KR20190137146A - Composition for pretreatment of electroless plating, pretreatment method for electroless plating, electroless plating method - Google Patents

Abstract

The present invention provides an electroless plating pretreatment composition, a pretreatment method, and an electroless plating method that can exhibit high plating precipitation and reduce the number of steps without using harmful chromic acid and expensive palladium. do. The present invention provides a composition for pretreatment of electroless plating comprising 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions.

Description

Composition for pretreatment of electroless plating, pretreatment method for electroless plating, electroless plating method

The present invention relates to a composition for pretreatment of electroless plating, a pretreatment method for electroless plating, and an electroless plating method.

In recent years, resin molded bodies have been used as automobile parts for the purpose of lightening automobiles. For this purpose, for example, ABS resins, PC / ABS resins, PPE resins, polyamide resins, and the like are used as the resin molded bodies. In order to impart high quality and aesthetics, plating of copper or nickel is performed. Moreover, also as a method of providing a conductive circuit to a resin substrate and forming a conductor circuit, the method of forming a plating film, such as copper, on a resin substrate is performed.

As a general method of forming a plating film on resin materials, such as a resin substrate and a resin molded object, after roughening the surface of a resin material by the etching process with chromic acid, it neutralizes and pre-dips as needed, Subsequently, using a colloidal solution containing a tin compound and a palladium compound, a catalyst for electroless plating is applied, and then an activation treatment (accelerator treatment) for removing tin is performed to sequentially perform electroless plating and electroplating. The method is done.

However, in the above-described method, since chromic acid is used, there is a problem that it is harmful to the environment and human body. In addition, since expensive palladium is used to impart a catalyst, there is a problem that the cost is high. Moreover, after performing an etching process process, it is necessary to perform a catalyst addition process further, and there exists a problem that a process increases.

As a method of forming a plating film on a resin material, a physical solution containing a metal activator molecular species is etched in contact with a component to be plated, and brought into contact with a solution of a reducing agent capable of reducing the metal activator molecular species, and the part is electroless The method of metal plating by contacting with the plating solution is proposed (refer patent document 1).

However, in the method of patent document 1, there exists a room for examination about the component of an activator molecular species, and there exists a problem that formation of a plating film is not enough.

Therefore, development of an electroless plating pretreatment composition, a pretreatment method, and an electroless plating method that can exhibit high plating precipitation and reduce the number of steps without using harmful chromic acid and expensive palladium are possible. It is required.

Patent Document 1: Japanese Patent No. 4198799

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is possible to exhibit high plating precipitation properties without using harmful chromic acid and expensive palladium, and to further reduce the number of steps. It is an object to provide a method and an electroless plating method.

The present inventors earnestly studied to achieve the above object, and as a result, the composition for pretreatment of electroless plating containing 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions, pretreatment method and electroless plating According to the method, it has been found that the above object can be achieved, and the present invention has been completed.

That is, the present invention relates to a composition for pretreatment of the following electroless plating, a pretreatment method and an electroless plating method.

1. A composition for pretreatment of electroless plating comprising 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions.

2. The composition for pretreatment of electroless plating according to item 1, wherein the manganese valence of the manganese ions is 3 or more.

3. The composition for pretreatment as described in item 1 or 2 whose pH is 2 or less.

4. As a pretreatment method of electroless plating of resin material,

It has a process 1 which makes the to-be-processed surface of the said resin material contact the composition for pretreatment,

The pretreatment composition contains 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions,

A method for pretreatment of electroless plating, characterized by the above-mentioned.

5. As electroless plating method of resin material,

(1) Process 1 which makes the to-be-processed surface of the said resin material contact the composition for pretreatment, and

(2) it has a process 2 which makes the to-be-processed surface of the said resin material contact an electroless plating liquid,

The pretreatment composition contains 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions,

Electroless plating method characterized in that.

6. The electroless plating method according to item 5, wherein the electroless plating solution contains a reducing agent that exhibits catalytic activity with respect to silver.

According to the composition for pretreatment of electroless plating of the present invention, high plating precipitation can be exhibited in electroless plating in a later step without using harmful chromic acid and expensive palladium. In addition, according to the composition for pretreatment of electroless plating of the present invention, it is not necessary to perform the etching step and the catalyst applying step separately, so that the process at the time of performing electroless plating can be reduced.

