JP5177395B2 - Modification method of resin surface - Google Patents

Description

The present invention relates to a reforming how the resin surface which is fixed directly to a solid surface.

In general, a metal surface as a solid is coated with a resin for corrosion prevention. As the resin, a method of fixing a resin film, a method of fixing a resin powder, or the like is known.
Conventionally, for example, in the case of a resin film made of a fluororesin, fine unevenness is imparted to the solid surface, and the resin film is fixed to the solid surface with an adhesive (for example, JP-A-2005-186595, JP, 2000-348975, A, etc.).

  Conventionally, for example, in the case of a resin powder made of a fluororesin such as polytetrafluoroethylene (PTFE), a method of fixing to a solid surface by thermal spraying is known (see, for example, JP-A-2002-60432). ). This is a coating of fluorine resin as a film in a flame generated by gas combustion. The fluorine resin is subjected to rapid heating in the flame and reaches a solid surface to be applied in a molten state. A film is formed on the solid surface. Hydrogen, acetylene, methane, or the like is used as the combustion gas.

JP 2005-186595 A JP 2000-348975 A JP 2002-60432 A

  By the way, conventionally, in the resin fixing technique to the solid surface, in the case of the resin film, there has been a problem that it is difficult to fix directly to the solid surface. The reason is that since there is no functional group chemically bonded to the resin surface, the bonding force at the interface is not necessarily good. Therefore, in the former resin film fixing technique, unevenness is imparted to the surface of the adherend to enhance the bonding by the anchoring effect, and a large amount of adhesive is used for fixing. However, there has been a problem that the appearance of the solid surface is impaired by the provision of surface irregularities, or the manufacturing process is complicated by the use of an adhesive, and further, there is a limit to the miniaturization of the product.

  On the other hand, in the conventional technology for fixing resin powder to a solid surface, the resin is directly fixed to the solid surface, but the fluororesin is in a molten state in a flame generated by high-temperature gas combustion. There has been a problem that the resin powder is not deteriorated. Further, the bonding strength with the solid substrate is not necessarily good. In order to prevent deterioration, it is conceivable that the resin powder is fixed to the solid substrate by spraying at a low temperature. However, if the powder is simply sprayed at a low temperature, the binding force with the solid substrate is further decreased. Resulting in.

The present invention has been made in consideration of the above problems, and an object thereof is to provide a reforming how the resin surface with improved adherence to the solid surface of the resin to be fixed directly to a solid surface.

In order to achieve such an object, the resin surface modification method of the present invention involves irradiating a resin surface with a quantum beam, immersing the resin in a dispersion in which a triazine thiol derivative is dispersed, The triazine thiol derivative is bonded.
The resin may have any form such as a resin film or resin powder.
In addition, the quantum beam indicates all electromagnetic waves and particle beams in a broad sense, but here has an ionizing effect on the irradiated resin. X-rays, γ rays Short-wavelength ultraviolet rays, fast charged particle beams, fast neutron rays and other radiation, electron beams, ion beams, and the like.

Thereby, when a quantum beam is irradiated on the resin surface, the resin surface is activated. The reason is that the resin surface irradiated with the quantum beam emits electrons to become ions, or decomposes to generate radicals. This is because the generated ions and radicals act as a reaction initiator, so that ionic polymerization or radical polymerization can be easily started.
In addition, since the resin surface irradiated with the quantum beam is activated, the triazine thiol derivative is reliably bonded to the resin surface in the dispersion. The resin surface irradiated with the quantum beam emits electrons to become ions, or decomposes to generate radicals. The generated ions and radicals act as reaction initiators. The triazine thiol derivative in the solvent forms thiyl radicals by the reaction initiator on the resin surface. A thiyl radical causes a double bond cleavage reaction of an allyl group by addition to a disulfide bond or an allyl group on the resin surface. In this way, it is considered that a polymerized film is formed on the resin surface by causing a coupling with a thiyl radical or an addition reaction of all other molecules to an allyl group.

