JPH08302214A - Resin composition for electroless plating and method of electroless plating - Google Patents

Abstract

PURPOSE: To obtain a resin composition for electroless plating in high efficiency capable of omitting the etching process. CONSTITUTION: This resin composition for electroless plating comprises (a) a polymer (A) containing one or two chemical structures, namely a structure where a part of hydrogens in the polymer are substituted with halogen or nitrile groups and a structure having double bonds between aromatic substitutents on the polymer main chain, and (b) at least one of followings 1 and 2. (b) 1: a polymer (B) having one or two functional groups possible to form a metal salt, (b) 2: a low-molecular-weight compound having these functional groups and is compatible with polymer (A). In the electroless plating process, 1) a coated layer is formed on a non-conductive plating surface, 2) a negative static charge is applied at temperature higher than the glass-transition point, 3) discharged after cooling followed by the plating process including, application of a catalyst and its activation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition suitable for a new electroless plating method which does not require a surface corrosion step, and an electroless plating method using the same. More specifically, the present invention makes it possible to form a firmly adhered plating film by omitting the step of corroding the surface to be plated after degreasing and performing the electroless plating step after the catalyst application step. The present invention relates to a resin composition for electroless plating, and an electroless plating method by which a completely new surface treatment method of applying a negative high voltage to the surface of the coating film can be applied to obtain a plating film that is more firmly adhered. Moreover, the coating film of the composition of the present invention can change its composition within the range of the combination of structures defined according to the substrate, and can be applied to various kinds of substrates. Therefore, although the field of application of the present invention covers all fields requiring electroless plating, a particularly expected field is the field of electromagnetic wave shielding.

[0002]

2. Description of the Related Art Electroless plating is usually carried out as a conductive step for electrolytically plating a non-conductive plastic molded product. It is a pretreatment for corroding the plated surface of the molded product by some method. Is performed to form fine corrosion holes on the surface, and then the electroless plating is performed to bond the plating layer to the base material surface by the anchoring effect of the metal deposited on the inner surface of the corrosion holes.

A method of using an adhesive for electroless plating as a method for electroless plating of plastics is known as a method for producing a printed wiring board (Japanese Patent Laid-Open Nos. 2-8281 and 3-22081).
Etc.), this adhesive for electroless plating has a composition having a greater corrosion effect than the base material, and is a method that requires a corrosion step after applying the adhesive.

Further, conventional techniques for producing electromagnetic wave shielding materials include a method of applying a conductive paint, spraying zinc, laminating a conductive plastic filled with a conductive substance, or sandwich-molding as a core material. However, of these, the application of conductive paint is most prevalent. However, the effect is not sufficient in any of them, and even the most popular conductive paint is extremely expensive, and the coating film needs to be thick, and the coating cost becomes expensive. Recently, the electromagnetic wave shielding effect of the electroless plating film has been highly evaluated, but it has not been widely used due to the problems described later.

[0005]

The above-mentioned conventional electroless plating method for plastics always requires a corrosion step, and in this step, a sulfuric acid-chromic acid mixed solution treatment is generally performed, which is strong and dangerous. Since a large amount of various corrosive liquids are used, pollution control is required, and there is a restriction that it cannot be carried out in the absence of this countermeasure equipment, and the economic burden of pollution control costs cannot be avoided.

In addition, in order to satisfy the adhesiveness with the plating layer, the plastic itself as a material is also modified so as to be easily corroded according to each resin, and there is also a dedicated resin grade suitable for electroless plating. in use.
However, in this case, there is a problem that some of the characteristics originally possessed by the resin are sacrificed and the price of the resin becomes expensive.

As a method of solving these problems, a method of forming a coating on which the electroless plating coating adheres without corroding the surface to be plated can be considered. As such a method, Japanese Patent Publication No. 6-33461 discloses a method of forming a coating film containing chitosan or a chitosan derivative on the surface to be plated and performing electroless plating without corrosion. However, this method has a problem in that the adhesion of the coating film to the base material to be plated is not sufficient and an undercoat paint is required to compensate for this. In the examples described in the publication, an acrylic undercoat paint is used, and examples without an undercoat are not described. Also peel strength is JI
Only the result of the cross-cut test according to SK6800.8.5.

Further, Japanese Patent Publication No. 3-51790 discloses a method for improving the bonding strength of an electroless plating metal layer by using the following copolymers of monomers as a binder for an activating substance. It is disclosed that an electroless plating film having good adhesion can be obtained when performing. Monomers containing cyano groups, optionally substituted (methyl) styrene ring, methacrylic acid esters, unsaturated carboxylic acid esters. However, this method is not only due to the cumbersome production method in which the binder itself is copolymerized under a pressure with a special combination of monomers, and the coating of the binder alone is not electroless plated, which is more expensive. In this method, an organic compound of a noble metal is kneaded as an activator into this binder by a roller mill or the like. That is, this method requires a complicated manufacturing process as described above and uses a composition containing a noble metal as a coating for electroless plating, and further spray coating such that electromagnetic wave shield plating is performed on a two-dimensional surface. If it is necessary to take into consideration the loss of the coating material, it is a very expensive electroless plating method.

The present inventor has proposed a method for solving the above-mentioned problems in terms of environment, economy and performance of electroless plating which does not require a corrosion step and can be easily carried out and has excellent performance and economy. After examining the method, we have already applied for 3 patents (Japanese Patent Application No. 1-198207: Japanese Patent Application Laid-Open No. 3-64481, Japanese Patent Application No.
1-334164: Japanese Patent Application Laid-Open No. 3-193881, Japanese Patent Application No. 2-221930: Japanese Patent Application Laid-Open No. 4-
103771). The present inventors are further studying the mechanism of adhesion between the plating film and the coating film of the above invention, and found that the adhesion strength is remarkably increased by applying a negative electrostatic voltage to the coating film surface. Then, the resin composition in which such an effect of the application of the electrostatic voltage appears strongly was examined. It has also been found that some of these resin compositions can obtain a plating film having a practical peel strength even when electroless plating is directly performed without applying an electrostatic voltage.

