JPH09291367A - Surface treating agent for plating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a surface treating agent for plating capable of rigidly sticking a plated film on a base material and capable of treating in a temp. range in which an org. polymer base material is stable at the time of plating a metallic layer on the base material such as ceramic, glass, org. polymer and metal. SOLUTION: This surface treating agent for the base material is used at the time of sticking the metallic film on the surface of the base material and composed of at least one kind metallic superfine particles selected from among Au, Pt, Pd, Rh, Ag and Ni, a fixing agent fixing the superfine particles on a layer to be plated and consisting of an org. compd. containing the metal, a film reinforcing agent and an org. solvent, and heat decomposition temp. of the fixing agent and that of the film reinforcing agent are approximated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for plating, more specifically, ceramics, glass, organic polymers,
The present invention relates to a surface treatment agent for plating which, when a plating film is plated on a base material such as metal, adheres the plating film to the base material more strongly.

[0002]

2. Description of the Related Art Conventionally, many techniques have been studied for providing a plating film layer on the surface of a non-metallic material such as ceramics, glass, organic polymer, etc., and imparting metallic properties such as good electrical conductivity and thermal conductivity. There is. For example, electrolytic plating performed in a liquid phase, electroless plating, vapor deposition performed in a gas phase, sputtering, etc. are typical.

Of these, a typical electroless plating process is well known as a method of metallizing the surface of an electrically insulating material. For example, when the material to be plated is a ceramic such as an aluminum oxide sintered body, an aluminum nitride sintered body, or a silicon carbide sintered body, metal palladium fine particles are preliminarily attached to the surface thereof, and a plating film is formed using this as a nucleus. The ceramic surface was metallized. The metal palladium fine particles are produced by bringing an aqueous solution containing palladium ions into contact with the surface of the ceramic material and reducing the same. In addition, an etching process must be performed to draw a pattern on the substrate.

[0004]

However, generally, when plating is performed, the problem is the adhesiveness between the formed plating film and the layer to be plated. In the case of electroless plating, the results show that the adhesion of the plating film is very poor because the fine palladium particles, which are the nucleus for forming the plating film, are not firmly adhered to the surface of the material to be plated.

When the above ceramics sintered body is used,
The adhesion is slightly improved by the anchoring effect, aided by the unevenness of the material surface. However, the conventional technique cannot be applied to glass having a smooth material surface. When the conventional technique is actually applied to glass, a plating film is formed, but there is a drawback that the generated plating film is peeled off from the glass due to a slight contracting force accompanying the film growth.

When an organic polymer is plated, the surface of the material is as smooth as glass, and the adhesion to the plated film is poor. The present invention improves such problems.
When plating a metal layer on a substrate such as ceramics, glass, organic polymer, metal, etc., the plating film can be firmly attached to the substrate and the organic polymer substrate can be treated in a stable temperature range. It is intended to provide a treatment agent.

[0007]

That is, a feature of the present invention is a surface treatment agent for a base material used when a plating film is attached to the surface of the base material, and is Au, Pt, Pd, R.
At least one kind of ultrafine metal particles selected from h, Ag, and Ni, a fixing agent made of an organic compound containing a metal for fixing the ultrafine metal particles to a layer to be plated, a film reinforcing agent, and an organic solvent, It is a surface treatment agent for plating in which the thermal decomposition temperatures of the fixing agent and the membrane reinforcing agent are approximated.

Further, the present invention can be dissolved in an organic solvent when 0.1 to 10 mol of the above-mentioned fixing agent and 0.01 to 5 mol of the above-mentioned membrane reinforcing agent are added to 1 mol of the metal of the ultrafine metal particles. When a viscosity adjusting material composed of a polymer material is mixed, when the ultrafine metal particles are previously dispersed independently in a polymer, or when the ultrafine metal particles are independently dispersed in an organic solvent. Including cases.

