JP2009108337A - Electroless plating method, electroless plating apparatus and electromagnetic interference shield material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase a plating rate in electroless plating, and to prolong the lifetime of a plating solution. <P>SOLUTION: An electroless plating apparatus 10 comprises an electroless plating tank 16 filled with plating solution 16A, and a current-carrying device 20 which carries the current in a conductive metal pattern 12A consisting of a mesh-like thin wire pattern of a laminate 12 to heat the conductive metal pattern 12A during the electroless plating. The current-carrying device 20 has a power supply roller 22 on a cathode side in contact with the conductive metal pattern 12A of the laminate 12 on an inlet side of the electroless plating tank 16, and a power supply roller 24 on an anode side in contact with the conductive metal pattern 12A of the laminate 12 on an outlet side of the electroless plating tank 16. The conductive metal pattern 12A is conducted by the power supply rollers 22, 24, and a part in a vicinity of the conductive metal pattern 12A is heated in the plating solution. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electroless plating method for performing electroless plating on a substrate including a conductive metal pattern, an electroless plating apparatus, and an electromagnetic wave shielding material formed by the electroless plating method.

In recent years, a technique for producing an electromagnetic wave shielding film of a plasma display panel (PDP) by patterning fine lines using a silver salt photography technique or a printing method has been studied.
A requirement for fulfilling the electromagnetic wave shielding function is to laminate a metal on a thin wire, and electroless plating can be used as one of the lamination methods. In electroless plating, the temperature of the plating solution is usually increased for high-speed and short-time plating. In this case, however, there is a problem that the remaining amount of plating metal per hour is reduced and the life of the plating solution is shortened. For this reason, speeding up of electroless plating and long life of the plating solution cannot be satisfied at the same time.

  On the other hand, Patent Document 1 describes a galvanic start, and discloses a method of causing an electrochemical reaction by applying a potential corresponding to a deposition reaction potential in an electroless plating solution. In this method, the sample to be plated and the electrode are placed so as to face each other in the plating solution to cause a plating reaction.

  In Patent Document 2, the surface potential of the primary plating film with a pretreatment agent that does not contain metal ions, the surface current density of the primary plating film is lower than the most base surface potential in the electroless treatment liquid of the secondary plating, Further, a method of performing secondary plating after adjusting so as to be base is disclosed.

  Patent Document 3 discloses a method of applying a negative potential to developed silver during immersion in an activation solution containing a noble metal. According to this method, it is described that the noble metal adsorbed on the developed silver pattern formed by the diffusion transfer method is reduced and acts as a plating catalyst to enable electroless plating.

However, in any method of Patent Documents 1 to 3, it is difficult to simultaneously achieve high speed plating and long life of the plating solution.
JP 2001-131760 A JP 2003-155573 A JP 2004-269992 A

  The present invention has been made in view of such circumstances, and an electroless plating method, an electroless plating apparatus, and an electroless plating capable of increasing the plating speed in electroless plating and extending the life of a plating solution. An electromagnetic shielding material formed by the method is provided.

  In order to solve the above problems, the invention according to claim 1 is an electroless plating method for performing metal plating on a substrate including a conductive metal pattern, wherein the conductive metal is formed during the electroless plating. The pattern is characterized in that the pattern is electrically energized and electroless plating is performed while heating the conductive metal pattern.

  According to the first aspect of the present invention, electroless plating is performed while heating only the vicinity of the conductive metal pattern by electrically energizing the conductive metal pattern during the electroless plating. Thereby, the plating rate to the formed metal pattern can be increased, the plating amount per hour can be increased, and the resistance value can be decreased. Further, since the overall temperature of the plating solution is not increased, the plating metal remaining rate per time is increased, and the life of the plating solution is extended.

  According to a second aspect of the present invention, in the electroless plating method according to the first aspect of the present invention, the electric current is applied in a range of 1.5 A / dm 2 or less.