Further, the hypothesis on the mechanism of deposition and adhesion of the electroless plating film on the coating film of the present composition by applying a negative electrostatic voltage, which will be described later, is deduced, and if the main chain of the polymer contains a positive structure. Then, it was considered that the plating film was deposited and the film adhered to the coating film even if a negative electrostatic voltage was not applied, and such a resin composition was examined. The present inventors have completed the present invention having a wide range of application based on the results of the above-mentioned examination.

[0011]

Means for Solving the Problems That is, the present invention provides a polymer (A) having one or more chemical structures selected from the group (a) below and at least one of the following (b) 1 and 2. A resin composition for electroless plating, which comprises: (A) A chemical structure in which a part of hydrogen in the polymer main chain is substituted with a halogen group or a nitrile group, and a chemical structure having a double bond in a portion sandwiched between aromatic substituents in the polymer main chain. . (B) 1, a polymer (B) having a functional group capable of forming a metal salt, 2, a low molecular weight compound (C) having a functional group capable of forming a metal salt, and having compatibility with the polymer (A) [Hereinafter, simply referred to as "compound (C)"].

There are many resin compositions composed of such combinations. Among them, for example, even if the following resin composition is subjected to the electroless plating step after the catalyst application step while omitting the corrosion treatment step, It has been found that a remarkable effect is obtained in that a plating film having a peeling strength that can withstand practical use is obtained. These resin compositions are extremely versatile resin compositions for electroless plating that can be applied to a base material to be plated (hereinafter simply referred to as "base material") made of a large number of various resins.

The first is that the polymer (A) has a chlorine content of 3
The resin composition is 0% or less of chlorinated polypropylene, and the polymer (B) is a propylene / maleic anhydride copolymer or a 1,4-polybutadiene / maleic anhydride copolymer. This resin composition is a combination of (a) a chemical structure in which a part of main chain hydrogen is replaced with a halogen group, and (b) a carboxy group as a functional group capable of forming a metal salt. Have.

The second is a resin composition in which the polymer (A) is polychloroprene and the polymer (B) is either a polyester having a carboxy group and a hydroxyl group at a terminal or a 1,2-polybutadiene / maleic anhydride copolymer. It is a thing. This resin composition is a combination of (a) a chemical structure in which a part of main chain hydrogen is replaced with a halogen group, and (b) a carboxy group as a functional group capable of forming a metal salt. Have.

No. 3 is a resin composition comprising an acrylonitrile / acrylic acid ester copolymer as the polymer (A). This resin composition has (a) a chemical structure in which a part of hydrogen in the main chain is replaced with a nitrile group as a chemical structure, and (b) a carboxy group as a functional group capable of forming a metal salt. It is also included in the polymer.

No. 4, the polymer (A) is a styrene / butadiene / styrene block copolymer, and the polymer (B) is a styrene / maleic anhydride copolymer,
Alternatively, the resin composition is composed of either 1,4-polybutadiene / maleic anhydride copolymer. This resin composition can form a metal salt of (b) 1 with a chemical structure having a double bond in a portion sandwiched between aromatic substituents of a polymer main chain as the structure of (a). It has a carboxy group in combination as a functional group.

The fifth is that the polymer (A) is a vinyl chloride / maleic anhydride copolymer, and the polymer (B) of (b) 1 is 1,4-polybutadiene / maleic anhydride copolymer, or (b) 2. A resin composition using any of aromatic carboxylic acids as the compound (C). This resin composition has a chemical structure in which a part of main chain hydrogen is replaced with a halogen group as the structure of (a), and (b) 1
It has a combination with a carboxy group as a functional group capable of forming a metal salt of.

Next, the electroless plating method according to the present invention comprises:
A coating film of a resin composition for electroless plating containing a polymer (A) having one or more chemical structures selected from the group of (a) below and at least one of the following (b) 1 and 2,
After forming on the plated surface of the non-conductor, a negative electrostatic voltage is applied to the coating film of the resin composition at a temperature equal to or higher than the glass transition point of the resin composition, and then applied at a temperature lower than that temperature. The electroless plating method is characterized in that the voltage is released, and then a plating step including a catalyst application and activation step is performed. (A) A chemical structure in which a part of hydrogen in the polymer main chain is substituted with a halogen group or a nitrile group, and a chemical structure having a double bond in a portion sandwiched between aromatic substituents in the polymer main chain. . (B) 1, a polymer (B) having a functional group capable of forming a metal salt, 2, a compound (C) having a functional group capable of forming a metal salt, and having compatibility with the polymer (A).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the above-described resin composition for electroless plating according to the present invention and a method for electroless plating of a non-conductor using the same will be described in more detail. Examples of the polymer (A) having a chemical structure in which hydrogen in the main chain of the group (a) is replaced with halogen include olefin homopolymers, chlorinated products of polyolefins including copolymers of olefins and copolymers of olefins with monomers other than olefins, Also included are homopolymers of vinyl chloride or copolymers of vinyl chloride with other monomers (vinyl monomers and diolefins), polychloroprene, and the like.

Polymers (A) having a chemical structure in which hydrogen in the main chain of group (a) is replaced with a nitrile group include acrylonitrile homopolymers and acrylonitrile monomers and other monomers such as styrene, butadiene, acrylic acid, There are copolymers such as acrylic acid esters. Note that these copolymers may be derivatives substituted with an alkyl group, a phenyl group, or the like, and the copolymer with a diene monomer may have a hydrogenated double bond.

The polymer (A) having a chemical structure having a double bond in a portion sandwiched between aromatic substituents of the polymer main chain is a copolymer of styrene and a diene monomer, for example, styrene / butadiene / styrene block copolymer. (Hereinafter abbreviated as SBS), styrene-isoprene-styrene block copolymer (hereinafter abbreviated as SIS) and the like, and the styrene content in the copolymer is preferably 30-40%, and the styrene content is preferably high.

