Substrate manufacturing method and substrate manufacturing device

Abstract

To solve the problem in which a glass substrate lacks adhesion strength for a metal plating film, making it impossible to form circuit patterns on the glass substrate.SOLUTION: A glass substrate 101 is immersed in a treatment liquid. The treatment liquid 201 contains metal ions. The glass substrate 101 is subjected to ultrasound 801 to reduce the ionic bond between Si-O- and Na+, causing Na+ in the glass substrate 101 to elute into a treatment liquid 201a. The metal ions have a greater binding force to Si-O- than that of monovalent Na+ ions, making them easily substitutable. The substituted metal ions within the glass substrate 101 bind to electroless plating metal, thereby forming an electroless plating film 116 on the surface of the glass substrate 101.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for forming a plating film on the surface of an inorganic material substrate such as a glass substrate or a ceramic substrate, a method for manufacturing a glass substrate, an apparatus for manufacturing a glass substrate, a method for processing a glass substrate, an apparatus for processing a glass substrate, a method for processing an inorganic material substrate such as a ceramic substrate, a method for forming a metal wiring pattern for mounting electronic elements or the like on an inorganic material substrate such as a glass substrate wiring substrate or a ceramic wiring substrate, a wiring circuit board on which electronic components or the like are mounted, and an infrared ray or the like light-shielding glass substrate 101 for use as car window glass. [Background technology]

[0002] For example, it is laminated on a glass substrate (glass substrate), a metal film is formed over the entire surface, and then the metal film is patterned using photolithography technology to provide metal wiring. In order to pattern the metal film, it is necessary to treat the surface of the glass substrate to improve the adhesion of the metal film.

[0003] Patent Document 1 discloses a chemical strengthening process in which glass containing sodium is brought into contact with an inorganic salt containing a specific salt, thereby ion-exchanging Na in the glass with K in the inorganic salt. Patent Document 2 discloses a process in which a metal-containing inorganic substance is mixed with a strong acid aqueous solution, and the metal-containing inorganic substance is dispersed in the strong acid aqueous solution to obtain a dispersion. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2019-006615 [Patent Document 2] Patent Publication No. 2012-250423 Summary of the Invention [Problem to be solved by the invention]

[0005] Photolithography of glass substrates requires many steps, such as resist coating, exposure, development, etching, etc., and is complicated. In addition, glass substrates do not have the adhesive strength of metal plating films, so it is not possible to form circuit patterns on glass substrates. [Means for solving the problem]

[0006] The glass substrate manufacturing apparatus of the present invention comprises a glass substrate having alkali metal ions, a treatment liquid containing metal ions, and an ultrasonic device that outputs ultrasonic waves, and is characterized in that the glass substrate is immersed in the treatment liquid, and the ultrasonic wave is irradiated from the ultrasonic device to the glass substrate while the glass substrate is immersed in the treatment liquid.

[0007] In addition, the method for manufacturing a glass substrate of the present invention is characterized in that a glass substrate having alkali metal ions is immersed in a treatment liquid 201 containing metal ions, and ultrasonic waves 801 are irradiated to the glass substrate, thereby replacing the alkali metal ions with the metal ions.

[0008] The glass substrate 101 is immersed in a processing solution 201. The processing solution 201 contains metal ions. Ultrasonic waves 801 are applied to the glass substrate 101 to form a Si-O - and Na + By weakening the ionic bond of Na in the glass substrate 101, + The metal ions are eluted into the treatment liquid 201a. + Si-O ions - The metal ions displaced in glass substrate 101 bond with the metal of the electroless plating, forming electroless plating film 116 on the surface of glass substrate 101. Effect of the Invention

[0009] The present invention has been made in view of the above circumstances, and provides a method for producing a plating layer made of a material that is difficult to plate. The adhesiveness can be easily improved without using special chemicals or photolithography techniques. It is possible to form plating, wiring patterns, plating substrates, wiring substrates, and light-shielding glass having good properties. [Brief description of the drawings]