[0009]

In the treating agent of the present invention, ultrafine metal particles and
A fixing agent made of an organic compound containing a metal for fixing the ultrafine metal particles to a layer to be plated, a film reinforcing agent, and an organic solvent were used to approximate the thermal decomposition temperatures of the fixing agent and the film reinforcing agent. As a result, the reaction rates of the fixing agent and the membrane reinforcing agent are matched at the time of firing to form a strong treatment layer in which the respective metal oxides produced from the fixing agent and the membrane reinforcing agent are bonded together. The fine particles serve as nuclei to deposit metal ions and form a strongly adhered plating film.
Further, the viscosity adjusting material maintains the viscosity of the treating agent at an appropriate level to maintain good handling during screen printing.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The ultrafine metal particles used in the surface treatment agent for plating are composites in which the ultrafine metal particles are previously dispersed independently in a polymer, and ultrafine metal particles are independently dispersed in an organic solvent. It is possible to use the one that has been made. In the case of a composite, it is necessary to form the polymer layer in a thermodynamically non-equilibrium state. Specifically, this is a vacuum deposition method in which a polymer is heated in a vacuum to melt and evaporate to solidify a polymer layer on a substrate, or a thermal decomposition method, the polymer is melted at a melting temperature or higher, In this state, there is a method such as a rapid quenching solidification method in which the polymer layer is immediately put into liquid nitrogen or the like to be rapidly cooled and a polymer layer is attached onto the substrate.

In the case of a vacuum deposition method, a vacuum degree of 10 ^-4 to 10 ^-6 Torr and a deposition rate of 0.1 to 100 μm / min, preferably 0.1 to 10 ^-6 Torr, using an ordinary vacuum deposition apparatus.
At 5 to 5 μm / min, a polymer layer can be obtained on a substrate such as glass.

In the thermal decomposition method, a polymer as a raw material is thermally decomposed and vaporized in a closed space under reduced pressure, and the vaporized substance is solidified to a thermodynamically nonequilibrium state (metastable structure). A method for producing a recycled polymer, in which a predetermined amount of the charged polymer is thermally decomposed and vaporized, and then this vaporized substance is agglomerated into the regenerated polymer in the heat treatment region, and the vaporized substance is not agglomerated. Is a method of obtaining a regenerated polymer in which the oily low molecular weight substance is not mixed by aggregating with the oily low molecular weight substance in the cooling region.

In the melting rapid solidification method, the polymer is melted and cooled at a rate not lower than the critical cooling rate specific to the polymer to obtain a polymer layer. The polymer layer thus obtained is placed in a non-equilibrium state, which is thermodynamically unstable, and transitions to an equilibrium state over time.

The polymer used here is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET), polyvinyl alcohol, polyphenylene sulfide (PP).
S), polystyrene (PS), polycarbonate, polymethylmethacrylate, etc., which preferably have a molecular cohesive energy of 2000 cal / mol or more. The polymer includes a crystalline polymer and an amorphous polymer which are generally referred to. As for the molecular cohesion energy, see Chemical Chemistry Handbook, edited by The Chemical Society of Japan (issued in 1974)
On page 890.

Subsequently, the thermodynamically non-equilibrium polymer layer is transferred to the step of bringing the metal layer into close contact with the surface thereof. In this step, a metal layer is deposited on the polymer layer by a method such as depositing a metal on the polymer layer using a vacuum vapor deposition apparatus, or directly adhering a metal foil or a metal plate to the polymer layer. As the metal, Au (gold), Pt (platinum), Pd
(Palladium), Rh (rhodium), Ag (silver), Ni
(Nickel) and the like.

The composite in which the metal layer and the polymer layer are in close contact with each other is heated at a temperature not lower than the glass transition point and not higher than the melting point of the polymer to bring the polymer layer into a stable state. As a result, the metal of the metal layer becomes 100 nm or less and becomes ultrafine metal particles having a maximum particle size distribution in the region of 1 to 10 nm and diffuses and permeates into the polymer layer. The metal layer adhering to the polymer layer also decreases in thickness until it relaxes, and eventually disappears. The ultrafine particles are distributed in the polymer layer without aggregation. In this case, the content of the ultrafine particles is 0.01 to 80% by weight, but this content can be adjusted by changing the production conditions of the polymer layer or the thickness of the metal layer.

The method for producing the composite is not limited to the above-mentioned method, but for example, a gas phase method belonging to the melt vaporization method, a liquid phase method belonging to the precipitation method, a solid phase method or a dispersion method is used to prepare ultrafine metal particles. There are a method of mechanically mixing fine particles with a polymer composed of a solution or a melt, a method of simultaneously evaporating a polymer and a noble metal and mixing them in a gas phase.