Examples of the functional group (b) capable of forming the metal salts 1 and 2 include a carboxy group, a mercapto group and a sulfonic acid group. Among them, a carboxy group is particularly preferable. The carboxy group may be a metal salt or ester in addition to the free acid. Examples of the polymer (A) having a carboxy group include a polyacrylate, a copolymer of maleic anhydride and various vinyl monomers, a polymer having a carboxy group in the side chain such as a graft copolymer of maleic anhydride, and a terminal such as polyester. There is a polymer having a carboxy group. In addition to these polymers (B), it has the chemical structure of group (a) and is compatible with the polymer (A),
Aliphatic carboxylic acids such as stearic acid and palmitic acid (adipic acid) and aromatic carboxylic acids such as benzoic acid, phthalic anhydride, salicylic acid, thiosalicylic acid having a mercapto group, and the like compound having a carboxy group (C) But it is okay. These compounds can be mixed and used within a range compatible with the polymer (A) having the chemical structure of group (a). Among the above polymers (B), polybutadiene / maleic anhydride copolymer is particularly preferable. The polybutadiene / maleic anhydride copolymer exhibits good electroless plating properties when combined with the polymer (A) having various chemical structures (a).

Further, a mercapto group, a sulfonic acid group, etc.,
A mercapto group contained in a usual compound (C) such as thiophenol, mercaptobenzothiazole or p-toluenesulfonic acid, as long as it is compatible with the polymer (A) having the chemical structure of group (a), It may be a sulfonic acid group.

For the combination of (a) and (b),
(B) 1 in the polymer (A) having the chemical structure of (a) group
The polymer having a functional group capable of forming a metal salt of, for example, acrylonitrile / acrylic acid copolymer, carboxy group-containing chlorinated polypropylene, vinyl chloride / maleic anhydride copolymer, etc. can be used alone, and further (b) When the polymer (B) of No. 1 or the compound (C) of (b) 2 is used together, remarkably good electroless plating property is exhibited.

In the case of the combination of the polymer (A) having the chemical structure of group (a) and the polymer (B) having a functional group capable of forming the metal salt of (b) 1, both of them are used as a coating agent. The compatibility is required, but the compatibility is not necessarily required when the resin composition for molding is prepared, as long as sufficient dispersion can be obtained between the two. In the case of the combination of the polymer (A) having the chemical structure of group (a) and the compound (C) having a functional group capable of forming a metal salt of (b) 2, as described above, the compatibility between them is is necessary.

For molded articles made of various base materials, a solution prepared by dissolving the electroless plating resin composition of the present invention in a solvent is applied to the surface to be plated to form a coating film, and the coating film surface will be described later. Electrostatic plating can be performed by performing the static voltage application without performing the corrosion process. Further, depending on the composition of the resin composition for electroless plating, there are some that can perform electroless plating by omitting the corrosion step without applying a static voltage. In any of the above cases, it is necessary to select a coating film composition having good adhesion to the substrate to which it is applied.

Further, among the resin compositions of the present invention, those having a mechanical property that can be used as a molding material do not need to have a coating film formed on the surface thereof, and the resin composition of the present invention can be molded as it is in the same manner as in the case of the coating film. Electroless plating is possible. Examples thereof include acrylonitrile / acrylate copolymer (Example 2-1), a composite resin composition comprising hydrogenated nitrile rubber and zinc polyacrylate (Example 2-).
3) etc. are mentioned.

Further, for the purpose of improving the adhesion between the base material and the coating film, a polymer additive which does not inhibit the deposition of the plating film,
For example, hydrogenated SBS (hereinafter abbreviated as SEBS), an elastomer such as ethylene-vinyl acetate copolymer, which serves as a base material of a hot-melt adhesive, and a tackifier may be added.

The electroless plating method according to the present invention is an electroless plating method which does not require a corrosive step for the above resin composition, and the resin composition for electroless plating according to the present invention is provided on the surface to be plated of the base material. After forming the coating film, a negative static voltage is applied to the coating surface at a temperature equal to or higher than the glass transition point of the resin composition, the applied voltage is released at a temperature lower than the temperature to which the voltage is applied, and the catalyst is continuously applied. A method for performing electroless plating including an activation step. When the substrate is made of the resin composition according to the present invention as described above, it is not necessary to form a film of the resin composition, and a negative electrostatic voltage is applied as it is at a temperature equal to or higher than the glass transition point, and then as described above. Similarly, it is a method of performing electroless plating.

As a method of applying a negative electrostatic voltage to the plated surface, a ground electrode plate is arranged on the side opposite to the plated surface of the sample piece, and the negative electrode plate is placed through a non-adhesive film such as Teflon. Either contact the surface to be plated or separate the plate from the surface to be plated and apply without contact. In case of non-contact, the interval is 1-4mm
The degree is preferred. A wide interval requires a high applied voltage. Further, it is preferable that the opposite surfaces of the ground electrode plate and the negative electrode plate are completely covered with a non-adhesive film such as Teflon to prevent discharge between both electrode plates.

The temperature at the time of applying an electrostatic voltage is essential to be a temperature above the glass transition point when the surface of the coating film or molded product of the resin composition for electroless plating according to the present invention is in a dry state containing no solvent. Therefore, at a temperature below this, the orientation of polar groups is not considered, which is not preferable. The applied voltage needs to be 2-6 kv, and in order to obtain the same effect, the voltage may be high at low temperature and low at high temperature.

The reason why the temperature for releasing the applied voltage is made lower than the temperature at the time of applying the voltage to make a temperature difference is that the alignment effect due to the voltage application is attenuated when the voltage is applied and the voltage is released at the same temperature. This is for the purpose of preventing it, and shows a negative effect at the same temperature as when the voltage is applied and when the voltage is released without lowering the applied voltage. The temperature for releasing the applied voltage is theoretically preferably a temperature equal to or lower than the glass transition point, but it is not necessarily limited, and it is sufficient if there is a sufficient temperature difference between the temperature when the voltage is applied and the temperature when the voltage is released. It is experimentally recognized that there is no problem if the temperature difference is 50 ° C. In addition, it is preferable to release the voltage with a low voltage.

