JP6264596B2 - Manufacturing method of plated products - Google Patents

Description

  The present invention relates to a method for producing a plated product in which a plating film pattern is formed on the surface of a glass substrate.

  Conventionally, paper phenol base materials, paper epoxy base materials, glass epoxy base materials, ceramic base materials, and the like are used as circuit base materials used in products such as home appliances and transportation equipment. Since these base materials have different electrical characteristics, mechanical characteristics, and prices, they are properly used according to the performance and cost required for the product. At present, glass substrates are attracting attention as circuit boards, and attempts have been made to form metal film patterns on the surface of glass substrates. A glass substrate has the advantage that it has excellent thermal stability and is inexpensive as compared with a conventionally used substrate.

  In Patent Document 1, an energy beam is irradiated on the surface of an insulating substrate, which is an object to be plated, and this energy beam is irradiated on a predetermined portion of the substrate surface. A liquid containing a substance in a compound state is brought into contact with the surface of the insulating substrate, the substrate is cleaned to remove the remaining fluid, and then the irradiation surface of the energy beam is changed to a predetermined chemical plating solution. A selective plating method is described in which a metal is deposited by chemical plating on the adherend portion by contact. Thereby, it is said that a complicated and fine metal deposition pattern can be manufactured.

  However, in the plating method described in Patent Document 1, there was no description or suggestion of forming a metal film pattern on the surface of the glass substrate.

  In Patent Document 2, in a metal wiring forming method for forming a metal wiring on the surface of an insulator, a picosecond laser beam having a pulse width of the order of picoseconds or a femtosecond laser beam having a femtosecond order is used as the laser light. Irradiating the surface of an insulator containing silver ions that is transparent with respect to the wavelength of the light, reducing silver ions to silver atoms in the irradiated region to generate silver atoms in the irradiated region, irradiated with the laser beam A metal film is deposited on the insulator by immersing the insulator in which silver atoms are generated in the irradiated region in an electroless plating solution maintained at a predetermined temperature for a predetermined time, and depositing a metal using the silver atoms as catalyst nuclei. A metal wiring forming method for forming a metal wiring is described. In the examples, examples using photosensitive glass as an insulator are described. Thereby, it is said that a metal wiring can be formed by a simple process and a small number of steps.

  However, in the plating method described in Patent Document 2, a special glass substrate must be used, and the glass substrate is more expensive than a conventionally used substrate. There is a limit to disseminating widely.

JP-A-60-149783 JP 2008-41938 A

  The present invention has been made to solve the above problems, and provides a method for easily producing a plated product in which a plating film pattern having good adhesion is formed on the surface of a glass substrate. It is intended.

The object is a method for manufacturing a plated product in which a plating film pattern is formed on the surface of a glass substrate, the first step of irradiating a part of the surface of the glass substrate with a pulsed laser, and the glass The second step of attaching an electroless plating catalyst to the surface of the substrate, and the pulsed laser is irradiated by bringing the glass substrate into contact with a liquid containing a compound that deactivates the catalyst or a compound that removes the catalyst A third step of selectively deactivating or selectively removing the catalyst adhering to a portion that has not been applied, and a region irradiated with the pulsed laser after electroless plating after the third step And a fourth step of selectively forming a plating film only on the substrate. This is solved by providing a method for manufacturing a plated product.

At this time, the pulse width of the pulse laser is preferably 1 × 10 ⁻¹⁸ to 1 × 10 ⁻⁴ seconds. The plating film is preferably at least one selected from the group consisting of nickel, copper, silver, gold, palladium, platinum, rhodium, ruthenium, tin, iron, cobalt, and alloys thereof.

  In the third step, the compound that deactivates the catalyst is preferably a sulfur compound. At this time, the sulfur compound is preferably a compound having at least one functional group selected from the group consisting of a thiocarbonyl group, a thiol group, and a sulfide group.

  In the third step, it is also preferable that the compound for removing the catalyst is a chelate compound or a cyanide. At this time, the compound for removing the catalyst is preferably at least one chelate compound selected from the group consisting of amino acids, amino alcohols, polyamines, polycarboxylic acids, and polyketones.

  According to the present invention, it is possible to easily manufacture a plated product in which a plating film pattern having good adhesion is formed on the surface of a glass substrate.