  According to the second aspect of the present invention, when the electroless plated object has the conductive metal pattern formed on the resin film and the energization amount is within this range, the plating rate can be increased sufficiently, It is possible to suppress damage to the substrate or the fine line pattern due to.

  The invention according to claim 3 is an electroless plating method for performing metal plating on a substrate including a conductive metal pattern, and performing energy irradiation on the conductive metal pattern, thereby performing the electroless plating. And electroless plating while heating the conductive metal pattern.

  According to the third aspect of the present invention, the metal pattern is heated by irradiating the conductive metal pattern with energy, and only the vicinity of the metal pattern is heated during the electroless plating. Is called. Thereby, the plating rate to the formed metal pattern can be increased, the plating amount per hour can be increased, and the resistance value can be decreased. In addition, the life of the plating solution is extended as in the first aspect.

  According to a fourth aspect of the present invention, in the electroless plating method according to the third aspect, the energy irradiation is performed by at least one selected from a laser beam, an electron beam, an ion beam, or a heat ray. .

  According to the invention described in claim 4, since the energy irradiation is performed by at least one kind selected from a laser beam, an electron beam, an ion beam or a heat ray, the conductive metal pattern can be locally heated. .

  The invention according to claim 5 is the electroless plating method according to any one of claims 1 to 4, wherein the conductive metal pattern is a pattern including 1 to 50 μm mesh fine wires. It is characterized by.

  According to the fifth aspect of the present invention, since the conductive metal pattern is a pattern including fine mesh wires of 1 to 50 μm, the conductive metal pattern is heated by Joule heat or energy irradiation due to electric conduction, and the conductive metal pattern Only the vicinity of the pattern can be heated.

  The invention according to claim 6 is the electroless plating method according to any one of claims 1 to 5, wherein a surface resistance value of the conductive metal pattern is 10 to 1000Ω / □. It is a feature.

  According to the sixth aspect of the present invention, since the surface resistance value of the conductive metal pattern is 10 to 1000Ω / □, the conductive metal pattern is heated by Joule heat or energy irradiation caused by electric conduction. Only the vicinity can be heated.

  The invention according to claim 7 is the electroless plating method according to any one of claims 1 to 6, wherein the conductive metal pattern exposes and develops a photosensitive material containing silver halide. It is characterized by being formed.

  According to the seventh aspect of the present invention, the conductive metal pattern is formed by exposing and developing a photosensitive material containing silver halide, and a desired fine line pattern can be formed.

  According to an eighth aspect of the present invention, in the electroless plating method according to any one of the first to seventh aspects, the base is a long base on which a conductive metal pattern is continuously formed. And the electroless plating is carried out by continuously conveying the elongated substrate.

  According to the eighth aspect of the present invention, the base is a long base on which conductive metal patterns are continuously formed, and the long base is continuously conveyed for electroless plating. Compared to the treatment, the plating treatment length per hour is large, and electroless plating can be performed efficiently.

  The invention according to claim 9 is an electroless plating apparatus for performing metal plating on a substrate including a conductive metal pattern, which is filled with an electroless plating solution and into which the substrate is introduced, And an electrically energizing device for electrically energizing the conductive metal pattern and heating the electroconductive metal pattern during the electroless plating.

  According to the ninth aspect of the present invention, the substrate including the conductive metal pattern is introduced into the electroless plating tank filled with the electroless plating solution. Furthermore, when the conductive metal pattern is electrically energized by the electrical energization device, only the vicinity of the conductive metal pattern is heated during electroless plating, and electroless plating is performed. Thereby, the plating rate can be increased, the amount of plating per hour can be increased, and the resistance value can be decreased. Further, since the overall temperature of the plating solution is not increased, the plating metal remaining rate per time is increased, and the life of the plating solution is extended.

  The invention according to claim 10 is an electroless plating apparatus for performing metal plating on a substrate including a conductive metal pattern, the electroless plating tank being filled with an electroless plating solution and introducing the substrate. And an energy irradiation device that irradiates the conductive metal pattern with energy and heats the conductive metal pattern during the electroless plating.