The obtained composite is mixed and dissolved in a solvent consisting of an organic solvent such as metacresol, dimethylformamide, cyclohexane and formic acid to obtain an ultrafine particle dispersion paste in which ultrafine particles are uniformly dispersed. Since the ultrafine particles have a small particle size and interact with the polymer, separation and precipitation from the polymer and aggregation of the ultrafine particles do not occur in the paste.

Further, ultrafine metal particles independently dispersed in an organic solvent are produced by a method called an in-gas evaporation method as disclosed in, for example, JP-A-3-34211. This is obtained by introducing a helium-inert gas into the chamber to evaporate the metal, cooling by condensation with an inert gas, and condensing.In this case, α-terpineol is generated at the stage where the particles immediately after generation are in an isolated state. The surface of the particles is coated by introducing the vapor of an organic solvent such as toluene.

The fixative used in the present invention is, for example, Ba,
Mg, Si, P, Al, Ca, Ti, V, Cr, Mn,
Organic compounds containing metals such as Fe, Co, Ni, Cu, Zr, In, Sn and Pb, alkoxides of these metals such as ethoxide and propoxide, naphthenates,
The object of the present invention can be achieved by using organic acid salts such as acetate salts and organic complex salts such as acetylacetone complex salts and oxine complex salts.

The above-mentioned fixing agent becomes a metal oxide by baking the treating agent, or polymerizes by a polycondensation reaction to suppress the particle growth of the ultrafine metal particles, and at the same time, the surface of the substrate as the material to be plated and the ultrafine metal particles. Acts as an adhesive that firmly attaches. Considering the plating pretreatment liquid and the electroless plating liquid, Al, Ti, In, Sn and Si are preferable. For example, as specific examples, Al-acetylacetone salt, ethylacetoacetic acid diisopropoxide Al, Al
-Oxine complex salt, Si-propoxide, tetraethoxysilane, tetrapropoxytitanium, tetrabutoxytitanium, Ti-acetylacetone salt, stearic acid Ti, I
Examples thereof include n-acetylacetone salt, In-isopropoxide, In octylate, Sn-ethoxide, Sn-isoaminoxide, and Sn-acetylacetone salt.

The compounding amount is 0.1 to 10 mol, preferably 0.2 to 4 mol, per 1 mol of metal of the ultrafine metal particles. If it is less than 0.1 mol, the ultrafine metal particles will not be aggregated to be catalytically active and cannot be adhered to the substrate. On the other hand, if the amount exceeds 10 moles, the fixative surrounds the ultrafine metal particles and loses catalytic activity, and the film formed on the surface of the substrate is easily broken and peeled off due to crystallization of the fixative.

The membrane reinforcing agent used in the present invention is M '(M'
Is Si, B, P, In, Sn) and is an organic compound containing an element represented by. This can improve the strength of the produced film. Specifically, tetra-i-
Propoxysilane, γ-ureidopropyltriethoxysilane, silicone oil, polysiloxane, triethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, diethoxydimethylsilane, triethyl borate, tristearyl borate, triphenyl borate, phosphoric acid There are tricresyl, triphenyl phosphate, iproniazide phosphate, diphenyl phosphate, phosphonoacetic acid, phosphoramidon, di-n-butyl phosphate, triethyl phosphate, tri-n-amyl phosphate and the like. This addition amount is 0.01 to 5 mol per 1 mol of the metal of the ultrafine metal particles. If the amount of the film reinforcing agent added exceeds 5 mol, the plating deposition property and the growth property deteriorate.

In the present invention, as the fixing agent and the membrane reinforcing agent, those having similar thermal decomposition temperatures are used. The difference in thermal decomposition temperature between the fixative and the membrane reinforcing agent is 30 ° C.
Is preferably within. If it exceeds this, the reaction rates of the fixing agent and the membrane reinforcing agent are different during firing, and it becomes impossible to form a strong treatment layer in which the respective metal oxides produced from the fixing agent and the membrane reinforcing agent are bonded.

The thermal decomposition temperatures of typical Ti-acetylacetone salts and tetraethoxysilane, which are the above-mentioned fixing agents, are around 540 ° C. and 550 ° C., respectively, and polysiloxane and γ-which are membrane reinforcing agents. Each thermal decomposition temperature of ureidopropyltriethoxysilane is around 570 ° C, and 515
It is around ° C.