It is the figure which showed an example of the irradiation method of a pulse laser. It is the image which image | photographed the metal-plating goods in Example 1 using the microscope. It is the image which image | photographed the external appearance after the tension test in Example 1 using the microscope. It is the image which image | photographed the metal-plating goods in Example 2 using the microscope. It is the image which image | photographed the metal-plating goods in the comparative example 1 using the microscope.

  The present invention relates to a method for producing a plated product in which a plating film pattern is formed on the surface of a glass substrate. The manufacturing method of the present invention includes the following first to fourth steps. Hereinafter, each step will be described.

  In the first step, a part of the surface of the glass substrate is irradiated with a pulse laser. The kind of glass base material used at a 1st process is not specifically limited, Soda lime glass, borosilicate glass, quartz glass etc. are mentioned. These glass base materials can be suitably selected according to the use of the plated product. When cost is important, soda lime glass is preferable. When importance is attached to thermal stability, quartz glass or borosilicate glass is preferred, and quartz glass is more preferred. When importance is attached to the small amount of impurities contained in the glass substrate, quartz glass or borosilicate glass is preferred, and quartz glass is more preferred. Although the thickness of a glass base material is not specifically limited, Usually, it is 0.02-5 mm. The shape is not particularly limited. Moreover, the glass base material which improved the mechanical strength by heat processing can also be used. As such a glass substrate, after glass is heated, it is cooled to a glass surface layer by physical exchange glass obtained by generating a compressive stress in the vicinity of the surface layer by rapid cooling or by ion exchange treatment while heating the glass. Examples thereof include chemically strengthened glass obtained by introducing alkali ions having a large ion radius and generating compressive stress in the vicinity of the glass surface layer.

In the present invention, it is important to use a pulse laser. When a pulse laser is used, multiphoton absorption can be caused even with a transparent substrate such as glass. Multiphoton absorption is more likely to occur as the laser peak power (W) increases. If the energy is the same, the peak power (W) becomes larger as the pulse width becomes shorter. Therefore, the shorter pulse width is preferable. From this viewpoint, the pulse width (second) of the pulse laser is preferably 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁷ seconds or less, and 1 × 10 ⁻⁹ seconds or less. It is more preferable that the time is 1 × 10 ⁻¹⁰ seconds or less. Thus, by making the pulse width extremely short, the peak power of the laser can be made very high, and multiphoton absorption can be caused. The lower limit of the pulse width of the pulse laser is not particularly limited, but is usually 1 × 10 ⁻¹⁸ seconds or longer, and preferably 1 × 10 ⁻¹⁵ seconds or longer. And if it sets so that the processing point (focus) of a laser may become the surface of a glass base material, it will become possible to process the surface of a glass base material.

  The average output at the processing point is preferably 0.01 to 1000 W. When the average output at the processing point is less than 0.01 W, a plating film with good adhesion may not be obtained. On the other hand, when the average output at the processing point exceeds 1000 W, the damage to the glass substrate increases. The repetition frequency of the pulse laser is not particularly limited, but is usually 1 kHz to 1000 MHz.

  The type of laser is not particularly limited, and a solid laser such as a YAG laser, a fiber laser, or a semiconductor laser; a gas laser such as a carbon dioxide gas laser or an excimer laser can be used. The wavelength of the pulse laser is not particularly limited, and can be set as appropriate depending on the type of the glass substrate to be used, and is usually 100 to 12000 nm. From the viewpoint of easy pulse oscillation, a YAG laser is preferable, and a neodymium YAG laser is more preferable. In the neodymium YAG laser, a 1064 nm laser beam called a fundamental wave (first harmonic) is generated. By using the wavelength converter, laser light having a wavelength of 532 nm called second harmonic, laser light having a wavelength of 355 nm called third harmonic, and laser light having a wavelength of 266 nm called fourth harmonic can be obtained. In the production method of the present invention, the first to fourth harmonics can be appropriately selected according to the purpose.

