JP2010121143A - Post-processing agent of etching for resin-formed body, post-processing method using the same, and plating method for resin-formed body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new processing method capable of forming a plating layer having sufficient adhesiveness when executing the etching treatment by using an etching liquid containing manganate in the electroless plating for a resin-formed body, and to provide a processing agent used in the processing method. <P>SOLUTION: In the post-processing method of etching for a resin-formed body, the resin-formed body is etched by using the etching liquid containing manganate in a pre-processing step of the electroless plating to the resin-formed body, and the resin-formed body is brought into contact with the post-processing agent consisting of an aqueous solution containing a reducing compound and an amine compound. In a plating method for the resin-formed body, after executing the post-processing of the etching to the resin-formed body by the above-described post-processing method of etching, a catalyst for electroless plating is imparted to the resin-formed body, the electroless plating is executed, and as necessary, the electric plating is executed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a post-treatment agent used after an etching treatment with an etching solution containing a manganate, a post-treatment method using the post-treatment agent, and a plating method for a resin molded body by a treatment step including the post-treatment method.

  In recent years, resin molded bodies have been used as automobile parts for the purpose of reducing the weight of automobiles. For this purpose, for example, ABS resin, PC / ABS resin, PPE resin, polyamide resin and the like are used, and plating such as copper and nickel may be applied to give a high-class feeling and aesthetic appearance. Many.

  As a method of forming an electroplated film on a resin molded body, after degreasing and etching, neutralization and pre-dip are performed as necessary, and then a colloidal solution containing a tin compound and a palladium compound is used. A general method is to apply an electroless plating catalyst, perform an activation treatment (accelerator treatment) as necessary, and perform electroless plating and electroplating sequentially.

  In this case, for example, when an ABS resin is used as an object to be processed, a chromic acid mixed liquid composed of a mixed liquid of chromium trioxide and sulfuric acid is widely used as the etching processing liquid. However, the chromic acid mixture contains toxic hexavalent chromium, which has an adverse effect on the working environment. In addition, in order to treat wastewater safely, neutralization precipitation is performed after reducing hexavalent chromium to trivalent chromium ions. Therefore, complicated treatment is required for wastewater treatment. For this reason, it is desirable not to use an etching treatment liquid containing chromic acid in consideration of safety during work in the field and the environmental impact of wastewater.

As an etchant that can replace the chromic acid mixture, an etchant containing manganate as an active ingredient is known. As such an etchant, an alkaline etchant containing a permanganate and an alkali metal hydroxide (see Non-patent Document 1 below), an acidic etchant containing a permanganate and an inorganic acid (the following non-patent patent) Document 2) is known. However, when performing etching treatment of the resin molding using these etching solutions, when performing electroless plating after applying the catalyst, deposition failure of the electroless plating may occur. There are also known problems such as a manganese component being brought in and adversely affecting the deposition properties of electroless plating. Therefore, in order to be able to form a good electroless plating film by an etching process using an etching solution containing a manganate, an improvement in the processing process is desired.
Surface Technology Handbook, Surface Technology Association, pp.329, 1998 Electroless plating Fundamentals and applications, Electroplating workshop, pp.133, 1994

  The present invention has been made in view of the above-described state of the art, and its main purpose is to perform an etching process using an etching solution containing a manganate in an electroless plating process for a resin molded body. Furthermore, it is to provide a novel processing method capable of forming a plating layer having sufficient adhesion, and a processing agent usable in the processing method.

  The present inventor has intensively studied to achieve the above-described object. As a result, after performing an etching treatment using an etching solution containing manganate as an active ingredient on the resin molded body, by performing a post-treatment with a treating agent containing a reducing compound and an amine compound, The manganese salt adhering to the surface of the resin molding can be almost completely removed to prevent the manganese component from being brought into the catalyst solution. Furthermore, the amount of adsorption of the catalyst is increased, and a stable and excellent plating film is formed. I found out that it would be possible. The present invention has been completed as a result of further research based on these findings.

