JP2006028484A - Resin surface treatment agent and resin surface treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin surface treatment agent and a surface treatment method using the same, by which a resin surface is activated, adhesion strength between a polyimide resin film and a metal wire can be improved, adhesion strength between a polyimide resin film and another resin can be improved, resulting in excellent productivity and low treatment cost. <P>SOLUTION: The resin surface treatment agent contains as an active ingredient at least one cerium compound selected from tetravalent and trivalent cerium compounds. The surface treatment method comprises causing the surface treatment agent containing as an active ingredient at least one cerium compound selected from tetravalent and trivalent cerium compounds to come into contact with the surface of a resin and then treating the resultant with an acidic aqueous solution. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a surface treatment agent for activating a resin surface and a resin surface treatment method.

  Among wiring boards used in electronic devices, flexible printed wiring boards have excellent characteristics such as bendability, thinness, and lightness. Among the flexible printed wiring boards, a two-layer structure in which polyimide as a base film and copper as a conductive layer are bonded without using an adhesive is excellent in heat resistance, and demand is increasing.

As a method for producing the base material of the flexible printed wiring board having the two-layer structure, there are a plating method, a sputtering method, a casting method, and a lamination method. Among these production methods, the plating method and the sputtering method have a feature that the degree of freedom of selection of polyimide is large and the production method is easy.
The plating method is a method in which a conductive thin seed layer is formed on a polyimide film by electroless plating, and then a copper conductor layer is formed by electrolytic plating. The sputtering method is a method in which a conductive thin seed layer is formed on a polyimide film by sputtering, and then a copper conductor layer is formed by electrolytic plating.

  As the plating method, a semi-additive construction method has been proposed. In this semi-additive method, in order to obtain adhesion between the electroless copper plating layer and the interlayer insulation material, conventionally, the surface of the insulation material is formed with a chemical including an alkaline permanganate solution, and the plating layer is formed on the uneven surface. Was forming.

  On the other hand, with recent downsizing and higher performance of electronic devices, the pitch between patterns has become narrower, and the signal frequency has also increased.

  If the electroless copper plating layer is formed on the uneven surface as described above, it is easy to generate copper etching residue when forming a pattern by etching. However, particularly when the pattern interval is narrow, the etching residue causes problems such as ion migration. There was a problem that was easily induced.

  In addition, when the clock frequency of the current flowing through the conductor increases, the current flows only near the surface of the conductor due to the skin effect. At this time, if there is unevenness at the interface between the copper plating layer and the insulating material, signal transmission is slow. There is also a problem of becoming.

  Polyimide resin is used as an insulating material for flexible substrates, and it is required that the polyimide base material be in close contact with a resin such as a bonding sheet or a photo solder resist. There is a problem that the material is limited because it is greatly different depending on the type of resin of the other party and does not adhere at all depending on the type.

  As a method for improving the adhesion with the resin by treating the copper surface, blackening treatment (formation of copper oxide with a strong alkaline aqueous solution) is sometimes performed. Problems are expected.

Furthermore, since polyimide is generally inferior in adhesion to metal, the substrate produced by the plating method or sputtering method has a problem that adhesion between the polyimide film, the seed layer and the copper layer is low. Therefore, Patent Document 1 below proposes that the polyimide surface be plasma-treated to improve the adhesion between the seed layer and the copper layer.
JP-A-3-56541

  However, the plasma processing requires an expensive processing apparatus and has a problem that productivity is low because it is necessary to perform processing in a vacuum atmosphere.

  In order to solve the problems of the prior art, the present invention provides a resin surface treatment agent having excellent productivity and low processing cost, and a resin surface treatment method using the same.

  The present invention is a resin surface treatment agent containing at least one cerium compound selected from tetravalent and trivalent as an active ingredient.

  The resin surface treatment method of the present invention is characterized in that a surface treatment agent containing at least one cerium compound selected from tetravalent and trivalent as an active ingredient is brought into contact with the surface of the resin.

  INDUSTRIAL APPLICABILITY The present invention can activate the resin surface, improve the adhesive strength between various resins such as polyimide resin film and metal wiring, and improve the adhesive strength between the resin film and other resins. In addition, it is possible to provide a resin surface treatment agent having excellent productivity and low processing cost, and a resin surface treatment method using the same.

