JPH0583664B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for electroless plating of fibers.

Prior art and its problems In order to perform electroless plating with copper, nickel, cobalt, etc. on a plated object that does not have catalytic activity, a catalytic substance is attached to the plated object to increase the catalytic activity. It is necessary to grant. The following methods are known as such methods.

B. Sensitize the surface of the plated object with a sensitizer solution consisting of a hydrochloric acid acidic stannous chloride solution,
Next, a method of activating with an activator solution containing noble metal ions such as Pd, Au, Ag, etc.

(b) A method in which the material is immersed in a catalyst solution, which is a Pd-Sn sol solution, and then activated with an accelerator solution.

However, if electroless plating is performed by applying resist ink to parts of the object to be plated that do not require plating before or after the activation treatment in a) or b) above, When the material is water-permeable, such as fiber, the activating liquid or plating liquid penetrates inside, and the disadvantage is that the contours of the areas that require plating and those that do not need to be plated are not sharp. be.

As a method to improve these defects, water-permeable materials to be plated such as fibers are treated with a sensitive solution containing stannous chloride and hydrochloric acid, washed with water, dried, and then treated with a solution consisting of palladium chloride and hydrochloric acid. Alternatively, a water-soluble paste made by adjusting a solution of silver salt and ammonia to the desired viscosity with a water-soluble polymer substance is applied to the area that requires plating to activate it, and then the unnecessary water-soluble paste is removed. , followed by electroless plating.

However, in this method, it is necessary to treat the fibers to be coated with a solution consisting of stannous chloride and hydrochloric acid, wash with water, dry, and then apply a water-soluble paste. , the process becomes complicated. Furthermore, a water-soluble paste of a solution of palladium chloride and hydrochloric acid has a low pH and the presence of free hydrochloric acid, so there is a problem in that it severely corrodes the equipment and dryer used. In addition, if silver is activated with a water-soluble paste of ammonia solution, copper plating is possible, but plating of nickel and other heavy metals is difficult, and the stability of this water-soluble paste is also poor. There is a problem. Furthermore, in areas activated with catalyst materials such as palladium chloride salts and silver salts, the adhesion of the catalyst materials is insufficient, so the water-washing process to remove unnecessary water-soluble paste may cause adhesion. There is a problem that the catalyst material easily falls off and it is difficult to perform plating with good reproducibility.

Means for Solving the Problems The present inventor has conducted extensive research in order to find a method for electroless plating on water-permeable materials that do not have catalytic activity, such as fibers. As a result, a paste-like composition containing a palladium salt as a catalyst for electroless plating and a mineral oil-based O/W emulsion paste binder resin and adjusted to a pH of 3 to 7 was applied to the fiber surface and heat-treated. It has been found that by carrying out this method, the catalyst substance can be attached to the fiber surface very easily, and the adhesion force is very strong. In addition, since this paste-like composition has a moderate viscosity, when applied to fibers, it does not penetrate into the fibers, and the boundary between the applied and uncoated areas becomes clear, so it can be applied to the fibers easily. It was also found that it is suitable as a pretreatment for burning.

That is, the present invention includes:) mineral oil-based O/W emulsion paste 50 to 95% by weight;) palladium salt 0.01 to 3.0%;
wt%, and) binder resin 0.5-3.0 wt%
The present invention relates to a method for electroless plating on fibers, which comprises applying a paste composition containing the above and having a pH of 3 to 7 onto the fiber surface, heat-treating the composition, and then performing electroless plating.

The paste composition of the present invention contains a palladium salt, a mineral oil-based O/W emulsion paste, and a binder resin as active ingredients, and has a pH adjusted to 3 to 7.

As the palladium salt, a divalent palladium salt can be used, and for example, palladium chloride, palladium bromide, palladium nitrate, palladium sulfate, etc. can be used. These palladium salts are usually used as an aqueous solution with a concentration of about 1 to 50 g/g. To this aqueous solution, depending on the amount of palladium salt used, an amount of hydrochloric acid required to dissolve the palladium salt is added.

