JP5327494B2 - Method for producing catalyst concentrate for electroless plating and method for applying plating catalyst using the same - Google Patents

Description

The present invention relates to a method for producing a catalyst concentrate for electroless plating and a method for applying a plating catalyst using the same.

  In recent years, downsizing, high performance, and multi-functionality of electronic components have been promoted, and higher density such as fine patterning has also been promoted in wiring boards used therefor. In recent years, the formation of wiring by the semi-additive method has become the mainstream of fine pattern formation. A general semi-additive method is to roughen the insulating layer with an oxidizing agent such as permanganic acid, impart a palladium catalyst, perform electroless copper plating, and electroless copper as exemplified in JP-A-3-217526. In this method, a resist pattern is formed on the plating, the resist is removed after pattern electroplating, and electroless copper plating other than the conductor circuit is removed by etching. As the palladium catalyst, a Pd—Sn colloidal catalyst is generally used. This Pd-Sn colloidal catalyst is produced by mixing polymolar tin (II) chloride and palladium chloride in an acidic solution containing excess chloride ions. The colloid diameter is said to be about 500 mm, and since it is relatively large, it has been suggested that the adhesiveness and the deterioration of the insulating property are adversely affected.

  In recent years, in the semi-additive process, an example using a catalyst composed of palladium ions and an amine complexing agent as exemplified in JP-A-1-279964 and JP-A-1-195281 has been increasing. As exemplified in JP-A-5-202483, when a catalyst composed of palladium ions and an amine complexing agent is used, the time required for the catalyst application process can be shortened while maintaining the adhesion and insulation of the conductor pattern. it can. These catalysts are generally used alkaline. In actual operation, the catalyst composed of the palladium ion and the amine complexing agent is stored in a concentrated solution of about 3 to 40 and diluted before use. Thereby, the transportation cost of the catalyst can be reduced. The higher the concentration factor, the more the catalyst transportation cost can be reduced.

JP-A-3-217526 Japanese Laid-Open Patent Publication No. 1-227964 JP-A-1-195281 JP-A-5-202483

  It has been found that the catalyst composed of the palladium ion and the amine complexing agent has a high concentration ratio, and the stability is extremely poor when the pH is high. Furthermore, the inventors have clarified the following after intensive research. The catalyst comprising the high concentration, high pH palladium ion and the amine complexing agent changes its complex structure during storage, and a substitution reaction with an aqua ligand is observed. This substitution reaction depends on the hydroxide ion concentration and palladium ion concentration in the liquid. Therefore, the higher the pH, the more likely the catalyst will deteriorate. Furthermore, the higher the concentration factor, the more likely the catalyst will deteriorate. Therefore, conventionally, countermeasures have been taken by storing the palladium concentrate in an acidic region having a pH of 4 or less without complex formation, and performing dilution and complex formation at the time of use. This method has the following problems in the industry.

Non-complexed palladium concentrate prepared at the factory by a manufacturer specializing in plating chemicals is sold to customers. Each manufacturer of the supplier performs complex formation by changing the palladium concentrate from (acidic) to (neutral or alkaline). This complex formation requires aging for about 2 hours at high temperature and may fail. In other words, it is necessary for each manufacturer to purchase a complex formation process that is most likely to fail. The present invention improves the above problems and provides a method for producing a concentrated catalyst solution for electroless plating with good storage stability, and also provides an optimum use method (plating catalyst application method).