  In the present invention, the adhesion strength of the resin surface can be improved in a smooth state by chemically treating the resin surface without roughening. Therefore, it is possible to obtain a resin surface particularly suitable for electronic materials corresponding to fine patterns and higher clock frequencies. In addition, it is possible to improve the adhesion between resins with low adhesion. The resin surface using the treatment agent of the present invention showed no change in the shape of the resin surface in the surface observation (× 3,500) in the SEM photograph.

  The present inventors have found that when a resin surface is brought into contact with an aqueous solution containing a tetravalent and / or trivalent cerium compound, the surface becomes excellent in adhesion to metals, particularly copper. Moreover, it discovered that this surface was excellent also in adhesiveness with other resin. Furthermore, it discovered that the surface treating agent of this invention was excellent in the solubility of the smear produced when a polyimide-type resin was pierced by a laser or a drill process.

That is, the present invention is achieved by the following configuration.
(1) A resin surface treatment agent comprising a tetravalent and / or trivalent cerium compound as an active ingredient.
(2) A surface treatment method in which a surface treatment agent containing a tetravalent and / or trivalent cerium compound as an active ingredient is brought into contact with the surface of the resin.

  Here, the active ingredient refers to a concentration range of 0.01 to 50% (mass%, the same applies hereinafter) or 0.00001 to 2 mol / kg in terms of cerium concentration.

  The present invention is described in detail below.

  The tetravalent cerium compound used in the present invention is a component capable of modifying the resin surface to a surface excellent in adhesion to other members such as metals and resins. It is also a component that dissolves resin smear. Specific examples thereof include hexanitratocerium (IV) salts such as diammonium cerium (IV) nitrate and potassium cerium nitrate (IV), tetraammonium cerium sulfate (IV), and cerium (IV) sulfate. . The cerium compound may be a hydrate such as tetraammonium cerium (IV) sulfate dihydrate, cerium sulfate (IV) tetrahydrate and the like. Two or more tetravalent cerium compounds may be used in combination.

  The trivalent cerium compound used in the present invention includes cerium acetate (III), ammonium cerium nitrate (III), cerium carbonate (III), cerium chloride (III), cerium fluoride (III), cerium nitrate (III), sulfuric acid It may be cerium (III), cerium (III) bromide, cerium (III) iodide, cerium (III) oxalate, cerium (III) perchlorate, cerium (III) sulfide and hydrates thereof. . Two or more of the trivalent cerium compounds may be used in combination.

  Of course, a tetravalent cerium compound and a trivalent cerium compound may be used in combination.

  The surface treatment agent of the present invention is preferably a solution of a tetravalent and / or trivalent cerium compound. The solvent is preferably water, but can be used without particular limitation as long as it can dissolve tetravalent and / or trivalent cerium compounds such as alcohol.

  Hereinafter, the case where the surface treatment agent of the present invention is a preferred form of a solution will be described as an example.

  The total concentration of tetravalent and / or trivalent cerium compounds in the surface treatment agent is preferably 0.01 to 50% by mass, and more preferably 0.1 to 30% by mass. If the concentration is less than 0.01% by mass, the reactivity with the resin tends to decrease, and if it exceeds 50% by mass, it becomes difficult to dissolve. The case where the cerium compound of the present invention is expressed in terms of effective concentration mol / kg in an aqueous solution will be described. The range of the cerium concentration in this case is preferably an effective concentration: 0.00001 to 2 mol / kg. If it is less than 0.00001 mol / kg, it is not effective, and if it is more than 2 mol / kg, it will not dissolve unless it is heated, and even if dissolved, the stability is very poor. The preferred concentration is in the range of 0.0001 to 1.5 mol / kg, and if it is less than 0.0001 mol / kg, it takes time until the effect is obtained, and the effect and the improvement in adhesiveness are somewhat insufficient, and 1.5 If more, heating is required. A more preferred concentration is in the range of 0.001 to 1 mol / kg. If it is less than 0.001 mol / kg, there is an effect, but it takes a long time. If it is more than 1, it tends not to be completely dissolved unless heated. Optimal concentration: 0.01 to 0.9 mol / kg.

  Various additives may be further added to the surface treatment agent of the present invention, for example, acids such as nitric acid, sulfuric acid, perchloric acid, formic acid, acetic acid for improving the stability of cerium compounds, and polyimide-based compounds. You may mix | blend the surfactant etc. which improve the wettability and reactivity with respect to resin and other resin.