Then, the resin in which the triazine thiol derivative is formed on the surface as described above is fixed to, for example, a solid metal surface. For example, when the resin is a resin film, it is bonded to a metal surface and then fixed by heat treatment. Further, for example, when the resin is a powder resin, it is bonded to the metal surface using a known cold spray or the like, and then fixed by heat treatment.
In this case, the resin is directly fixed to the solid surface, and the triazine thiol derivative is chemically bonded to the solid surface, so that the fixing property of the resin is improved. The reason is that the thiol group at the terminal of the triazine dithiol derivative gives and receives electrons from the solid when bonded to the solid. The triazine thiol derivative with excess electrons donates hydrogen present in the triazine ring to the solid, and the thiol group immediately becomes a thiyl radical. The formation of thiyl radicals is thought to promote chemical reactions with the solid surface.

  In the above configuration, when the resin is resin powder, the average diameter D is preferably in the range of D = 5 μm to 1 mm. More desirably, the average diameter D is in the range of D = 50 μm to 500 μm. A fine powder tends to agglomerate itself and is difficult to uniformly disperse in a solvent. On the other hand, if it is too large, the ratio of the modified area of the powder becomes small, and it is difficult to obtain the fixing strength at the time of film formation.

  The resin may be either a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include hydrocarbon resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, and polytetrafluoroethylene. Tetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) Halogen-containing resins such as any of these fluorine-containing resins, polyamide-type resins such as nylon, polyether resins such as polyacetal, polyester resins such as polysulfone and polycarbonate polyethylene terephthalate, acrylic resins such as polymethyl methacrylate, etc. It is done. Examples of the thermosetting resin include polyimide resin, polyamideimide resin, polyetherimide resin, epoxy resin, melamine resin, silicon resin, and furan resin.

  Moreover, the said triazine thiol derivative is set as the structure selected from the triazine dithiol derivative shown with the following general formula as needed.

In the formula, R ₁ represents CH ₂ ═CHCH ₂ —, CH ₂ ═CH— (CH ₂ ) ₈ —, CH ₂ ═CH— (CH ₂ ) ₉ —, CH ₂ ═CH (CH ₂ ) ₄ COOCH ₂ CH ₂ −, CH ₂ ═CH (CH ₂ ) ₈ COOCH ₂ CH ₂ —, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —, R ₂ is CH ₂ ═CHCH ₂ —, CH _{2 = CH- (CH 2) 8} -, CH 2 = CH- (CH 2) 9 -, CH 2 = CH (CH 2) 4 COOCH 2 CH 2 -, CH 2 = CH (CH 2) 8 COOCH 2 CH ₂ −, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —. M is an alkali composed of any one of Li, Na, K, and Ce.

Moreover, it is set as the structure which used the electron beam or the X-ray as needed, and the irradiation dose was set to the range of 30-200 kGy. When the irradiation dose is 30 kGy or more, the irradiation effect is seen and effective. However, when the irradiation dose exceeds 200 kGy, the sample is severely damaged and the surface modification function is lowered. Therefore, the range of 30 to 200 kGy is preferably selected.
The electron beam irradiator has a structure in which an electron beam generator heated by a filament is arranged and sealed in a high vacuum. Electrons generated at the hot cathode are accelerated by a potential difference (for example, acceleration voltage 60 kV) from the irradiation window, pass through the window, and irradiate the resin with an electron beam. The irradiation dose is controlled by the irradiation distance, irradiation time, and filament current value.

