JP3885436B2 - Method and apparatus for surface modification of fluororesin - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface modification method and apparatus for a fluororesin such as a fluororesin tube coated on the surface of a pressure roll in a fixing device used in an image forming apparatus such as a printer or a copying machine. Fluorine resin surface modification method for improving affinity and adhesiveness of fluorine resin (including molded products) with poor hydrophilicity, while having excellent releasability And an apparatus for the same.
[0002]
[Prior art]
Conventionally, various techniques have been proposed as a surface modification method for the fluororesin. For example, (1) a method using a tetrahydrofuran solution of metallic sodium and naphthalene, (2) a method using glow discharge and plasma treatment, (3) a high-frequency sputter etching method, (4) a laser irradiation method in a gas atmosphere of boric acids, (5) A technique in which a light-absorbing substance is kneaded into a workpiece and laser irradiation is reported.
[0003]
However, these techniques have problems such as danger, poor reforming effect, physical damage to the surface, and limited range of workpieces.
[0004]
Therefore, as a technique that can solve these problems, a technique for modifying the surface of the fluororesin and the molded body with an ultraviolet pulse laser has been proposed in the past few years as shown below. Yes.
[0005]
That is, as a method of modifying the surface of the fluororesin and the molded body with this ultraviolet pulse laser, (6) as described in Japanese Patent Application Laid-Open No. 06-192452, substitution of fluorine groups is performed using a hydrazine gas atmosphere. (7) A reforming method using a fluorosurfactant and an ultraviolet absorbing compound as disclosed in JP-A-07-207049, (8) High purity (as disclosed in JP-A-06-228343) There have been proposed reforming methods using water of 100 MΩ · cm or more and utilizing the good transmittance.
[0006]
More specifically, (6) the surface modification method for the surface of a fluorinated polymer molded article according to Japanese Patent Application Laid-Open No. 06-192452 is directed to an ultraviolet laser having a wavelength of 250 nm or less in the presence of hydrazines in the fluorinated polymer molded article. It is configured to irradiate light to make the surface of the polymer molded article hydrophilic.
[0007]
In addition, (7) the method of modifying the surface of a fluororesin molded body according to Japanese Patent Application Laid-Open No. 07-207049 is the same as that of the ultraviolet laser in the presence of an ultraviolet absorbing compound and a fluorosurfactant on the surface of the fluororesin molded body. It is configured to irradiate light.
[0008]
Further, in the above (8) surface modification method of fluororesin according to Japanese Patent Laid-Open No. 06-228343, the fluororesin is brought into contact with high-purity water, and a desired portion of the contact surface between the fluororesin and the water is formed. A desired part of the fluororesin is made hydrophilic by irradiation with ultraviolet rays.
[0009]
[Problems to be solved by the invention]
However, these surface modification methods for fluororesins have the following problems. The method (6) involves a chemical treatment using a hydrazine gas or an organic acid anhydride, and thus has a problem of not only occupational hygiene but also a large risk of adversely affecting the human body. In addition, the effect of surface modification of the fluororesin is low. Further, in the method (7), although the effect of surface modification of the fluorine-based resin can be obtained, two kinds of solutions of an ultraviolet absorbing compound and a fluorine-based surfactant are required, and processing steps such as coating and spraying steps are required. Increases the work efficiency. Moreover, there is a problem in occupational hygiene when the surfactant is used at a high concentration. Furthermore, in the method (8), not only does an expensive and large-sized pure water treatment device be required to produce high-purity water, but it is also very difficult to maintain an environment in which the purity does not decrease for a long time. In addition, the cost is significantly increased, and the reforming effect is lower than when a solvent is used. In addition, since ArF EXL (excimer laser) is used, the gas life is short, so that there is a problem that work efficiency is poor.
[0010]
Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and its object is to use a solution containing a low concentration and safe amine solvent as an ultraviolet absorber, and to process It is an object of the present invention to provide a surface modification method and apparatus for a fluororesin capable of performing uniform and efficient surface modification processing on an object.
[0011]
Another object of the present invention is to provide a fluorine resin surface modification method and apparatus capable of efficiently obtaining a desired modification condition by controlling the number of repetitions of ultraviolet laser energy. There is.