  Then, a part of the surface of the glass substrate is irradiated with a pulse laser. Although the irradiation method of the pulse laser to a glass base material is not specifically limited, For example, the method shown in FIG. 1 is mentioned. FIG. 1 is a diagram showing an example of a pulse laser irradiation method. As shown in FIG. 1, an irradiation area is set on the surface of the glass substrate. In a later step, a plating film is selectively formed only in the region irradiated with the pulse laser, that is, in this irradiation area. Then, after irradiating the laser at a predetermined scanning speed in the x direction (right direction in FIG. 1) from the point indicated by St, the laser is moved at a predetermined interval in the y direction (upward direction in FIG. 1), − After irradiating the laser in the x direction (left direction in FIG. 1) at a predetermined scanning speed, the laser is moved again in the y direction at a predetermined interval. The irradiation spot diameter corresponds to the beam diameter of the laser, but the irradiation spots do not have to overlap each other, and there may be an interval between the irradiation spots. In this method, the laser irradiation amount per unit area can be adjusted by appropriately adjusting the scanning speed and interval (pitch interval).

  From the viewpoint of the adhesion of the plating film, the arithmetic average roughness (Ra) of the glass surface irradiated with the pulse laser is preferably 0.1 μm or more, and more preferably 0.2 μm or more. On the other hand, if the value of Ra is too large, the strength of the plated product may be lowered. Therefore, Ra is preferably 10 μm or less, and more preferably 5 μm or less. Ra in this specification is a value obtained by a method based on JIS B 0601 (2001).

  Next, in a second step, an electroless plating catalyst is adhered to the surface of the glass substrate. The electroless plating catalyst is not particularly limited as long as it contains a metal element having a catalytic action with respect to the electroless plating solution. As the metal element, palladium (Pd), silver (Ag), copper (Cu), nickel (Ni), aluminum (Al), iron (Fe), cobalt (Co), zinc (Zn), gold (Au) , Platinum (Pt), tin (Sn), and the like. These metal elements can be appropriately selected depending on the type of electroless plating solution used in the fourth step. And after processing a glass base material with the aqueous solution containing the said metal element, it can process with the aqueous solution containing a reducing agent, and can activate an electroless-plating catalyst.

  Next, in the third step, in the glass substrate, the catalyst adhering to a portion not irradiated with the pulse laser is selectively deactivated or the catalyst is selectively removed.

  The method for removing the catalyst in the third step is not particularly limited, and examples thereof include a method for subjecting the glass substrate to ultrasonic treatment and a method for washing the surface of the glass substrate with running water. However, from the viewpoint of more selectively deactivating or removing the catalyst adhering to the portion not irradiated with the pulse laser, a method of bringing the glass substrate into contact with a liquid containing a compound that deactivates the catalyst or the above A method of bringing the glass substrate into contact with a liquid containing a compound for removing the catalyst is preferable. The glass substrate can be brought into contact with the solution by immersing the glass substrate in a solution containing a compound that deactivates the catalyst, by immersing the glass substrate in a solution containing a compound that removes the catalyst, or by losing the catalyst. The method of apply | coating the liquid containing the compound to be activated to a glass base material and the method of apply | coating the liquid containing the compound which removes a catalyst to a glass base material are mentioned.

  In the third step, when the glass substrate is brought into contact with a liquid containing a compound that deactivates the catalyst, the compound is preferably a sulfur compound. The present inventors prepared a glass base material to which a palladium catalyst is attached, the chemical composition of the surface of the glass base material before immersion in a liquid containing a sulfur compound, and the glass after immersion in a liquid containing a sulfur compound. The chemical composition of the substrate surface was analyzed using a photoelectron spectrometer (XPS). As a result, it was found that palladium was present on the surface of the substrate even after immersion in a liquid containing a sulfur compound. It was also found that the position of the peak derived from palladium changes when immersed in a liquid containing a sulfur compound. The present inventors consider that this result indicates that the sulfur atom is coordinated to palladium, and this presumes that the palladium catalyst is deactivated.

  The sulfur compound is preferably a compound having at least one functional group selected from the group consisting of a thiocarbonyl group, a thiol group, and a sulfide group. Examples of the sulfur compound having a thiocarbonyl group include thiourea. Examples of the sulfur compound having a thiol group include triazine thiol, mercaptobenzothiazole, mercaptoacetic acid, and thiocyanic acid. Examples of the sulfur compound having a sulfide group include dimethyl sulfide and methionine.

  If the concentration of the liquid containing the sulfur compound is too low, the catalyst may not be selectively deactivated. From this viewpoint, the concentration of the sulfur compound is preferably 0.001 ppm or more. On the other hand, if the concentration of the sulfur compound is too high, the catalyst attached to the portion irradiated with the pulse laser may be deactivated. From this viewpoint, the concentration of the sulfur compound is preferably 100 ppm or less.