As a method for forming a coating film of the resin composition according to the present invention, in addition to the above-mentioned method of applying an electrostatic voltage after coating and drying, a method of applying a non-contact electrostatic voltage in the process of forming a coating film is also available. Can be used. For example, when the coating agent containing the resin composition according to the present invention is applied to the surface to be plated, immediately after the application, and when it is a molded article of the resin composition itself, immediately after wetting the surface to be plated with a solvent, the solvent is In the state of remaining, it is not necessary to raise the temperature, and it is possible to form a coating film having improved electroless plating property by drying while applying a static voltage in a non-contact manner (see Example 3-10).

For example, when an ABS resin is used as the base material, after the film is formed, the temperature when the voltage is applied is 80 ° C. and the temperature when the voltage is released is 3
0 ° C is applied. For the operation of applying and releasing this voltage, in the laboratory, the substrate on which the film has been formed is placed in an oven, a voltage is applied, the substrate is taken out from the oven as it is, cooled, and then the applied voltage is released. To continuously perform this operation industrially, when the substrate is a continuous sheet or a plate-shaped product, the surface to be plated is heated using a tunnel-type hot air heating device or an infrared irradiation device, and then the negative electrode plate is used. And a ground electrode plate are passed between them to apply a static voltage, and the plates are cooled by cold air while running.

When the base material is a molded product, the surface to be plated is heated in the same manner as before, and then an electrode plate similar to the surface to be plated is prepared with a wire net or the like, and a cold air is passed through the net while applying a static voltage. It can be sent and cooled. Further, as described above, when the surface to be plated is wet with a solvent and static voltage can be applied to the surface, it can be carried out in the same manner, but at this time it is not necessary to heat the surface to be plated. The air may be blown to accelerate the drying.

The base material to which the coating agent comprising the resin composition for electroless plating of the present invention can be applied directly to the electroless plating method of the present invention is a general-purpose resin such as polypropylene or super engineering plastic such as polyimide. It is a wide range of materials including thermoplastic and thermosetting resins. Furthermore, when considering and using a primer for the purpose of improving the adhesion between the coating agent and the substrate, it is applicable to all non-conductive materials ranging from artificial materials such as ceramics and glass to natural materials such as wood and leather. Has the potential of.

As described above, electroless plating is carried out after applying a negative electrostatic voltage to the surface of the molded product or coating film of the resin composition having the combination of the structure (A) and the functional group (B). Then, the peel strength of the plating film is increased as compared with the case where no static voltage is applied. The reason is considered as follows. The nitrile group and the halogen atom, which are substituted with hydrogen atoms in the main chain of the structure of (A), have strong electronegativity, and when a negative electrostatic voltage is applied at a temperature above the glass transition point, it is opposite to the application surface. The carbon atoms to which these substituents are bound are strongly positive on the side to which the electrostatic voltage is applied.

The effect of the double bond in the portion sandwiched between the aromatic substituents of the main chain is considered as follows.
Even in the repeating structure of a unit in which a mere aliphatic chain without a double bond and an aromatic substituent are bonded, there is a difference in electron density distribution between the aromatic ring part and the aliphatic chain part, and The part has a low electron density. The presence of additional double bonds between the aromatic rings means that the movable π is distributed perpendicular to the bond plane.
Since the electron has electrons, the π electron moves to the side opposite to the voltage application surface by the application of the negative voltage, and the electron density further decreases in the portion between the aromatic rings on the voltage application surface.

Microscopically considering the distribution state of the electron density on the voltage application surface, due to the orientation of the functional group (A) and the movement of π electrons, the portion having the negative substituent and the double bond is different from the other portion. It is thought that the electron density is lower and the electron distribution on the surface is expressed in a three-dimensional manner. Hereinafter, this state is tentatively referred to as "electronic depression".

When a surface having "electron pits" is immersed in a catalyst solution of a mixture of palladium and stannous chloride in which paradium forms negative complex ions, the complex ions containing palladium are converted to the "electron pits". It is presumed that strong peeling strength is exhibited by being metallized by reduction with stannous chloride in an acidic solution and binding to the functional group of (B) at this time.

This concept also applies to the inventions of the present inventors already filed (Japanese Patent Application No. 1-333464 and Japanese Patent Application No. 2-221930). That is, these inventions are different from the present invention in that a group that reacts with a metal to form a salt is not an essential component and that the electron density distribution of molecules is not forcibly changed by applying an electrostatic voltage. However, due to the composition of the coating agent for electroless plating and the relationship between the coating agent and the base material, if the expression of "electronic depression" is used on the coated surface, it is a shallow "electronic depression".
Is presumed to have been formed. When there are "electron depressions", it is considered that the adhesion of palladium is good even if it is shallow, and that the thin electroless plating film has an adhesion strength that can withstand the cross-cut test.

[0042]

EXAMPLES The effect of the resin composition having the structure (a) and the functional group (b) in various combinations in electroless plating will be specifically described below with reference to examples. The procedures, evaluation methods, and base materials of the coated samples in these examples are as follows.

1. Implementation procedure (1) Preparation of sample coated with coating agent for electroless plating A thermoplastic resin injection molding test piece or a thermosetting resin press molding test piece having a thickness of 2 to 3 mm is 25 × 70 m
The coating agent according to the present invention prepared by cutting into m size and prepared in each of the examples is applied by a reciprocating stroke with a spray gun (coating thickness, about 2 μm) except for special cases, and dried at room temperature.