[0012]
[Means for Solving the Problems]
  In order to solve the above problems, the invention described in claim 1 is a surface modification method for a fluororesin that modifies the surface of a fluororesin containing fluorine as a terminal group. Irradiate the surface of the fluororesin with ultraviolet laser light in the presence of a solution containing an amine solvent.In addition, the solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent.This is a surface modification method for a fluororesin.
[0013]
Here, the fluorine-based resin containing fluorine as a terminal group includes both the fluorine-based resin itself and a molded body thereof (molded body made of a fluorine-containing organic polymer compound). Examples of the fluorine resin contained in the group include tetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), and tetrafluoroethylene / perfluoroalkoxyethylene copolymer (PFA). And tetrafluoroethylene / ethylene copolymer (ETFE). These specific forms are not particularly limited.
[0015]
Moreover, the invention described in claim 2 is a surface modification method for a fluororesin that modifies the surface of a fluororesin containing fluorine as a terminal group.In a state where a solution containing an amine solvent is present on the surface of the fluororesin,By irradiating the surface of the fluorine resin with ultraviolet pulse laser light, the fluorine resin is modified, and by controlling the number of times of irradiation with the ultraviolet pulse laser light, a desired modification state of the fluorine resin is achieved. GetIn addition, the solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent.This is a surface modification method for a fluororesin.
[0016]
Furthermore, the invention described in claim 3 is a fluorine resin surface modification method for modifying the surface of a fluorine resin containing fluorine as a terminal group, and a solution containing an amine solvent on the surface of the fluorine resin. Irradiate the surface of the fluororesin with ultraviolet laser light in a state in which a thin film is uniformly formedIn addition, the solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent.This is a surface modification method for a fluororesin.
[0017]
Solution containing the amine solventas, Trimethylamine ((CH_Three)_ThreeN), triethylamine ((CH_Five)_ThreeN) chain aliphatic amines, or aniline (C₆H_FiveNH₂), Naphthylamine (C_TenH₇NH₂) And other cyclic aromatic amine aqueous solutions, acetonitrile solutions, or ethanol solutionsCan mention.
[0018]
In addition, piperidine (C_FiveNH₆), Ethileimine (C₂H_FiveN) or triethylamine ((CH_Five)_ThreeN), hexylamine (C₆H₁₃NH₂) Is highly toxic as is apparent from FIG. 8 showing the data values of sputum oral LD50.
[0019]
Therefore,In this inventionAmong the amine-based solvents, pyridine (C) is a non-aromatic series of cyclic amines that have good reactivity and high safety._FiveH_FiveIt is desirable to use an aqueous solution in which N) is dissolved.
[0020]
further,Claim 4The invention described in 1) is a fluorine resin surface modification apparatus for modifying the surface of a fluorine resin containing fluorine as a terminal group, and forms a thin film of a solution containing an amine solvent on the surface of the fluorine resin. A thin film forming means; and an ultraviolet laser light irradiation means for irradiating the surface of the fluororesin with ultraviolet laser lightThe solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent.This is a surface modification device for a fluororesin.
[0021]
or,Claim 5In the invention described in the above, the thin film forming means presses the ultraviolet transmitting member against the surface of the fluorine resin coated with the solution containing the amine solvent, and controls the pressing force of the ultraviolet transmitting member. Uniformly forming a thin film of a solution containing the amine solventClaim 4This is a surface modification device for fluororesin.
[0024]
Claim 67. The fluororesin surface modification apparatus according to claim 5, wherein the purity of pyridine used in the aqueous pyridine solution is about 99.9% deer grade 1 or more. It is.
[0025]
Claim 7The invention described in the above item is characterized in that the purity of water used in the aqueous pyridine solution is 0.2 μS (Siemens) / cm or more, and the concentration of the aqueous pyridine solution is 2% or less.Claim 4 or 5It is a surface modification apparatus of the described fluorine resin.
[0026]
further,Claim 8The invention described in 1 is characterized in that the ultraviolet laser beam irradiation means irradiates a KrF excimer laser beam.Claim 4 or 5It is a surface modification apparatus of the described fluorine resin.
[0029]
Furthermore,Claim 94. The surface modification method for a fluororesin according to claim 1, wherein the purity of pyridine used in the aqueous pyridine solution is about 99.9% deer grade 1 or more. It is.
[0030]
Here, as the pure water used in the pyridine aqueous solution, for example, distilled water is used, and the purity of water used in the pyridine aqueous solution is, for example, 0.2 μS (Siemens) / cm or more. As the concentration of the pyridine aqueous solution,For exampleIt is set to an extremely low concentration of 2% or less.
