KR100757048B1 - Metal and rare metal non-electronic colloidal plating solution and their plating on fabric surface - Google Patents

Abstract

A nanometal colloidal solution for electroless plating which enables a chelating agent, a dispersant and a surfactant as additives to be simultaneously used in a metal salt and ammonia complex of the metal salt, particularly a silver ammonia complex of the metal salt, and has excellent water dispersibility while exhibiting the reproducibility of particle size distribution in a high concentrated metal salt solution is provided. A metal or precious metal colloidal solution for electroless plating comprises: a chelate dispersant composed of an acrylic acid derivative and a copolymer of maleic anhydride; and a reductant selected from water-soluble alcohols, thioglycol, thioglycolic acid and thiourea. The precious metal includes gold and silver, and salts of the precious metal are in the form of tetrachloroauric acid, silver nitrate, silver acetate, silver perchlorate, silver sulfate, and silver-ammonia complex. The metal includes copper, nickel and aluminum, and salts of the metal are in the form of copper sulfate, copper chloride, nickel sulfate, nickel chloride, and aluminum sulfate.

Description

Metal and Rare Metal Non-Electronic Colloidal Plating Solution and Their Plating on Fabric Surface}

The present invention relates to the preparation of an electroless metal colloidal plating solution having excellent dispersibility and a method of forming an electroless plating film on the surface of a fiber using the gastric plating solution.

BACKGROUND OF THE INVENTION A method of metal-plating an organic substrate on a noble metal or metal by an electroless plating method or a method of colloidating fine metal particles is well known.

When noble metal or metal is plated on the fiber as an organic material, the antimicrobial inherent to the metal, antistatic performance or electromagnetic shielding characteristics due to the general conduction performance of the metal can be added to the fiber, and its application range is gradually expanding.

When electroless plating of precious metals or metals on the fibers as organic materials, it is not easy to strongly adhere the metals to the fibers, which should be able to make an electroless plating solution that can control the particle size and the deposition rate of the deposited metal to an appropriate level at the same time. This is because a dense metal film can be formed on the fiber surface.

Even if fine metal nuclei of fine particles are produced, if the formation rate is too fast or coarse metal particles are produced, it is impossible to form a dense metal film on the surface of the fiber.

The method for preparing metal and precious metal colloidal electroless solutions has been steadily known in recent years. In the case of electroless plating of silver, which is frequently used for textile clothing among precious metals, silver nitrate is added to an aqueous solution of silver nitrate to obtain a silver ammonia complex. Ammonia complex- Electroless plating of silver using precursors involves the use of EDTA as a chelating agent (public publication 2005-74951, publication 2001-81958, Japanese Patent Application Laid-Open No. 1-165771), but when silver precipitates on an organic substrate, There is a tendency to coarsen and a tendency for silver to be deposited in plating baths for a long time, and a method of using Pd catalyst to compensate for this is known (Japanese Patent Application Laid-Open No. 2-101173). It is known to obtain silver colloids by using the Korean public publication 2005-40226.

As silver precursor, silver acetate itself, silver perchlorate, silver nitrate, silver sulphate and silver sulfate are used as polyacrylic acid as a dispersant (Republic of Korea 2000-239713), but they tend to precipitate quickly due to insufficient stability of particles. Using PVP, PVB as stabilizer and organic alcohol as solvent (published in Korea 2004-96791), using gelatin and surfactant as dispersant (Korean publication 10-473478), using gamma rays (Korean notification) 10-479847), a method using a polymeric pigment dispersant and an alcohol solvent (published in Republic of Korea 2003-22660) and the like are known.

The role of chelating agents, dispersants and surfactants as additives in the preparation of electroless plating metals and precious metal colloidal solutions is well known.

However, these additives cannot be used simultaneously for metal salts and ammonia complexes of metal salts, especially silver ammonia complexes. In addition, high concentrations of 5 to 15% of metal salt solutions exhibit particle size distribution reproducibility and provide excellent water dispersibility. It is not easy to make

Accordingly, an object of the present invention is to provide a colloidal solution having excellent dispersion performance while solving the above problems.