Furthermore, if necessary, the dispersion liquid in which the triazine thiol derivative is dispersed has a structure in which water or a solution obtained by mixing at least one of cyclohexane, benzene, carbon tetrachloride, and diethyl ether is used as a solvent. For the triazine thiol derivative, it is desirable to select a compound having at least one allyl group as a functional group. Although the reason is not clear, triazine thiol derivatives of alkali salts such as Li, Na, K, and Ce dissolved in water were effective in modifying the resin surface. In particular, when the irradiated resin is a fluororesin, it is difficult to get wet with water, so mixing the resin and a highly compatible solvent improves the wettability of the irradiated resin, resulting in an activated powder or film. It is easy to get wet and can be uniformly modified. The triazine thiol derivative having an allyl group forms a highly three-dimensionally cross-linked polymer film on the powder or film surface, thereby realizing more reliable fixation.

  Moreover, the said dispersion liquid is 10-45 degreeC as needed, and it is set as the structure which immerses a resin in this dispersion liquid for 8 hours or more. It is desirable to stir the dispersion from time to time. When the processing temperature is high, side reactions such as oxidation are likely to occur, and when the processing temperature is low, the reaction is difficult to occur. Further, if the treatment time is short, the reaction is insufficient, and an immersion treatment of 8 hours or longer is desirable.

According to reforming how the resin surface of the present invention, since the bound triazine thiol derivative on the resin surface, when sticking the resin to a metal surface as for example, a solid, together with the resin is brought directly fixed to a solid surface, The triazine thiol derivative is chemically bonded to the surface of the solid, and thus the adhesion of the resin can be improved. Also, since the resin surface is irradiated with the quantum beam, the resin surface is activated and the triazine thiol derivative can be reliably bonded.

Hereinafter, with reference to the accompanying drawings, with the reforming how the resin surface according to the embodiment of the present invention will be described in detail.
The resin targeted by the resin surface modification method according to the embodiment of the present invention may be either a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include hydrocarbons such as polyethylene and polypropylene. Resin, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene tetrafluoride (PTFE), ethylene tetrafluoride / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), halogen-containing resins such as fluorine-containing resins such as ethylene-tetrafluoroethylene copolymer (ETFE), polyamide resins such as nylon, polyether resins such as polyacetal, polysulfone, polycarbonate polyethylene terephthalate, etc. Acrylic such as polyester resin and polymethyl methacrylate Such systems resin. Examples of the thermosetting resin include polyimide resin, polyamideimide resin, polyetherimide resin, epoxy resin, melamine resin, silicon resin, and furan resin.

The resin may be in any form such as a resin film or resin powder.
When the resin is a resin powder, the average diameter D is preferably in the range of D = 5 μm to 1 mm. More desirably, the average diameter D is in the range of D = 50 μm to 500 μm. The fine powder is likely to agglomerate itself and difficult to uniformly disperse in a solvent described later. On the other hand, if it is too large, the ratio of the modified area of the powder becomes small, and it is difficult to obtain the fixing strength at the time of film formation, so the powder size in the above range is selected.

  The triazine thiol derivative is selected from triazine dithiol derivatives represented by the following general formula.

In the formula, R ₁ represents CH ₂ ═CHCH ₂ —, CH ₂ ═CH— (CH ₂ ) ₈ —, CH ₂ ═CH— (CH ₂ ) ₉ —, CH ₂ ═CH (CH ₂ ) ₄ COOCH ₂ CH ₂ −, CH ₂ ═CH (CH ₂ ) ₈ COOCH ₂ CH ₂ —, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —, R ₂ is CH ₂ ═CHCH ₂ —, CH _{2 = CH- (CH 2) 8} -, CH 2 = CH- (CH 2) 9 -, CH 2 = CH (CH 2) 4 COOCH 2 CH 2 -, CH 2 = CH (CH 2) 8 COOCH 2 CH ₂ −, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —. M is an alkali composed of any one of Li, Na, K, and Ce.

  As shown in FIG. 1, the resin surface modification method according to the embodiment of the present invention includes a quantum beam irradiation step (1) for irradiating a resin surface with a quantum beam, and a triazine thiol derivative dispersed in the resin surface A bonding treatment step (2) in which the triazine thiol derivative is bonded to the resin surface by dipping in the dispersion liquid and a drying step (3) for drying the resin surface bonded with the triazine thiol derivative are provided. Hereinafter, each step will be described in detail.