The present invention is as follows.
A method for producing a catalyst concentrate for electroless plating containing a 1.2-valent palladium compound and an amine complexing agent, and after preparing a catalyst concentrate for electroless plating at a pH of 10 or higher, a buffer for adjusting pH The pH is 4 or more and less than 10 , and the concentration ratio (n) with respect to the electroless plating catalyst solution is in the range of 3 to 40 ( palladium concentration of 0.005 n to 2.0 ng / L, of palladium ion and amine complexing agent). A method for producing a concentrated catalyst solution for electroless plating, wherein the molar ratio is adjusted to a range of 1: 1 to 1:20 (n is a real number of 3 to 40) .
2. Item 2. The method for producing a catalyst concentrate for electroless plating according to Item 1, wherein the catalyst concentrate for electroless plating is adjusted to be alkaline (pH 7 or higher) from the pH of the catalyst concentrate for electroless plating.
3. Item 3. The catalyst concentrate for electroless plating according to Item 1 or 2, wherein a divalent palladium compound and an amine complexing agent are complexed when a catalyst concentrate for electroless plating is prepared at a pH of 10 or more. Manufacturing method .
4 . Item 1 wherein the pH adjusting buffer is selected from oxalic acid, tartaric acid, acetic acid, citric acid, phthalic acid, 2- (N-morpholino) ethanesulfonic acid, citric acid, collidine, imidazole, phosphoric acid, and boric acid 3. A method for producing a catalyst concentrate for electroless plating according to any one of 3 above.
5 . Item 5. The method for producing a catalyst concentrate for electroless plating according to Item 4 , wherein the buffer is boric acid.
6 . Concentration ratio of the electroless plating catalyst concentrate is n times, and boric acid concentration, for electroless plating according to claim 5, characterized in that in the range of 0.2n~10n (g / L) A method for producing a catalyst concentrate (n is a real number of 3 to 40) .
7 . Item 7. The method for producing a concentrated catalyst solution for electroless plating according to any one of Items 1 to 6 , wherein the amine complexing agent comprises two or more amine complexing agents.
8 . 3 process, then, an electroless plating catalyst concentrate obtained by the process of electroless plating catalyst concentrate according to any one claim 1 to 7 in which the pH is immersed object to be plated in an aqueous solution of 3 or less A plating catalyst application method comprising a step of immersing an object to be plated in an electroless plating catalyst solution diluted by 40 times and adjusted to pH 7 or higher.
9 . Item 9. The method for applying a plating catalyst according to Item 8 , comprising a step of immersing the object to be plated in an aqueous solution containing an amine-based additive before the step of immersing the object to be plated in an aqueous solution having a pH of 3 or less.

  In addition to providing a catalyst concentrate for electroless plating with good storage stability, it is possible to provide a method for applying a plating catalyst using the same.

Actually used by diluting the electroless copper plating concentrate obtained by the method of electroless copper plating concentrate according to the invention with a divalent palladium compound, since enrichment solution you containing the amine complexing agent To do. If it is an n-fold concentrated solution, it is diluted n-fold and used. Hereinafter, n is defined as the concentration ratio (= dilution ratio). The concentration factor n is preferably in the range of 3-40. If the concentration rate is smaller than this, the transportation cost becomes higher, and if the concentration rate is higher than this, the stability becomes insufficient.

Examples of the divalent palladium compound include palladium chloride, palladium fluoride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium oxide, palladium sulfide and the like. Of these, palladium chloride is preferred. It is desirable as palladium concentration in the range of 0.005 n ~2.0 n g / L.

  An amine complexing agent is a compound in which one or more hydrogen atoms of ammonia are substituted with a hydrocarbon residue R, and is a complexing agent for Pd ions. Here, ammonia is also included. The amine retains an unshared electron pair on the N atom and tends to complex with palladium ions. As amines, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pyridine, 2-aminopyridine, 3-aminopyridine , 4-aminopyridine, ethylenediamine, ethanolamine, triethanolamine, linear amine compounds such as ethylenediaminetetraacetic acid, and cyclic amine compounds, and one or two or more of them are used. If the amine complexing agent is too strong, the solubility of the palladium complex will decrease, and if the amine complexing agent is too hydrophilic, the adsorptivity to the resin will decrease. Need to be considered. The molar ratio of palladium ion to amine complexing agent is preferably in the range of 1: 1 to 1:20.

  Usually, palladium ions and amines are easily complexed at pH 10 or higher. However, if the electroless plating catalyst concentrate prepared at a pH of 10 or more is stored as it is, a problem occurs. As a result of intensive research, the inventors have found that the catalyst concentration solution for electroless plating composed of palladium ions and amines changes in the complex structure as the palladium concentration is higher and the hydroxide ion concentration is higher, and the absorption spectrum is changed. I understand. It has been found that the reaction rate can be expressed by the following equation (1).