(2) Static voltage applying / releasing method Unless otherwise specified, the contact applying method shown in FIG. 1 is used. That is, the sample 2 coated with the coating agent 1 prepared by the method described in the above (1) is applied between the negative electrode plate 3 whose opposite surface is completely covered with the Teflon film 5 and the ground electrode plate 4, and the coated surface is the negative electrode. The plate is sandwiched toward the plate 3, and the bipolar plate sandwiched between the plates is further fixed by a sandwiching clip 7 with two microscope slide glasses 6. Charge this into a thermostat heated to a predetermined temperature,
After 5 minutes, a negative voltage of 6 kv was applied by the DC high voltage generator 8 and after 30 seconds, the voltage was applied to the outside and taken out,
The temperature is returned to room temperature by blowing cold air (measured with a radiation thermometer), and the applied voltage is released. In the examples, the non-contact application method and the static voltage application method are specified, but when the distance between the electrode plate and the sample film surface is not described, this distance is 1.2 m.
m. The method is by sandwiching the glass slice as a spacer between both ends of the sample piece.

(3) Electroless plating method Chemical solution used: Degreasing agent A-screen A220 (manufactured by Okuno Chemical Industries Co., Ltd.) Catalyst solution Catalyst C (manufactured by the same company) Reaction accelerating solution Hydrochloric acid electroless copper plating solution TSP 810 (Okuno Pharmaceutical Co., Ltd.) Industrial Co., Ltd.) Electrolytic copper plating solution Elecopper II (manufactured by the same company) Electroless nickel plating solution for electromagnetic wave shielding TSP 4
8 (manufactured by the same company) Plating condition 1 (plating condition for 90 ° peel test sample) Degreasing (50 ° C, 5 minutes) -Washing-Catalyst solution immersion (at room temperature, 5
Min) -Reaction accelerator solution immersion (room temperature, 5 minutes) -Washing-Hot water bath (50 ° C, immersion 1 minute) -Electroless copper plating solution immersion (50
(° C., 10 minutes) -Washing-Drying-To form a peeling test part in the longitudinal direction on the plating film of the sample piece, two parallel cuts with a space of 10 mm and a length of 50 mm or more and at right angles to the cut ends. Make a break. This cut sample is subjected to electrolytic copper plating under the following conditions so that the thickness of the plated film is about 40 μm. Electrolytic copper plating (25 ° C, 90 minutes, 3Amp./dm2) Plating condition 2 (electromagnetic wave shield plating condition) Until immersion in a hot water bath, the same electroless copper plating solution as in plating condition 1 (50 ° C, 15 minutes) -Washing- Immersion in catalyst solution (room temperature, 5 minutes) -Immersion in reaction accelerator solution (room temperature, 5 minutes)
Min) -immersion in electroless nickel plating solution (50-55 ° C, 5
Min) -Washing-Drying-

2. Evaluation method The adhesion strength of each of the samples prepared under the plating conditions 1 and 2 was evaluated by the following method. (1) Sample according to plating condition 1 According to JIS (Japanese Industrial Standard) H 8630 “Adhesion test method for plating on plastics”. (2) Sample according to plating condition 2 Not in conformity with JIS K 5400 8.5 “Adhesion test method for paint: Granite tape method adhesion test”.

3. Base material of coated sample Table 1 shows the types of resin used as the base material and their brands.
Shown in Regarding the type of resin, JIS K 68
99-1992 (ISO 1043-1: 1987).

[0048]

[Table 1]

Example 1 The polymer having the structure of (a) was divided into three groups, a halogen-containing polymer, a nitrile group-containing polymer and a polymer having a double bond between aromatic substituents. A coating agent was prepared by combining the functional group of (b) with each other, and the coating agent was applied to various base materials to prepare coated sample pieces. The results of the electroless plating test performed on the sample pieces of these examples are shown in Tables 2 to 4 and Tables 5 and 6 for each category. The resin component of the coating agent is represented by the symbol according to the JIS. Those marked with * in the table are
For comparison, in the same combination of (a) and (b), an example in which no static voltage is applied will be shown.

Category 1 (Examples Mainly Containing Halogen-Containing Polymer: Examples 1-1 to 17) Example 1-1 Low-chlorinated polypropylene (hereinafter abbreviated as "LCPP")
(Note 1-1) 0.5 parts by weight, polyester adhesive (Note 1-
2) Dissolve 1.5 parts by weight and 3 parts by weight of SEBS in 95 parts by weight of toluene to prepare a coating agent. Applicable resin: PP (1), static voltage application temperature: 100 ° C.

Example 1-2 A 2 wt% toluene solution of carboxy group-containing LCPP (Note 1-3) was used as a coating agent. Applicable resin: PP (1), static voltage application temperature: 100 ° C.

Example 1-3 2.25 parts by weight of carboxy group-containing LCPP (Note 1-3),
A coating agent was prepared by dissolving 0.25 part by weight of stearic acid in 97.5 parts by weight of toluene. The applied resin and static voltage application conditions are the same as in Example 1-2 except that non-contact application is performed.

Example 1-4 0.5 parts by weight of carboxy group-containing LCPP (Note 1-3), 1 part by weight of thiosalicylic acid, ethylene / vinyl acetate copolymer (hereinafter abbreviated as "E / VAC") (Note 1-4) ) 2.5 parts by weight and 1 part by weight of ester gum (Note 1-5) are dissolved in toluene to prepare a coating agent. The applied resin and the static voltage application temperature are the same as those in Example 1.
Same as -2.

Example 1-5 1.5 parts by weight of carboxy group-containing LCPP (Note 1-3), propylene / maleic anhydride copolymer (hereinafter referred to as "P / MA")
(Note 1-6) 3.5 parts by weight was dissolved in 95 parts by weight of toluene to prepare a coating agent. Applicable resin: PP (1), PP
(2). Static voltage application temperature: 100 ° C.

Example 1-6 0.8 parts by weight of carboxy group-containing LCPP (Note 1-3), P /
MA (Note 1-6) 1.2 parts by weight, E / VAC (Note 1-4) 2.0
A coating agent is prepared by dissolving 1.0 part by weight of rosin-modified phenolic resin (Note 1-7) in 95 parts by weight of toluene. The applied resin and static voltage application conditions are the same as in Example 1-5.