Mineral oil-based O/W emulsion paste is made by adding a polyethylene glycol diester type or diether type thickener and a nonionic surfactant to mineral oil such as mineral turpentine or furnace oil, and adding it to water according to a conventional method. It is emulsified. Here, the thickener is RCOO(CH ₂ CH ₂ O) _o COR or RCH ₂ O(CH ₂ CH ₂ O) nCH ₂ R [wherein R is C ₉ to _{C 21} saturated or unsaturated carbonized It is hydrogen, and n is an integer from 100 to 500. ] A polyethylene glycol diester or diether represented by the following is used. As the activator, a nonionic surfactant with an HLB of 8 to 18 is preferable, and for example, polyethylene glycol ether of a higher alcohol having 10 or more carbon atoms, nonylphenol, or octylphenol can be used. The proportions of each component of mineral oil-based O/W emulsion paste are (a) 30 to 70% by weight of mineral oil, (b) 1.0 to 5.0% by weight of thickener and activator in total (however, 100 parts by weight of thickener) (10 to 1000 parts by weight of the active agent), and (c) the balance is water.

If such a mineral oil-based O/W emulsion paste is used, the palladium salt can be easily transferred from the paste composition to the fibers during the heat treatment process, and the palladium salt can be firmly attached to the fibers.

As the binder resin, resins commonly used for pigment printing can be used, including acrylic resins,
Examples include vinyl resins, olefin resins, butadiene resins, and urethane resins. Particularly preferred resins include acrylic resins or vinyl resins copolymerized with small amounts of crosslinkable monomers, such as N-methylolacrylamide and glycidyl acrylate. Usually, these binder resins are used in an emulsified dispersion state,
The resin solid content is approximately 20 to 60% by weight.

The proportion of each component in the paste composition of the present invention is:
Mineral oil based O/W emulsion glue 50-95% by weight, palladium salt 0.01-3.0% by weight, and binder resin
It is necessary to set it as 0.5-3.0 weight%. Therefore, it is necessary to blend the mineral oil-based O/W emulsion paste, palladium salt aqueous solution, and binder resin dispersion so that the concentrations of each active ingredient fall within the above ranges.

If the amount of palladium salt is less than 0.01% by weight, the amount of catalyst will be insufficient and plating will be difficult to precipitate.
If it exceeds 3.0% by weight, the plating on the catalyst-applied area will become black, resulting in poor appearance, which is not preferred. Furthermore, if the amount of binder resin exceeds 3.0% by weight, the resin content thickly coats the surface of the palladium salt and inhibits the catalytic activity of the palladium salt, while if it is less than 0.5% by weight,
This is not preferred because it reduces its effectiveness as a binder.

A paste composition containing each component in the above proportions has a viscosity of about 1,000 to 100,000 cps, which is suitable for coating on fibers. If the viscosity of the paste composition is particularly in the range of about 3,000 to 50,000 cps, it will be easy to accurately apply a desired pattern to fibers, and it will exhibit particularly excellent properties as a pretreatment agent for partial plating. Therefore, as a pretreatment agent for partial plating, mineral oil-based O/
The type, concentration, amount used, etc. of the W emulsion glue, palladium salt aqueous solution, and binder resin dispersion, etc.
It is preferable to select so that the ratio of each component falls within the above composition range and the viscosity is approximately 3000 to 50000 cps. If the viscosity is within this range, it will be possible to accurately apply the paste composition in the desired pattern to the fibers, and since the paste composition will not penetrate into the fibers, it will be possible to form clear contours. Partial plating can be obtained.

In the present invention, the pH of the paste composition is 3 to 3.
7, preferably 4-6. If the pH is less than 3, the adhesion of the palladium salt to the fibers will be insufficient, and the palladium salt will easily fall off from the fibers during the water washing process after applying the paste composition and heat treatment, resulting in poor adhesion in the electroless plating process. On the other hand, if the pH exceeds 7, palladium hydroxide will be generated and the palladium particles will become coarse during storage of the paste composition, which is undesirable because metal precipitation will deteriorate. This is not preferable because the adhesion strength decreases. In order to adjust the pH to 3 to 7, specifically, soda carbonate, potassium carbonate,
Alkali metal salts such as caustic soda, caustic potassium, sodium hydrogen carbonate, potassium hydrogen carbonate, aqueous ammonia, etc. can be used.

In the present invention, the paste composition prepared in this way is applied to the parts of the fibers that require electroless plating and heat-treated to firmly adhere the palladium salt as a catalyst substance to the fibers. be able to. There are no particular restrictions on the coating method; for example, a method of printing a desired pattern using a normal printing machine, such as a flat screen, rotary screen, or roller, or a method of coating using a coater such as a knife coater or a roll coater. It can be processed using the following methods.