  The solvent used in the liquid containing the compound that deactivates the catalyst is not particularly limited, and is usually water or alcohol. When the glass substrate is immersed in a liquid containing a compound that deactivates the catalyst, the temperature at which the glass substrate is immersed is not particularly limited, and is usually 5 to 90 ° C. The time for immersing the glass substrate is not particularly limited, and is usually 1 second to 30 minutes. Examples of the method of applying a liquid containing a compound that deactivates the catalyst to a glass substrate include a method of applying the liquid to a glass substrate by a spray method.

  In a 3rd process, when making a glass base material contact the liquid containing the compound which removes a catalyst, it is preferable that the said compound is a chelate compound or a cyanide. From the viewpoint of handleability, the compound that removes the catalyst is preferably at least one chelate compound selected from the group consisting of amino acids, amino alcohols, polyamines, polycarboxylic acids, and polyketones. Examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and the like. Examples of amino alcohols include triethanolamine. Examples of the polyamine include ethylenediamine. Examples of the polycarboxylic acid include citric acid, succinic acid, maleic acid, fumaric acid, tartaric acid, and potassium tartrate. Examples of the polyketone include acetylacetone.

  The present inventors have prepared a glass substrate to which a palladium catalyst is attached, the chemical composition of the surface of the glass substrate before being immersed in the liquid containing the chelate compound, and the glass after being immersed in the liquid containing the chelate compound The chemical composition of the substrate surface was analyzed using a photoelectron spectrometer (XPS). As a result, it was found that the palladium catalyst on the surface of the base material was removed by immersing in a liquid containing a chelate compound. Moreover, when the liquid after immersing a glass base material was investigated using the ICP emission spectrometer, it turned out that the said liquid contains palladium.

  Examples of the cyanide include potassium cyanide and sodium cyanide.

  If the concentration of the chelate compound or cyanide is too low, the catalyst may not be selectively removed. From this viewpoint, the concentration of the chelate compound or cyanide is preferably 0.001M or more. On the other hand, if the concentration of the chelate compound or cyanide is too high, the catalyst attached to the portion irradiated with the pulse laser may be removed. From this viewpoint, the concentration of the chelate compound or cyanide is preferably 3M or less.

  The solvent used for the liquid containing the compound for removing the catalyst is not particularly limited, and is usually water or alcohol. The temperature at which the glass substrate is immersed is not particularly limited and is usually 5 to 90 ° C. The time for immersing the glass substrate is not particularly limited, and is usually 1 second to 30 minutes. Examples of the method of applying a liquid containing a compound for removing the catalyst to a glass substrate include a method of applying the liquid to a glass substrate by a spray method.

  In the fourth step, electroless plating is performed after the third step, and a plating film is selectively formed only in the region irradiated with the pulse laser. At this time, the plating film is preferably at least one selected from the group consisting of nickel, copper, silver, gold, palladium, platinum, rhodium, ruthenium, tin, iron, cobalt, and alloys thereof. Here, the said alloy means the alloy containing 50 mass% or more of these at least 1 sort (s) of metal elements.

  As the electroless plating used in the fourth step, electroless nickel plating, electroless copper plating, electroless silver plating, electroless gold plating, electroless palladium, electroless platinum plating, electroless rhodium plating, electroless ruthenium plating , Electroless tin plating, electroless iron plating, electroless cobalt plating, or electroless alloy plating thereof. Here, the electroless alloy plating refers to electroless plating containing 50% by mass or more of these at least one metal element. You may perform this process in multiple times, changing the kind of electroless plating.

  As described above, according to the manufacturing method of the present invention, a desired plating film pattern can be accurately formed on the surface of a glass substrate without using a special glass substrate. As demonstrated in the examples described later, when a pattern was formed by a pulse laser and then electroless plating was performed, a plating film could be formed in the region irradiated with the laser. However, when the third step was not performed, a plating film was formed not only in the region irradiated with the laser but also in the region not irradiated with the laser (Comparative Example 1). If the production method of the present invention is used, the catalyst adhering to the portion not irradiated with the laser can be selectively deactivated or selectively removed, so that only the region irradiated with the laser is selectively plated. A film can be formed.