In addition, according to the electroless plating pretreatment method of the present invention, since the surface to be treated of the resin material is brought into contact with the composition for pretreatment, the surface to be treated can be etched and a silver catalyst can be given to the surface to be treated. The surface to be treated of the material can be easily processed, and the pretreatment step can be reduced.

In addition, according to the electroless plating method of the present invention, in the pretreatment step, the surface to be treated of the resin material is brought into contact with the composition for pretreatment, whereby the surface to be treated is etched, and a silver catalyst can be given to the surface to be treated. Since the catalyst provision process and the accelerator treatment process become unnecessary, the to-be-processed surface of a resin material can be processed easily, and the process at the time of electroless plating can be reduced.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

One. Electroless  Composition for pretreatment of plating

The electroless plating pretreatment composition (hereinafter also simply referred to as "pretreatment composition") of the present invention contains 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions. Since the composition for pretreatment of this invention contains a specific amount of manganese ion and a specific amount of monovalent silver ion, the fall of the etching force with respect to the to-be-processed surface of a resin material is suppressed, and provision of a catalyst becomes enough.

For example, in the composition for pretreatment containing manganese ions and palladium ions, the etching power of manganese ions falls by containing palladium ions. In addition, in the composition for pretreatment containing chromic acid and silver ions, precipitation of silver chromic acid (Ag ₂ CrO ₄ ), which is an insoluble precipitate, is generated in the composition, and silver ions are discharged out of the system, and the provision of catalyst is insufficient. .

On the other hand, since the composition for pretreatment of this invention contains a manganese ion and monovalent silver ion, after contacting the to-be-processed surface of a resin material, the to-be-processed surface is contacted with an electroless plating liquid, and adhesiveness is favorable to a to-be-processed surface. A plating film can be formed.

In addition, since the composition for pretreatment of this invention contains manganese ion and monovalent silver ion, since the process and the process of a process can be performed simultaneously by contacting the to-be-processed surface of a resin substrate, a catalyst provision process can be skipped. Become.

In addition, the composition for pretreatment of this invention does not need to use a palladium-tin colloidal solution like the conventional catalyst provision process, and the activation process (accelerator process) process for removing tin can also be skipped.

That is, according to the composition for pretreatment of this invention, high plating precipitation property can be exhibited in the electroless plating in a post process, without using harmful chromic acid and expensive palladium. In addition, according to the composition for pretreatment of electroless plating of the present invention, since the etching step and the catalyst applying step do not need to be performed separately, and the accelerator treatment step does not need to be performed, the process for electroless plating is greatly shortened. do.

(Manganese ions)

Manganese ions are not particularly limited as long as they have an oxidizing power. 3 or more are preferable, as for the valence of manganese of manganese ion, 4 or more are more preferable, and 7 is still more preferable. For example, the manganese ions contained in the composition for pretreatment may be in the state of manganese ions of a metal ion alone such as trivalent manganese ions and tetravalent manganese ions, or in the state of manganese ions such as permanganate ions which are manganese ions of seven valent manganese. good. Among them, tetravalent manganese ions and permanganate ions are preferable, and permanganate ions are more preferable from the viewpoint of more excellent etching power. In addition, divalent manganese ions do not have an oxidizing power, and even though they are used alone, etching of the surface of the resin material does not proceed, but may be used in combination with manganese 3 or more manganese ions.

Manganese ions may be used individually by 1 type, and may use 2 or more types together.

The manganese salt for imparting manganese ions to the pretreatment composition is not particularly limited, and manganese sulfate (II), manganese phosphate (III), manganese oxide (IV), sodium permanganate (VII), potassium permanganate (VII), and the like can be given. Can be. Among these, manganese phosphate (III), manganese oxide (IV), sodium permanganate (VII), and potassium permanganate (VII) are preferable, and sodium permanganate (VII) is preferable from the point which can provide manganese ion which is more excellent in etching power. , Potassium permanganate (VII) is more preferred.

Manganese may be used individually by 1 type, and may use 2 or more types together.