[0010] [Figure 1] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Diagram 2] FIG. 1 is an explanatory diagram of a manufacturing method for a chemically strengthened glass substrate or the like. [Diagram 3] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 4] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Diagram 5] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 6] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 7] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 8] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 9] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 10] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 11] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 12] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 13] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 14] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 15] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 16] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 17]1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 18] 1 is an explanatory diagram of a plating method and manufacturing apparatus for a glass substrate or the like according to the present invention. [Figure 19] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 20] 4A to 4C are explanatory diagrams of the method for producing a circuit board according to the present invention. [Figure 21] FIG. 2 is a flowchart showing a method for manufacturing a circuit board according to the present invention. [Figure 22] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. [Figure 23] 4A to 4C are explanatory diagrams of the method for producing a circuit board according to the present invention. [Figure 24] 1 is an explanatory diagram of a plating method for a glass substrate or the like according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described below with reference to the drawings showing the embodiments. In the embodiments described in the specification and drawings, some parts may be omitted, enlarged, or reduced in size in order to facilitate understanding or to facilitate drawing. The embodiments of the present invention described in this specification and the drawings may be combined in part or in whole with each other.

[0012] In this specification and drawings, a processing method, a plating method, and a manufacturing apparatus for a glass substrate 101 are illustrated, but the present invention is not limited thereto. For example, it goes without saying that the present invention can be applied even if the glass substrate 101 is a plate or structure of an inorganic material such as a ceramic substrate. It also goes without saying that the glass substrate 101 may be a plate or object made of a mixture of inorganic materials such as glass and ceramic. In the embodiment, the glass substrate 101 is mainly described, but it does not have to be a substrate, and may be, for example, a glass sheet or a thin glass film.

[0013] Furthermore, it goes without saying that the present invention can also be applied to a member or method in which a substrate having a base material made of a material other than glass, such as a metal, and a surface coated with glass is subjected to metal ion substitution or metal transfer on the surface of the glass coating.

[0014] In the present specification and the embodiments in the drawings, a plate-like substrate such as a glass substrate 101 or a ceramic substrate 101 is described as an example, but the present invention is not limited to a plate-like or flat substrate. For example, the substrate may be cylindrical, spherical, or lenticular.

[0015] Examples of the glass substrate 101 include substrates or base materials made of soda glass, lime glass, quartz glass, lead glass, borosilicate glass, and crystallized glass. Examples of the ceramic substrate 101 include substrates or base materials made of aluminum oxide, alumina, aluminum nitride, beryllium oxide, and the like.

[0016] 2 is an explanatory diagram of an ion exchange treatment method for a glass substrate 101. The ion exchange treatment for a glass substrate 101 is carried out by converting various monovalent cations contained in a treatment liquid 201 into K + The ions contained in the processing liquid 201 are introduced into the glass substrate 101 by replacing the alkali metal ions such as those mentioned above.

[0017] In the specification and drawings of the present invention, matters and parts that are not necessary for the explanation are omitted or not shown. For example, in Fig. 2(a), negative ions are also generated in the treatment liquid 201, but are not shown. Also, the thickness of each layer is shown diagrammatically for the purpose of illustration. The above matters are the same in other embodiments, drawings, etc. of the present invention.

[0018] In the glass substrate 101, at room temperature, alkali metal ions form strong ionic bonds with oxygen shared by Si or Al in the glass substrate 101. However, the thermal energy obtained by raising the temperature of the glass substrate 101 to 300° C. or higher weakens the bonding force between the oxygen and the alkali metal ions, making the alkali metal ions mobile.

[0019] When the glass substrate 101 in which the alkali metal ions are mobile is immersed in a treatment liquid 201 such as a molten salt containing any monovalent cation, a concentration gradient is generated between the ions in the glass substrate 101 and the ions contained in the treatment liquid 201. The generated concentration gradient acts as a driving force to cause mutual diffusion between the ions in the glass substrate 101 and the ions contained in the treatment liquid 201, resulting in ion exchange.

[0020] As shown in FIG. 2, when the treatment is performed at a temperature lower than the glass transition temperature, the glass substrate 101 is brought into contact with a molten salt 201 of an alkali metal having a larger ionic radius than the alkali metal contained in the glass substrate 101. + (Glass)<->K + Ion exchange is performed using a method similar to that used with molten salts (Fig. 2(a)). Through ion exchange, alkali metal ions, which occupy a large volume, diffuse into the glass, increasing the compressive stress on the surface of the glass and improving the mechanical strength of the glass.