The present inventors use a acrylic acid derivative and a maleic anhydride copolymer as a chelating dispersant as a multifunctional additive capable of satisfying both the chelating effect and the dispersant effect and adding a suitable water-soluble alcohol to the form of the metal salts above or their concentration. The present invention has been completed since it is possible to make a nano colloidal solution which is not affected and maintains excellent dispersibility and to plate a dense metal layer on an organic substrate.

Precious metals in the present invention may be gold, silver, platinum, palladium and the like, but gold and silver are preferred, and the metals mean nickel, copper, aluminum.

The following describes mainly the electroless plating of silver.

Known silver electroless plating solution is silver salt, silver nitrate, silver acetate, silver perchlorate and silver sulfate are dissolved in distilled water, and then reducing agent is added to make silver colloidal solution, or silver nitrate is added to aqueous solution of silver ammonia to form silver ammonia complex. A method of reducing and plating silver by plating is used. At this time, when formaldehyde is added to the aqueous solution of silver ammonia complex as a reducing agent, the silver precipitates at high speed while the solution becomes dark brown.

At this time, if a chelating agent or a dispersing agent is added to the electroless plating solution, it is possible to adjust the speed and size of the precipitated silver to nanoparticle level.

In the present invention, the acrylate dispersant and the maleic anhydride copolymer as chelating dispersant which can simultaneously give the chelating effect and the dispersing effect-hereinafter referred to as the chelating dispersant-add about 10-30% by weight of silver salt, silver nitrate, silver acetate Silver, silver perchlorate and sulfuric acid can be used as silver precursors or silver ammonia complexes as silver precursors.The precipitation rate of silver is very slow even in the presence of a reducing agent at room temperature, and the particles are uniform in size. The resulting silver colloidal solution with excellent water dispersion stability can be obtained.

In the acrylic acid derivative and maleic anhydride chelate dispersant polymer, the monomer molar ratio of each polymer is acrylic acid: methacrylic acid: maleic anhydride = X: Y: Z where the mole fractions of X and Y are x and y, respectively, x (%) = 100X / (X + Y), y (%) = 100Y / (X + Y) and x + y = 100 (%). At this time, x and y each have a value in the range of 0 ≦ x ≦ 100 and 0 ≦ y ≦ 100. The range of Z may have a range of molar ratios of (X + Y) × 0.1 ≦ Z ≦ (X + Y) × 3 relative to the total moles of each X and Y, but the preferred range is (X + Y) × 0.2 ≦ Z ≦ (X + Y) × 1.5. The use of ring-opened fumaric acid and maleic acid and mixtures thereof in place of maleic anhydride can be used in the same molar ratio as Z, but it is economical to use maleic anhydride which is easy to purchase industrially.

The polymerization conditions were similar to the polymerization conditions of the acrylic acid derivatives in the aqueous solution of maleic anhydride, which was saponified with some caustic soda, to the iron + trivalent iron (III) salt (salts were acetate, nitrate, ammonium citrate, ammonium oxalate, Ammonium sulphate, perchlorate, or diphosphate.) The catalyst is heated to 90 ° C. while adding 0.001 to 0.05% of the total monomer weight, and then the acrylic acid derivatives, hydrogen peroxide and persulfate radical initiators are slowly The reaction is carried out at 90 ° C / 3hr while being introduced. The obtained molecular weight can be obtained a polymer in the range of 3,000 ≤ Mw ≤ 1,000,000. It is convenient to use a polymer having a molecular weight of 3,000 ≤ Mw ≤ 300,000. Fully or partially saponified with ₁ R ₂ R ₃ Namines or the acidic polymer itself may be used. Where R ₁ , R ₂ , R ₃ is C _{1 ~ 16} alkyl group, or an aromatic or alkyl R ₁ each , R ₂ , R ₃ Either one or two alkyl groups are 1 to 20 polyethylene oxide, polypropylene oxide and ethylene oxide, or a copolymer of propylene oxide.)