  The invention described in claim 16 is a fluorine resin characterized in that the surface is modified by the surface modification method for a fluorine resin according to any one of claims 1 to 15.
  Furthermore, the invention described in claim 17 is the fluororesin according to claim 16, which is bonded to silicone rubber.
[0031]
[Action]
The present invention basically irradiates the surface of a fluorine resin with ultraviolet laser light in a state where a solution containing an amine solvent is present on the surface of the fluorine resin.
[0032]
Further, in the present invention, a processing member made of a fluororesin or a molded body thereof is placed on a processing stage via a solution containing an amine solvent, and the pressing force of the ultraviolet transmitting member is controlled, so that the amine system It is formed into a thin film of a solution containing a solvent, and the surface of the fluororesin or its molded body is modified by laser irradiation. The solution used for the modification is formed to have a uniform thin film thickness by the pressing force of the ultraviolet transmitting member and the thin film forming means, and the degree of modification of the irradiated portion is efficiently generated in a desired state by controlling the number of repetitions of the ultraviolet laser. Furthermore, the solution used for reforming is a catalyst using a low concentration amine solvent, and can be safely reformed.
[0033]
Furthermore, in the present invention, by using only a low-concentration pyridine aqueous solution when the solvent is pure water (distilled water) as a solution containing an amine-based solvent, a desired degree of modification can be achieved more safely and efficiently. The inventor has found that it can be obtained.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below with reference to the drawings.
[0035]
FIG. 2 is a schematic configuration diagram showing a surface modification device for a fluorine resin to which a surface modification method for a fluorine resin according to an embodiment of the present invention is applied.
[0036]
In the figure, reference numeral 11 denotes a laser generator for generating krF (wavelength: 248 nm) excimer laser light. The krF excimer laser light LB emitted from the laser generator 11 is reflected by mirrors 12, 13, and 14. Then, the fluororesin molded product as the workpiece placed on the processing stage 22 is irradiated. At that time, between the mirror 12 and the mirror 13, there is a diaphragm 15 that functions to narrow down the krF excimer laser beam LB emitted from the laser generator 11, and a shutter 16 that opens and closes the irradiation state of the excimer laser beam LB. And a mac 17. Further, a lens 18 that forms an image of the krF excimer laser beam LB emitted from the laser generator 11 is disposed between the mirror 14 and the processing stage 22. The lens 18 is used for focusing. It is driven by the drive device 19 along the Z1 axis direction which is the vertical direction. Further, the machining stage 22 is driven by the machining stage driving device 24 in the θ1 direction around the vertical axis, in the θ2 direction around the horizontal axis, in the θ3 direction around the horizontal axis perpendicular to the θ2 direction, and in a horizontal plane. Can be driven along the X-axis direction and the Y-axis direction. A monitor device 25 for monitoring the processing state on the processing stage 22 is disposed above a position different from the processing position of the processing stage 22. The monitor device 25 includes a measurement camera 26 that measures a workpiece on the processing stage 22, a focus drive device 27 that drives the focus of the measurement camera 26, and a workpiece measured by the measurement camera 26. A feedback control panel 28 that feeds back the processing state of the object to the laser generator 11 is provided. The feedback control panel 28 is connected to a laser generation control panel 29 that controls the laser generator 11.
[0037]
Note that the number of mirrors is not limited to three depending on the device configuration, and may be used as appropriate, or may be configured without using a mirror. Further, the shutter 16 may be omitted if it is not necessary.
[0038]
Further, as shown in FIG. 3 and FIG. 4, the fluorine is formed on the processing stage 22 so that the surface of the fluorine-based resin molded body 20 as a workpiece is directed toward the lens 18 via the fibrous body 21. A resin-based molded body 20 is placed. As this fluorine-based resin molded body 20, for example, a film-shaped molded body made of a fluorine-based resin is used, but the shape of the fluorine-based resin molded body 20 is not limited to the film shape, and other Of course, it may be of any shape. The fibrous body 21 is a fibrous member having good air permeability. As a specific example, paper with good air permeability having a uniform thickness of about 100 μm can be used. The processing stage 22 is provided with one or more vent holes 31 opened on the surface thereof, and communicates with the vacuum pump 23 through an internal space. When the vacuum pump 23 is operated and sucked, the space inside the processing stage 22 becomes negative pressure, and the fibrous body 21 is adsorbed through the vent hole 31. Further, since the fibrous body 21 is a member having good air permeability, the workpiece 20 is sucked through the fibrous body 21 and adsorbs the workpiece 20 to the processing stage 22 via the fibrous body 21. It can be fixed.