That is, the present invention provides a post-treatment agent used after an etching treatment with an etching solution containing the following manganate, a post-treatment method using the post-treatment agent, and a plating method for a resin molded body by a treatment step including the post-treatment method Is to provide.
1. The post-processing agent used after the etching process of the resin molding by the etching liquid containing a manganate consisting of the aqueous solution containing a reducing compound and an amine compound.
2. Furthermore, the post-processing agent of said claim | item 1 which consists of aqueous solution containing an inorganic acid.
3. Amine compound has the general _formula: (wherein, n is a number of _{1~5) H 2 N (CH 2} CH 2 NH) n H ethyleneamines represented by, polyethyleneimines, and the general formula:

(Wherein R ¹ is a propyl group or an aminopropyl group that may have a substituent on the nitrogen atom, and R ² is an propyl group, an aminopropyl group that may have a substituent on the nitrogen atom, or 3. A post-treatment agent according to item 1 or 2, which is at least one compound selected from the group consisting of propylamines represented by:
4). Item 4. The post-treatment agent according to Item 3, wherein the amine compound is a polyethylene imine having a number average molecular weight of 5,000 to 200,000.
5). Item 5. The post-treatment agent according to any one of Items 1 to 4, after performing an etching treatment on the resin molded body using an etching solution containing a manganate in a pretreatment step of electroless plating on the resin molded body. A method for post-processing the etching of the resin molded body, wherein the resin molded body is brought into contact with the resin molded body.
6). The etching solution containing manganate is a group consisting of 20 to 1200 g / L of inorganic acid, 0.01 to 40 g / L of manganate, and halogen oxo acid, halogen oxo acid salt, persulfate and bismuth acid salt. The post-processing method of said claim | item 5 which is the aqueous solution containing 1-200 g / L of at least 1 type of component chosen from.
7). A resin molded body characterized in that after the post-etching treatment for the resin molded body is performed by the method of item 5 or 6, an electroless plating catalyst is applied to the resin molded body, and then electroless plating is performed. Electroless plating method for.
8). A plating method for a resin molded article, wherein electroplating is performed after the electroless plating is performed by the method of Item 7 above.

  Hereinafter, the plating method for the resin molded body including the post-treatment process using the post-treatment agent of the present invention will be described in detail.

The object to be treated in the post-treatment agent of the present invention is a resin molded body. The type of resin is not particularly limited, and in particular, a good electroless plating film can be formed on various resin materials that have been conventionally etched with a mixed acid of chromic acid-sulfuric acid. For example, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a resin in which the butadiene rubber component of the ABS resin is replaced with an acrylic rubber component (AAS resin), and a butadiene rubber component in the ABS resin is replaced with an ethylene-propylene rubber component It is possible to form a good electroless plating film using a styrene resin such as resin (AES resin), acrylonitrile-styrene copolymer resin (AS), polystyrene resin (PS) or the like as an object to be treated. In addition, an alloyed resin of the styrene resin and polycarbonate (PC) resin (for example, an alloy resin having a PC resin mixing ratio of about 30 to 70% by weight) or the like can be suitably used. Furthermore, polyacrylonitrile resin (PAN), polycarbonate resin (PC), polyamide resin (PA), nonyl, polyphenylene ether resin, polyphenylene oxide resin and the like having excellent heat resistance and physical properties can be used as well.

  There are no particular limitations on the shape, size, etc. of the resin molded body, and it is possible to form a good plating film excellent in decorative properties, physical properties, etc., even on a large object to be processed having a large surface area. Such large resin products include radiator grills, wheel caps, medium- and small-sized emblems, door-handles and other automotive parts, electrical and electronic exterior parts, and faucets used around water. Game machine related products such as metal fittings and pachinko parts.

Etching treatment process In the present invention, the etching treatment is performed using an etching solution containing manganate as an active ingredient.

  Etching treatment liquid containing manganate as an active ingredient includes alkaline etching liquid containing permanganate and alkali metal hydroxide as active ingredients, and acidic etching liquid containing permanganate and inorganic acid as active ingredients. In the present invention, any of these known etching solutions can be used.

  For example, as the alkaline etching solution, an aqueous solution containing about 40 to 70 g / L permanganate such as potassium permanganate and sodium permanganate and about 10 to 30 g / L sodium hydroxide can be used. It is not limited to this.

  Examples of the acidic etching solution include about 0.1 to 50 g / L permanganate such as potassium permanganate and sodium permanganate, and 100 to 100 inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid. An aqueous solution containing about 600 g / L can be used, but is not limited thereto.

  Etching using these etching solutions may follow a known method.