As the organic solvent used in the present invention, a solvent which does not aggregate the ultrafine metal particles in the treating agent and dissolves the fixing agent is selected. When using a composite in which ultrafine metal particles are independently dispersed in a polymer in advance, metacresol, methylformamide, chlorophenol, dimethylimidozolidinone, dichloromethane and the like are preferable. On the other hand, when the ultrafine metal particles independently dispersed in an organic solvent are used, xylene, benzene, toluene, diphenylmethane, terpineol and the like are preferable.

In the treatment agent containing the ultrafine metal particles, the fixative, the membrane reinforcing agent, and the organic solvent, the addition amount of the ultrafine metal particles, the fixing agent, and the membrane reinforcing agent, which are the fixed components, is the same as that in the treatment liquid. The concentration is 0.0001 to 50% by weight, and is preferably appropriately determined by the method of attaching the treatment liquid to the substrate.

The viscosity adjusting material used in the present invention maintains the viscosity of the treating agent at an appropriate level to maintain good handling during screen printing. This viscosity adjusting material is preferably decomposed at a low temperature during firing, but is not particularly limited as long as it is soluble in an organic solvent. Examples of the viscosity adjusting material include celluloses such as nitrocellulose, ethyl cellulose, cellulose acetate, and butyl cellulose; acrylics such as methyl acrylate; nylon 6;
Polyamides such as nylon 11 and nylon 12, polyesters such as polyethylene terephthalate and polycaprolactone, polyethers such as polyoxymethylene, polycarbonates, polyvinyls such as polystyrene, polybutadiene and polyisoprene.

Although the concentration of the viscosity adjusting material is determined depending on the purpose of use of the treating agent, the concentration in the treating liquid is 50% by weight at maximum. Also in the treatment agent containing the viscosity adjusting material, the ultrafine metal particles and the fixing agent are 0.1 to 10 moles, preferably 0.2 to 4 moles, relative to 1 mole of metal of the ultrafine metal particles. The amount of the ultrafine metal particles and the fixing agent added is 0.0001 to 50% by weight in terms of the concentration in the treatment liquid, and is preferably appropriately determined by the method of adhering the treatment liquid to the substrate.

In the preparation of the above treatment agent, a predetermined amount of ultrafine metal particles are dispersed in an organic solvent. A viscosity adjusting material is previously added and dissolved in the organic solvent. Finally, the fixative is added and stirred well. Processing agents are ceramics, glass,
It is applied to a substrate such as an organic polymer or a metal by brush coating, screen printing, dipping, spraying, knife coating or the like. Among them, in the screen printing, a base material (glass) is placed below a horizontally placed screen (for example, polyester plain weave, 255 mesh) with an interval of several millimeters. After the treatment agent is placed on this screen, the treatment agent is spread over the entire surface of the screen using a scraper. At this time, there is a space between the screen and the base material. Subsequently, the squeegee presses the screen to the extent that the screen comes into contact with the base material, and the screen is moved to form an arbitrary pattern on the base material. Then, the base material 10
It is left to stand in the atmosphere of 0 to 200 ° C. for 10 to 30 minutes to remove the organic solvent and dried, or dried in a closed container while being deaerated, and then the polymerization or firing step is performed.

In the polymerization or calcination step, in the case of a fixing agent (metal alkoxide) which undergoes a polycondensation reaction, the temperature is from room temperature to 300.
Heat treatment in air in the temperature range of ° C. Also, from 300
The object of the present invention can be achieved even when a metal oxide is obtained by heating at a temperature of 800 ° C. to cause oxidative decomposition. When a fixing agent that does not undergo polycondensation is used, it is oxidized and decomposed into a metal oxide in the air at a temperature of 300 ° C or higher.

The base material obtained by depositing the treating agent and baking the surface has a plated layer on which ultrafine metal particles are independently dispersed. The ultrafine metal particles are not completely surrounded and are partially exposed. After this is treated with acid and washed with water, put it in a plating tank and perform electroless plating,
Metal ions are deposited from the exposed ultrafine metal particles as nuclei,
A plated film is produced. That is, on the surface of the base material, the ultrafine metal particles are independently dispersed in the layer to be plated, and these are relatively concentrated on the surface. Then, a plating film in which metal ions are deposited is formed on the surface of the layer to be plated.
The effect of the treatment agent of the present invention is exhibited when glass or ceramics having a smooth surface is used as the substrate to be plated. Moreover, since the plating does not deposit on a place other than the pattern, the circuit can be manufactured as it is. If necessary, pattern formation may be performed by etching. The plating is generally performed by electroless plating.