(Meth) acrylamide, (meth) acrylonitrile, hydroxy C _1-6 alkyl (meth) acrylate, C _1-6 alkyl (meth) acrylate, N-vinyl pyrrolidone vinyl when synthesizing chelate dispersant polymer Dispersion performance can also be adjusted by using acetates, such as 1-20%, compared to X + Y + Z.

The amount of chelating dispersant polymer used is 3% to 300% by weight of silver nitrate. Under 3%, the rate of reduction of silver complex is fast and the size of silver produced can be uneven or coarse. In addition, as for a suitable use range, 5%-100% are preferable.

In addition, when an excessive amount of the water-soluble alcohol is added to the mixture of the silver complex and the chelating dispersant polymer, the stability of the plating solution further increases even after the addition of the reducing agent, and no silver colloidal solution is produced even when left at room temperature for one month or more. Therefore, by mixing the appropriate amount of alcohol, it is possible to control various temperature conditions and plating speed to the organic substrate to be plated.

The water-soluble alcohols used are monohydric alcohols or ethylene glycol, propylene glycol and glycerin or their water-soluble derivatives. Monohydric alcohol is a straight-chain and branched alcohols of C _{1 ~ 4} glycol and polyethylene glycol, or their C _{1 ~ 4} monoalcohol ether derivatives, propylene glycol and polypropylene glycol or their C _{1 ~ 4} monoalcohol ether derivative, glycerin For example, polyethylene glycol of glycerin or ether derivatives of polypropylene glycol and mixtures thereof may be used. The amount of nitric acid may be used in the range of 20% to 5,000% by weight, but 30% to 1,000% is appropriate. Excessive use of alcohol tends to coarsen the size of silver to be reduced.

The amount of ammonia water used to make the silver ammonia complex is 4 ~ 10 times the weight of silver salt, and the reducing agent of silver ammonia complex and silver salt itself is formalin, glyoxal, hydrazine, hydroxylamine, alkanolamine, citric acid, succinic acid, L- Ascorbic acid and salts thereof, lotel salt, dextrose, glucose, thioglycol, thioglycolic acid, thiourea and the like are used about 2 to 4 times the silver salt equivalents.

The mixing procedure is to dissolve silver nitrate in distilled water to form a silver complex with an appropriate amount of ammonia water, and to add the chelating dispersant polymer and alcohol to mix uniformly, and then add a reducing agent such as formaldehyde to obtain a silver colloidal solution. Or reddish-brown light fluorescent transparent electroless liquid is obtained. The electroless plating solution obtained above can be used to plate an organic substrate. The organic substrates used here are synthetic fibers such as polyester, nylon and polyacrylate, semi-synthetic fibers such as acetate, rayon, cupra, and polynosic. Regenerated fibers such as tencel, cellulose fibers such as cotton, animal fibers such as silk, wool, and the like, and the like.

The electroless plating colloidal solutions of gold, nickel, copper and aluminum can be carried out in the scope of the present invention except for the ammonia water used to make the silver complex, thereby obtaining each stable water-dispersible colloidal solution. Each of the metal salts are used tetrachloride Keumsan (HAuCl ₄ .4H ₂ O), copper sulfate, copper chloride, copper acetate, nickel sulfate, nickel chloride, aluminum sulfate and the like.

The organic substrate to be plated is activated with palladium chloride and tin chloride, and then washed with sulfuric acid solution to be treated before plating.

When attempting to plate an organic substrate pretreated with an existing unstabilized electroless silver plating solution, the organic substrate should be first deposited in the silver complex and secondly deposited in the reducing agent solution to be washed or sprayed with the reducing agent solution later.