(1) Quantum beam irradiation step This is a step of irradiating the resin surface with a quantum beam, and an electron beam was used as the quantum beam. As shown in FIG. 2, the electron beam was irradiated to the resin surface with the electron beam irradiation apparatus. The electron beam irradiation dose was in the range of 30 to 200 kGy.
The electron beam irradiation apparatus has a structure in which an electron beam generator 1 heated by a filament is arranged and sealed in a high vacuum. Electrons generated at the hot cathode are accelerated by a potential difference with the irradiation window (for example, acceleration voltage 60 kV), pass through the window, and irradiate the resin W placed on the table 3 in the irradiation chamber 2 with an electron beam. . In the case of the resin powder, the resin powder was placed uniformly, and a stainless steel mesh was placed on the powder so that the powder was not scattered by charging by irradiation. After adjusting the irradiation distance to a predetermined height, the irradiation chamber 2 was closed and evacuated. When the irradiation chamber became 5 × 10 ⁻² Pa or less, preparation for irradiation was performed, and irradiation was performed under predetermined conditions. Irradiation was stopped and the atmosphere was released while introducing nitrogen gas into the irradiation chamber.

(2) Bonding treatment step The irradiated resin is immersed in a dispersion in which the triazine thiol derivative is dispersed to bond the triazine thiol derivative to the resin surface. The dispersion is set to 10 to 45 ° C., and the resin is immersed in the dispersion for 8 hours or more. The dispersion in which the triazine thiol derivative was dispersed was a solvent in which at least one of cyclohexane, benzene, carbon tetrachloride, and diethyl ether was mixed with water.
In the embodiment, 0.5 g of 6-allylamino-1,3,5-triazine-2,4-dithiol-monosodium salt is weighed, and 500 ml of cyclohexane and water are mixed at a ratio of 1: 1. Into the solvent. Sufficient stirring was performed to prepare a dissolved dispersion treatment liquid. This treatment liquid was allowed to stand at room temperature for 1 hour and confirmed to be 23 ° C. The irradiated resin was put into this treatment liquid and left for one day and night (12 hours) with stirring. The liquid once treated here was discarded.

(3) Drying step The resin is dried. It vacuumed to about 10 Pa with the vacuum dryer, and dried at about 40 degreeC for 4 hours. When the resin was powder, the dispersion was filtered with filter paper to separate the resin powder and liquid. The resin powder on the filter paper was similarly evacuated to about 10 Pa with a vacuum dryer and dried at about 40 ° C. for 4 hours. As a result, a surface-modified resin was obtained.

Then, the resin in which the triazine thiol derivative is formed on the surface as described above is fixed to, for example, a solid metal surface. For example, when the resin is a resin film, it is bonded to a metal surface and then fixed by heat treatment. Further, for example, when the resin is a powder resin, it is bonded to the metal surface using a known cold spray or the like, and then fixed by heat treatment.

Thereby, as shown in FIG. 3, since these modified resins are bonded with the triazine thiol derivative, the triazine thiol derivative is chemically bonded to the solid substrate, and thus the bond strength is further improved. An improvement in fixing property is achieved. As a result, the metal substrate can be formed with a film coated with a resin film or the like for antifouling, rust prevention or releasability, and the function of the resin can be exhibited.

Next, examples of the present invention will be described.
[Example 1]
In Example 1, a resin film of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) having a thickness of 50 μm was used.
Then, with an electron beam irradiation apparatus (min-EB manufactured by Ushio Electric Co., Ltd.), an electron beam obtained at 60 kV, 200 μA, and an irradiation distance of 50 mm was irradiated in a vacuum for 5 minutes. The irradiation dose at this time was about 100 kGy.
Then, the resin irradiated with an electron beam was subjected to a 1: 1 mixed solution of 6-diallylamino-1,3,5-triazine-2,4-dithiol-monosodium salt with water and cyclohexane (1 g / l, temperature 23 ° C. ) For 8 hours and then dried to obtain a modified resin film.