Example 1-7 3 parts by weight of carboxy group-containing LCPP (Note 1-3), 2 parts by weight of maleated 1,4 polybutadiene (hereinafter abbreviated as MAPB 1,4) (Note 1-8) were added to 95 parts by weight of toluene. Dissolve in a part to prepare a coating agent. The applied resin and static voltage application conditions were the same as in Example 1-5 except that non-contact application was performed.

Examples 1-8 Vinyl chloride / maleic anhydride copolymer (hereinafter referred to as "VC /
Abbreviated as "MA") (Note 1-9) 5 wt% tetrahydrofuran (hereinafter abbreviated as "THF") solution was used as a coating agent and ABS
Applies to (1) and PC (1). Static voltage application temperature, ABS
(1): 80 ° C, PC (1): 120 ° C.

Examples 1-9 Examples in which the compound having a functional group (B) was added to the above examples. A coating agent was prepared by dissolving 4 parts by weight of VC / MA (Note 1-9) and 1 part by weight of salicylic acid in 95 parts by weight of THF. The applied resin and the temperature at which the electrostatic voltage was applied were both in Example 1
Same as 8.

Example 1-10 Thiophenol was blended in place of the salicylic acid blended in Example 1-9. The coating agent preparation method, applied resin, and static voltage application temperature were all the same as in Example 1-9.

Example 1-11 Thiosalicylic acid was compounded in place of the salicylic acid compounded in Example 1-9. The coating agent preparation method is described in Example 1-9.
Same as Applicable resin: ABS (1), ABS (2), PVC,
PC (1), PC (2), (PC + ABS), (PC + PB
T), (PA + PPE), PES, PF. Static voltage application temperature: 80 ° C for ABS and PVC, 120 ° C for others.

Example 1-12 4 parts by weight of VC / MA (Note 1-9), polyester adhesive
(Note 1-2) 1 part by weight was dissolved in 95 parts by weight of THF to prepare a coating agent. Applicable resin: PVC, PC (1). Static voltage application temperature: 80 ° C for PVC, 120 ° C for PC (1).

Example 1-13 A coating agent was prepared by dissolving 4 parts by weight of VC / MA (Note 1-9) and 1 part by weight of p-toluenesulfonic acid in 95 parts by weight of THF.
Applicable resin: (PC + ABS). Non-contact static voltage application, application temperature: 120 ° C.

Example 1-14 3 parts by weight of VC / MA (Note 1-9), MAPB 1,4 (Note 1-8)
A coating agent was prepared by dissolving 2 parts by weight of the above in 95 parts by weight of THF. Applicable resin: (PC + ABS), PC (2), (PA
+ PPE), EP. Non-contact static voltage application, application temperature: 12
0 ° C.

Example 1-15 A coating agent was prepared by dissolving 1.5 parts by weight of chloroprene (Note 1-10) and 3.5 parts by weight of a polyester adhesive (Note 1-2) in 95 parts by weight of toluene. Applicable resin: PBT, PC (1), U
P, PF, PUR-T (thermoplastic polyurethane resin).
Static voltage application temperature: 120 for PC, PBT, UP and PF
℃, PUR-T is 80 ℃.

Example 1-16 Chloroprene (Note 1-10) 1.5 parts by weight, 1,2-polybutadiene / maleic anhydride copolymer (hereinafter referred to as "MAPB"
1, 2 ") (Note 1-11) 3.5 parts by weight was dissolved in 95 parts by weight of toluene to prepare a coating agent. Applicable resin: (PC
+ PBT), UP. Non-contact static voltage application, application temperature: 12
0 ° C.

Examples 1-17 Highly chlorinated polypropylene (hereinafter abbreviated as "HCPP")
(Note 1-12) 1.5 parts by weight, styrene / maleic anhydride copolymer (hereinafter abbreviated as "SMA") (Note 1-13) 3.5 parts by weight methyl ethyl ketone (hereinafter abbreviated as "MEK") 9
Dissolve in 5 parts by weight to prepare a coating agent. Applicable resin: ABS
(1), (PC + ABS). Static voltage application temperature: ABS (1)
80 ℃, (PC + ABS) 120 ℃.

(Note 1-1) Nippon Paper's "Super Klon 8"
03MW ”(low chlorinated polypropylene, chlorine content 29.
5%) (Note 1-2) Toyobo "Byron 300" (copolyester, -COOH, -OH at both ends) (Note 1-3) Nippon Paper's "Super Clone 822" (carboxyl group-containing low chlorine) Polypropylene, chlorine content 24.
5%) (Note 1-4) "Eva Flex 450" manufactured by Mitsui Petrochemical
(Ethylene / vinyl acetate copolymer, vinyl acetate content 45%) (Note 1-5) Arakawa Chemical Co., Ltd. "Ester gum AAV" (rosin ester) (Note 1-6) Mitsui Toatsu Chemical's "maleinized PP" (propylene・ Maleic anhydride copolymer, maleic anhydride content 15%) (Note 1-7) Arakawa Chemical's "Tamanor 145" (rosin modified phenolic resin) (Note 1-8) Nippon Soda's "solid maleated 1,4 polybutadiene" AN4120 "(maleic anhydride content 20%) (Note 1-9) Nippon Zeon's" Adhesive PVC resin for paints 4
00X110A "(vinyl chloride / maleic anhydride copolymer, maleic anhydride content about 5% <estimated value>) (Note 1-10) Denkachloroprene M3 manufactured by Denki Kagaku Kogyo
0 "(general-purpose chloroprene, Mooney viscosity 38 ± 4) (Note 1-11) Nippon Soda" solid maleated 1,2 polybutadiene AN2120 "(maleic anhydride content 20%) (Note 1-12) Asahi Denka ADEKA PLEN CP-1 "(highly chlorinated polypropylene, chlorine content 64%) (Note 1-13)" Dailark D350 "manufactured by Arcco Chemical
(Impact-resistant styrene-maleic anhydride copolymer, maleic anhydride content 15%)

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

Category 2 (Examples mainly comprising nitrile group-containing polymer: Examples 2-1 to 3) Example 2-1 Acrylonitrile / acrylic acid ester copolymer (abbreviated as "A / A") (Note 2-1) ) From a press sheet of isopropyl alcohol (“I
(Abbreviated as "PA"), the surface is washed, and then a static voltage is applied at an applied temperature of 110 ° C.