[0039]
By the way, in the first embodiment, a thin film forming means for forming a thin film of a solution containing an amine solvent on the surface of the fluorine resin, and an ultraviolet laser light irradiation means for irradiating the surface of the fluorine resin with ultraviolet laser light. It is comprised so that it may be provided. The thin film forming means presses the ultraviolet transmitting member against the surface of the fluorine resin coated with a solution containing an amine solvent, and controls the pressing force of the ultraviolet transmitting member, thereby reducing the amine solvent. The thin film of the solution containing is comprised so that it may form uniformly. Further, as the ultraviolet laser light irradiation means, one that irradiates KrF excimer laser light is used.
[0040]
That is, in the first embodiment, as shown in FIG. 1, the fluororesin molded body 20 is placed on the processing stage 22 as a member to be processed. As the fluorine-based resin molded body 20, for example, as shown in FIG. 5, a film-like fluorine-based resin molded body 20 made of tetrafluoroethylene / perfluoroalkoxyethylene copolymer (PFA) is used. A solution 30 containing a low-concentration amine solvent is applied to the surface of the fluororesin molded body 20. As the solution 30 containing the amine solvent, for example, an acetonitrile solution of trimethylamine is used. Further, an ultraviolet transmitting member 31 made of a quartz plate or the like is pressed on the surface of the fluororesin molded body 20 to which the solution 30 containing the amine solvent is applied. The ultraviolet transmitting member 31 has a constant thickness (for example, 3 mm) and is formed with high precision so that both the front and back surfaces are flat and parallel to each other.
[0041]
The ultraviolet transmissive member 31 can be controlled by the film thickness control device 32 so as to be parallel to the processing stage 22 and the surface of the fluororesin molded body 20 along the vertical direction. The ultraviolet transmissive member 31 is moved little by little along the vertical direction by the film thickness control device 32 to control the gap G between the lower surface of the ultraviolet transmissive member 31 and the surface of the fluororesin molded body 20. In addition, the thin film of the solution 30 containing the amine solvent is uniformly formed on the surface of the fluororesin molded body 20. It has been confirmed by experiments of the present inventors that the thinner the thin film of the solution 30 containing the amine solvent, the higher the modification effect of the fluororesin molded body 20, and the solution 30 containing the amine solvent. The film thickness is set to several tens of μm, for example.
[0042]
In the above-described configuration, in the fluorine resin surface modifying apparatus according to this embodiment, a solution containing a low concentration and safe amine solvent is used as an ultraviolet absorber as follows. And uniform and efficient surface modification.
[0043]
That is, in this embodiment, the krF excimer laser beam LB emitted from the laser generator 11 is converged on the workpiece 20 by the condenser lens 18 through the projection mask 17 as shown in FIG. Since the oscillated laser beam LB is an ultraviolet ray having a wavelength of 248 nm, the laser beam LB is transmitted through the ultraviolet ray transmitting member 31 placed on the workpiece 20 on the processing stage 22 and has a uniform thin film as shown in FIG. The workpiece 20 is irradiated through a solution 30 that absorbs ultraviolet rays. As shown in FIG. 5, the fluorine bond on the surface of the fluororesin molded body 20 is generated by generating a radical called a substrate by a photochemical reaction on the surface of the fluororesin molded body 20 that is an irradiated workpiece. It can be separated and the CH group can be efficiently substituted. The energy density of the irradiated laser beam LB is low enough to cause a slight ablation reaction (reaction that breaks and separates the molecular chain of the fluororesin) (<90 mj / cm).²) Is used to control the number of repetitions of the laser beam LB irradiation, so that a desired modification can be efficiently obtained.
