JPS6164882A - Manufacturing method of plating material - Google Patents

Abstract

PURPOSE:To obtain a plated plastic material by supporting noble metallic ions on a plastic material with a surface treating agent having noble metal capturing action and by forming a metallic film having high bonding strength by electroless plating. CONSTITUTION:Phenol resin powder is well mixed with an aminosilane com pound such as gamma-aminopropyltriethoxysilane as a surface treating agent having noble metal capturing action and an aqueous PdCl soln., and the mixture is dried and held at about 110 deg.C to support Pd ions on the surface of the powder. This powder is put in an electroless plating, soln., preferably an electroless nickel plating soln., and plating is carried out under stirring to obtain nickel plated powder. By this method a plated material suitable for use as a resin additive for providing electric conductivity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing plated aluminum, and more specifically to the production of a plated material by forming a metal film with excellent adhesion on the surface of particles of synthetic resin powder by electroless plating. The purpose of the method is to provide a conductive paint or a resin additive VcXi11 for imparting conductivity.

2. Description of the Related Art Generally, it is known to form an electroless plating film on the surface of any material, whether inorganic or organic. Recently, various conductive materials have been actively developed in the fields of antistatic and electromagnetic shielding, and one proposed material is electroless plating on inorganic powder.

However, in general, inorganic powder plated products have disadvantages such as poor dispersibility when blended into YC synthetic resins or paint vehicles because of their large specific gravity, although the plated film is relatively good.

On the other hand, for this reason, a proposal has recently been made for a conductive material in which an electroless nickel plating film is formed on a resin powder as an organic material (Japanese Patent Application Laid-Open No. 1975-10-Dej3). The material is subjected to pretreatment operations such as etching sensitization or activation, and typical examples include the following methods: N/tin, stannous fluoride/-/09/l immersion or spray treatment in an acidic aqueous solution of hydrochloric acid for several minutes at room temperature) → catalytic treatment (O0/
~ / 9/l #1 Palladium chloride salt m@Immersion or spray treatment at room temperature for several minutes in a water injection solution (N) → Electroless plating; (2) Catalytic treatment (o, t I!/l Palladium chloride, l ~3 g/l stannous chloride hydrochloric acid colloidal aqueous solution for several minutes at room temperature immersion treatment) → Activation treatment (hydrochloric acid or sulfuric acid 10-10% or caustic soda 10-10% water 81 liquid VC at room temperature (Immersion treatment for several minutes) → Electroless plating.

In both of these conventional methods, chemical (chromic acid-fi)
! The adhesion of the plating film will be poor unless the surface of the object to be plated is roughened mechanically or by immersion in an acid mixture at 30 to 0° C. for several hours. It is impossible to mechanically disturb the powder, and if it is etched for cultural reasons, there is a risk that the fine particles will dissolve.Furthermore, filtration and washing are difficult, and wastewater treatment is also time-consuming. It just costs money (there is also an economic problem).

However, as mentioned above, even after conventional pretreatment and electroless plating, the synthetic resin base material is not only generally hydrophobic but also more elastic than inorganic base materials, so the plating film does not adhere to the base material. Weak adhesion.

In particular, when blending into synthetic resins, when mixing with plating powder using various mixers, Vcjl! Because of the frictional action exerted on the force-applied coating, cracks or peeling of the plated coating often occurs, making it impossible to obtain the desired electrical conductivity.

Problems to be Solved by the Invention In view of the above, the second invention is to form a highly adhesive plating film on the surface of a synthetic resin. That is, the present invention enables a strong electroless plating film to be formed by supporting a noble metal on the surface of a synthetic resin using a certain kind of noble metal scavenger, without chemically or physically etching the surface of the synthetic resin as in the conventional method. The present invention has been completed based on the discovery that this is possible.

The means to solve the problem, that is, the gist of the present invention is to use synthetic resin material 1.
(c) Metsu 1 characterized in that electroless plating is carried out after supporting noble metal ions with a noble metal-trapping surface treatment agent.
! Depends on the method of manufacturing the kettle.

In the present invention, the type of synthetic resin does not matter as long as the plating material is a synthetic resin material.

Examples of these synthetic resins include phenol resin, epoxy resin, polyester resin, nylon resin, polyion 2-in resin, vinyl chloride resin, polystyrene resin, AB8 resin, and the like.