  According to invention of Claim 10, the base | substrate containing a conductive metal pattern is introduce | transduced into the electroless-plating tank filled with the electroless-plating liquid. Furthermore, by irradiating the conductive metal pattern with energy by the energy irradiation device, only the vicinity of the conductive metal pattern is heated during the electroless plating, and the electroless plating is performed. Thereby, the plating rate can be increased, the amount of plating per hour can be increased, and the resistance value can be decreased. Further, since the overall temperature of the plating solution is not increased, the plating metal remaining rate per time is increased, and the life of the plating solution is extended.

  An electromagnetic wave shielding material according to an eleventh aspect of the present invention is formed by the electroless plating method according to any one of the first to eighth aspects.

  According to the eleventh aspect of the present invention, since the electromagnetic wave shielding material is formed by the electroless plating method according to any one of the first to eighth aspects, the plating speed is increased for a short time. The surface resistance value can be lowered by this treatment, and an electromagnetic shielding material excellent in productivity can be provided.

  As described above, according to the present invention, the plating rate can be increased in electroless plating, and the life of the plating solution can be extended.

Embodiments of the present invention will be described with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function throughout all the drawings, and the overlapping description may be abbreviate | omitted.
FIG. 1 shows an electroless plating apparatus 10 to which the electroless plating method according to the first embodiment of the present invention is applied. The electroless plating apparatus 10 is an apparatus for laminating a metal (in this embodiment, Cu) by electroless plating on a conductive metal pattern 12A (hereinafter referred to as a laminate 12) laminated on a substrate 12.

  In the electroless plating apparatus 10, the laminated body 12 is conveyed in a fixed direction (arrow direction in FIG. 1) by a feed roll and a take-up roll (not shown). The electroless plating apparatus 10 is provided with a support roller 14 that guides the back surface of the laminate 12, and an electroless plating tank 16 in which a plating solution 16 </ b> A is stored is disposed downstream of the support roller 14 in the transport direction. It is installed. In the electroless plating tank 16, two support rollers 18 for guiding the back surface of the laminated body 12 are disposed substantially parallel to each other in the vicinity of both ends in the longitudinal direction of the electroless plating tank 16. Yes. The laminated body 12 is conveyed in a certain direction (the arrow direction in FIG. 1) through the plating solution 16 </ b> A while being guided by the two support rollers 18. In this embodiment, the roller portions of the support rollers 14 and 18 are made of polypropylene.

  The electroless plating apparatus 10 is provided with an electric energization apparatus 20 that heats the conductive metal pattern 12A during electroless plating by energization. The electrical energization device 20 is a cathode-side power supply roller that is in contact with the conductive metal pattern 12A between the support roller 14 and the upstream side (left side in the figure) support roller 18, that is, at the top of the inlet side of the electroless plating tank 16. 22, and an anode-side power supply roller 24 that contacts the conductive metal pattern 12 </ b> A at the upper part on the outlet side of the electroless plating tank 16. A rubber pressing roller 28 that presses the conductive metal pattern 12 </ b> A against the power supply roller 22 is disposed at a position facing the power supply roller 22 with the laminate 12 interposed therebetween. In the present embodiment, the power supply rollers 22 and 24 are formed of SUS316. 1 is a power supply for electrically energizing the conductive metal pattern 12A via the power supply rollers 22 and 24. In the electroless plating apparatus 10, the long belt-like laminate 12 can be continuously conveyed by the support rollers 14, 18, etc., and electroless plating can be performed.

  While the laminate 12 disposed in the electroless plating apparatus 10 is conveyed, the conductive metal pattern 12A is electrically energized via the power supply roller 22. The energization may be performed using either a DC power supply or an AC power supply, preferably 1.5 A / dm 2 or less, and more preferably 0.3 A / dm 2 or more and 1.5 A / dm 2 or less. Although depending on the resistance value of the conductive metal pattern, when the energization amount is excessively increased in order to increase the heat generation amount, the laminate 12 is immersed in the plating solution and at the same time, the fine wires of the conductive metal pattern 12A. Some may tear. For this reason, it is preferable to appropriately adjust the energization amount according to the resistance value of the conductive metal pattern, and the preferable current range in the present invention is 1.5 A / dm 2 or less.