  The concentration range of the strong acid is not particularly limited, and the effect of stabilizing the cerium compound is improved depending on the amount added, but is usually 50% or less, preferably 5 to 30%. If the concentration is too high, the metal is easily eroded when the material to be treated is a material in which a resin and a metal coexist.

  The surface treating agent of the present invention can be easily adjusted by dissolving each of the above components in a solvent such as water. The water is preferably water from which ionic substances such as ion exchange water and impurities have been removed.

  The resin to be treated with the surface treating agent of the present invention may be any resin. Preferred resins include polyimide, epoxy, cyanate, acrylic, acrylic-epoxy, acrylic-butadiene-styrene (ABS), aramid, polyvinyl chloride (PVC), polypropylene (PP), and polycarbonate. (PC), urethane, polyethylene (PE), polyamide, and the like. Among these, it is particularly preferable to use a polyimide resin. There is no particular limitation on the polyimide resin, for example, polypyromellitic imide, polybiphenylimide, polyketone imide, polyamide imide, polyester imide, polyether imide, polyamide ester imide, polyimidopyrolone imide, polyhydanton imide, polyoxazole imide Any resin having an imide structure such as cyanate-modified bismaleimide or silicone-modified polyimide may be used.

  When the polyimide resin surface is treated with the surface treatment agent of the present invention, the wettability is improved by treating the polyimide resin surface with an alkaline aqueous solution in which sodium hydroxide, potassium hydroxide, monoethanolamine or the like is dissolved in advance. It is preferable.

  As a method of bringing the surface treatment agent of the present invention into contact with the resin surface, for example, a spray method, a shower method, an immersion method, or the like is used.

  Although there is no limitation in particular in the conditions at the time of making a surface treating agent and the resin surface contact, the temperature of a surface treating agent is preferable 20-50 degreeC, and 1-30 minutes are preferable for contact time.

  Since the residue of the cerium compound tends to adhere to the resin surface after the resin surface is treated with the surface treating agent of the present invention, it is preferable to dissolve and remove them with an acidic aqueous solution, followed by washing with water and drying.

  Basically, trivalent cerium compounds have the same effect as tetravalent, but trivalent cerium has the advantage that it is difficult to leave a residue on the resin surface after surface treatment. Therefore, when trivalent cerium is used, it is not necessary to perform post-treatment with an acid.

  Examples of the acidic aqueous solution include aqueous solutions of sulfuric acid, hydrochloric acid, nitric acid and the like. The concentration of the acidic aqueous solution is preferably about 0.01 to 50%.

  The conditions for the treatment with the acidic aqueous solution are not particularly limited, but it may be usually immersed at 20 to 50 ° C. for 2 to 30 minutes.

  The resin treated with the surface treating agent of the present invention has improved adhesion to other members such as metals, resins, ceramics and glass. Examples of the metal include an electroless plating film such as copper, nickel / chromium alloy, and aluminum, a sputtering film, and a vapor deposition film. Examples of the resin include phenol resin, epoxy resin, heat-resistant epoxy resin, cyanate-modified bismaleimide resin, silicon carbide resin, polyphenylene ether, polyimide resin, and liquid crystal polymer.

Preferred combinations are as follows.
Resin and metal: Polyimide resin-copper, epoxy resin-copper, cyanate resin-copper, aramid resin-copper, ABS resin-nickel resin-resin: polyimide resin-epoxy resin, polyimide resin- (acrylic / epoxy) resin Preferred resin For example, polyimide, epoxy, cyanate, acrylic (acryl-epoxy), ABS, and aramid resin.

Examples of specific uses of each combination include the following.
(1) Epoxy resin or cyanate resin-copper An interface between an insulating layer (epoxy resin or cyanate resin) of a multilayer printed wiring board and a conductive layer (copper). Examples of the multilayer printed wiring board include a substrate in which a glass fiber fabric is impregnated with an epoxy resin and a substrate in which an aramid fiber nonwoven fabric is impregnated with an epoxy resin.
(2) Polyimide resin-epoxy resin or polyimide resin or cyanate resin Bonding for bonding the polyimide substrate and the upper polyimide substrate when laminating the interface between the solder resist (epoxy) and the polyimide substrate and the multilayer printed wiring board Interface with sheet (epoxy, polyimide, cyanate) (3) Epoxy resin-acrylic resin or acrylic-epoxy resin Solder resist and marking ink (acrylic, acrylic-epoxy) for marking printing on the surface of solder resist (epoxy) (4) Epoxy resin-epoxy resin (5) Interface between solder resist (epoxy) surface and mold resin (epoxy)