In the composition for pretreatment of the present invention, the content of manganese ions is 10 mg / L or more. When content of manganese ion is less than 10 mg / L, a resin material cannot fully be etched and the adhesiveness of the film formed by electroless plating falls. 10 mg / L-100 g / L are preferable, as for content of manganese ion, 100 mg / L-50 g / L are more preferable, 0.2 g / L-30 g / L are more preferable, 0.5 g / L-15 g / L are especially preferable, and 0.5 g / L-10 g / L is the most preferable. By making the minimum of content of manganese ion into the said range, the etching power of the composition for pretreatment improves further. Moreover, by making the upper limit of content of manganese ion into the said range, generation | occurrence | production of the precipitation of manganese dioxide in the composition for pretreatment is further suppressed, and bath stability further improves.

(Silver ions)

The silver ion which the composition for pretreatment of this invention contains is monovalent silver ion. The silver salt for imparting monovalent silver ions is not particularly limited as long as it is capable of imparting stable monovalent silver ions in the bath when dissolved in the pretreatment composition, and the counterion forming the silver salt does not adversely affect manganese ions. Do not. Specifically, silver sulfate (I), silver nitrate (I), and silver oxide (I) are mentioned. Among these, silver nitrate (I) is preferable because of its high solubility and easy industrial use. In addition, the plating of resins formed by resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene resin and polycarbonate (PC) resin, and the like that plating is difficult to deposit is further improved. Since sulfuric acid property is favorable and the adhesiveness of a plating film is hard to fall further, silver sulfate (I) is preferable.

Silver salt may be used individually by 1 type, and may use 2 or more types together.

In the composition for pretreatment of the present invention, the content of monovalent silver ions is 10 mg / L or more. If content of monovalent silver ion is less than 10 mg / L, electroless plating cannot fully precipitate. 10 mg / L-20 g / L are preferable, as for content of monovalent silver ion, 50 mg / L-15 g / L are more preferable, and 100 mg / L-10 g / L are more preferable. By carrying out the minimum of content of monovalent silver ion in the said range, a sufficient amount of silver catalyst will adsorb | suck to the surface of a resin material, and an electroless plating film will precipitate more fully. Moreover, even if the upper limit of content of monovalent silver ion is more than the said upper limit, it does not adversely affect, but by setting it as said upper limit, the usage-amount of silver salt can be suppressed and cost can be reduced.

As silver ions, monovalent silver obtained by adding and dissolving metal silver in an acidic manganese bath may also be used. The acid for forming the acidic manganese bath is not particularly limited, and inorganic acids and organic sulfonic acids can be used.

Examples of the inorganic acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid and boric acid. Among these, sulfuric acid is preferable at the point which is further excellent in wastewater treatment property.

Examples of the organic sulfonic acid include aliphatic sulfonic acids having 1 to 5 carbon atoms such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and pentansulfonic acid; Aromatic sulfonic acids, such as toluene sulfonic acid, a pyridine sulfonic acid, and a phenol sulfonic acid, etc. are mentioned. Among these, since the bath stability of the composition for pretreatment is favorable, a C1-C5 aliphatic sulfonic acid is preferable.

The said acid may be used individually by 1 type, and may use 2 or more types together.

The acid concentration in the composition for pretreatment of this invention is not specifically limited, For example, 100-1800 g / L is preferable as a total acid concentration, and 800-1700 g / L is more preferable.

(Other ingredients)

The composition for pretreatment of this invention may contain the high molecular compound other than the said manganese ion and the said silver ion. It does not specifically limit as a kind of high molecular compound, In the point which can promote plating precipitation property, a cationic polymer can be used suitably. 0.01-100 g / L is preferable and, as for content of a high molecular compound, 0.1-10 g / L is more preferable.

(menstruum)

In the composition for pretreatment of this invention, it is preferable that the said manganese ion, the said silver ion, and the other component added as needed are contained in a solvent. It does not specifically limit as said solvent, Water, alcohol, the mixed solvent of water and alcohol, etc. are mentioned.

Since the solvent is excellent in safety, water is preferable, that is, it is preferable that the composition for pretreatment of this invention is aqueous solution.