In the present invention, using a silver colloidal electroless plating solution sufficiently stabilized with a chelating dispersant, a rapid dyeing machine, a jigger dyeing machine, and a winch dyeing machine for immersing and circulating the organic substrate pretreated in an electroless plating solution formed by a method of one bath or A silver film can be formed by electroless plating silver on an organic substrate using a patching machine that is squeezed by immersion, patched, and rotated for a long time. At this time, the plating temperature and time is adjusted to the amount of the chelating dispersant polymer and the alcohol so as to be about 20 ~ 60 ℃ / 3 ~ 5hr.

The present invention will be described in detail through the following examples.

<Example 1>

1 g of silver nitrate was uniformly dissolved in 100 g of distilled water, and then 5 g of 28% ammonia water was added to form a silver ammonia complex. Then, 0.3 g of chelating dispersant polymer fully calibrated with caustic soda and 1 g of ethanol were further added to the aqueous solution of silver ammonia complex. While stirring, 3 g of a 30% formalin aqueous solution was slowly added while stirring the mixed solution, and the mixture was left at room temperature to gradually obtain a reddish brown fluorescent silver colloidal solution.

<Example 2>

Dissolve 10 g of silver nitrate uniformly in 100 g of distilled water, add 45 g of 28% ammonia water to form a silver ammonia complex, and then add 5 g of chelating dispersant polymer fully causticized with caustic soda and 4 g of ethanol to the aqueous solution of silver ammonia complex and stir well. While slowly adding 30 g of 30% formalin aqueous solution while stirring, the mixture was stirred and left at room temperature to gradually obtain a dark red brown colloidal solution.

<Example 3>

1 g of silver nitrate is uniformly dissolved in 100 g of distilled water, and then 0.3 g of acidic chelate dispersant polymer partially saponified with amine (polyethylene laurylamine, LN-12) and 1 g of ethanol are added to the aqueous solution of nitrate and stirred well with 30% formalin. When the mixed liquid is stirred at room temperature after slowly adding 3 g of aqueous solution, a silver colloidal solution having excellent water dispersibility is obtained.

<Example 4>

Dissolve 1 g of Geum tetrachloride uniformly in 100 g of distilled water, and then add 0.3 g of a 30% saponified acidic chelate dispersant polymer with caustic soda and 1 g of ethanol to the solution and stir well while adding 1.5 g of sodium hypophosphite slowly. When the mixture is left at room temperature after stirring, a red gold colloidal solution having excellent water dispersibility is obtained.

<Example 5>

0.4 g of copper sulfate was uniformly dissolved in 100 g of distilled water, and 0.5 g of acidic chelate dispersant polymerized with 30% caustic soda and 1 g of ethanol were further added to the aqueous solution of silver nitrate, and stirred slowly, while 0.6 g of sodium hydrosulfite was slowly added. A copper colloidal solution having excellent reddish brown water dispersibility is obtained.

<Example 6>

1 g of nickel sulfate was uniformly dissolved in 100 g of distilled water, and then 0.6 g of acidic chelating dispersant polymer 30% saponified with caustic soda and 1 g of ethanol were further added to the aqueous solution of silver nitrate, and stirred well while slowly adding 2 g of sodium borohydride. When the mixture is left at room temperature after stirring, a nickel colloidal solution having excellent water dispersibility is obtained.

<Example 7>

1 g of aluminum sulfate was uniformly dissolved in 100 g of distilled water, and 0.5 g of a 30% saponified acidic chelating dispersant polymer with caustic soda and 1 g of ethanol were further added to the aqueous solution of silver nitrate and stirred while slowly adding 1.5 g of sodium hypophosphite. After stirring, the mixture was left at room temperature to obtain an aluminum colloidal solution having excellent water dispersibility.

<Test Example 1>

100% ^{40, s} tin chloride 0.1% aqueous solution of a 2-minute immersion and then 0.5% of a clean again washed with water and then washed with aqueous sulfuric acid solution, and then Example 1 is a colloidal solution 200L is in filled jigger dyeing machine 40 ℃ / 1hr prepared as After plating at 60 ° C./1hr, the silver was further electroless plated, washed with 0.5% caustic soda solution and washed with water to obtain a silver-plated cotton fabric.