  In the present invention, in particular, the inorganic acid is about 20 to 1200 g / L, the manganate is about 0.01 to 40 g / L, and the group consisting of halogen oxoacid, halogen oxoacid salt, persulfate, and bismuth acid salt. It is preferable to use an etching solution made of an aqueous solution containing about 1 to 200 g / L of at least one selected component. After performing an etching treatment on the resin molded body using such an etching solution, a catalyst for electroless plating is provided, and then electroless plating is performed to obtain a good electroless plating film having high adhesion. It becomes possible to form.

  Among the active ingredients in the etching solution described above, inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, carbonic acid, sulfurous acid, nitrous acid, phosphorous acid, boric acid, hydrogen peroxide, perchloric acid. Etc. can be used. Of these, sulfuric acid, hydrochloric acid and the like are particularly preferable. These inorganic acids can be used singly or in combination of two or more. The content of the inorganic acid needs to be about 20 to 1200 g / L, and preferably about 300 to 1000 g / L.

  Of the effective components in the etching solution, permanganate is particularly preferable as the manganate. The permanganate may be a salt in an aqueous solution, and specific examples thereof include sodium permanganate and potassium permanganate. Manganates can be used singly or in combination of two or more. The content of manganate is required to be about 0.01 to 40 g / L, and preferably about 0.1 to 10 g / L.

  Among the active ingredients in the etching solution, specific examples of halogen oxoacids include hypohalous acid, halous acid, halogen acid, perhalogen acid and the like. As the halogen oxoacid salt, the above-mentioned water-soluble salts of halogen oxoacids can be used. For example, sodium halogen oxoacid, potassium halogen oxoacid, etc. can be used. As the persulfate, water-soluble persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate can be used. Moreover, as bismuth acid salt, water-soluble bismuth acid salt, such as sodium bismutate and a potassium bismuthate, can be used. The halogen oxoacid, halogen oxoacid salt, persulfate and bismuth acid salt can be used singly or in combination of two or more. In particular, it is preferable to use at least one component selected from the group consisting of perhalogen acids such as perchloric acid, perbromic acid, and periodic acid, salts of the perhalogen acid, persulfates, and bismuth salts.

  In the etching solution described above, the content of at least one component selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuth acid salts needs to be about 1 to 200 g / L. Yes, preferably about 10 to 100 g / L.

  Preferable specific examples of the etching solution include at least one inorganic acid selected from the group consisting of sulfuric acid and hydrochloric acid, at least one manganate selected from permanganate, perchloric acid, perbromic acid, An aqueous solution containing at least one halogenoxoacid selected from the group consisting of iodic acid and salts thereof can be mentioned.

  In order to perform an etching process using the above-described etching solution, a surface to be processed of a resin molded body that is a processing target may be brought into contact with the etching solution. The specific method is not particularly limited, and any method that can sufficiently bring the surface of the surface to be processed into contact with the etching solution may be used. For example, a method of spraying the etching solution onto the object to be processed can be applied, but normally, a method of immersing the object to be processed in the etching solution enables efficient processing.

  The etching process conditions are not particularly limited, and may be determined appropriately according to the degree of the target etching process. For example, when performing an etching process by immersing an object to be processed in an etching solution, the temperature of the etching solution may be about 30 ° C. to 70 ° C., and the immersion time may be about 3 to 30 minutes.

  If the surface of the resin molded body, which is the object to be processed, is severely soiled, the degreasing process may be performed according to a conventional method prior to the etching process.

Etching post-treatment method In the present invention, after performing an etching treatment using an etching solution containing the above-described manganate as an active ingredient, a post-treatment agent comprising an aqueous solution containing a reducing compound and an amine compound as an active ingredient is used. Then, post-etching is performed.

  By this post-treatment, manganese adhering to the resin surface can be efficiently removed. As a result, it is possible to prevent manganese from being brought into the catalyst solution and improve the electroless plating deposition property, thereby forming a uniform and good electroless plating film. In particular, the etching treatment is performed using an etching solution composed of an aqueous solution containing at least one selected from the group consisting of the above-described inorganic acids, manganates, and halogenoxoacids, halogenoxoacid salts, persulfates, and bismuthates. When performing, by using the post-treatment agent of the present invention, not only manganese adhering to the resin surface but also halogen compounds can be almost completely removed, and the excellent performance of the above-described etching solution can be sufficiently obtained. It is possible to form a good electroless plating film having high adhesion and excellent uniformity.