It does not specifically limit as alcohol, Conventionally well-known alcohol, such as ethanol, can be used.

When using the mixed solvent of water and alcohol, it is preferable that the density | concentration of alcohol is low, and it is preferable that an alcohol concentration is about 1-30 mass% specifically ,.

It is preferable that the composition for pretreatment of this invention is acidic. Since the composition for pretreatment is acidic, the etching process of a resin material becomes further enough. 2 or less are preferable and, as for pH of the composition for pretreatment of this invention, 1 or less is more preferable.

2. resin material Electroless  Plating Pretreatment Method

The pretreatment method of electroless plating of the resin material of this invention has the process 1 which makes the to-be-processed surface of the said resin material contact the composition for pretreatment, The said pretreatment composition is 10 mg / L or more of manganese ion and 10 mg / It is a pretreatment method of electroless plating containing L or more monovalent silver ions.

(Step 1)

Process 1 is a process of making the to-be-processed surface of the said resin material contact the composition for pretreatment.

As the composition for pretreatment, what was described as a composition for pretreatment of the electroless plating mentioned above can be used.

It does not specifically limit as a method of making the to-be-processed surface of a resin material contact the composition for pretreatment, It is good to make it contact in accordance with a conventionally well-known method. As the method, the method of immersing a resin material in the composition for pretreatment, the method of spraying the composition for pretreatment on the to-be-processed surface of a resin material, etc. are mentioned. Among these, since the contact efficiency is further excellent, the method of immersing a resin material in the composition for pretreatment is preferable.

The temperature of the composition for pretreatment in process 1 is not specifically limited, 30-100 degreeC is preferable, 40-90 degreeC is more preferable, 50-80 degreeC is still more preferable. By making the minimum of the temperature of the composition for pretreatments into the said range, the etching and catalyst provision of the surface of a resin material become further more sufficient. Moreover, the film external appearance which is further excellent in decorability can be obtained by making the upper limit of the temperature of the composition for preprocessing into the said range.

3-60 minutes are preferable, as for the contact time of the composition for pretreatment and the to-be-processed surface of a resin material in the process 1, 5-50 minutes are more preferable, 10-40 minutes are still more preferable. By making the minimum of contact time into the said range, the etching and catalyst provision of the surface of a resin material become further more sufficient. Moreover, the film external appearance which is further excellent in decorability can be obtained by making the upper limit of a contact time into the said range.

In addition, in the case of using the conventional chromic acid-sulfuric acid liquid mixture, silver cannot be stably present as an ion in the pretreatment composition because addition of monovalent silver ions to the bath immediately produces precipitation of silver chromic acid (Ag ₂ CrO ₄ ). Therefore, when the chromic acid-sulfuric acid liquid mixture of the prior art is used, it is difficult to use the composition for pretreatment containing silver ions like this invention.

It does not specifically limit about resin which forms the resin material used as a to-be-processed object, Various resin materials with which the etching process is conventionally performed by the mixed acid of chromic acid-sulfuric acid can be used, The electroless plating film favorable with respect to the resin material can be used. Can be formed. As the resin forming the resin material, for example, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), resin in which butadiene rubber component of ABS resin is replaced with acrylic rubber component (AAS resin), butadiene rubber component of ABS resin Styrene resin, such as resin (AES resin) replaced with this ethylene-propylene rubber component, etc. are mentioned. In addition, an alloying resin of the styrene resin and polycarbonate (PC) resin (for example, an alloying resin having a mixing ratio of PC resin of about 30 to 70% by mass) may be suitably used. Moreover, polyphenylene ether resin, polyphenylene oxide resin, polybutylene terephthalate (PBT) resin, polyphenylene sulfide (PPS) resin, polyamide resin, etc. which are excellent in heat resistance and a physical property can also be used.

The shape, size, and the like of the resin material are not particularly limited, and according to the pretreatment method of the present invention, a good plating film excellent in decorative properties, physical properties, and the like can be formed also for a large-scale resin material having a large surface area. As such a large resin material, automobile related parts, such as a radiator grille, a wheel cap, medium and small emblems, and a door handle; Exterior articles in electrical and electronic fields; Faucet brackets used in tap water; And organic engine products such as pachinko parts.