  Moreover, the plating film formed with the manufacturing method of this invention has the outstanding adhesiveness. In recent years, with the reduction in weight and performance of products, the performance required for plated products has become strict, and plated products with a finer film pattern are required. However, when the pitch of the pattern becomes finer, higher adhesion of the plating film is required. Therefore, when obtaining a plated product having a fine film pattern, the merit of using the manufacturing method of the present invention is great.

  Another step may be provided after the fourth step in the production method of the present invention. Examples of the other processes include an electrolytic plating process and various surface treatment processes. Electrolytic plating includes electrolytic nickel plating, electrolytic copper plating, electrolytic silver plating, electrolytic gold plating, electrolytic palladium plating, electrolytic tin plating, electrolytic iron plating, electrolytic bismuth plating, electrolytic platinum plating, electrolytic rhodium, electrolytic ruthenium, and electrolytic zinc plating. Or these electrolytic alloy plating is mentioned. Here, the electroless alloy plating refers to electrolytic plating containing at least 50% by mass of these at least one metal element. Examples of the various surface treatment steps include a step of spraying metal by a cold spray method and a step of applying a metal paste. The metal used at this time is copper, tin, gold, silver, nickel, iron, palladium, ruthenium, rhodium, iridium, indium, zinc, aluminum, tungsten, chromium, magnesium, titanium, silicon, or an alloy thereof. These other steps may be performed a plurality of times, and the steps may be the same or different. Moreover, the mechanical strength of a glass base material can also be improved by heat processing after a 4th process.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these.

Example 1
[Laser irradiation]
(Glass substrate)
Soda lime glass ("Matsunami slide glass S7213") having a length of 76 mm, a width of 26 mm, and a thickness of 1.1 mm was prepared as a glass substrate.

(Processing method)
A pulse oscillation all solid-state laser “Talisker HE” manufactured by Coherent Japan Co., Ltd. was used.
Wavelength: 355nm
Average output: 2W
Average output at the processing point: 0.8W
Pulse width: 20 picoseconds Frequency: 50 kHz

  And the pulse laser was irradiated to the glass base material by the method shown in FIG. Specifically, an irradiation area of 20 mm × 10 mm was set on the surface of the glass substrate. In this irradiation area, a pulse laser was irradiated from the point indicated by St to the right end of the irradiation area in the x direction at a scanning speed of 100 mm / second. Then, the pulse laser was moved by 15 μm in the y direction, and the pulse laser was irradiated to the left end of the irradiation area at a scanning speed of 100 mm / sec in the −x direction. By repeating this, the entire irradiation area was irradiated with a pulse laser.

  When the surface of the glass substrate was observed after the pulse laser irradiation, it was found that the surface was processed as a series of spots (concave portions) as shown in FIG. When one spot diameter was measured, the spot diameter was about 15 μm.

[Electroless plating]
(Preprocessing)
The laser-processed glass substrate was immersed in an aqueous potassium hydroxide solution (concentration: 50 g / L) kept at 50 ° C. for 5 minutes. Thereafter, the glass substrate was washed with ion exchange water. Next, the glass substrate was immersed in a conditioning solution (concentration: 50 mL / L, “Sulcup THRU-CUP MTE-1-A” manufactured by Uemura Kogyo Co., Ltd.) kept at 50 ° C. for 5 minutes. Thereafter, the glass substrate was washed with ion exchange water.

(Electroless plating catalyst adhesion treatment)
The pretreated glass substrate was immersed in a room temperature palladium catalyst solution (concentration: 50 mL / L, “Activator A-10X” manufactured by Uemura Kogyo Co., Ltd.) for 1 minute. Thereafter, the glass substrate was washed three times with ion exchange water.

(Activation process)
The glass substrate to which the palladium catalyst was adhered was immersed in an aqueous sodium hypophosphite solution (concentration: 0.27 M) kept at 50 ° C. for 30 seconds to activate the palladium catalyst. Thereafter, the glass substrate was washed with ion exchange water.

(Catalyst deactivation treatment)
The activated glass substrate is immersed in a thiourea aqueous solution (concentration: 0.1 ppm) kept at 50 ° C. for 1 minute to selectively deactivate the palladium catalyst adhering to the portion not irradiated with the pulse laser. I let you. Thereafter, the glass substrate was washed three times with ion exchange water.