Further, the shape of the resin may be any shape or molded product such as spherical, oval, fibrous, etc., and the size is not particularly limited.

The present invention, when electroless plating is applied to a synthetic resin base material as described above, performs a pretreatment process in which noble metal ions are supported on the surface of the resin base material using the metal-trapping surface treatment agent. In the present invention, the noble metal scavenging surface treatment agent refers to at least one functional group such as a carboxyl group, an ester group, an amine group, a hydroxyl group, a nitrile group, a halogen group, or an alkoxy group bonded to silicon or titanium. Refers to an organic compound that has more than one precious metal ion and is capable of forming a medium or salt of precious metal ions.

Such noble metal scavenging surface treatment agents include, for example, r-aξnoglobiltriethoxysilane, r-methacryloxyglobiltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and the like. Aminosilane compounds, hexylamine, trimethylenediamine, amine compounds such as diaminododecane, dicarbonyl compounds such as maleic acid, sebacic acid, adipine, glycol compounds such as triethylene glycol, polyethylene glycol, diglycolamine, etc. , malonitrile, nitrile compounds such as polyacrylonitrile, titanate compounds such as inglobil tri(dioctyl pyro7 osphate) titanate, titanium di(octyl pyro7 phosphate) oquinacetate, inglobil triisostearoyl titanate, maleated polybutadiene Butadiene polymers such as carboxylated polybutadiene, glycol-terminated polybutadiene, acrylonitrile/butadiene copolymer, polybutadiene, and unsaturated fatty acids such as linoleic acid and lylunic acid are used.

Also, here, the term "precious metal" refers to gold plated from a chemical plating solution to the surface of a base material, such as a powder surface! It refers to a noble metal that exhibits a catalytic effect when depositing A, such as palladium, platinum, gold, etc., with palladium being the most preferred.

Surface Vc1 of resin base material! j all 1! In order to support the above-mentioned surface treatment agent, the surface treatment agent may be mixed with a suitable solvent such as water, ethyl alcohol, acetone, toluene, methylformamide, dimethyl sulfoxide, dioxane, etc.
Dissolve in organic solvent such as to make a solution, and add one to this solution!
A wet method involves bringing the base material, such as a synthetic resin powder, into contact with the resin at room temperature or under heating using a method such as dipping, and then evaporating the solvent, or a dry method, in which a solution is mechanically applied using a Henschel mixer or the like. There are laws etc. The concentration of the surface treatment agent in the solution and the amount used are not particularly limited, although they vary depending on the surface area and physical properties of the Mego base material, such as the powder, and the type of surface Mjl agent and fI*. An amount of the surface treatment agent that can form a monomolecular layer on the surface of the substrate is required.

As a method for supporting noble metal ions on the surface with the above-mentioned surface treatment agent, there are cases in which a mixed solution of the surface treatment agent and noble metal ions is prepared in advance and the above-mentioned treatment is carried out, or a method in which the above-mentioned surface treatment is carried out in advance. After that, immersion, spraying, or infiltration mixing may be performed in an aqueous noble metal salt solution.

When the solvent is water, the former method is more preferable in terms of operation, in which the noble metal ions are treated with a solution in which they have been previously captured with a surface treatment agent.

In any case, the concentration of the soluble noble metal salt such as noble metal chloride is preferably o, o r -o, si/l.

After the metal is supported on the surface of the plating substrate, the solvent is removed by a desired method such as heating or air drying, and then dried.

In addition, for surface treatment agents that undergo dehydration condensation upon heating, not only the volatilization of a single Vcff1 medium but also o, s~
It is preferable to perform a heat treatment at 130° C. for 3 hours and further VC to cure the resin.

Support of noble metal ions on synthetic resin plating base material 1 (-
i Although the weight of those meetings and the type of surface treatment agent vary depending on the purpose of use, in the case of
．． 00/~o, i*ms, preferably 0. θl~0.0
The range of the road ffi range is appropriate.

In this way, after the pretreatment, the electroless plating treatment is performed.

In the present invention, such an organic material is subjected to chemical plating treatment to form a metal film on its surface. In this case, various conventionally known chemical plating solutions may be used as the chemical plating solution. can. In addition, various metals can be mentioned as metals added to the plating solution to form a surface film on the plating substrate, such as Ni.
'+CO+Ag TALL +Cu +Pd rPt
+Rh, Ru +FQ, etc. can be mentioned. In addition, the metal film formed on the surface of the plating base material can be
Alloys, e.g. Ni Co * Ni W + Ni
It can also be composed of Fe l Co-w 1Co-Fe etc., but when forming an alloy film, VC
In this case, a plurality of metal salts may be added to the plating solution as desired.