By the process 1 demonstrated above, the to-be-processed surface of a resin material contacts a composition for pretreatment, and the to-be-processed surface is processed.

In the pretreatment method of the present invention, the degreasing treatment may be performed before the step 1 in order to remove dirt on the surface to be processed of the resin material. The degreasing treatment is not particularly limited, and the degreasing treatment may be performed according to a conventionally known method.

In the pretreatment method of the present invention, after step 1, in order to remove manganese adhering to the surface of the resin material, post-treatment may be performed using a post-treatment liquid containing an inorganic acid.

The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid and boric acid. Among these, hydrochloric acid is preferable at the point which is excellent in the removal property of manganese.

The said inorganic acid may be used individually by 1 type, and may use 2 or more types together.

The content of the inorganic acid in the post-treatment liquid is not particularly limited, and may be about 1 to 1000 g / L.

It does not specifically limit as a post-processing method, For example, what is necessary is just to immerse the resin material preprocessed according to the said pretreatment method for about 1 to 10 minutes in the post-processing liquid of about 15-50 degreeC of liquid temperature. By the said post-processing, the precipitation and appearance of the plating film formed can be improved further.

According to the pretreatment method of the electroless plating of the resin material described above, the treated surface of the resin material can be etched, and a silver catalyst can be given to the treated surface, so that the high plating precipitation property in the electroless plating in a later step Can be represented.

3. resin material Electroless  Plating method

The electroless plating method of the resin material of this invention makes the process 1 and (2) the to-be-processed surface of the said resin material contact the electroless-plating liquid to (1) contact the to-be-processed surface of the said resin material with the composition for pretreatment. In the step 2, the pretreatment composition is an electroless plating method containing 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions.

(Step 1)

Process 1 in the electroless plating method of the resin material of this invention is the same as the process demonstrated as process 1 in the pretreatment method of the electroless plating of the resin material mentioned above.

(Process 2)

Step 2 is a step of bringing the surface to be treated of the resin material into contact with an electroless plating solution.

It does not specifically limit as a method of making the to-be-processed surface of the said resin material contact an electroless plating liquid, It is good to make it contact in accordance with a conventionally well-known method. As the method, since the contact efficiency is further excellent, the method of immersing the to-be-processed surface of a resin material in an electroless plating liquid is preferable.

It does not specifically limit as an electroless plating liquid, A conventionally well-known self-catalyst type electroless plating liquid can be used. As said electroless plating liquid, an electroless nickel plating liquid, an electroless copper plating liquid, an electroless cobalt plating liquid, an electroless nickel-cobalt alloy plating liquid, an electroless gold plating liquid, etc. are mentioned.

It is preferable that an electroless plating liquid contains the reducing agent which shows catalytic activity with respect to silver as a reducing agent. Dimethylamine borane, formalin, glyoxylic acid, tetrahydroboric acid, hydrazine, etc. are mentioned as said reducing agent.

The conditions for contacting the surface to be treated of the resin material with the electroless plating solution are not particularly limited. For example, when the resin material is immersed in the electroless plating solution, the liquid temperature of the electroless plating solution is set to about 20 to 70 ° C, and the immersion time is 3 It may be about 30 minutes.

Content of the reducing agent in an electroless plating liquid is not specifically limited, About 0.01-100 g / L is preferable and about 0.1-10 g / L is more preferable. By setting the lower limit of the content of the reducing agent in the above range, the precipitation property of the plating is further improved, and the stability of the electroless plating bath is further improved by setting the upper limit of the content of the reducing agent in the above range.

In the electroless plating method of this invention, you may repeat process 2 or more times as needed. By repeating step 2 two or more times, two or more layers of electroless plating films are formed.

In order to improve the precipitation of electroless plating, the electroless plating method of the present invention may be subjected to an activation treatment with an activation treatment liquid containing a reducing agent and / or an organic acid before step 2.

It does not specifically limit as a reducing agent used for an activation process, Dimethylamine borane, formalin, glyoxylic acid, tetrahydroboric acid, hydrazine, hypophosphite, erythorbic acid, ascorbic acid, hydroxylamine sulfate, hydrogen peroxide, glucose, etc. are mentioned. . Among these, dimethylamine borane, formalin, glyoxylic acid, tetrahydroboric acid, and hydrazine are preferable at the point which plating precipitation property is further more favorable.