  FIG. 2 shows an electroless plating apparatus 30 to which the electroless plating method according to the second embodiment of the present invention is applied. In addition, the same code | symbol is provided to the member same as 1st Embodiment, and the overlapping description is abbreviate | omitted. As shown in FIG. 2, the electroless plating apparatus 30 has two support rollers 32 arranged on the inlet side and the outlet side of the electroless plating tank 16 instead of the power supply rollers 22 and 24 shown in FIG. It is installed. Further, in the electroless plating apparatus 30, the conductive metal pattern of the laminate 12 is located at the upper part on the inlet side of the electroless plating tank 16 and downstream of the upstream side (right side in FIG. 2) support roller 32. An energy irradiation device 34 for irradiating energy to 12A is disposed. The energy irradiation device 34 is disposed at a position facing the conductive metal pattern 12A, and irradiates the conductive metal pattern 12A with energy.

  Examples of means for applying energy to the conductive metal pattern 12A of the laminate 12 include electromagnetic waves such as microwaves, laser beams, electron beams, ion beams, and heat rays. In particular, a laser beam, an electron beam, an ion beam, and a heat ray are preferable in that they can be locally finely heated, and it is preferable to irradiate the conductive metal pattern 12A with at least one kind selected from these. A laser beam is preferably used because it is relatively small and can be easily irradiated with energy.

As the wavelength of the laser beam, any wavelength from ultraviolet light to infrared light can be selected as long as the conductive metal pattern has absorption, but preferably infrared light of 700 nm to 1700 nm and / or 360 nm or less. UV light. Typical lasers include semiconductor lasers such as AlGaAs and InGaAsP, excimer lasers such as Nd: YAG laser, ArF, KrF, and XeCl, and dye lasers. Also, a surface emitting semiconductor laser or a multimode array in which these are arranged one-dimensionally or two-dimensionally can be used.
Further, these laser beams may use higher harmonics such as second harmonic and third harmonic. These laser beams may be irradiated continuously or may be irradiated a plurality of times in the form of pulses.

  In such an electroless plating apparatus 30, the laminate 12 is guided by the support rollers 14 and 32 and conveyed in the direction of the arrow, and the laminate 12 is introduced into the plating solution 16 </ b> A in the electroless plating tank 16. In the electroless plating tank 16, the laminate 12 is conveyed in the direction of the arrow through the plating solution 16 </ b> A while being guided by the two support rollers 18. At the entrance of the electroless plating tank 16, the energy irradiation device 34 irradiates the conductive metal pattern 12 </ b> A of the laminated body 12 with a laser beam, so that the conductive metal pattern 12 </ b> A is locally heated. For this reason, electroless plating can be performed while heating only the vicinity of the conductive metal pattern 12A of the laminate 12 during the electroless plating.

  As a method for forming a conductive metal pattern on a substrate, for example, an emulsion layer containing a silver halide emulsion is coated on a belt-like substrate film, and the material is exposed by an exposure device (not shown), and a development processing device. A method using photographic technology for developing, fixing, washing, etc. (not shown), or a method of drawing conductive ink containing conductive particles on a substrate by printing or an ink jet printer to form a conductive metal pattern, etc. Is used. By these treatments, a patterned thin line-shaped conductive metal pattern 12A can be formed in the laminate 12.

  In addition, the conductive metal pattern formed by the above method is imparted with activity by reduction by contact with a reducing agent and / or treatment with a solution containing a catalyst in order to increase the efficiency of electroless plating. It can be carried out. As the reducing agent, for example, a known reducing agent such as sodium borohydride can be used. Usable catalysts include noble metals such as Pd, which may be ions or metals. In the case where the catalyst is applied as ions, it is possible to combine a reduction treatment after the application. These treatments can accelerate the electroless plating rate.