[0021] K + Due to the diffusion of the isotopes, the glass in the surface layer of the glass substrate 101 has a larger linear expansion coefficient than the inner glass, so that the compressive stress on the surface increases as the glass cools, improving the mechanical strength of the glass (FIG. 2(b)).

[0022] 3 is an explanatory diagram of the plating method of the present invention for the glass substrate 101. In the present invention, by introducing an ultrasonic device, ion exchange is possible even in a general aqueous solution or organic solvent.

[0023] It is also effective to form a protective film or protective sheet (not shown) on the glass substrate 101 or the like to protect it from the processing liquid 201. It is also effective to form or place a protective film or protective sheet, and pattern the protective film or protective sheet into a predetermined shape or arrangement by etching or the like.

[0024] Examples of the protective film or protective sheet include polyimide resin, polyamide resin, epoxy resin, silicone resin, fluororesin, and sheets of these resins, as well as vapor-deposited films of metals, etc.

[0025] At the locations or positions where the protective film or protective sheet has been peeled off or removed by patterning, the treatment liquid 201 comes into direct contact with the surface of the glass substrate 101 or the like. Alternatively, the protective film or protective sheet before curing is cured by exposing it to ultraviolet light, and the uncured portions are removed by washing. At the locations where the protective film or protective sheet has been removed, replacement of metal ions and the like, progression and movement of metals occur or are promoted. After the replacement of metal ions and the like and the progression of metals, the remaining protective film or protective sheet is removed with a stripping liquid or the like.

[0026] By applying ultrasound to the solution, the Si-O - M + The electrostatic bond between oxygen and ions (electrostatic bond) represented by (M: Li, Na, etc.) is weakened, and the same effect as in the case of molten salt is obtained. + The ion exchange reaction occurs in molten salts. + The above Si-O - M + The electrostatic bond between oxygen and ions (M: Li, Na, etc.) becomes weaker, and ion exchange becomes more active. The exchange rate of metal ions becomes faster, which reduces processing time and material costs.

[0027] The plating method for the glass substrate 101 of the present invention is as follows. + The Na ions in the glass are replaced with other metal ions. Even if the glass substrate 101 is placed in water, + is not dissolved in water.

[0028] In the present invention, ultrasonic waves are applied to the glass substrate 101 to form a Si-O - and Na +At this time, the ionic bond between the metal ions (Ni 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Au + , Au 2+ , Ag + , Ag 2+ etc.) and Na + A reaction occurs in which

[0029] By using a plurality of ultrasonic devices 301 and irradiating ultrasonic waves 801 of different frequencies, a phase difference between different ultrasonic waves occurs, and the ultrasonic application state is enhanced where the phase differences match. Alternatively, the ultrasonic application state is reduced where the phase differences do not match. By generating ultrasonic phase states in this way, a distribution of the application state of ultrasonic waves 801 can be generated on the glass substrate 101, etc., and the replacement of metal ions, etc., and the progression of metal can be changed at each position, forming or generating a distribution of metal plating states.

[0030] Divalent metal ions are monovalent Na + Si-O ions - The divalent metal ion is easily replaced by two Si-O - This is the principle of ion exchange using ion exchange resin. By applying ultrasonic waves, metal ions are arranged on the surface layer of the glass substrate 101. Depending on the arrangement or distribution of the metal ions, a metal plating film can be formed and configured.

[0031] The arrangement of metal ions is promoted and progressed by applying ultrasonic waves 801 to the glass substrate 101, applying an electric field due to a DC voltage between the front and back surfaces of the glass substrate 101, and heating the wiring formation area on the surface of the glass substrate 101 using a carbon dioxide laser or the like.

[0032] The movement or amount of movement of the metal ions changes when an electric field is applied by a DC voltage and heating is performed by the laser light 105. This change or movement is measured and monitored by a DC ammeter to control the movement or replacement state of the metal ions.

[0033] In the second step of the present invention, the glass substrate 101 obtained in the first step is washed with pure water, and then immersed in an electroless plating solution to perform electroless plating. Since the surface layer of the glass substrate 101 contains metal ions, these metal ions and the metal ions in the electroless plating solution are reduced by a reducing agent to form metallic bonds, and a metal film 116 (electroless plating film 116) is formed or configured on the surface layer of the glass substrate 101. In the third step of the present invention, electrolytic plating film 117 is formed on electroless plating film 116 on the surface of glass substrate 101 obtained in the second step.