The said reducing agent may be used individually by 1 type, and may use 2 or more types together.

It does not specifically limit as a density | concentration of the reducing agent in an activation process liquid, 0.1-500 g / L is preferable, about 1-50 g / L is more preferable, and its 2-25 g / L is more preferable.

The organic acid used for the activation treatment is not particularly limited, formic acid, oxalic acid, glycolic acid, tartaric acid, citric acid, maleic acid, acetic acid, propionic acid, malonic acid, succinic acid, lactic acid, malic acid, gluconic acid, glycine, alanine, aspartic acid, glutamic acid, Iminodiacetic acid, nitrilotriacetic acid, fumaric acid, and the like. Among them, formic acid, oxalic acid, glycolic acid, tartaric acid, citric acid, and maleic acid are preferable from the viewpoint of further improved plating precipitation.

The said organic acid may be used individually by 1 type, and may use 2 or more types together.

It does not specifically limit as a density | concentration of the organic acid in an activation process liquid, 0.1-500 g / L is preferable, about 1-50 g / L is more preferable, and its 2-25 g / L is more preferable.

It does not specifically limit as an activation process method, For example, what is necessary is just to immerse the resin material preprocessed by the said process 1 for several seconds-about 10 minutes in the activation process liquid of liquid temperature of about 15-50 degreeC.

As an electroless plating method of the resin material of this invention, after process 2, you may further have an electroplating process.

In the electroplating step, after the step 2, an activation treatment may be performed with an aqueous solution such as an acid or an alkali, if necessary, and the electroplating may be performed by electroplating.

The electroplating solution is not particularly limited, and may be appropriately selected from conventionally known electroplating solutions according to the purpose.

It does not specifically limit as an electroplating method, For example, the resin material in which the electroless-plated coating film was formed by the said process 2 in the activation process liquid of about 15-50 degreeC of liquid temperature for several seconds on the conditions of about 0.1-10 A / dm <^2> current density. It may be immersed in about 10 minutes.

Example

An Example and a comparative example are shown to the following, and this invention is concretely demonstrated to it. However, this invention is not limited to an Example.

(Production of electroless plating film)

As a resin material to be plated, a flat plate (10 cm × 5 cm × 0.3 cm, surface area of about 1 dm ² ) of an ABS resin (manufactured by UMG ABS Co., Ltd., trade name: UMG ABS3001M) was prepared. The plating film was formed.

First, the resin material was immersed at 40 degreeC for 5 minutes in alkaline degreasing liquid (Okuno Seiyaku Kogyo Co., Ltd. product, Ace Clean A-220 bath), and it washed with water.

Subsequently, the additive was added to the water as a solvent by the compounding shown in Table 1 and 2, and the composition for pretreatment of an Example and a comparative example was prepared. The resin material after water washing was immersed in the prepared pretreatment composition on conditions of immersion temperature 68 degreeC and immersion time 30 minutes.

Finally, the resin material was immersed at 40 ° C for 10 minutes in an electroless plating solution prepared by adding an additive to water as a solvent in the formulations shown in Tables 1 and 2 to form an electroless plating film.

The coverage and adhesiveness of the plating film formed by the above method were evaluated in accordance with the following method.

(1) coverage

The ratio of the area where the electroless plating film was formed on the surface of the resin material was evaluated as the coverage. The case where the whole surface of the resin material surface was coat | covered was made into 100% of coverage.

(2) peel strength measurement

Performing an electroless plating film is formed, and immersing the resin material in the copper sulfate plating bath and a current density of 3 A / dm ^2, 120 minutes to an electroplating treatment under the conditions of temperature 25 ℃, to form a copper plating film to prepare a sample. The sample was dried at 80 ° C. for 120 minutes and allowed to stand until it reached room temperature. Subsequently, a 10 mm wide cutout was put into the plated film, and the plated film was pulled in a direction perpendicular to the surface of the resin material using a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-J 1 kN). The peel strength was measured. The results are shown in Table 3.