  That is, it is suggested that the electroless plating catalyst composed of palladium ions and amines is difficult to store in a concentrated solution in a complexed state. Therefore, the present invention is characterized in that a catalyst concentrate for electroless plating is prepared at a pH of 10 or more, and the pH is adjusted to a range of 4 or more and less than 10, and stored. Desirably, a catalyst concentrate for electroless plating is prepared at a pH of 10 or higher, and the pH is adjusted to a range of 6 to 9 and stored. Although it depends on the type of amine, if the pH is 10 or more, the complex structure tends to change. On the contrary, when the pH becomes acidic, the complex structure tends to change. The essence of the present invention is to store a catalyst concentrate for electroless plating prepared under strong alkaline conditions (pH 10 or more) with an alkali to weak acid (pH 4 or more and less than 10), and preferably without alkali stored with an alkali to weak acid. It is to use the catalyst concentrate for electroplating more alkaline (pH 7 or more) than the storage conditions.

The concentrated solution preferably contains a buffer solution for pH adjustment. Examples of the buffer include oxalic acid, tartaric acid, acetic acid, citric acid, phthalic acid, 2- (N-morpholino) ethanesulfonic acid, citric acid, collidine, imidazole, phosphoric acid, boric acid, etc. preferable. By adding boric acid, it becomes possible to bring the concentrated catalyst solution for electroless plating made of strong alkali into a pH range of 4-10. This buffer solution has a buffer capacity even in a storage solution, and also has a buffer capacity when actually used as a catalyst for electroless plating. The boric acid concentration is preferably in the range of 0.2 n to 10 n (g / L). For example, if the concentration ratio (= dilution ratio) n is 5 times, the boric acid concentration is preferably in the range of 1 to 50 g / L. When the boric acid concentration is lower than this, the buffering capacity is insufficient, and when the boric acid concentration is higher than this, there is a problem that the Pd adsorption amount decreases.

  For example, the electroless plating catalyst 10-fold concentrated liquid (1 L) is produced as follows. First, 0.5-5 g / L of sodium chloride is added to pure water. Next, 0.1-20 g / L of palladium chloride is added. Subsequently, 1 to 20 ml of 1N sodium hydroxide and an amine complexing agent having a molar concentration of 1 to 20 times that of palladium are added to adjust the pH to 10 or more. Thereafter, 2 to 100 (g / L) boric acid is added to adjust the pH to a range of 4 or more and less than 10.

The electroless plating catalyst concentrate is diluted n times. From the viewpoint of the stability and characteristics of the liquid, it is preferable to adjust the pH to be alkaline (pH 7 or higher). As for pH at the time of use, 7-12 are more preferable, and the range of 8-11 is especially preferable.

Hereinafter, an example of a method of using the diluted solution (diluted n times) of the above-described electroless plating catalyst concentrate will be described. First, an object to be plated such as a resin is immersed in an aqueous solution containing an amine-based additive. The pH of the aqueous solution is preferably alkaline. As the amine-based additive, amino alcohols and aminosilanes are preferable. Since the amino group contained in these amine-based additives tends to be positively charged, it becomes easy to adsorb the negatively charged palladium complex. An example of such an aqueous solution is CLC201 (trade name, manufactured by Hitachi Chemical Co., Ltd.). Subsequently, washing with water is performed to remove excess amine-based additives.

  Thereafter, the object to be plated is immersed in an aqueous solution having a pH of 3 or less through an etching process or the like as necessary. Thereby, since the amino group adsorbed on the surface of the object to be plated can be positively charged, the amount of palladium adsorbed is improved. After the object to be plated is immersed in an aqueous solution having a pH of 3 or less, the object to be plated is immersed in the Pd catalyst diluent (diluted solution of the electroless plating catalyst concentrate). The immersion time is preferably 1 to 10 minutes, and the immersion temperature is preferably 10 to 50 ° C.