[Example 2]
In Example 2, the PFA resin film was irradiated with X-rays. As the X-ray irradiation apparatus, an industrial X-ray apparatus (Rdioflex 250EGM) manufactured by Rigaku Corporation was used. Since it was irradiation in the atmosphere, in order to suppress the oxidation reaction after irradiation, a PFA film was put in a transparent bag prepared in advance, and was sucked and sealed with a vacuum sealer. A sample containing a PFA film was placed immediately below the X-ray irradiation apparatus at a position where the distance becomes 50 mm, and X-rays obtained at 5 mA at 200 kV were irradiated for 3 minutes. The irradiation dose at this time was about 60 kGy.
The irradiated film was mixed with a solvent (1 g / l, temperature 23 ° C.) of benzene of 6-diallylamino-1,3,5-triazine-2,4-dithiol-monosodium salt and water in a ratio of 1: 1. ) For 8 hours and then dried to obtain a modified resin film.

[Examples 3 to 5]
Example 3 used polyethylene as a resin, Example 4 used a polyimide resin, and Example 5 used an ethylene-tetrafluoroethylene copolymer. In Examples 3-5, all except resin were processed on the same conditions as Example 1.
[Examples 6 and 7]
In Example 6, 6-monoallylamino-1,3,5-triazine-2,4-monodithiol sodium salt was used as the triazine thiol derivative.
In Example 7, 6-diallylamino-1,3,5-triazine-2,4-dithiol disodium salt was used as the triazine thiol derivative.
In Examples 6 and 7, all treatments were performed under the same conditions as in Example 1 except for the triazine thiol derivative.

[Examples 8 to 10]
In Example 8, the irradiation dose was adjusted by changing the current value and the irradiation time of the electron beam irradiation apparatus, and the irradiation dose was set to 60 kGy. Example 9 was 150 kGy and Example 10 was 200 kGy. In Examples 8 to 10, all treatments were performed under the same conditions as in Example 1 except for the irradiation dose.
[Example 11]
In Example 11, the immersion treatment temperature of the dispersion was set to 35 ° C. All other conditions were the same as in Example 1.
[Examples 12 and 13]
In Example 12, the dispersion immersion time was 12 hours, and in Example 13, 24 hours. All other conditions were the same as in Example 1.

[Examples 14 to 16]
In Examples 14 to 16, a powder of tetrafluoroethylene / hexafluorinated polypyrene copolymer (FEP) having an average diameter D of D = 150 μm (particle size range: 100 to 200 μm) was used. Further, the powder to be modified was put into a transparent bag, evacuated to about 10 Pa, and sealed with a sealer.
In Example 14, the electron beam with one absorbed dose set to about 20 kGy was irradiated twice. Example 15 was irradiated four times. In Example 15, the irradiation was performed 8 times. The actually measured radiation absorption doses at this time were 37, 75, and 140 kGy, respectively.
Then, the resin irradiated with the electron beam was treated with 6-allylamino-1,3,5-triazine-2,4-dithiol-monosodium salt in water (0.5 g / l, temperature 23 ° C.) all day and night (12 hours). It was immersed and then dried to obtain a modified resin powder. Using this modified resin powder, a film was prepared by a cold spray method.
In cold spray, a high-pressure carrier gas supplied from helium is branched into two paths, and one carrier gas is supplied to a nozzle of a spray gun via a gas heater. The other carrier gas is fed to the powder feeder, and is supplied to the spray gun of the cold spray device together with the material powder as the carrier gas. The powder supply amount was adjusted to a supply amount of 3 g / min by measuring the powder falling weight per minute from the supplier. The pressure of the carrier gas (He gas was used in this experiment) was adjusted to a pressure of 0.41 MPa with a pressure regulator with the main stopper of the gas cylinder opened. Next, the supply pressure on the gas heater side, which is the other carrier gas supply path, was adjusted to 0.35 MPa, approximately 0.06 MPa lower than the carrier gas pressure. Thereafter, the gas temperature was set to 135 ° C. with a heater. The distance between the tip of the spray gun and the substrate was set to 10 mm, the gun traverse lateral speed was set to 50 mm / min, and the gun traverse longitudinal pitch was set to 1 mm, and sprayed onto a previously prepared aluminum (Al) substrate to obtain a cold spray coating.
The obtained cold spray film was left on a hot plate set at a temperature of 230 ° C. for 1 hour and subjected to a peeling test.