Chemical plating in this case! Suri: Well, conventionally known method V
Generally, plating W (containing metal salts, reducing agents, complexing agents, buffers, stabilizers, etc.) is adopted. Sodium phosphate, sodium borohydride, aminoborane, formalin, etc. are used, and as complexing agents and slowing agents, formic acid, acetic acid, cono-li(), citric acid, tartaric acid, su/go(+l) are used.
, glyph/, ethyl/diamine, EDT, ') reethanolamine, etc. are employed.

A typical composition of a chemical plating solution is C1, for example, Kinmen salt.
θ~koo 9/l 1 hypophosphite 0. J~3o1
/l, pH buffer s, J o o 94, and preferably such plating? In addition to &, Green S ~ Co I/l can be added as l'cWa auxiliary additive.

Also, as a pond plating liquid, gold C1 salt lo +7a o
o, 9/l, carboxylate 10~/DO11/l
, Honichika Alkali 10-40 q/i, Charcoal Alkali! -10! /11 Formalin lO~λoornl
Typical examples include: 'L plating, y, 5 gold, and metal plating, including copper and silver.Chemical plating treatment is '1y1, usually at a temperature of 20~? j 'C
As a uniform film is formed on the surface of the base material, stirring,
For example, it is preferable to carry out the reaction while stirring the air.

When performing chemical plating treatment, d* is l1ii+! Pretreated powder tS is added to the prepared chemical plating bath, but in the present invention, when the plating base material is powder, water, a diluted plating treatment agent, a plating aging solution, or a part constituting the plating agent is added. Plating can also be carried out by adding an rζ chemical plating solution to a slurry in which powder is uniformly dispersed using a solution of 1 as a dispersion medium.

Table 11 VC according to the present invention: Synthetic resin powders having a film of > exhibit gold luster, have good conductivity, and contain various fillers such as reinforcing agents, colorants, extenders, etc. applied as. In particular, Vζ is advantageously applied as a filler for plastics and rubber.

The synthetic resin powder having a metal film of the present invention can be added to plastics by about 10 to 0 weight to improve the decorative properties, electromagnetic shielding properties, antistatic properties, and mechanical properties of plastics. Such a plastic composition is suitable as a material for films, sheets, pipes, and other molded objects because of its ability to impart strength.

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

Example/N// Epoxy resin powder 109 with an average particle size of j μm was mixed with 100 ml of an organic compound having various functional groups as shown in Table 1 in a solvent (water, ethanol, toluene, acetone, dimethylformamide, etc.). The concentration O,j~/, dissolved in
After being immersed in a solution of 0 Jusha Co., Ltd. for 1 hour at room temperature while stirring, it was dried at a temperature of 10° C. to volatilize the solvent. Next (CO
0/9/l palladium chloride salt mMI aqueous solution 0
ml, soaked at room temperature for 70 minutes without stirring, filtered,
The resin powder was washed once with 00 ml of demineralized water to support palladium ions on the resin powder. Next, this pretreated epoxy resin powder is put into an electroless nickel plating solution having the composition shown in Table 1 below, and without stirring, it is plated at a solution temperature of AO, - deS to metallize it. A nickel plating powder with a rate of 7 was obtained.

Nickel sulfate, 2 z g/1 sodium hypophosphite -! I/1 citric soda J 011/l acetic acid soda
t s l/1pH (sulfuric acid or caustic acid)
e, s to j, j A small amount of the obtained taming powder was placed in a 4-ml cup, and after it was crushed with a JO second threshold, the degree of peeling of the plating film was observed using a microscope. The results are shown in Table 1 together with the appearance and 2-da conductivity. The conductivity was measured using a tester. The symbol O shown in the table indicates good quality, and Δ indicates slightly poor quality.

Table λ Example Surface treatment agent Layering force Conductivity
Appearance Hirotrimethylene diamine Δ Q O
j Diaminododecane Δ aO
6 maleic acid Δ O6g
Linoleum Δ OΔta
Polymethylmethacryle) QOOlo Polyacrylonitrile -, OOjno Polybutadiene △ Q △Example 1
2 to 1 phenolic resin powder with average particle size λ-ρm 5ottt-
Various 7-run force knopling agents tsm& shown in Table J
and palladium chloride t, s mg water ffl'WlλO
The particles were dried while being mixed, and then held at 1C/10C for 1 hour to support palladium ions on the particle surface.