<Test Example 2>

The same treatment as in Example 8 was conducted except that a 100% polyester fabric was used to obtain a gold silver plated polyester fabric.

<Test Example 3>

After fixing the heat-reactive urethane resin and thioglycol to the 100% polyester fabric and immersed in the silver plating solution of Example 1 for 30 minutes at room temperature to obtain a silver gray plated polyester fabric.

<Test Example 4>

After fixing the heat-reactive urethane resin and thioglycol to the 100% cotton fabric, and then immersed in the silver plating solution of Example 1 for 30 minutes at room temperature to obtain a silver-plated cotton fabric.

<Test Example 5>

The fabric obtained in Test Example 2 was copper plated with the solution obtained in Example 4 to obtain a polyester fabric coated with silver and copper.

In the present invention, chelating dispersants and alcohols composed of acrylic acid derivatives and maleic anhydride copolymers are applied to the preparation of electroless colloidal solutions of metals and precious metals. It was also possible to make nano colloidal solutions of metals and precious metals with excellent reproducibility.

Claims (13)

An electroless plating solution for metals and precious metals, comprising a chelating dispersant consisting of a copolymer of an acrylic acid derivative and maleic anhydride, a water-soluble alcohol and a reducing agent selected from thioglycol, thioglycolic acid and thiourea. The plating solution according to claim 1, wherein the precious metals are gold and silver, and their salts are gold tetrachloride, silver nitrate, silver acetate, silver perchlorate, silver sulfate, or silver-ammonia complexes. 2. The plating solution according to claim 1, wherein the metal is copper, nickel or aluminum and their salts are in the form of copper sulfate, copper chloride, nickel sulfate, nickel chloride or aluminum sulfate. The method of claim 1, wherein the monomer molar ratio of each polymer in the chelating dispersant polymer is x (y) = 100X / when the fractions of X and Y in acrylic acid: methacrylic acid: maleic anhydride = X: Y: Z are respectively. (X + Y), y (%) = 100Y / (X + Y) and x + y = 100 (%), where x and y are in the range 0≤x≤100, 0≤y≤100 A plating solution, wherein Z is in a range of molar ratios of (X + Y) × 0.1 ≦ Z ≦ (X + Y) × 3 to the total moles of X and Y. The plating solution according to claim 4, wherein the ring-opened fumaric acid and maleic acid or mixtures thereof are used instead of maleic anhydride. The iron + trivalent iron (III) salt as a catalyst in the polymerization of the chelate dispersant (salts are acetate, nitrate, ammonium citrate, ammonium oxalate, ammonium sulphate, perchlorate, Or diphosphate) type catalyst. The method of claim 1, wherein the polymerized chelating dispersant is included as a saponification agent, which may be completely or partially saponified with alkalis of alkaline earth metals, ammonia and amines of R ₁ R ₂ R ₃ N or acidic polymers. Itself (where R ₁ , R ₂ , R ₃ is C _{1 ~ 16} alkyl group or aromatic group and R ₁ each , R ₂ , R ₃ Or one or two alkyl groups having a degree of polymerization of 1 to 20 polyethylene oxide, polypropylene oxide and ethylene oxide, or a copolymer of propylene oxide). The method according to claim 4, wherein 1 to 20% by weight of (meth) acrylamide, (meth) acrylonitrile, and hydroxy C _1-6 alkyl (meth) acryl as additives for the polymerization of the chelating dispersant compared to X + Y + Z. Elate, C _1-6 alkyl (meth) acrylate, N-vinyl pyrrolidone, vinyl acetate is added to the plating solution. The method of claim 1, wherein the water-soluble alcohol is a plating solution, characterized in that one C _{1 ~ 4} is an alcohol, ethylene glycol, propylene glycol, glycerol, or a derivative thereof. delete delete delete delete