  For the plating treatment on the metal pattern, electroless plating (chemical reduction plating or displacement plating), or a combination of both electroless plating and electrolytic plating can be used. The electroless plating of the present invention is not particular to the plating metal type in the electroless plating solution as long as it is an electroless plating that can be plated on a metal pattern to obtain a desired surface resistance value. Electrolytic copper plating.

  Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agent, formalin, glyoxylic acid, copper ligand, EDTA, triethanolamine, etc. Examples of the additive for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine. Examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

  The surface resistance value of the conductive metal pattern 12A before the plating treatment is preferably 10 to 1000Ω / □, more preferably 20 to 500Ω / □, and most preferably 30 to 200Ω / □. preferable. Further, the surface resistance value of the metal pattern after the plating treatment is preferably 10Ω / □ or less, more preferably 1.0Ω / □ or less, further preferably 0.5Ω / □ or less, Most preferably, it is 0.1Ω / □ or less.

  Moreover, it is preferable that the conductive metal pattern 12A is a pattern including 1 to 50 μm mesh-like fine lines. When a conductive metal film including a mesh-like thin line is used as a translucent electromagnetic wave shielding material, the line width of the metal pattern is preferably 30 μm or less, more preferably 15 μm or less, and preferably 10 μm or less. Most preferred. Furthermore, the line spacing of the metal pattern is preferably 50 μm or more and 1000 μm or less, more preferably 200 μm or more and 500 μm or less, and most preferably 250 μm or more and 400 μm or less. Further, the metal pattern may have a portion whose line width is larger than 50 μm for the purpose of ground connection or the like.

Moreover, parts other than said metal pattern have transparency (Hereinafter, the part which has transparency other than this metal pattern is called a light transmissive part.). The transmittance of the light transmissive part is preferably 90% or more, more preferably 95% or more, and most preferably 97% or more. In addition, the process which raises the light transmittance of a light transmissive part can also be performed by an oxidation process etc. after a development process and the plating process of this invention. Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment.
The transmittance of the light transmissive part refers to the transmittance indicated by the average of the transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support (translucent electromagnetic shielding material) The transmittance of the transparent part) / (the transmittance of the support) × 100 (%).

  In the metal pattern, the surface of the metal pattern is also preferably subjected to blackening treatment from the viewpoint of increasing the contrast and preventing the metal pattern from deteriorating with time. The blackening treatment is performed using electrolytic plating such as blackened copper, blackened nickel, blackened tin, blackened nickel-tin, blackened nickel-zinc, or oxidation treatment performed in the printed wiring board field. be able to.

  Since the conductive metal film according to the present invention has high electromagnetic wave shielding properties and translucency, imaging such as CRT, EL, liquid crystal display, plasma display panel, other image display grat panel, or CCD. It can be used as an electromagnetic shielding film by being incorporated in a semiconductor integrated circuit for use. In particular, the plasma display is preferably used for a plasma display because the image quality can be maintained or improved without significantly reducing the luminance.

  Note that the use of the conductive metal film according to the present invention is not limited to the display device and the like, but a measuring device that generates electromagnetic waves, a window or a case for looking inside the measuring device or the manufacturing device, a radio tower Or a window of a building or a window of a car that may be damaged by electromagnetic waves due to high-voltage lines or the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

A silver halide emulsion A was prepared according to the method shown below.
(Emulsion A adjustment)
・ 1 liquid:
750 ml of water
20g gelatin
Sodium chloride 1.6g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5 ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7 ml

  Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated at 40 ° C. for 120 minutes.

  To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring to form 0.15 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were further added over 2 minutes to grow particles to 0.18 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.