(Electroless Ni plating treatment)
The glass substrate is immersed in an electroless Ni plating solution having a pH of 4.4 kept at 75 ° C. for 35 minutes, subjected to electroless Ni plating treatment, and an electroless Ni plating layer having a thickness of 5 μm is formed on the surface of the glass substrate. Formed. Thereafter, the substrate was washed three times with ion exchange water. The composition of the electroless Ni plating solution is as follows.
・ "ELN240 M2" manufactured by Nippon Electroplating Engineers Co., Ltd. (EEJA): 150mL / L
・ "ELN240 M1" manufactured by Nippon Electroplating Engineers Co., Ltd. (EEJA): 50mL / L
・ "ELN240 R3" manufactured by Nippon Electroplating Engineers Co., Ltd. (EEJA): 6mL / L

(Substitution Au plating treatment)
The glass substrate on which the Ni plating layer is formed is dipped in a gold plating solution (“PRECIOUSFAB IGS8000SPF” manufactured by EEJA) kept at 55 ° C. for 10 minutes, and a substituted Au having a thickness of 0.05 μm is formed on the Ni plating layer. A plating layer was formed to obtain a plated product.

[Evaluation]
(Surface observation)
The surface of the obtained plated product was observed with a microscope. The obtained image is shown in FIG. 2 in FIG. 2 is a glass substrate, and 2 is a displacement gold plating film. As shown in FIG. 2, by performing the “catalyst deactivation treatment”, a plating film was selectively formed only in the region irradiated with the pulse laser.

(Adhesion test)
The adhesion test was performed according to the soldering test method described in JIS H8504. The L-shaped metal fitting at this time was an oxygen-free copper plate having a plate thickness of 0.5 mm. And after press-molding to the designated shape so that the area of a soldering part might be set to 5 mm x 5 m, nickel plating with a film thickness of 3 micrometers was given as a foundation | substrate, and 0.05 micrometers film thickness gold plating was given. On the other hand, after applying solder (φ8 mm × t0.2 mm) to the surface of the plated product, it was heated at 300 ° C. for 1 minute. Then, the L-shaped bracket and the plated product were soldered to obtain a test piece. The obtained test piece was attached to an Instron tensile tester “3382 floor-standing type test system”, and an adhesion test was performed. As the solder, a lead-free solder paste “TSC-254-5042SF 12-1” manufactured by Tarutin Kester was used. FIG. 3 shows an image after the tensile test. As shown in FIG. 3, the plating film peeled off with the glass.

Example 2
In “electroless plating catalyst adhesion treatment”, the time of immersion in the palladium catalyst solution was changed to 2 minutes, and “catalyst removal treatment” was performed instead of “catalyst deactivation treatment”. In “catalyst removal treatment”, a plated product was obtained in the same manner as in Example 1 except that a glass substrate that had been activated in a glycine aqueous solution (concentration: 0.05 M) at room temperature was immersed for 30 seconds. Was observed with a microscope. The obtained image is shown in FIG. 4 in FIG. 4 is a glass substrate, and 2 is a substituted Au plating film. As shown in FIG. 4, by performing the “catalyst removal treatment”, a plating film was selectively formed only in the region irradiated with the pulse laser. And the adhesiveness test was done like Example 1. As a result, the plating film peeled off with the glass.

Example 3
A plated product was obtained in the same manner as in Example 1 except that the glass substrate was changed to 76 mm × 26 mm × 1.1 mm borosilicate glass (“Matsunami slide glass S1127”). And the adhesiveness test was done like Example 1. As a result, the plating film peeled off with the glass.

Example 4
The glass substrate is changed to tempered glass of 70 mm length × 30 mm width × 0.55 mm thickness (“Dragontrail” manufactured by AGC Asahi Glass), and the average output at the processing point is 1.1 W when irradiated with pulsed laser. The glass substrate was irradiated with a pulse laser in the same manner as in Example 1 except that the moving distance in the y direction was changed to 6 μm and the scanning speed was changed to 300 mm / second. “Dragontrail” is a chemically strengthened glass, in which Na ⁺ on the glass surface is replaced with K ⁺ .

  Using a color 3D laser microscope “VK-9700” (50 × observation magnification) manufactured by Keyence Corporation, the arithmetic average roughness (Ra) of the portion irradiated with the pulse laser by a method based on JIS B 0601 (2001) ) Was measured. As a result, Ra was 0.41 μm.

  After measuring the surface roughness, a plating film was formed on the surface of the glass substrate in the same manner as in Example 2. As a result, a plating film was selectively formed only in the region irradiated with the pulse laser. And when the adhesiveness test was done like Example 1, the plating film peeled off with glass.