  The surface treating agent of the present invention is useful, for example, for improving adhesiveness with a conductive layer of a flexible wiring board having a two-layer structure in which a conductive layer is formed on a polyimide resin film. Moreover, it is useful for improving adhesiveness with an adhesive of a flexible wiring board having a three-layer structure in which a conductive layer is formed on a polyimide resin film via an adhesive. Moreover, it is useful for improving the adhesiveness between the polyimide resin layer and the conductive layer of the multilayer flexible wiring board in which a plurality of polyimide resin layers and conductive layers are alternately laminated. Further, it is useful for improving the adhesion with an underfill agent when a semiconductor element on which a protective film made of polyimide resin is formed is directly mounted on a printed wiring board. Further, it is useful for improving the adhesion with an etching resist when coating an etching resist for forming a via hole on a polyimide resin substrate. Moreover, it is useful for improving the adhesiveness with a cover lay of a polyimide resin substrate such as a flexible printed wiring board or a flex / rigid printed wiring board. Further, it is useful for improving the adhesion with a solder resist that protects the surface of the wiring board and a bonding film that is an interlayer insulating resin of a multilayer flexible wiring board. In addition, the present invention can also be applied to a wiring substrate in an image display device such as a substrate of a liquid crystal display device or an electroluminescence substrate.

  The surface treating agent of the present invention is also useful for removing smears produced when various resins such as polyimide are drilled by laser or drilling.

  FIG. 1 is a schematic cross-sectional view in which a surface 1 of a resin 1 in one embodiment of the present invention is activated, electroless copper plating 3 is applied to the activated surface, and electrolytic copper plating 4 is applied to the surface.

(Examples 1-7 and Comparative Examples 1-2)
In this example, various cerium compounds were used to test adhesion to a resin.

  A polyimide film having a thickness of 25 μm (trade name “Kapton 100EN” manufactured by Toray DuPont) was immersed in a 5% aqueous sodium hydroxide solution for 5 minutes and then washed with water. The obtained film was immersed in a treatment solution having the composition shown in Table 1 at 50 ° C. for 5 minutes and then washed with water. Subsequently, it was immersed in 30% sulfuric acid aqueous solution for 5 minutes, washed with water and dried.

  Electroless copper plating was performed on one side of the treated polyimide film to form a copper film having a thickness of 0.15 μm. Next, electrolytic copper plating was performed to form a copper film having a total thickness of 35 μm, and then heated at 150 ° C. for 30 minutes. In addition, the heating after the plating is a treatment for stabilizing the crystal structure of the copper film.

  Comparative Example 1 is a case where the cerium compound concentration is low, and Comparative Example 2 is an example where no cerium compound is used.

  Subsequently, the strength when peeling the copper plating film from the polyimide film was measured in accordance with JIS C 6481. The results are shown in Table 1.

  As described above, it was confirmed that the sample of this example had high strength when the copper plating film was peeled off from the polyimide film, and the adhesiveness was improved.

(Examples 8 to 11 and Comparative Example 3)
In this example and comparative example, an adhesion test between an acrylic / epoxy resin and an acrylic resin was performed.

  Examples 8 to 11 in which a copper foil having a thickness of 18 μm is coated on both sides with an acrylic / epoxy resin (solder resist manufactured by Taiyo Ink Manufacturing Co., Ltd .: PSR-4000Z26) on one surface of a glass cloth epoxy resin impregnated copper clad laminate Prepared as.

  These examples were immersed in each treatment solution in Table 2 for 1 minute at 40 ° C., then washed with water and dried, and UV curable marking ink (UVR-110WN121 manufactured by Taiyo Ink Co., Ltd.) was applied to the top surface of the acrylic epoxy resin and exposed. It was exposed (exposure amount 1200 to 1300 mj) with a machine (Nanotech ES-20m) and UV cured. After UV curing, heat treatment was further performed at 150 ° C. for 10 minutes.

  As comparative example 3, what changed the composition of the liquid immersed after application of acrylic epoxy resin to the processing liquid of comparative example 3 of Table 2 was prepared.

  Thereafter, a cross-cut (2 mm square) tape peeling test (method based on JIS C5012) was performed. The results are shown in Table 2.

  Evaluation criteria in Table 2: No-good with peeling and good with no peeling.