・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. 8 g of gelatin was added to the emulsion after washing and desalting, adjusted to pH 5.6 and pAg 7.5, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization to obtain optimum sensitivity at 0 ° C., 100 mg of 1,3,3a, 7-tetraazaindene as stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as preservative It was. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 μm and a coefficient of variation of 9% was obtained. (Finally, the emulsion had pH = 5.7, pAg = 7.5, conductivity = 60 μS / m, density = 1.28 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.)

(Preparation of coated material)
In accordance with the formulation shown below, an emulsion layer and a UL layer were prepared as a coated product.

<Emulsion layer>
The emulsion A was subjected to spectral sensitization by adding sensitizing dye (D-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag , Surfactants (Sa-1), (Sa-2) and (Sa-3) were added so that the coating amounts were 60 mg / m ² , 40 mg / m ² and 2 mg / m ² , respectively, and citric acid was added. The coating solution pH was adjusted to 5.6.

<UL layer>
Gelatin 0.23 g / m ²
Compound (Cpd-7) 40 mg / m ²
Compound (Cpd-14) 10 mg / m ²
Preservative (Proxel) 1.5mg / m ²
In addition, the coating liquid of each layer added the thickener represented by the following structure (Z), and adjusted the viscosity.

<Support>
Undercoat layer first and second layers of the following composition were coated on the emulsion surface side and back surface side of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) from the side close to the substrate. The coating was performed by a bar coating method, and the substrate before coating of each layer was subjected to corona discharge treatment.

<Undercoat layer 1>
Core-shell type vinylidene chloride copolymer (1) 15 g
2,4-dichloro-6-hydroxy-s-triazine 0.25 g
Polystyrene fine particles (average particle size 3μ) 0.05g
Compound (Cpd-20) 0.20 g
Colloidal silica 0.12g
(Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.)
100g with water

  Furthermore, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness became 0.9 μm.

<2nd undercoat layer>
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-21) 0.02 g
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g
Proxel 3.5 × 10 ⁻³ g
Acetic acid 0.2g
100g with water

  This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

[Back side]
(Undercoat layer 1st layer)
Acrylic latex 1g
Anionic surfactant 0.06g
Nonionic surfactant 0.06g
Sb-doped SnO2 fine particles 0.3g
Spherical silica fine particles (average particle size 0.3μ) 0.05g
Carbodiimide crosslinking agent 0.05g
100g with water

  The coating solution was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness was 0.9 μm.

(Undercoat layer 2nd layer)
Acrylic latex 1g
Anionic surfactant 0.06g
Carnauba wax dispersion 0.05g
Epoxy crosslinking agent 0.05g
100g with water

  This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

(Production of Samples S-1 and S-2)
First, two layers of the UL layer and the emulsion layer from the side closer to the support as the emulsion surface side were coated on the support with the above-mentioned subbing layer in the order of a simultaneous multi-layer by a slide bead coater method while maintaining at 35 ° C. It was passed through a set zone (5 ° C.). Here, Cpd-7, which is a hardener, was added to the UL layer immediately before coating and added to the emulsion layer by diffusing from the UL layer. Then, on the side opposite to the emulsion surface, from the side closer to the support, the conductive layer and the back layer were coated in the order of the conductive layer and the back layer simultaneously with the addition of the hardener solution by the curtain coater method, and the cold air set zone (5 ° C) was formed. I let it pass. When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone. Sample S-1 thus obtained was a photosensitive material having an applied silver amount of 4 g / m ² and Sample S-2 was an applied silver amount of 7.5 g / m ² .

(Development sample creation)
Samples S-1 and S-2 were exposed and developed according to the following method to obtain developed silver base samples (development samples) SD-1 and SD-2. The surface resistance values of the obtained samples were 110Ω / □ and 50Ω / □, respectively.

(Exposure processing)
A grid-like pattern capable of giving a developed silver image of line / pitch = 15 μm / 485 μm was exposed on an emulsion layer of each dried sample using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. At this time, the exposure amount was adjusted to be optimal for each sample.