[0044]
At that time, the processing stage 22 moves the processing stage driving device 24 in the rotational directions θ1, θ2, and so on at the position of the measurement camera 26 of the monitor device 25 so that the processing surface of the workpiece 20 is perpendicular to the laser beam LB. Drive to θ3 and adjust. The focus of the measurement camera 26 is adjusted by the focus drive device 27. Thereafter, the height between the processing stage 22 and the processing surface of the processing member 20 is measured. The processing stage drive device 24 is driven in the Y direction to move the processing member 20 to the processing position, and processing by the laser beam LB is performed. By processing the beam of the excimer laser beam LB, the surface of the workpiece 20 is processed into a shape corresponding to the opening shape of the mask 17. The degree of modification of the processing member 20 can be controlled by the intensity of the laser beam and the irradiation time, and the laser generation control panel 29 controls the generation of the laser beam LB according to the set value.
[0045]
Thus, in the above-described embodiment, as shown in FIG. 1, the surface of the fluororesin molded body 20 is exposed to ultraviolet rays in the state where the solution 30 containing the amine solvent exists on the surface of the fluororesin molded body 20. The laser beam LB is irradiated.
[0046]
Moreover, in the said embodiment, the to-be-processed member 20 which consists of a fluororesin molded object is mounted on the processing stage 22 via the solution 30 containing an amine solvent, and the pressing force of the ultraviolet transmissive member 31 is controlled. Thus, it is formed on a thin film of a solution 30 containing an amine solvent, and the surface of the fluororesin molded body 20 is modified by irradiation with a laser beam LB. The solution used for modification is formed with a uniform thin film thickness by the pressing force of the ultraviolet transmitting member 31 and the thin film control device 32, and the degree of modification of the irradiated portion is efficiently generated in a desired state by controlling the number of repetitions of the ultraviolet laser. Furthermore, the solution 30 used for reforming is a catalyst using a low-concentration amine solvent and can be safely reformed.
[0047]
Example 1
A fluororesin, for example, a PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) film 20, using an acetonitrile solution of trimethylamine 4% concentration, KrF (wavelength: 248 nm) excimer laser beam LB (energy density: 75 mj / cm)²) Was irradiated for 20 seconds at 100 Hz for a pulse number of 2000 shots, the measured pure water contact angle of the irradiated part showed about 60 °, and it was confirmed that the water was modified to fresh water. Further, when an acetonitrile solution having a concentration of 2% trimethylamine is used as the solution 30 with the same material, the energy density is 75 mj / cm.²The contact angle with water was improved to around 60 ° with a pulse number of 3000 shots.
[0048]
FIG. 6 shows the results of an experiment for confirming how the measured value of the pure water contact angle changes when the number of times of excimer laser beam LB irradiation is constant and the concentration of trimethylamine is changed. As can be seen from FIG. 6, when the concentration of trimethylamine is 2% or more, the measured value of the pure water contact angle can be modified to about 60 ° and does not depend on the concentration of trimethylamine.
[0049]
Thus, sufficient modification occurred with a solution of amine solvent having a low concentration of several percent, affinity could be obtained, and modification processing could be performed safely.
[0050]
Example 2
In general, a wetness index test method for Japanese Industrial Standard K6768 film is specified for measuring the wet state. The solution conditions were the same as in Example 1, and only the number of laser repetitions was changed to measure the wetting index and the measured pure water contact angle of the Japanese Industrial Standard K6768 film to evaluate the degree of modification. As a result, it was found that the wetting index and the measured value of pure water contact angle of the Japanese Industrial Standard K6768 film have a substantially linear correspondence as shown in FIG. Thus, the relationship between the wetting index and the contact angle is proportional, and it has been found that the desired modification can be efficiently realized by controlling one of the laser irradiation conditions.
[0051]
Example 3
A fluororesin, for example, a PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) film 20, using a 1% pyridine aqueous solution, KrF (wavelength: 248 nm) excimer laser beam LB (energy density: 75 mj / cm)²) Was irradiated at a frequency of 3000 shots for 30 seconds at 100 Hz, the measured value of the pure water contact angle of the irradiated part was about 50 °, confirming that it was greatly modified to new water.
[0052]
Example 4
When an aqueous solution of 2% pyridine is used for the same material, the energy density of KrF (wavelength: 248 nm) excimer laser beam LB is 25 mj / cm.²Even when the number of pulses was reduced to 1000 shots, the pure water contact angle of the irradiated part could be improved to around 55 °. As described above, the present inventors have found a reforming process capable of efficiently generating a reformed state with a low concentration solution and a low number of repetitions and obtaining sufficient affinity.