From the results in Table 3, a plating film formed by immersion in the electroless plating solution after being immersed in the pretreatment compositions of Examples 1 to 5 containing 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions. It was found that silver had a high coverage and excellent adhesiveness.

In addition, since the coating film formed by immersion in the pretreatment compositions of Examples 1 to 5 and then immersed in an electroless plating solution is sufficiently covered with 100% coverage, a catalyst is provided by a separate catalyst application step, It turned out that it is not necessary to raise a coverage. For this reason, by using the electroless plating pretreatment composition of this invention, adhesion of the catalyst to the surface of the jig used at the time of formation of an electroless plating film is suppressed, and precipitation of the plating film on the surface of a jig is suppressed. I knew that. Thereby, when forming an electroless plating film using a jig repeatedly, the plating film which precipitated on the surface of a jig peels in a granular shape, and the resin material surface which enters into the electroless plating film of the resin material surface in each process is produced. Generation of irregularities in the electroless plating film is suppressed.

In general, when pretreatment is carried out on a resin material by etching with chromic acid, and then a catalyst for electroless plating using a colloidal solution containing a tin compound, a palladium compound and the like is given, chromic acid becomes a catalyst poison. The adhesion of the catalyst to the surface of the jig is suppressed, and the deposition of the plated film on the surface of the jig is suppressed. However, when chromic acid is not used in consideration of the environment and the like, there is a problem that the unevenness of the electroless plated film formed on the surface of the above-mentioned resin material occurs due to precipitation of the plated film on the jig.

On the other hand, after immersion in the composition for pretreatment of this invention, since the coating film formed by immersing in an electroless plating liquid is fully coat | covered at 100%, a catalyst is provided by a separate catalyst provision process, and a coating is carried out. There is no need to increase the rate. For this reason, adhesion of a catalyst to the surface of the jig used at the time of formation of an electroless plating film is suppressed, precipitation of the plating film on the surface of a jig is suppressed, and the electroless plating film formed on the surface of the resin material mentioned above is suppressed. The occurrence of unevenness is suppressed.

When the comparative examples 1 and 7 which do not contain a manganese ion used the composition for pretreatment of the comparative example 2 whose manganese concentration is less than 10 mg / L, it turned out that the adhesiveness of a plating film is low.

Moreover, when the composition for pretreatment of Comparative Examples 3 and 4 whose monovalent silver ion concentration is less than 10 mg / L was used, it turned out that the plating film formed is inferior to a coverage.

When the composition for pretreatment of Comparative Example 5 containing 50 mg / L of divalent palladium ions is used instead of monovalent silver ions, the coverage of the plated film to be formed does not decrease, but the adhesion of the plated film is lowered. I knew that. In addition, when the composition for pretreatment of Comparative Example 6 containing 20 mg / L of divalent palladium ions was used, although the grade of the adhesive fall of a plating film is smaller than the comparative example 5, the coverage of the plating film formed is a comparative example. It was lower than five.

In addition, from the comparison of Comparative Examples 3 and 7, it was found that when silver sulfate (I) was used as the silver salt for imparting monovalent silver ions, the coverage of the plated film was further improved.

Claims (6)

A pretreatment composition for electroless plating comprising 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions. The composition for pretreatment of electroless plating according to claim 1, wherein the manganese valence of the manganese ions is 3 or more. The composition for pretreatment according to claim 1 or 2, wherein the pH is 2 or less. As a pretreatment method of electroless plating of a resin material,
It has a process 1 which makes the to-be-processed surface of the said resin material contact the composition for pretreatment,
The pretreatment method for electroless plating, wherein the pretreatment composition contains 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions. As the electroless plating method of the resin material,
(1) Process 1 which makes the to-be-processed surface of the said resin material contact the composition for pretreatment, and
(2) having a step 2 of bringing the surface to be treated of the resin material into contact with an electroless plating solution,
The electroless plating method, wherein the composition for pretreatment contains 10 mg / L or more of manganese ions and 10 mg / L or more of monovalent silver ions. The electroless plating method according to claim 5, wherein the electroless plating solution contains a reducing agent that exhibits catalytic activity with respect to silver.