<Test example>
First, the following test was carried out on the above-mentioned examples together with the following Comparative Examples 1-11.
[Comparative Example 1]
In Comparative Example 1, 6-diallylamino-1,3,5-triazine-2,4-dithiol was used as the triazine thiol derivative. The other conditions were all treated under the same conditions as in Example 1.
[Comparative Examples 2 to 4]
In Comparative Example 2, the irradiation dose was adjusted by changing the current value and irradiation time of the electron beam irradiation apparatus, and the irradiation dose was set to 0 kGy. Comparative Example 3 was 20 kGy, and Comparative Example 4 was 250 kGy. In Comparative Examples 2 to 4, all treatments were performed under the same conditions as in Example 1 except for the irradiation dose.
[Comparative Examples 5 to 7]
Comparative Example 5 used ethanol as a solvent for the dispersion, Comparative Example 6 used benzene, and Comparative Example 7 used diethyl ether. All other processing was performed under the same conditions as in Example 1.
[Comparative Examples 8 and 9]
In Comparative Example 8, the immersion treatment temperature of the dispersion was 5 ° C., and Comparative Example 9 was 50 ° C. All other processing was performed under the same conditions as in Example 1.
[Comparative Example 10]
In Comparative Example 10, the immersion treatment time of the dispersion was 4 hours. All other processing was performed under the same conditions as in Example 1.
[Comparative Example 11]
In Comparative Example 11, a resin film of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) having a thickness of 50 μm and not subjected to irradiation treatment was used.

[Comparative Example 12]
In Comparative Example 12, the same coating as in Example 14 was used except that tetrafluoroethylene / hexafluorinated polypyrene copolymer (FEP) resin powder having an average particle size of 150 μm (100 to 200 μm) and not irradiated was used. .

First, with respect to Examples 1 to 16, together with Comparative Examples 1 to 11, qualitative analysis was performed and the elemental composition ratios of nitrogen (N) and sulfur (S) were calculated.
The elemental analysis is a qualitative analysis of whether or not nitrogen (N) and sulfur (S), which are constituent elements of the triazine thiol derivative, are detected on the surface of the modified resin. For qualitative analysis, X-ray photoelectron spectroscopy (XHI ULVAC-PHI PHI-5600) was used. The XPS measurement area was 800 μmφ, and the photoelectron extraction angle was 45 °. The treated resin was ultrasonically washed with methanol, and then rinsed and washed.

  The results are shown in FIG. In Examples 1 to 16, N and S caused by the triazine thiol derivative were detected, and in Comparative Examples 1 to 11, it was found not to be detected. In these examples, the resin surface has been modified with a triazine thiol derivative bonded thereto. That is, an element derived from a triazine thiol derivative is detected on the surface of the resin in which a resin irradiated with a quantum beam is immersed in a dispersion in which a triazine thiol derivative is dispersed. Was found to be bound.