(Development processing)
Development samples SD-1 and SD-2 each having a lattice-like fine line pattern were prepared by performing the following development processing on the exposed sample.

・ Development processing process Temperature Time Black and white development 20 ° C 60 seconds Fixing 35 ° C 40 seconds Rinse 1 * 35 ° C 60 seconds Rinse 2 * 35 ° C 60 seconds Drying 50 ° C 60 seconds

The composition of each treatment liquid is as follows.
[Black and white developer 1L prescription]
Hydroquinone 20g
Sodium sulfite 50g
40g potassium carbonate
Ethylenediamine tetraacetic acid 2g
Potassium bromide 3g
Polyethylene glycol 2000 1g
Potassium hydroxide 4g
Adjust to pH 10.3

[Fixing solution 1L prescription]
ATS 1.2M Ammonium iodide 5g
Ammonium sulfite monohydrate 25g
Acetic acid 5g
Ammonia water (27%) 1g
Adjust to pH 6.2

(Preparation of electroless plating solution)
An electroless plating solution having a formulation shown in Table 1 was prepared, and the pH was adjusted to 12.3.

[Example 1]
The obtained substrate sample SD-1 is immersed in a 1 mM aqueous solution of PdCl ₂ at 25 ° C. for 5 minutes, and then the plating time becomes 5 min while energizing at 0.5 A / dm 2 in the electroless plating apparatus 10 shown in FIG. Then, electroless plating was carried out. The temperature of the plating solution was 40 ° C.

[Examples 2 to 5]
The electroless plating was performed in the same manner as in Example 1 except that the current value to be energized in the electroless plating apparatus 10 was changed. Table 2 shows the energization amount and the surface resistance value of the obtained sample.

Example 6
Electroless plating was performed in the same manner as in Example 1 except that the substrate sample to be used was changed to SD-2.

[Examples 7 to 8]
Electroless plating was performed in the same manner as in Example 6 except that the current value to be energized was changed.

Example 9
The substrate sample SD-1 is immersed in a 1 mM aqueous solution of PdCl ₂ at 25 ° C. for 5 minutes, and then the electroless plating apparatus shown in FIG. 2 is irradiated with an infrared laser of 830 nm at an energy of 20 J / cm ^{2 on} the transported sample. 30 was carried out so that the plating time was 5 min, and electroless plating was performed at a plating solution temperature of 40 ° C.

Example 10
Electroless plating was performed in the same manner as in Example 9 except that the base sample to be used was changed to SD-2.

[Comparative Example 1]
The obtained substrate sample SD-1 was immersed in a 1 mM aqueous solution of PdCl ₂ , transported so that the plating time was 5 min, and electroless plating was performed at a plating solution temperature of 40 ° C. At the time of electroless plating, plating was carried out without applying electrical current or energy irradiation to the substrate sample.

[Comparative Example 2]
Electroless plating was performed in the same manner as Comparative Example 1 except that the substrate sample to be used was changed to SD-2.

Example 11
5 g of silver nitrate and 20 g of trisodium citrate were dissolved in 150 ml of ion exchange water, and an aqueous solution in which 5 g of sodium borohydride was dissolved in 50 ml of ion exchange water was slowly added with stirring. Methanol was added to the obtained dispersion to precipitate Ag particles, and the supernatant was removed and washed. The washed particles were redispersed in a mixed solvent of cyclohexanol and 2-ethoxyethanol (volume ratio 50:50) to prepare a 10% by weight Ag / Ag ₂ O mixed fine particle dispersion.
Using this dispersion, a substrate sample SD-3 of 120Ω / □ was prepared by drawing on a substrate using a piezo-type ink jet printer in accordance with graphic information of 485 pitch 15 μ line width inputted in advance by a computer.
The obtained base sample SD-3 was subjected to electroless plating in the same manner as in Example 2.