  Furthermore, by including an amine compound in the post-treatment agent of the present invention, the amount of catalyst adsorbed on the surface of the resin molded body, which is the object to be treated, can be increased in the catalyst application step described later, and stable and good plating is achieved. A film can be formed. In particular, as a method for imparting a catalyst, a catalyst-accelerator method, that is, a method of performing an activation treatment after performing a catalyst treatment with an acidic mixed colloid solution (catalyst solution) containing palladium chloride and stannous chloride. In the case of adopting the above-described post-treatment agent, even if the palladium concentration in the catalyst liquid is low, the amount of adsorption of the catalyst can be increased, and the deposition of electroless plating is improved. Thus, it is possible to form a plating film having a good appearance by subsequent electroplating.

  Moreover, according to the post-treatment agent of the present invention, the removal of the manganese salt adhering to the resin surface and the surface adjustment for increasing the adhesion amount of the catalyst can be performed by a single treatment. Therefore, the pretreatment process is simplified.

  Examples of the reducing compound contained in the post-treatment liquid of the present invention include polyvalent metal compounds having a reducing action such as tin chloride, tin sulfate, iron chloride, and iron sulfate; fructose, maltose, lactose, fructose, maltose, lactose Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, benzaldehyde, cinnamaldehyde, perylaldehyde, etc .; ascorbic acid, ascorbic acid stearate, sodium ascorbate, L-ascorbic acid palmitate, L-ascorbic acid Ascorbic acids such as aeglucoside; hydrazines such as hydrazine, hydrazine sulfate, hydrazine hydrochloride, hydrazine carbonate, hydrazine hydrobromide, hydrazine dibromide; formic acid, acetic acid, butyric acid, aqua Monocarboxylic acids such as rillic acid, palmitic acid, oleic acid, glyoxylic acid and their salts; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, repargylic acid, sebacic acid Dicarboxylic acids such as maleic acid and salts thereof; aliphatic hydroxy acids such as lactic acid, tartaric acid and citric acid and salts thereof; hydroxylamines such as hydroxylamine sulfate, hydroxylamine hydrochloride and hydroxylamine phosphate; sulfurous acid, thio Examples thereof include sulfur-containing compounds such as sulfuric acid and hydrogen sulfide; iodine-containing compounds such as silver iodide, potassium iodide and sodium iodide. The above-mentioned reducing compounds can be used singly or in combination of two or more. In particular, tin chloride, tin sulfate, ascorbic acid, sodium ascorbate, hydrazine sulfate, hydrazine hydrochloride, hydroxylamine sulfate, hydroxylamine hydrochloride, thiosulfuric acid and the like are preferably used.

  The concentration of the reducing compound in the post-treatment liquid is preferably about 0.5 to 100 g / L, and more preferably about 5 to 30 g / L.

Examples of the amine compound contained in the post-treatment agent include ethyleneamines represented by the general formula: H ₂ N (CH ₂ CH ₂ NH) _n H (where n is a numerical value of 1 to 5). , Polyethyleneimines, and general formula:

(Wherein R ¹ is a propyl group or an aminopropyl group that may have a substituent on the nitrogen atom, and R ² is an propyl group, an aminopropyl group that may have a substituent on the nitrogen atom, or It is a hydrogen atom.) At least one compound selected from the group consisting of propylamines represented by:

  In the above general formula, the propyl group may be an n-propyl group or an isopropyl group. In the aminopropyl group that may have a substituent on the nitrogen atom, examples of the substituent include lower alkyl groups such as a methyl group.

  Among these amine compounds, examples of ethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

  Polyethyleneimines are water-soluble polymers obtained by polymerizing ethyleneimine, and those having a number average molecular weight of about 300 to 500,000 can be suitably used, and more preferably, the number average molecular weight is 5,000 to 200,000. Something about can be used.

  Examples of propylamines include propylamine, isopropylamine, diisopropylamine, diaminopropylamine, methylaminopropylamine, dimethylaminopropylamine and the like. Among these, particularly preferred amine compounds include propylamine, isopropylamine, diaminopropylamine and the like. These amine compounds can be used singly or in combination of two or more.

  In the present invention, it is particularly preferable to use polyethyleneimines having a number average molecular weight of about 5,000 to 200,000 as the amine compound. By using a post-treatment agent containing such an amine compound together with the reducing compound described above, it is possible to increase the amount of catalyst adsorbed on the resin surface at the same time as efficiently removing manganese adhering to the resin surface. The deposition property of electrolytic plating is improved, and it is possible to stably form a good plating film.

