin substrate surface modification device Can be provided.

  Therefore, the resin substrate surface modification apparatus of the present invention can dramatically improve the processing speed of the laser ablation process, and can further reduce the production cost. It is particularly useful as an apparatus used for pretreatment at the time of application.

It is a schematic sectional drawing of suitable one Embodiment of the surface modification apparatus of the resin base material of this invention. It is a schematic sectional drawing of the vicinity of the cover for shielding gas atmosphere holding | maintenance of the surface modification apparatus of the resin base material shown in FIG. It is a schematic sectional drawing of other suitable embodiment of the surface modification apparatus of the resin base material of this invention. It is a schematic longitudinal cross-sectional view which shows the relationship between a target and laser beam. It is a schematic sectional drawing of the shield gas atmosphere holding cover vicinity of the surface modification apparatus of the resin base material in which the shield gas atmosphere holding cover provided with a gas rectification part is arrange | positioned.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Laser beam generator 1, 2 ... Reflector plate, 3 ... Processing container, 3A ... Launch port, 4 ... Optical system, 4A ... Condensing lens, 5 ... Target, 6 ... Gas supply means, 7 ... Shield gas atmosphere maintenance use cover, 8 ... resin substrate 9 ... filter, 11 ... target drive, L ... laser light, P ... plasma gas flow a ... shielding gas, the perpendicular of L 1 _... target surface.

Claims (7)

A laser light generator for generating laser light;
A processing container into which the laser beam is introduced;
A target for generating scattered particles by the laser light irradiated on the surface;
A gas supply means for supplying a shielding gas to a space between the resin base material whose surface is modified by attaching the scattered particles scattered from the launch port of the processing container and the target;
A cylindrical body having a first opening edge and a second opening edge having a size equal to or larger than the first opening edge at both ends, the first opening edge being joined to the launch port, and a second opening edge A shield gas atmosphere holding cover in which an opening edge is disposed close to the surface of the resin substrate;
An apparatus for modifying a surface of a resin substrate, comprising:   The apparatus for modifying a surface of a resin substrate according to claim 1, wherein a distance between the second opening edge of the cover for holding a shielding gas atmosphere and the surface of the resin substrate is 30 mm or less.   3. The resin according to claim 1, further comprising a filter that is connected to the second opening edge of the shield gas atmosphere holding cover and has a tip that abuts against the surface of the resin base material. Surface modification equipment for base materials.   Using the surface modification apparatus for a resin base material according to any one of claims 1 to 3, the surface of the target is irradiated with laser light to generate vacuum ultraviolet light having a wavelength of 50 nm to 100 nm and scattered particles. A method for modifying the surface of a resin substrate, wherein the scattering particles are adhered to the surface of the resin substrate while irradiating the vacuum ultraviolet light.   The method for modifying the surface of a resin substrate according to claim 4, wherein the space between the target and the resin substrate is a shield gas atmosphere having an oxygen content of 6% by volume or less.   The method for modifying a surface of a resin substrate according to claim 4 or 5, wherein the positional relationship between the target and the resin substrate is relatively moved. The method for modifying the surface of a resin substrate according to any one of claims 4 to 6, wherein a speed of moving the target or the resin substrate is 400 mm / min or more.

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