Next, the fibers coated with the paste composition are
By heat treating at a temperature of 80 to 180°C, preferably 100 to 140°C, the palladium salt contained in the paste composition can be firmly attached to the fibers.

After heat treatment, unfixed palladium salts and activators are removed by washing with water, and the surface is activated with sulfuric acid, hydrochloric acid, etc. according to a conventional method, and then plated by immersion in an electroless plating solution. Do this.

The fibers to which the plating method of the present invention can be applied include synthetic fibers such as polyester, acrylonitrile, polyamide, and polyvinyl alcohol, acetate,
These include semi-synthetic fibers such as triacetate, recycled fibers such as rayon, natural fibers such as silk and cotton, mineral fibers such as glass fiber, and mixed fibers thereof, which may be in the form of fibers, or may be yarns,
It may be in the form of textile products such as woven fabrics, knitted fabrics, and non-woven fabrics.

Metals that can be electrolessly plated by the method of the present invention include copper, nickel, cobalt,
Examples include iron, silver, tin, platinum, and alloys thereof.

Effects of the Invention According to the method of the present invention, a catalyst substance can be firmly attached to fibers without requiring complicated operations, so that electroless plating can be easily applied to fibers. Furthermore, since the boundary between the areas to which the catalyst has been applied and the areas to which the catalyst has not been applied becomes clear, it becomes possible to apply partial plating in any pattern to the fibers.

Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Mineral oil-based O/W consisting of 60% by weight of mineral turpentine, 1% by weight of distearate of polyethylene glycol (molecular weight 6000), 0.7% by weight of polyethoxynonylphenol ether (number of moles of E ^O added: 10%), and 38.3% by weight of water. Consists of 80% by weight of emulsion glue, 40g/4% by weight of palladium chloride solution (1% HCl aqueous solution), 3.5% by weight of self-crosslinking acrylic emulsion resin (40% resin content), and 10g/12.5% by weight of caustic soda aqueous solution, PH5 A uniform paste-like composition with a viscosity of 20,000 cps was prepared at .0.
This paste composition contains 80% by weight of mineral oil-based O/W emulsion paste, 0.16% by weight of palladium salt, and 1.4% by weight of binder resin.

Using this paste composition, a tortoiseshell pattern was printed on well-cleaned polyester taffeta using a flat screen, and after heat treatment at 140°C for 2 minutes,
Wash thoroughly with water, immerse in 10% sulfuric acid at 30℃ for 5 minutes,
Washed with water. Next, copper sulfate 8 g/, 37% formalin 8 ml/, EDTA 12 g/, caustic soda 9
The sample was immersed for 30 minutes at 40°C in an electroless copper plating solution containing 1 g/g of potassium ferrocyanide and 1 g/g of potassium ferrocyanide. As a result, copper was deposited only in the hexagonal pattern areas to which the catalyst was applied, and the boundary between the areas where copper was deposited and the areas where copper was not deposited was clear.

On the other hand, when a similar process is carried out using a paste composition whose pH is adjusted to less than 3, copper does not precipitate because the palladium falls off rapidly during the water washing process before entering the plating solution. Ta. Further, when similar treatment was carried out using a paste composition to which no self-crosslinking acrylic emulsion resin was added, copper precipitation was not good.

Example 2 Nickel chloride 20 instead of electroless copper plating solution
g/, sodium citrate 30g/, sodium hypophosphite 15g/, ammonium chloride 30g/
Using an electroless nickel plating solution consisting of
The treatment was carried out in the same manner as in Example 1, except that the sample was immersed for a minute. As a result, glossy nickel was deposited only on the hexagonal pattern area to which the catalyst had been applied.

Example 3 Emulsion glue 75 consisting of 60% by weight of furnace oil, 1.5% by weight of dilauryl ether of polyethylene glycol (molecular weight 6000), 1% by weight of polyethoxyoleyl ether (12 moles of E ^O added) and 37.5% by weight of water. Weight%, 40g/palladium chloride solution (1% HCl aqueous solution) 12% by weight, ethylene-vinyl acetate emulsion resin (resin content 45%) 5% by weight, and 40g/sodium carbonate aqueous solution 8.0% by weight,
A uniform paste-like composition with a pH of 4.5 and a viscosity of 7000 cps was obtained. In this paste composition,
Contains 75% by weight emulsion glue, 0.48% by weight palladium salt, and 2.25% by weight binder resin.