[0034] 1 is an explanatory diagram of the plating method for a glass substrate 101 of the present invention. A container 107 (not shown) coated or formed with a plastic raw material containing fluorine atoms is filled with a treatment liquid 201, and the glass substrate 101 is immersed in the treatment liquid 201. An example of the plastic raw material containing fluorine atoms is polytetrafluoroethylene. Polytetrafluoroethylene is a polymer of tetrafluoroethylene, and is a fluororesin consisting only of fluorine atoms and carbon atoms. With the glass substrate 101 immersed, ultrasonic waves 801 are applied.

[0035] In the embodiment of the present invention, the metal ions of the glass substrate 101 are replaced, but the present invention is not limited to this. The substrate may be a plastic substrate, a ceramic substrate, a metal substrate, or other substrate other than an inorganic material, on whose surface an inorganic material such as a glass material is deposited, applied, or formed. The substrate is not limited to a plate-like substrate, but may be any other shape such as a cylindrical shape, a spherical shape, a triangular pyramid shape, or an arc shape. The substrate is not limited to a glass substrate, but may be a ceramic substrate.

[0036] Ultrasonic waves are sound waves with a frequency of 20 kHz or more. As the frequency of ultrasonic waves increases, they are more attenuated but have better directionality. Therefore, when irradiating glass substrate 101 using horn 303, it is preferable to use ultrasonic waves of a high frequency when ultrasonic waves 801 are irradiated to a small area by placing horn 303 close to glass substrate 101. Also, when irradiating the entire glass substrate 101 with ultrasonic waves, it is preferable to irradiate ultrasonic waves of a relatively low frequency.

[0037] A distribution of ultrasonic strengths can be generated by combining multiple horns 303 and irradiating ultrasonic waves 801. By generating a distribution of ultrasonic strengths, a distribution of the application state of ultrasonic waves 801 can be generated on the glass substrate 101 or the like. The replacement of metal ions and the progression of metal can be changed in response to the strength of ultrasonic waves 801, forming or generating a distribution of the metal plating state.

[0038] As described above, in the method for plating glass substrate 101, the method for processing a glass substrate, or the method for manufacturing a glass substrate of the present invention, the frequency of the ultrasonic waves is changed or altered in accordance with the unit area to which the ultrasonic waves are irradiated and the processing strength.

[0039] In one embodiment of the present invention, for example, 20 kHz, 1 to 100 W / cm 2 However, the ultrasonic wave having an output of is not limited to this condition. If the ultrasonic wave output is low, the reaction time becomes long, and if the ultrasonic wave output is too high, the glass substrate 101 may be broken. The frequency applied to the glass substrate 101 is set in consideration of the weight and area of ​​the glass substrate 101 so as not to match the resonant frequency of the glass substrate 101. If the resonant frequency of the glass substrate 101 is F (KHz), the frequency of the ultrasonic wave is set to F×0.8 or less and F×1.2 or more.

[0040] A horn 303 is attached to the output side of ultrasonic wave 801 of ultrasonic device 301, and is configured so that ultrasonic wave 801 can be applied to glass substrate 101 for ion replacement. The area irradiated on glass substrate 101 can be easily changed by replacing horn 303 with a different one.

[0041] Examples of the shape of horn 303 include a circle, a square, and a line. For example, in the case of a line shape, it is made to approximately match the size of the short side of glass substrate 101. A plurality of piezoelectric ceramic elements that generate ultrasonic waves 801 are arranged or mounted in a line so as to correspond to the length of the line. Linear horn 303 is moved sequentially in the direction of the long side of glass substrate 101 to perform metal replacement.

[0042] It is also preferable to configure a plurality of piezoelectric ceramic elements that generate ultrasonic waves 801 in a matrix to the size of circuit board 110, and to perform metal replacement on the circuit board 110 size.

[0043] It is preferable that the intensity of the ultrasonic waves 801 applied to the glass substrate 101 is weaker than the average value at the beginning of the application to the relevant portion, and the intensity is increased as the metal replacement progresses. This is presumably because the energy of the ultrasonic waves 801 required for the metal replacement increases the deeper into the glass substrate 101.