[0053]
Example 5
As shown in the second embodiment, in the method of obtaining a desired modified state by changing only the laser repetition number, the degree of modification tends to increase as the laser oscillation repetition number increases. When the solution conditions were the same as in Example 4 and the wetting index evaluation (JIS K6768) was performed by changing the number of pulses, as shown in FIG. 9, even when processed with a low number of pulses (1000 shots), sufficient The degree of modification (52 dyn / cm or more) was obtained.
[0054]
Example 6
The adhesiveness of the surface-modified fluororesin (PFA) was evaluated while changing the number of irradiation pulses. A low concentration (2% or less) pyridine aqueous solution is used as an ultraviolet absorbing material, and the laser energy density is 75 mj / cm.²The surface of fluororesin (PFA) was modified as follows. An adhesive (silicone manufactured by Toray Industries, Inc.) was applied to the modified fluororesin (PFA), and the adhesiveness (tensile strength test) with silicon rubber was evaluated. For comparison, the same evaluation was performed using an acetonitrile solution of triethylamine. As a result, as shown in FIG. 10, sufficient adhesive strength with a maximum load of 4 N or more could be obtained even with a low number of pulses (about 1000 shots). Thus, it has been found that by using an aqueous pyridine solution, the fluorine-based resin can be modified to such an extent that it has not only high hydrophilicity but also high lipophilicity and sufficient adhesive strength.
[0055]
Analysis example
Further, the present inventor found that when the fluororesin was modified using an aqueous pyridine solution as described above, how much the surface of the fluororesin was actually modified, that is, the fluorine present on the surface of the fluororesin. An analysis was performed to confirm how much (F) was replaced by other elements.
[0056]
The samples used for the analysis are a PFA sheet before modification and a PFA sheet after modification. The modification of the PFA sheet surface is performed by excimer laser beam LB (energy density 25 mj / cm²) Was irradiated with 3000 shots of pulses for 30 seconds at 30 Hz, and an aqueous solution of 1% pyridine was used.
[0057]
The analysis method is analysis by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS”). The apparatus used for this XPS method is ESCALAB-220i manufactured by VG.
[0058]
As a sample processing method, the sample was cut into an appropriate size and subjected to XPS measurement. The X-ray source is monochromatic AlKα, the analysis region is about 1 mmφ, and the detection depth is several nm.
[0059]
The analysis results are as follows.
[0060]
FIG. 11 shows the XPS wide spectrum of the PFA sheet before modification, and FIG. 12 shows the modified PFA sheet. Fluorine (F) is strongly detected from the surface of the PFA sheet before modification, but after modification, the peak intensity of fluorine (F) is drastically reduced, and it was not detected from the sheet before modification. , N were detected. The table of FIG. 13 summarizes the composition ratio of each element on the surface of the PFA sheet before and after the modification.
[0061]
14 and 15 show C1 before and after reforming._SOnly the portion of the spectrum is shown enlarged. C1 before reforming_SFrom the peak binding energy, C on the sheet surface is C-F.₂The C on the modified sheet surface is considered to be C—C or C bonded to C—H. Furthermore, the modified C1_SIn the peak, a small shoulder is recognized around 288 eV. From this shoulder binding energy, it is considered that C = O or C bonded to CHF also exists on the surface.
[0062]
As described above, the chemical state of the surface C and the composition ratio of the surface were clearly changed before and after the modification of the fluororesin, and a very high effect of the modification was recognized.
[0063]
In particular, from the surface of the modified PFA sheet, as shown in FIG. 13, fluorine (F), which was present at 69.2 atm% before the modification, is present at 0.3 atm% after the modification. It can be seen that the film is almost completely modified.
[0064]
【The invention's effect】
As is apparent from the above description, according to the present invention, a thin film is formed on a workpiece with an ultraviolet absorbing solution (a solution containing an amine solvent), and an ultraviolet transmitting member is placed thereon, and a pressing force is applied. By controlling the thickness, the thickness of the thin film can be kept uniform, and by performing laser irradiation, stable reforming can be performed. The solution used is safe because it has a low concentration. Furthermore, a desired modification can be efficiently realized by controlling the number of laser repetitions.
[0065]
Furthermore, in the present invention, by using only a low-concentration pyridine aqueous solution when the solvent is pure water (distilled water) as a solution containing an amine solvent, a desired modification condition (safer and higher efficiency) The present inventors have found a modification method and apparatus capable of realizing hydrophilicity and lipophilicity) and adhesive strength.