Using this paste composition, a line pattern was printed on nylon taffeta whose surface had been thoroughly cleaned using a roller machine, heat treated at 130°C for 3 minutes, thoroughly washed with water, and then soaked in a 10% sulfuric acid aqueous solution at 30°C for 5 minutes. After soaking for a minute, it was washed with water. Subsequently, it was immersed in the same copper plating solution used in Example 1 at 40°C for 30 minutes, and as a result, copper precipitated only in the part of the line pattern where the catalyst was applied, and in the part where copper was deposited and where it was not deposited. The boundaries between the parts were clear.

Example 4 The same process as in Example 3 was performed except that the electroless nickel plating solution used in Example 2 was used instead of the electroless copper plating solution and immersion was carried out at 40°C for 20 minutes. As a result, the catalyst Nickel was precipitated only on the line pattern portions that had been given.

Example 5 Mineral turpentine 57% by weight, distearate of polyethylene glycol (molecular weight 6000) 3% by weight
mineral oil-based O/W emulsion glue consisting of 40% water and 80% by weight, 40g/l palladium chloride solution (1% HCl aqueous solution) 4% by weight, self-crosslinking acrylic emulsion resin (resin content 40%) 3.5% % and 10 g/l caustic soda aqueous solution 12.5% by weight
A uniform sticky paste composition with a pH of 5 was prepared.

Using this paste composition, a ribbon pattern was printed on a polyester tropical cloth (basis weight 135 g/m ² ) using a flat screen printing machine, dried at 100°C for 3 minutes, and then subjected to high temperature (HT) steam treatment.
This was carried out at 105°C for 10 minutes. Next, heat this cloth to 80℃
After washing with water for 5 minutes, plating was performed at 40° C. for 15 minutes using the same electroless nickel plating solution used in Example 2. As a result, nickel plating was deposited only on the printed parts of the paste composition, and the boundaries between the parts where nickel was deposited and the parts where nickel was not deposited were clear, and a good partial plating film was formed.
When the surface resistance value of this plating film was measured using a surface resistance meter (Laresta, manufactured by Mitsubishi Yuka), it was found to be 12
It was Ω.

Also, when nickel plating is performed in the same manner, except that baking (dry heat) treatment is performed at 140°C for 3 minutes instead of the high temperature (HT) steam treatment described above, a good partial plating film can be obtained. formed,
The surface resistance value was 15Ω.

Comparative Example 1 In the paste composition used in Example 5,
A paste composition with the same composition was prepared without using the self-crosslinking acrylic emulsion resin.

Nickel plating treatment was performed on polyester tropical cloth in the same manner as in Example 5 except that this paste composition was used.
In both cases of steam treatment and baking (dry heat) treatment, the boundary between the nickel plating film and the unplated area becomes unclear, and a good partial plating film cannot be obtained. could not be formed. Furthermore, when the surface resistance value of the nickel plating film was measured in the same manner as in Example 5, the resistance value was high, exceeding the measurement limit (2×10 ⁶ Ω), and the conductivity was low.

Comparative Example 2 A palladium chloride solution was prepared by adding 3 ml of concentrated hydrochloric acid (35%) and water to 0.5 g of palladium chloride to make a total volume of 100 ml. Add 30 ml of the above palladium chloride solution to 20 ml of ammonia water (25%) to form a palladium ammine complex, then add 70 g of glucose and a 20% solution of Mayprocam NP-25 (manufactured by Sansho Co., Ltd.) to 500 ml of aqueous ammonia (25%).
g and water to make a total amount of 1000 g to prepare a sticky paste composition.

Instead of the paste composition used in Example 5,
Example 5 except for using the above paste composition
In the same manner as in Example 5, the same polyester tropical fabric used in Example 5 was subjected to nickel plating treatment, with high temperature (HT) steam treatment and baking (dry heat) treatment. In all cases, the paste composition fell off from the cloth during the water washing process, and almost no plating film could be formed.

Claims (1)

[Scope of Claims] 1. A paste composition containing 50 to 95% by weight of mineral oil-based O/W emulsion paste, 0.01 to 3.0% by weight of palladium salt, and 0.5 to 3.0% by weight of binder resin, and having a pH of 3 to 7, is applied to fibers. A method for electroless plating on fibers, which is characterized by applying electroless plating to fibers after applying the coating to the surface and subjecting it to heat treatment.