  Next, the metal Pd is formed on the surface of the object by immersing the object to be plated in the reducing agent aqueous solution. As the reducing agent aqueous solution, an aqueous solution of a reducing substance such as formaldehyde, stannous chloride, sodium hyposulfite, dimethylamine borane, lithium aluminum hydride, sodium borohydride or the like is used. The concentration of the reducing substance varies depending on its reducing power, but is preferably 0.01 to 10% by weight, more preferably 0.1 to 2% by weight, and pH = 7 to 14 is preferable.

  Plating is performed by immersing the object on which the metal particles are formed as described above in an electroless plating solution such as electrolytic copper plating. Examples of the electroless copper plating solution include CUST-201 (trade name, manufactured by Hitachi Chemical Co., Ltd.) and CUST-4600 (trade name, manufactured by Hitachi Chemical Co., Ltd.).

Example 1
In 200 ml of water, 2.6 g of sodium chloride and 4 g / L of palladium chloride are dissolved, 70 ml of 10% by weight isobutylamine and 22 ml of 4% by weight monomethylamine are added, and 6.2 ml of 1N NaOH is added and stirred. The pH was adjusted to 10 or higher. Then, 1 g / L of water and boric acid were added and stirred, pH was adjusted, and 2 L of electroless plating catalyst 5 times concentrated liquid was produced. The adjusted pH is shown in Table 1.

Example 2
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 2 g / L of boric acid was added. The adjusted pH is shown in Table 1.

Example 3
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 3 g / L of boric acid was added. The adjusted pH is shown in Table 1.

Example 4
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 5 g / L of boric acid was added. The adjusted pH is shown in Table 1.

Example 5
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 7.5 g / L of boric acid was added. The adjusted pH is shown in Table 1.

Example 6
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 10 g / L of boric acid was added. The adjusted pH is shown in Table 2.

Example 7
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 17.5 g / L of boric acid was added. The adjusted pH is shown in Table 2.

Comparative Example 1
A 5-fold concentrated solution of electroless plating catalyst was prepared in the same manner as in Example 1 except that boric acid was not added. The adjusted pH is shown in Table 2.

Comparative Example 2
An electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that boric acid was added in advance to 200 ml of water. The pH at this time was less than 10. It was found that it was cloudy from the beginning of the bath, and complex formation was not easily performed.

Comparative Example 3
A 2 L electroless plating catalyst 5-fold concentrated solution was prepared in the same manner as in Example 1 except that 0.5 g / L of boric acid was added. The adjusted pH is shown in Table 2.

Absorption spectrum test The electroless plating catalyst 5-fold concentrated solution prepared under the conditions of Examples 1 to 7, Comparative Example 1 and Comparative Example 3 was stored for 0 days, 30 days (one month), and 60 days (two months). After storage, the mixture was diluted 5 times, boric acid was added to 3.5 g / L, and the pH was adjusted to 9.8 with a 1 N aqueous sodium hydroxide solution. Next, the absorption spectrum was measured with a double beam spectrophotometer U-2001 (trade name, manufactured by Hitachi, Ltd.), and the absorbance (ABS) at 320 nm was measured.

Pd adsorption amount confirmation test A copper clad laminate MCL-E679F having a thickness of 0.6 mm was entirely etched with an etching solution. Next, the substrate was immersed in an electroless copper plating catalyst pretreatment liquid CLC-201 (trade name, manufactured by Hitachi Chemical Co., Ltd.) containing aminosilane at 50 ° C. for 5 minutes. Next, it was washed with water at room temperature (25 ° C.) for 3 minutes. Subsequently, the substrate was immersed in 10% by volume sulfuric acid at room temperature (25 ° C.) for 1 minute. Next, the electroless plating catalyst 5-fold concentrated solution prepared under the conditions of Examples 1 to 7, Comparative Example 1 and Comparative Example 3 is stored for 0 days, 30 days (one month), and 60 days (two months). After that, the substrate was treated with various electroless plating catalysts prepared by adding boric acid to 3.5 g / L and adjusting the pH to 9.8 with a 1 N aqueous sodium hydroxide solution. Went. Next, it was washed with water at room temperature (25 ° C.) for 1 minute. Subsequently, treatment was carried out for 5 minutes at room temperature (25 ° C.) with an aqueous solution containing sodium borohydride 0.15 wt% and sodium hydroxide 0.5 wt%. Next, it was washed with water at room temperature (25 ° C.) for 1 minute. Next, the substrate was immersed in aqua regia to dissolve palladium, and then the palladium in the solution was measured by atomic absorption method to measure the amount of palladium adsorbed on the substrate. For measurement of palladium, Polarized Zeeman Atomic Absorption Spectrometer Z-5310 (manufactured by Hitachi, Ltd., trade name) was used.