[Comparative Example 3]
The substrate sample SD-3 obtained in Example 11 was immersed in a 1 mM aqueous solution of PdCl ₂ , transported so that the plating time was 5 min, and electroless plating was performed at a plating solution temperature of 40 ° C. At the time of electroless plating, plating was carried out without applying electrical current or energy irradiation to the substrate sample.

[Comparative Example 4]
Electroless plating was performed in the same manner as in Comparative Example 1 except that the plating solution temperature was 52 ° C.

  Table 2 shows the surface resistance value of the sample after electroless plating and the remaining ratio of Cu after allowing the plating solution to pass for one day at the operating temperature.

  As shown in Table 2, it is clear that Examples 1 to 10 have lower surface resistance and higher plating speed than those of Comparative Example 1 by electroless plating for the same time. Moreover, from the comparison with the comparative example 4, Examples 1-10 have high Cu residual rate after 1-day progress, and temporal stability is favorable. Therefore, according to Examples 1 to 10, it is possible to simultaneously achieve high speed electroless plating and long life of the plating solution. Furthermore, according to Example 11, it turns out that this invention is effective also with respect to the base | substrate sample using a conductive ink.

  In addition, although this embodiment demonstrated the apparatus and manufacturing method which manufacture a light-transmitting electromagnetic wave shielding material, it is not restricted to this, For example, it has a fine line pattern which consists of fine electroconductive metal parts, such as other industrial goods The present invention can also be applied as a manufacturing apparatus and a manufacturing method of a light transmissive conductive material.

It is a schematic block diagram which shows the electroless-plating apparatus with which the electroless-plating method in 1st Embodiment of this invention was applied. It is a schematic block diagram which shows the electroless-plating apparatus with which the electroless-plating method in 2nd Embodiment of this invention was applied.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electroless plating apparatus 12 Laminated body 12A Conductive metal pattern 16 Electroless plating tank 16A Plating solution 20 Electric conduction apparatus 22 Feed roller 24 Feed roller 30 Electroless plating apparatus 34 Energy irradiation apparatus

Claims (11)

An electroless plating method for performing metal plating on a substrate including a conductive metal pattern,
An electroless plating method comprising conducting electricity to the conductive metal pattern during the electroless plating, and performing electroless plating while heating the conductive metal pattern.   2. The electroless plating method according to claim 1, wherein the electric current is applied in a range of 1.5 A / dm 2 or less. An electroless plating method for performing metal plating on a substrate including a conductive metal pattern,
An electroless plating method comprising performing electroless plating while heating the conductive metal pattern during the electroless plating by irradiating the conductive metal pattern with energy.   The electroless plating method according to claim 3, wherein the energy irradiation is performed by at least one selected from a laser beam, an electron beam, an ion beam, and a heat ray.   The electroless plating method according to any one of claims 1 to 4, wherein the conductive metal pattern is a pattern including 1 to 50 µm fine mesh wires.   6. The electroless plating method according to claim 1, wherein a surface resistance value of the conductive metal pattern is 10 to 1000 Ω / □.   The electroless plating method according to any one of claims 1 to 6, wherein the conductive metal pattern is formed by exposing and developing a photosensitive material containing silver halide. The base is a long base on which a conductive metal pattern is continuously formed,
The electroless plating method according to any one of claims 1 to 7, wherein the elongate substrate is continuously conveyed to perform electroless plating. An electroless plating apparatus for performing metal plating on a substrate including a conductive metal pattern,
An electroless plating tank filled with an electroless plating solution and into which the substrate is introduced;
An electrical energization device for electrically energizing the conductive metal pattern and heating the conductive metal pattern during the electroless plating;
An electroless plating apparatus comprising: An electroless plating apparatus for performing metal plating on a substrate including a conductive metal pattern,
An electroless plating tank filled with an electroless plating solution and into which the substrate is introduced;
An energy irradiation device that irradiates the conductive metal pattern with energy and heats the conductive metal pattern during the electroless plating;
An electroless plating apparatus comprising:   An electromagnetic wave shielding material formed by the electroless plating method according to any one of claims 1 to 8.

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