Example 2-2 A coating agent was prepared by dissolving 8 parts by weight of the A / A powder used in Example 2-1 in 92 parts by weight of a dimethylformamide / propylene carbonate mixed solvent (7: 3). P
A sample piece of IT (thermoplastic polyimide resin) is preheated to 230 ° C. in an oven, immersed in the coating agent for 10 seconds, then pulled up, dried at room temperature, an electrostatic voltage is applied to the coated sample piece, and an applied temperature of 110 ° C. .

Example 2-3 A sample piece was prepared from a pressed sheet of a composite material of hydrogenated nitrile rubber and zinc polyacrylate (Note 2-2), the surface of the test piece was washed with IPA, and then static voltage was applied. Temperature 80
° C.

(Note 2-1) "Barex 1" manufactured by Mitsui Toatsu Chemicals
043S ”(acrylonitrile-acrylic acid ester copolymer) (Note 2-2) Zeon 2000N series manufactured by Nippon Zeon (composite material of hydrogenated acrylonitrile-butadiene copolymer and zinc acrylate, zinc acrylate content about 30
%)

[0075]

[Table 5]

Category 3 [Combination of polymer (A) and polymer (B) having a double bond in a portion sandwiched between aromatic substituents in the main chain Example: Examples 3-1 to 1
0, Table 6]. Example 3-1 A coating agent was prepared by dissolving 2 parts by weight of SBS (Note 3-1) and 3 parts by weight of SMA (Note 1-13) in 95 parts by weight of MEK. Applicable resin:
ABS (1). Static voltage application temperature: 80 ° C.

Example 3-2 2 parts by weight of SBS (Note 3-1), polyester adhesive (Note
1-2) Dissolve 3 parts by weight of MEK in 95 parts by weight to prepare a coating agent. Applicable resin: PBT. Static voltage application temperature: 120 ° C.

Example 3-3 2 parts by weight of SBS (Note 3-1), MAPB1, 4 (Note 1-8)
A coating agent was prepared by dissolving 3 parts by weight in 95 parts by weight of toluene. Applicable resin: PC (2). Non-contact static voltage application, application temperature: 120 ° C

Example 3-4 A coating agent was prepared by dissolving 4 parts by weight of SBS (Note 3-2) and 1 part by weight of benzoic acid in 95 parts by weight of butyl acetate. Applicable resin: P
C (1). Static voltage application temperature: 120 ° C.

Example 3-5 A coating agent was prepared by dissolving 4 parts by weight of SBS (Note 3-3) and 1 part by weight of mercaptobenzothiazole in 95 parts by weight of butyl acetate. Applicable resin: (PS + PPE), static voltage application temperature:
80 ° C.

Example 3-6 A coating agent was prepared by dissolving 4 parts by weight of SIS (Note 3-4) and 1 part by weight of mercaptobenzothiazole in 95 parts by weight of butyl acetate. Applicable resin ABS (1). Static voltage application temperature 80 ° C.

Example 3-7 4 parts by weight of SBS (Note 3-1), p-toluenesulfonic acid 1
A coating agent was prepared by dissolving 95 parts by weight of MEK in 95 parts by weight. Applicable resin: ABS (1). Static voltage application temperature: 80 ° C.

Example 3-8 1 part by weight of SBS (Note 3-1), 1 part by weight of AS (Note 3-5), S
A coating agent was prepared by dissolving 3 parts by weight of MA (Note 1-13) in 95 parts by weight of MEK, and applied resins ABS (1), ABS (2),
(PS + PPE), heat resistant ABS, (PC + ABS). Static voltage application temperature: ABS (1), ABS (2), (PS + PP
E) is 80 ° C, heat resistant ABS, (PC + ABS) is 120
° C.

Example 3-9 A coating agent was prepared in the same manner except that a polyester adhesive (Note 1-2) was used instead of the SMA compounded in Example 3-8. Applicable resin (PS + PPE), PBT, PC
(1). Static voltage application temperature: 120 ° C.

Example 3-10 2 parts by weight of SBS (Note 3-1) and 8 parts by weight of SMA (Note 1-13) were melt-kneaded to obtain a resin composition. Immediately after wetting, 4kv by non-contact method
A negative voltage was applied, and the sample was dried by blowing air at room temperature.

(Note 3-1) Asahi Kasei "Toughprene 12"
5 "(SBS, styrene content 40%) (Note 3-2) Asahi Kasei" Sorprene 411 "(SBS,
Styrene content 40%) (Note 3-3) Asahi Kasei "Sorprene 414" (SBS,
Styrene content 30%) (Note 3-4) "SIS 5000" (styrene / isoprene copolymer / thermoplastic elastomer made by Japan Synthetic Rubber,
Styrene content 15%) (Note 3-5) Mitsui Toatsu Chemical's "Lightac-A" (acrylonitrile-styrene copolymer, acrylonitrile content 28%)

[0087]

[Table 6]

Example 4 An example of non-contact application in which the distance between the electrode plate and the surface of the sample piece was changed for the same sample will be described. In Example 3-8, the coating agent was applied to the ABS (1) sample piece, and the results of non-contact application with the gap between the electrode plate and the sample piece surface changed to 1 mm, 2 mm, and 4 mm are shown in Table 7. . The applied voltage was constant at a high voltage of 6 kv. The peel strength of the coating was displayed in comparison with the case of contact application of voltage.