  The concentration of the amine compound is preferably about 0.01 to 50 g / L, and more preferably about 0.02 to 10 g / L.

  It is preferable to add an inorganic acid to the post-treatment agent of the present invention. Thereby, manganese adhering to the resin surface can be removed more efficiently.

  As the inorganic acid, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, nitrous acid, phosphorous acid, boric acid, hydrogen peroxide, perchloric acid, nitrogen peroxide and the like can be used. These inorganic acids can be used singly or in combination of two or more. In particular, it is preferable to use sulfuric acid, hydrochloric acid or the like.

  The concentration of the inorganic acid in the post-treatment liquid is preferably about 5 to 500 g / L, and more preferably about 30 to 100 g / L.

  The treatment method using the post-treatment liquid is not particularly limited as long as it can sufficiently bring the workpiece and the post-treatment liquid into contact with each other. Usually, according to the method of immersing the workpiece in the post-treatment liquid, efficient treatment is possible. In this case, for example, the temperature of the post-treatment liquid may be about 20 to 60 ° C., and the object to be processed may be immersed for about 1 to 10 minutes.

Catalyst application process After performing the above-described etching treatment and post-treatment, a catalyst for electroless plating is applied.

  The method for applying the electroless plating catalyst is not particularly limited, and a catalyst for electroless plating such as palladium, silver, or ruthenium may be applied according to a known method. As a method for applying the palladium catalyst, for example, a known method such as a so-called catalyst-accelerator method, a sensitizer-activating method, or an alkali catalyst method can be employed.

  Among these methods, in particular, the catalyst-accelerator method is a preferable method in that a plating film is easily deposited uniformly on a resin molded product.

  As the catalyst liquid, an acidic mixed colloidal aqueous solution containing palladium chloride and stannous chloride which are usually used can be used. For example, a mixed colloidal solution containing about 0.01 to 0.6 g / L of palladium chloride, about 1 to 50 g / L of stannous chloride, and about 100 to 400 ml / L of 35% hydrochloric acid can be used. As a treatment method using a catalyst liquid, for example, a method of immersing in a liquid at about 20 to 40 ° C. for about 1 to 10 minutes can be employed. After the catalyst treatment, activation treatment may be performed using an accelerator solution such as an aqueous sulfuric acid solution, an aqueous hydrochloric acid solution, or an aqueous alkali metal hydroxide solution according to a conventional method. About the concrete processing method of these methods, processing conditions, etc., what is necessary is just to follow a well-known method.

  In addition, before catalyst provision, according to a conventional method, a pre-dip treatment with a hydrochloric acid aqueous solution can be performed. Thereby, it is possible to prevent the pretreatment liquid from being brought into the catalyst application liquid.

  As the pre-dip treatment, for example, an object to be treated may be immersed in an aqueous solution containing about 20 to 300 ml / L of 35% hydrochloric acid at a liquid temperature of about 15 to 30 ° C. for about 0.5 to 3 minutes. It is not limited to.

Plating process After applying the catalyst by the above-described method, electroless plating can form an electroless plating film having good adhesion and excellent uniformity on the surface of the resin molded body. it can.

  As the electroless plating solution, any known self-catalyzed electroless plating solution can be used. Examples of the electroless plating solution include an electroless nickel plating solution, an electroless copper plating solution, an electroless cobalt plating solution, an electroless nickel-cobalt alloy plating solution, and an electroless gold plating solution.

  The conditions for electroless plating may be the same as known methods. Further, if necessary, two or more electroless plating films may be formed.

  Furthermore, electroplating may be performed after electroless plating. In this case, after electroless plating, if necessary, activation treatment may be performed with an aqueous solution of acid, alkali, etc., and then electroplating may be performed. The type of electroplating solution is not particularly limited, and may be appropriately selected from known electroplating according to the purpose.

  According to the above-described method, a plating film having very high adhesion strength and excellent uniformity can be formed on the resin molded body.