  Tables 1 and 2 show the results of the absorption spectrum test and the Pd adsorption amount confirmation test.

  As shown in Table 1, the concentrated pH of the plating catalyst prepared in Examples 1 to 7 was less than 10. It was found that there was almost no change in the color of the catalyst, no change in absorbance, and no change in the Pd adsorption amount, and the storage stability was good. On the other hand, it was found that the plating catalyst concentrate prepared in Comparative Example 2 did not proceed well with complex formation when the pH at the time of preparation was less than 10, and the entire solution became cloudy. It was shown that complexation should be performed at a pH of 10 or higher. On the other hand, it is considered that the plating catalyst concentrates prepared in Comparative Examples 1 and 3 have a complex structure changing because the adjusted pH is 10 or more. It was found that the catalyst color, absorbance, and Pd adsorption amount all changed.

As described above in detail, according to the present invention, a catalyst concentrate for electroless plating with little change in catalyst color, change in absorbance, and change in Pd adsorption amount and good storage stability can be produced.

Claims (9)

A method for producing a catalyst concentrate for electroless plating containing a divalent palladium compound and an amine complexing agent, wherein the catalyst concentrate for electroless plating is prepared at a pH of 10 or higher, and then the pH is adjusted with a buffer for pH adjustment. In the range of 4 to less than 10 and the concentration ratio (n) to the electroless plating catalyst solution is in the range of 3 to 40 (as the palladium concentration of 0.005 n to 2.0 ng / L, of palladium ion and amine complexing agent). A method for producing a concentrated catalyst solution for electroless plating, wherein the molar ratio is adjusted to a range of 1: 1 to 1:20 (n is a real number of 3 to 40) . The method for producing a catalyst concentrate for electroless plating according to claim 1, wherein the catalyst concentrate for electroless plating is adjusted to be alkaline (pH 7 or more) from the pH of the catalyst concentrate for electroless plating. The catalyst concentration for electroless plating according to claim 1 or 2, wherein a divalent palladium compound and an amine complexing agent are complexed when a catalyst concentration solution for electroless plating is prepared at a pH of 10 or more. Liquid manufacturing method . The buffer for pH adjustment is selected from oxalic acid, tartaric acid, acetic acid, citric acid, phthalic acid, 2- (N-morpholino) ethanesulfonic acid, citric acid, collidine, imidazole, phosphoric acid, and boric acid. The manufacturing method of the catalyst concentrate for electroless plating in any one of -3. The method for producing a concentrated catalyst solution for electroless plating according to claim 4, wherein the buffer is boric acid. 6. The electroless plating according to claim 5, wherein the concentration ratio of the catalyst concentrate for electroless plating is n times, and the boric acid concentration is in the range of 0.2 n to 10 n (g / L). (N is a real number of 3 to 40). The method for producing a concentrated catalyst solution for electroless plating according to any one of claims 1 to 6, wherein the amine complexing agent comprises two or more types of amine complexing agents. A step of immersing an object to be plated in an aqueous solution having a pH of 3 or less, and then 3 of the catalyst concentrate for electroless plating obtained by the method for producing a catalyst concentrate for electroless plating according to claim 1. A plating catalyst application method comprising a step of immersing an object to be plated in an electroless plating catalyst solution diluted to 40 times and adjusted to pH 7 or higher.   The method for applying a plating catalyst according to claim 8, further comprising a step of immersing the object to be plated in an aqueous solution containing an amine-based additive before the step of immersing the object to be plated in an aqueous solution having a pH of 3 or less.