[0033]

Next, the present invention will be described in more detail with reference to specific examples.

Examples 1 and 2 and Comparative Examples 1 to 3 The compounding table shown in Table 1 is for screen printing.
This formulation was carried out by first adding a viscosity adjusting material to a predetermined amount of an organic solvent, stirring and sufficiently dissolving it, and then successively adding ultrafine metal particles obtained by vapor deposition in a gas, a fixing agent, and a film reinforcing agent and stirring. It was made. The fabrication temperature is room temperature. Alkali-free glass was used as the substrate to be treated.

In screen printing, the substrate was placed under a horizontally placed screen (for example, polyester plain weave, 300 mesh) with a spacing of several millimeters. After the treatment agent was placed on the screen, a squeegee was used to spread the treatment agent on the entire surface of the screen. Subsequently, the squeegee was pressed against the screen so that the screen was in contact with the substrate, and the screen was moved to apply the treatment agent to the surface of the substrate.

The substrate after application of the treatment agent was dried in air at 120 ° C. for 10 minutes, and then heat-treated in air at a temperature of 600 ° C. for 30 minutes. This base material was immersed in a commercially available acidic cleaner solution at room temperature for 1 to 5 minutes for cleaning. Then, it was plated. For the plating process, the sample is electroless plating bath (N
It was dipped in an i-B type electroless plating solution at 65 ° C. for 20 minutes for plating. The adhesiveness between the nickel film and the base material was evaluated by soldering the nickel film plated on the base material to a size of 2 × 2 mm to fix the conductive wire, and attaching a scale to the conductive wire and pulling. The results are also shown in Table 1.

[0037]

[Table 1]

As a result, in the embodiment in which the thermal decomposition temperatures of the fixing agent and the film reinforcing agent are approximated to each other, the adhesion of the plated film becomes strong, the substrate is destroyed, and further measurement becomes impossible. became. Moreover, the smoothness was improved and the film was glossy. However, when the silicon concentration of the film reinforcing agent is high, the plating deposition property and the growth property are deteriorated.

[0039]

As described above, in the treatment agent of the present invention, ultrafine metal particles, a fixing agent composed of an organic compound containing a metal for fixing the ultrafine metal particles to a layer to be plated, a membrane reinforcing agent,
It is composed of an organic solvent, and by approximating the respective thermal decomposition temperatures of the above-mentioned fixative and membrane reinforcing agent, the reaction rates of the fixative and membrane reinforcing agent are matched at the time of firing to generate the fixative and membrane reinforcing agent. It has the effect of forming a strong treatment layer in which the respective metal oxides are bonded, and the ultrafine metal particles of the treatment layer serve as nuclei to deposit metal ions and form a strongly adhered plating film. Further, the viscosity adjusting material maintains the viscosity of the treating agent at an appropriate level to maintain good handling during screen printing.

Claims (5)

[Claims] 1. A surface treatment agent for a base material used when a metal film is attached to the surface of the base material, which comprises Au, Pt, Pd, R.
At least one kind of ultrafine metal particles selected from h, Ag, and Ni, a fixing agent made of an organic compound containing a metal for fixing the ultrafine metal particles to a layer to be plated, a film reinforcing agent, and an organic solvent, A surface treatment agent for plating, wherein the thermal decomposition temperatures of the fixing agent and the membrane reinforcing agent are approximated to each other. 2. The fixing agent is added in an amount of 0.1 to 10 mol, and the membrane reinforcing agent is added in an amount of 0.01 to 1 mol, based on 1 mol of the metal of the ultrafine metal particles.
The surface treating agent for plating according to claim 1, which is added with 5 mol. 3. The surface treating agent for plating according to claim 1, wherein a viscosity adjusting material made of a polymer material which can be dissolved in an organic solvent is mixed. 4. The surface treating agent for plating according to claim 1, wherein the ultrafine metal particles are previously dispersed independently in a polymer. 5. The surface treating agent for plating according to claim 1, wherein the ultrafine metal particles are previously dispersed independently in an organic solvent.