Next, the powder ft which had been pretreated in this way was put into the same nickel plating solution as in Examples 1 to 1/1, and
Plating was carried out at a liquid temperature of 60 to 90° C. while stirring for 1 hour to obtain nickel plating powder with a metalization rate of qO.

9.7 pieces of the obtained glazing powder and 7.9 pieces of epoxy resin (
volume fraction aS%) t- in a mortar (mix, z c+oX
A plate of JC11×2 mm was molded, and its volume resistivity 1 was measured. The results are shown in Table 4.

Section J Table Black Surface treatment agent Comparative example of low inherent resistance at hardness 7 enol resin powder joI' with average particle size of JJm
j/l/l stannous chloride hydrochloric acid aqueous solution! 00m1f
l:.

After stirring for 5 minutes, the mixture was filtered and washed once with demineralized water. Next, it was added to o, ill/l palladium chloride hydrochloric acid acidic aqueous solution r o o ml, stirred for 10 minutes, and filtered.
Washed twice with demineralized water. The powder that has been pretreated in this way is put into the same electroless nickel plating solution as in Example /%// and plated with 4ON at a solution temperature of 90°C while stirring, resulting in nickel plating with a metalization rate of 0. A powder was obtained.

A plate was formed from 96 g of the obtained wolfberry powder in the same manner as in Example 1 ~/Gl, and the volume resistivity FL was measured to be /MΩ-CIm.

Example/j Phenol resin powder with an average particle size of 100 m is pretreated in the same manner as in Example 1, and then added to the electroless steel plating solution shown in Table 1 and heated to 60°C with stirring. Steel plating powder '4c with a metallization rate of 30% was obtained by plating at a high temperature.

Daihiromote f! 1 Copper tz9/Gi Paraformaldehyde tsg/IEDTA-1fNa
5oEi/1 Dibyridel / Oppm Potassium fecyanide - 〇ppm Copper-plated phenolic resin powder is then 1 shown in Table 3.
It was put into an electrolytic silver plating solution and plated at a solution temperature of ZS° C. without stirring to obtain a silver plating powder with a metalization rate of 10%.

Potassium silver cyanide 1011/1 Sodium shea/sl/1 Caustic nodal 4111/1 Potassium hydrogen boroide S,'ll/1 Resulting dusting powder 9.7-
The plate t'' was made of Japanese cedar in the same manner as in Example 1 to 4', and its volume resistivity was kept constant, Q, θJΩ-cm.

Real Rh 16 Clothes layer button (diameter/2mrn) made of synthetic resin (phenol-nylon mixture skin fat)! 0 OL-Jusha%
T-Aminobrobyltriethoxy7norane and O6ρ2
A mixed aqueous solution of palladium chloride (weight range) was added, stirred at room temperature, immersed for 7 to 30 minutes, separated, washed with water, and then dried.

Next, electroless nickel plating was performed in the same manner as in Example 1, and a uniform, strong, and clean nickel plating film was formed on all 7:f tans.

Since it forms a metal film with a high degree of compatibility, it can be effectively used as an electromagnetic shielding material, an antistatic material, and a conductive pigment.

Furthermore, during the plating process, the plated film is formed without chemically or mechanically etching the surface to be plated to roughen it by l/c, so that a plated film with reduced gloss can be obtained.

Patent applicant: Nippon Chemical Industry Co., Ltd. Procedural amendment (voluntary) October 2, 1982

Claims (1)

[Claims] 1. In a method for producing a synthetic resin plating material by pre-treating and then electroless plating a synthetic resin material, after the synthetic resin material is supported with noble metal ions using a noble metal-trapping surface treatment agent. A method for producing a plating material, characterized by electroless plating. 2. The method for producing a plating material according to claim 1, wherein the synthetic resin material is phenolic resin powder. 3. The method for producing a plating material according to claim 1, wherein the noble metal scavenging surface treatment agent is an aminosilane compound. 4. The method for producing a plating material according to claim 1, wherein the noble metal ion is a palladium ion. 5. The method for producing a plating material according to claim 1, wherein the electroless plating is electroless nickel plating.