Next, for Examples 1 to 13, a lamination adhesion experiment was performed together with Comparative Examples 1 to 11. In the lamination adhesion experiment, Examples 1 to 13 and Comparative Examples 1 to 11 were laminated and adhered to a metal substrate, and the tensile strength of the resin was measured in these test pieces. A stainless steel substrate (0.2 × 3 × 5 cm, degreased with acetone) was used as a metal substrate, a resin film was placed on the substrate, and the stainless steel substrate was overlaid with a chromium plated substrate and hot pressed. After applying a load of 50 kg / cm ² at 200 ° C. for 5 minutes with a hot press apparatus, an air-cooled substrate was prepared.

  In FIG. 5, the result of having measured the shear strength of the test piece which carried out the lamination | stacking adhesion experiment is shown. It can be seen that the modified resins according to Examples 1 to 13 are firmly fixed or adhered to the metal surface.

  Moreover, about Examples 14-16 and the comparative example 12, the peeling test was done. The test was repeated according to the following procedure. First, the substrate subjected to the cold spray coating treatment was left on a hot plate set and heated to 155 ° C. for 5 minutes. A thermosetting epoxy resin (NT-600 manufactured by Nitto Denko Corporation) was placed thereon and heated for 3 minutes. After 3 minutes, the substrate was taken out of the hot plate and air-cooled. When the temperature reached room temperature, the epoxy resin was taken out with an adhesive tape. These operations were performed until the epoxy resin was not peeled off.

  FIG. 6 shows the result of the peel test. In the modified resin powder which concerns on Examples 14-16, it turned out that a film | membrane is hard to peel and favorable fixing strength is acquired.

It is process drawing which shows the modification | reformation method of resin which concerns on embodiment of this invention. It is a figure which shows the outline of the electron beam irradiation apparatus used with the modification | reformation method of resin which concerns on embodiment of this invention. It is a figure which shows the effect | action of the modified resin which concerns on embodiment of this invention. It is a table | surface figure which shows the analysis result of the modified resin surface in the experiment which concerns on the Example of this invention. It is a table | surface figure which shows the sticking effect of the modified resin with respect to the solid base material in the experiment which concerns on the Example of this invention. It is a table | surface figure which shows the effect in the peeling test of the cold spray film by the modified resin powder with respect to the solid base material in the experiment which concerns on the Example of this invention.

Explanation of symbols

1 Electron Beam Irradiation Tube 2 Irradiation Chamber 3 Table W Resin

Claims (2)

The resin surface, irradiated with quantum beam, the resin was immersed in a dispersion obtained by dispersing the triazine thiol derivative, a method for modifying a resin surface of Ru bound to the triazine thiol derivative in the resin surface,
The triazine thiol derivative is selected from triazine dithiol derivatives represented by the following general formula:
[In the formula, R _{1, CH 2 = CHCH 2 -,} CH 2 = CH- (CH 2) 8 -, CH 2 = CH- (CH 2) 9 -, CH 2 = CH (CH 2) 4 COOCH 2 CH _2- , CH ₂ = CH (CH ₂ ) ₈ COOCH ₂ CH _2- , CH ₂ = CH (CH ₂ ) ₉ COOCH ₂ CH _2- , and R ₂ is CH ₂ = CHCH _2- , _{CH 2 = CH- (CH 2)} 8 -, CH 2 = CH- (CH 2) 9 -, CH 2 = CH (CH 2) 4 COOCH 2 CH 2 -, CH 2 = CH (CH 2) 8 COOCH 2 CH ₂ −, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —. M is an alkali composed of any one of Li, Na, K, and Ce. ]
The dispersion in which the triazine thiol derivative is dispersed is water or a solution obtained by mixing at least one of cyclohexane, benzene, carbon tetrachloride and diethyl ether in water,
A method for modifying a resin surface , wherein the dispersion liquid is set to 10 to 45 ° C., and the resin is immersed in the dispersion liquid for 8 hours or more . 2. The method for modifying a resin surface according to claim 1 , wherein an electron beam or X-ray is used as the quantum beam, and the irradiation dose is in the range of 30 to 200 kGy.