[0089]

[Table 7]

Example 5 As an example in which the applied temperature and the applied voltage were changed for the same sample, the coating agent of Example 1-9 was applied to a (PC + ABS) sample piece, and high voltage application was applied to the electrode plate and sample surface. Interval of 1m
Table 8 shows the results of an experiment conducted by changing the applied temperature and the applied voltage while keeping m constant. Unit is kg / cm. The peel strength of the control sample to which no voltage was applied was 0.8 kg / cm.

[0091]

[Table 8]

[0092]

Since the resin composition for electroless plating and the electroless plating method of the present invention have the above-mentioned constitutions, it is possible to omit the corrosion treatment step which is carried out in the conventional plating method. Not only easy electroless plating, but also difficult to corrode, such as unsaturated polyester BMC, SM
In addition to C, thermosetting resin such as melamine resin, phenol resin, epoxy resin, or polyimide resin,
Resin called super engineering plastic such as liquid crystal resin,
Manufacture of electromagnetic wave shielding material because electroless plating can be performed very easily without sacrificing the original properties of the resin, such as being modified and corroded so as to be easily corroded, and without extra effort. It is expected to be applied to. Also, for wood products, the plating method of the present invention can be applied by applying a paint or a primer after the surface treatment.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of how to apply a negative electrostatic voltage in an electroless plating method according to the present invention.

[Explanation of symbols]

 1. 1. A film of the resin composition for electroless plating of the present invention Sample piece (base material) 3. Negative electrode plate 4. Earth plate 5. Teflon film 6. Slide glass 7. Clip 8. DC high voltage generator

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 25/06 LDX C08L 25/06 LDX 27/06 KGW 27/06 KGW 33/08 LJA 33/08 LJA 33/20 LJM 33/20 LJM 35/00 LHS 35/00 LHS 53/02 LLY 53/02 LLY 67/00 LPB 67/00 LPB C09D 201/02 PDC C09D 201/02 PDC C23C 18/16 C23C 18 / 16 A 18/20 18/20 Z (72) Inventor Toshiyuki Kita 1-90, Tsurumaihito-cho, Nara, Nara 69-302 (72) Inventor Kazuya Sato 1-5-8, Jinguji, Katano, Osaka

Claims (10)

[Claims] 1. A polymer (A) having one or more chemical structures selected from the group (a) below, and (b) below:
At least one of 1 and 2 is contained, The resin composition for electroless plating characterized by the above-mentioned. (A) A chemical structure in which a part of hydrogen in the polymer main chain is substituted with a halogen group or a nitrile group, and a chemical structure having a double bond in a portion sandwiched between aromatic substituents in the polymer main chain. . (B) 1, a polymer (B) having a functional group capable of forming a metal salt, 2, a low molecular weight compound (C) having a functional group capable of forming a metal salt, and having compatibility with the polymer (A) . 2. The functional group capable of forming a metal salt is a carboxy group, a mercapto group and a sulfonic acid group.
The resin composition for electroless plating described. 3. The polymer (A) is a chlorinated polypropylene having a chlorine content of 30% or less, and the polymer (B) is either a propylene / maleic anhydride copolymer or a 1,4-polybutadiene / maleic anhydride copolymer. The resin composition for electroless plating according to claim 1. 4. The polymer (A) is polychloroprene, and the polymer (B) is either a polyester having a carboxy group and a hydroxyl group at a terminal or a 1,2-polybutadiene / maleic anhydride copolymer. Resin composition for electroless plating. 5. The resin composition for electroless plating according to claim 1, wherein the polymer (A) is an acrylonitrile / acrylic acid ester copolymer. 6. The polymer (A) is a styrene-butadiene-styrene block copolymer, and the polymer (B).
Is styrene / maleic anhydride copolymer or 1,4
A resin composition for electroless plating according to claim 1, which is one of polybutadiene / maleic anhydride copolymer. 7. The polymer (A) is a vinyl chloride / maleic anhydride copolymer, and the polymer (B) is 1,4-
Is it polybutadiene-maleic anhydride copolymer,
The resin composition for electroless plating according to claim 1, wherein the low molecular weight compound (C) is an aromatic carboxylic acid. 8. A polymer (A) having one or more chemical structures selected from the group (a) below, and (b) below:
After forming a coating film of the resin composition for electroless plating containing at least one of 1 and 2 on the plated surface of the non-conductive body,
A negative electrostatic voltage is applied to the coating film of the resin composition at a temperature equal to or higher than the glass transition point of the resin composition, and then the applied voltage is released at a temperature lower than the temperature, followed by a catalyst application and activation step. An electroless plating method comprising performing a plating step including. (A) A chemical structure in which a part of hydrogen in the polymer main chain is substituted with a halogen group or a nitrile group, and a chemical structure having a double bond in a portion sandwiched between aromatic substituents in the polymer main chain. . (B) 1, a polymer (B) having a functional group capable of forming a metal salt, 2, a low molecular weight compound (C) having a functional group capable of forming a metal salt, and having compatibility with the polymer (A) . 9. A polymer (A) having one or more chemical structures selected from the group (a) below, and (b) below:
A negative electrostatic voltage is applied to the surface of a resin molded product made of the resin composition for electroless plating containing at least one of 1 and 2 at a temperature equal to or higher than the glass transition point of the resin composition, and then lower than the temperature. An electroless plating method characterized in that an applied voltage is released at a temperature and then a plating step including a catalyst application and activation step is performed. (A) A chemical structure in which a part of hydrogen in the polymer main chain is substituted with a halogen group or a nitrile group, and a chemical structure having a double bond in a portion sandwiched between aromatic substituents in the polymer main chain. . (B) 1, a polymer (B) having a functional group capable of forming a metal salt, 2, a low molecular weight compound (C) having a functional group capable of forming a metal salt, and having compatibility with the polymer (A) . 10. The electroless plating method according to claim 8 or 9, wherein the coating film of the resin composition is formed by drying by non-contact application of static voltage in a state where the solvent remains on the surface to be plated.