  As is clear from Table 2, Examples 8 to 11 were not peeled off from the acrylic epoxy resin and the acrylic resin.

(Examples 12 to 16 and Comparative Examples 4 to 8)
This experiment tested the adhesion between epoxy resin, cyanate resin, aramid resin and copper.

  Thermo-compression bonding of three types of epoxy resin sheets 1 to 3 having a thickness of 40 μm, a cyanate resin sheet, and an aramid resin sheet on one surface of the same copper-clad laminate (resin sheet support) as in Examples 8 to 11 above, These copper-resin laminates were immersed in a 5% aqueous sodium hydroxide solution for 5 minutes and then washed with water.

Thereafter, each laminate was immersed in a treatment solution having the following composition at 50 ° C. for 5 minutes, washed with water, then immersed in a 30% aqueous sulfuric acid solution for 5 minutes, then washed with water and dried to give Examples 12 to 16.
Treatment liquid: 5.64% by mass of cerium (III) nitrate (0.1 mol / kg as cerium concentration)
Nitric acid 6.7% by mass
Ion exchange water remaining

  The three types of epoxy resin sheets are obtained by forming resins having different types and blending amounts in the form of sheets.

  On the other hand, the copper-resin laminated body which heat-pressed the said 3 types of epoxy resin sheet, cyanate resin, and the aramid resin sheet to the copper clad laminated body similarly was prepared as Comparative Examples 4-8.

  Electroless copper plating is performed on one side of the laminates of the examples and comparative examples to form a copper film with a thickness of 0.15 μm, and then a copper film with a total thickness of 35 μm is formed by electrolytic copper plating, at 150 ° C. for 30 minutes. Heated. Table 3 shows the results of visual observation and evaluation of the state of the resin side surface of each of these laminates after plating formation.

  Evaluation criteria in Table 3: No-good with peeling and good with no peeling.

  As is clear from Table 3, Examples 12 to 16 were not peeled between various resins and copper.

(Examples 17-18 and Comparative Examples 9-10)
This experiment is an adhesion test between a polyimide resin and an epoxy resin.

The same polyimide film as in Examples 1 to 7 was immersed in a 5% aqueous sodium hydroxide solution for 5 minutes and then washed with water. The obtained film was immersed in a treatment solution having the following composition at 50 ° C. for 5 minutes, washed with water, then immersed in a 30% aqueous sulfuric acid solution for 5 minutes, washed with water and dried.
Treatment liquid: cerium (III) nitrate 5.64% by mass (cerium concentration 0.1 mol / kg)
Nitric acid 6.7% by mass
Ion exchange water remaining

  An epoxy resin sheet was thermocompression bonded to one side of the obtained film and an untreated polyimide film as a comparative example to form a polyimide-epoxy resin laminated sheet.

  Of these laminated sheets, the treated film laminates were Examples 17 and 18, the untreated film laminated sheets were Comparative Examples 9 and 10, and a cross-cut (2 mm square) tape peel test was performed in the same manner as in Example 8. Table 4 shows the results of performing (method conforming to JIS C5012) and evaluating the results.

  Evaluation criteria in Table 4: No-good with peeling and good with no peeling.

  As apparent from Table 4, Examples 17 to 18 were not peeled off from the polyimide resin and the epoxy resin.

(Example 19 and Comparative Example 11)
This experiment tested ABS-nickel adhesion.

  An ABS molded product (10 × 10 cm 2 cm thick plate) was immersed in a 5% aqueous sodium hydroxide solution for 5 minutes and then washed with water.

Thereafter, it was immersed in a treatment solution having the following composition at 50 ° C. for 5 minutes, washed with water, then immersed in a 30% sulfuric acid aqueous solution for 5 minutes, then washed with water and dried to give Example 19.
Treatment liquid: 5.64% by mass of cerium (III) nitrate (0.1 mol / kg as cerium concentration)
Nitric acid 6.7% by mass
Ion exchange water remaining

  This ABS molded product is immersed in a solution consisting of palladium chloride, stannous chloride and hydrochloric acid for 2 minutes, then treated with sulfuric acid at 30 ° C. for 3 minutes, and then a nickel plating layer having a thickness of 1 μm is formed by electroless nickel plating. did.

  On the other hand, the same ABS molded product as in Example 19 that was not subjected to the above treatment was prepared as Comparative Example 20 and treated in the same manner as in Example 19 except that it was immersed in the above treatment solution to form an electroless nickel plating layer. .