Example 5
In the pulse laser irradiation, a pulse laser was applied to the glass substrate in the same manner as in Example 4 except that the average output at the processing point was 1.1 W, the moving distance in the y direction was 10 μm, and the scanning speed was changed to 50 mm / second Was irradiated. And the arithmetic mean roughness (Ra) of the location irradiated with the pulse laser was measured like Example 4. As a result, Ra was 2.81 μm.

  After measuring the surface roughness, a plating film was formed on the surface of the glass substrate in the same manner as in Example 2. As a result, a plating film was selectively formed only in the region irradiated with the pulse laser. And when the adhesiveness test was done like Example 1, the plating film peeled off with glass.

Comparative Example 1
A plated product was obtained in the same manner as in Example 1 except that “catalyst deactivation treatment” and “substitution Au plating treatment” were not performed, and the surface thereof was observed with a microscope. The obtained image is shown in FIG. Reference numeral 31 in FIG. 5 denotes a Ni plating film formed at a location irradiated with a pulse laser, and reference numeral 32 denotes a Ni plating film formed at a location not irradiated with a pulse laser on the surface of the glass substrate. As shown in FIG. 5, a plating film was formed on the entire surface of the glass substrate unless either “catalyst deactivation treatment” or “catalyst removal treatment” was performed. Moreover, the Ni plating film formed in the location which was not irradiated with the pulse laser was easily peeled off with the cellophane tape.

Comparative Example 2
In the pulse laser irradiation, the glass substrate was irradiated with the pulse laser in the same manner as in Example 4 except that the average output at the processing point was 1 W, the moving distance in the y direction was 10 μm, and the scanning speed was changed to 300 mm / second did. And the arithmetic mean roughness (Ra) of the location irradiated with the laser was measured like Example 4. FIG. As a result, Ra was 0.03 μm.

  After measuring the surface roughness, a plating film was formed on the surface of the glass in the same manner as in Example 2. As a result, a plating film was selectively formed only in the region irradiated with the pulse laser, but the plating film could be easily peeled off with a cellophane tape.

DESCRIPTION OF SYMBOLS 1 Glass base material 2 Substitution Au plating film 31 Ni plating film formed in the place irradiated with the pulse laser 32 Ni plating film formed in the place which does not irradiate the pulse laser of the glass substrate surface

Claims (4)

A method for producing a plated product in which a plating film pattern is formed on the surface of a glass substrate;
A first step of irradiating a part of the surface of the glass substrate with a pulsed laser;
A second step of attaching an electroless plating catalyst to the surface of the glass substrate;
Whether the glass substrate is brought into contact with a liquid containing a compound that deactivates the catalyst or a compound that removes the catalyst, and the catalyst adhering to a portion not irradiated with the pulse laser is selectively deactivated. Or a third step of selectively removing the catalyst;
A fourth step of performing electroless plating after the third step and selectively forming a plating film only in the region irradiated with the pulse laser;
The pulse laser has a wavelength of 100 to 12000 nm, an average output at a processing point of 0.01 to 1000 W, a pulse width of 1 × 10 ⁻¹⁸ to 1 × 10 ⁻⁴ seconds, and a frequency of 1 kHz to 1000 MHz,
The catalyst is palladium (Pd), silver (Ag), copper (Cu), nickel (Ni), aluminum (Al), iron (Fe), cobalt (Co), zinc (Zn), gold (Au), platinum. (Pt), containing at least one metal element selected from the group consisting of tin (Sn),
Compounds to deactivate the catalyst, a sulfur compound, and a compound of removing the catalyst, method of manufacturing a plated article, characterized in that the chelating compound to form a metal chelate complex. The manufacturing method according to claim 1 , wherein the plating film is at least one selected from the group consisting of nickel, copper, silver, gold, palladium, platinum, rhodium, ruthenium, tin, iron, cobalt, and alloys thereof. . The method according to claim 1 or 2 , wherein the sulfur compound is a compound having at least one functional group selected from the group consisting of a thiocarbonyl group, a thiol group, and a sulfide group. The chelating compound, an amino acid, amino alcohols, polyamines, polycarboxylic acids, the production method according to any one of claims 1 to 3, at least one of compounds selected from the group consisting of polyketone.

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