[Brief description of the drawings]
FIG. 1 is a configuration diagram showing a main part of a surface modification apparatus for a fluorine resin to which a surface modification method for a fluorine resin according to an embodiment of the present invention is applied.
FIG. 2 is a block diagram showing a fluororesin surface modification apparatus according to an embodiment of the present invention.
FIG. 3 is a plan view showing a processing stage.
FIG. 4 is a cross-sectional view showing a processing stage.
FIG. 5 is a chemical formula showing the molecular structure of PFA.
FIG. 6 is a graph showing experimental results.
FIG. 7 is a graph showing experimental results.
FIG. 8 is a graph showing toxicity data for amines.
FIG. 9 is a graph showing experimental results.
FIG. 10 is a graph showing experimental results.
FIG. 11 is a graph showing the analysis results.
FIG. 12 is a graph showing the analysis results.
FIG. 13 is a chart showing analysis results.
FIG. 14 is a graph showing an analysis result.
FIG. 15 is a graph showing the analysis results.
DESCRIPTION OF SYMBOLS 11: Laser generator, 20: Fluorine-based resin molding, 30: Solution containing amine solvent, 31: Ultraviolet transmitting member, 32: Film thickness control device.

Claims (10)

  In the fluorine resin surface modification method for modifying the surface of a fluorine resin containing fluorine as a terminal group, the surface of the fluorine resin is in a state in which a solution containing an amine solvent is present on the surface of the fluorine resin. Surface modification of a fluororesin characterized in that the solution containing the amine solvent is an aqueous pyridine solution using pure water of pyridine which is a cyclic non-aromatic amine solvent. Method.   In the fluorine resin surface modification method for modifying the surface of a fluorine resin containing fluorine as a terminal group, the surface of the fluorine resin is in a state in which a solution containing an amine solvent is present on the surface of the fluorine resin. By irradiating the ultraviolet pulse laser beam to the resin, the fluorine resin is modified, and by controlling the number of irradiation times of the ultraviolet pulse laser beam, a desired modified state of the fluorine resin is obtained, and A method for modifying a surface of a fluororesin, wherein the solution containing an amine solvent is an aqueous pyridine solution using pure water of pyridine, which is a cyclic non-aromatic amine solvent.   In the fluorine resin surface modification method for modifying the surface of a fluorine resin containing fluorine as a terminal group, the fluorine resin is formed in a state in which a thin film of a solution containing an amine solvent is uniformly formed on the surface of the fluorine resin. Fluorine resin characterized by irradiating the surface of a resin with ultraviolet laser light and the solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent Surface modification method.   In a fluorine resin surface modifying apparatus for modifying the surface of a fluorine resin containing fluorine as a terminal group, a thin film forming means for forming a thin film of a solution containing an amine solvent on the surface of the fluorine resin, and the fluorine An ultraviolet laser light irradiation means for irradiating the surface of the resin with ultraviolet laser light, and the solution containing the amine solvent is a pyridine aqueous solution using pure water of pyridine which is a cyclic non-aromatic amine solvent. A fluorine resin surface modification device.   The thin film forming means includes a solution containing the amine solvent by pressing an ultraviolet transmitting member against the surface of the fluororesin coated with the solution containing the amine solvent and controlling the pressing force of the ultraviolet transmitting member. The fluorine resin surface modification apparatus according to claim 4, wherein the thin film is uniformly formed.   The surface modification apparatus for a fluororesin according to claim 4 or 5, wherein the purity of pyridine used in the pyridine aqueous solution is about 99.9% or more deer grade 1.   The purity of water used in the pyridine aqueous solution is 0.2 μS (Siemens) / cm or more, and the concentration of the pyridine aqueous solution is 2% or less. Surface modification equipment.   6. The surface modification apparatus for a fluorine-based resin according to claim 4, wherein the ultraviolet laser beam irradiation means irradiates a KrF excimer laser beam.   The method for modifying the surface of a fluororesin according to any one of claims 1 to 3, wherein the purity of pyridine used in the aqueous pyridine solution is about 19.9% or more deer grade 1.   4. The purity of water used in the aqueous pyridine solution is 0.2 μS (Siemens) / cm or more, and the concentration of the aqueous pyridine solution is 2% or less. 5. Surface modification method of fluororesin.

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