  Table 5 shows the results of a cross-cut (2 mm square) tape peeling test (method conforming to JIS C5012) performed on the nickel plating surface in the same manner as in Example 8 after plating formation.

  Evaluation criteria in Table 5: No-good with peeling and good with no peeling.

  As is clear from Table 5, in Example 19, there was no peeling between ABS and nickel.

  INDUSTRIAL APPLICABILITY The present invention is useful in fields such as flexible printed wiring boards, fiber-reinforced resin-impregnated substrates and metal wiring, resins, and resin films and metal wiring that require improved adhesive strength.

FIG. 1 is a schematic cross-sectional view in which a resin surface in one embodiment of the present invention is activated, electroless copper plating is applied to the activated surface, and electrolytic copper plating is applied to the surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin 2 Surface treatment surface of resin 3 Electroless copper plating 4 Electrolytic copper plating

Claims (18)

  A resin surface treating agent comprising at least one cerium compound selected from tetravalent and trivalent as an active ingredient.   The resin surface treating agent according to claim 1, which is a solution containing at least one cerium compound selected from tetravalent and trivalent.   The resin surface treatment agent according to claim 2, wherein the solution is an aqueous solution.   The resin surface treating agent according to claim 2 or 3, wherein the concentration of at least one cerium compound selected from tetravalent and trivalent in the solution is in the range of 0.01 to 50 mass%.   The resin surface treating agent according to claim 2 or 3, wherein the concentration of at least one cerium compound selected from tetravalent and trivalent in the solution is in the range of 0.00001 to 2 mol / kg in terms of cerium concentration.   The resin surface treatment agent according to any one of claims 1 to 5, wherein the tetravalent cerium compound is at least one of hexanitratocerium (IV) salt, tetraammonium cerium sulfate, and cerium sulfate.   Trivalent cerium compounds include cerium acetate (III), ammonium cerium nitrate (III), cerium carbonate (III), cerium chloride (III), cerium fluoride (III), cerium nitrate (III), cerium sulfate (III), A cerium (III) bromide, a cerium (III) iodide, a cerium (III) oxalate, a cerium (III) perchlorate, a cerium (III) sulfide, and at least one of these hydrates. The resin surface treating agent according to any one of 5.   The resin surface treating agent according to any one of claims 1 to 7, wherein the resin is at least one of polyimide, epoxy, cyanate, acrylic, ABS, aramid, and a mixture thereof.   A resin surface treatment method comprising contacting a surface treatment agent containing at least one cerium compound selected from tetravalent and trivalent as an active ingredient on the surface of a resin.   The resin surface treatment method according to claim 9, wherein the surface treatment agent is a solution.   The resin surface treatment method according to claim 10, wherein a solution containing a tetravalent cerium compound is brought into contact with the surface of the resin and then treated with an acidic aqueous solution.   The resin surface treatment method according to claim 10 or 11, wherein the surface of the resin is treated with an alkaline aqueous solution before contacting with a solution containing at least one cerium compound selected from tetravalent and trivalent.   The resin surface treatment method according to any one of claims 10 to 12, wherein the solution containing at least one cerium compound selected from tetravalent and trivalent is an aqueous solution.   The resin surface treatment method according to claim 10, wherein the concentration of at least one cerium compound selected from tetravalent and trivalent in the solution is in the range of 0.01 to 50 mass%.   The resin surface treatment according to any one of claims 10 to 13, wherein the concentration of at least one cerium compound selected from tetravalent and trivalent in the solution is in the range of 0.00001 to 2 mol / kg in terms of cerium concentration. Law.   The resin surface treatment method according to claim 9, wherein the tetravalent cerium compound is at least one of hexanitratocerium (IV) salt, tetraammonium cerium sulfate, and cerium sulfate.   Trivalent cerium compounds include cerium acetate (III), ammonium cerium nitrate (III), cerium carbonate (III), cerium chloride (III), cerium fluoride (III), cerium nitrate (III), cerium sulfate (III), 9. Cerium (III) bromide, cerium (III) iodide, cerium (III) oxalate, cerium (III) perchlorate, cerium (III) sulfide and at least one of these hydrates The resin surface treatment method according to any one of 15.   The resin surface treatment method according to any one of claims 9 to 17, wherein the resin is at least one of polyimide, epoxy, cyanate, acrylic, ABS, aramid, and a mixture thereof.

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