The following remarkable effects are exhibited by the plating method including the step of performing the post-treatment using the post-treatment agent of the present invention after performing the etching treatment on the resin molded body with the etchant containing the manganate. .
(1) When performing an etching treatment with a manganate-containing etchant that is a highly safe etching treatment agent, the residue due to the etchant is efficiently removed to form a plating film with excellent uniformity. Is possible. In addition, manganese can be prevented from being brought into the catalyst solution. Furthermore, the amount of catalyst adsorbed on the resin molded body, which is the object to be processed, increases, and a good plating film can be stably formed.
(2) By using the post-treatment agent of the present invention, it is possible to perform the removal of the residue with the etching solution and the surface adjustment for increasing the catalyst adsorption amount by a single treatment. For this reason, the pretreatment process for electroless plating is simplified.
(3) In particular, when the catalyst-accelerator method is employed as the catalyst application method, a plating film having excellent uniformity is formed on the resin molded body by using the post-treatment agent of the present invention containing an amine compound. can do.
(4) When an aqueous solution containing at least one component selected from the group consisting of inorganic acids, manganates, and halogen oxoacids, halogen oxoacid salts, persulfates and bismuth acid salts is used as an etching solution. In particular, a plating film having excellent adhesion can be formed.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
The processing steps described in Table 1 below using a flat plate (10 cm × 5 cm × 0.3 cm, surface area of about 1 dm ² ) of ABS resin (trade name: Psycolac 3001M, manufactured by UMG ABS Co., Ltd.) as an object to be processed. Then, the treatment was performed by an immersion method, and electroless plating and electroplating were performed. As the post-treatment agents, the treatment agents described in Table 2 below were used. In addition, between each process, it washed with water.

  After performing electroless copper plating and electrolytic copper plating according to the steps described in Table 1 using each of the post-treatment agents described above, the ratio of the electroplated film formed on the surface of the resin molded body that is the object to be treated is measured. Then, the deposition property of electroplating was evaluated. Further, after the catalyst application step, the amount of Pd adsorbed on the resin surface was measured by ICP emission spectroscopy. Furthermore, the surface resistance value (kΩ) of the resin surface after electroless copper plating was measured. The results are shown in Table 4 below.

  As is clear from the above results, in the pretreatment method including the step of performing an etching treatment using an etching solution containing a manganate, after the etching using an aqueous solution containing a reducing compound and an amine compound as active ingredients. By performing the treatment, a sufficient amount of catalyst can be adsorbed on the resin surface, and a uniform electroplating film can be formed.

  On the other hand, when a post-treatment agent containing only one of a reducing compound and an amine compound is used, the amount of catalyst adsorbed on the resin surface is insufficient, resulting in poor electroless plating deposition. The electrolytic copper plating film hardly precipitates.

Claims (8)

The post-processing agent used after the etching process of the resin molding by the etching liquid containing a manganate consisting of the aqueous solution containing a reducing compound and an amine compound. Furthermore, the post-processing agent of Claim 1 which consists of aqueous solution containing an inorganic acid. Amine compound has the general _formula: (wherein, n is a number of _{1~5) H 2 N (CH 2} CH 2 NH) n H ethyleneamines represented by, polyethyleneimines, and the general formula:

(Wherein R ¹ is a propyl group or an aminopropyl group that may have a substituent on the nitrogen atom, and R ² is an propyl group, an aminopropyl group that may have a substituent on the nitrogen atom, or The post-treatment agent according to claim 1, which is at least one compound selected from the group consisting of propylamines represented by: The post-treatment agent according to claim 3, wherein the amine compound is a polyethylene imine having a number average molecular weight of 5,000 to 200,000. The pretreatment agent according to any one of claims 1 to 4, after performing an etching process on the resin molded body using an etching solution containing a manganate in a pretreatment step of electroless plating on the resin molded body. A method for post-processing the etching of the resin molded body, wherein the resin molded body is brought into contact with the resin molded body. The etching solution containing manganate is a group consisting of 20 to 1200 g / L of inorganic acid, 0.01 to 40 g / L of manganate, and halogen oxo acid, halogen oxo acid salt, persulfate and bismuth acid salt. The post-treatment method according to claim 5, which is an aqueous solution containing 1 to 200 g / L of at least one component selected from the group consisting of: 7. A resin molded body comprising: after post-etching the resin molded body by the method according to claim 5 or 6, applying a catalyst for electroless plating to the resin molded body, and then performing electroless plating. Electroless plating method for. A plating method for a resin molded body, wherein electroplating is performed after performing electroless plating by the method of claim 7.