[0044] Ultrasound is generated by vibrating piezoelectric ceramics. Piezoelectric ceramics are used, which convert electrical energy into vibrational energy. Piezoelectric ceramics are polycrystalline ceramics made by baking high-purity powder (titanium oxide, barium oxide, etc.) at high temperatures. When sound or vibration is applied to piezoelectric ceramics, a voltage is generated, and conversely, when voltage is applied, it vibrates. In order to generate large ultrasonic waves 801, many piezoelectric ceramics are used, and each piezoelectric ceramic is synchronized and applied to the glass substrate 101 with the same phase.

[0045] It is preferable to configure the frequency of the ultrasonic waves 801 so that it can be varied during the process. It is also preferable to change the frequency in accordance with the size and material of the glass substrate 101. It is also preferable to change the frequency in accordance with the concentration and replacement state of the processing liquid 201. The frequency can be easily changed by changing the AC voltage frequency of the electric signal applied to the piezoelectric ceramic element that generates the ultrasonic waves 801.

[0046] Ultrasonic transducers convert high-frequency power from an oscillator into ultrasonic vibrations, and come in two types: electrostrictive and magnetostrictive. Electrostrictive transducers expand and contract when a voltage is applied, while magnetostrictive transducers expand and contract when a magnetic field is applied. Currently, electrostrictive transducers are the most commonly used due to their ease of use.

[0047] Electrostrictive transducers mainly use lead zirconate titanate (commonly known as PZT), which vibrates when an AC voltage is applied. The operating frequency of PZT is approximately 400 kHz or higher. Transducers developed for low frequencies using this PZT are called bolt-clamped Langevin type transducers (BLT or BL transducers). The BL vibrator improves vibration performance by clamping the PZT vibrator between metal blocks and applying pressure with screws (bolts). In addition, since the metal part is also resonated, a vibrator that operates at frequencies from 15kHz to 200kHz can be created. The horn 303 is a reflector for concentrating and emitting ultrasonic waves 801 in a certain direction or for receiving the waves, and the shape and dimensions of the horn determine the directional characteristics of the sensor.

[0048] The higher the frequency and the larger the vibration area, the sharper the directivity becomes, and the more efficiently the sound waves can be emitted. The directional characteristics are greatly affected by the shape of the horn 303, the vibration mode of the transducer, etc. The shape of the sensor unit, the frequency used, the type of transducer, etc. are determined according to the desired operating area. The frequency of the ultrasonic wave 801 is preferably 20 kHz or more and 100 kHz or less.

[0049] The strength of the cavitation bubbles generated when ultrasonic waves are irradiated tends to decrease when the temperature is higher than 40° C. In order to activate the ion exchange on the surface of the glass substrate 101, it is preferable to perform the process at a temperature of 50° C. or higher, which is higher than 40° C.

[0050] Heating is performed at 40°C to 100°C (the boiling temperature of water), preferably 50°C to 100°C. However, when the processing liquid 201 is an organic solvent, it may be possible to heat it up to 250°C.

[0051] The higher the temperature, the faster the replacement speed of metal ions. It is not preferable to perform the treatment at a temperature up to the boiling point of the treatment liquid 201 from the standpoint of safety. On the other hand, a temperature below 40° C. is not preferable because the replacement speed becomes slow. It is preferable to perform the treatment at a temperature of 50° C. or higher.

[0052] In the case of a water-based treatment liquid 201, a strong acid diluted in pure water is exemplified. The strong acid is preferably a mixture of hydrochloric acid and nitric acid, hydrochloric acid, nitric acid, or sulfuric acid. The strong acid is mixed with water at a ratio of 1:1 to 1:3.

[0053] The treatment liquid 201 is not particularly limited as long as it is acidic, and may have a pH of 7 or less, and may be a weak or strong acid. Specifically, acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid, and citric acid are preferred. These acids may be used alone or in combination.

[0054] An organic solvent is exemplified as the processing liquid 201. Examples include alcohols, ethers, ketones, nitriles, amines, amides, and sulfur compounds.

[0055] Furthermore, an ionic liquid may be used as the treatment liquid 201. For example, imidazolium salts, pyrrolidinium salts, pyridinium salts, piperidinium salts, ammonium salts, and phosphonium salts are exemplified.

[0056] Unlike aqueous systems, acid is not required when replacing ions in an organic solvent. In other words, the glass substrate 101 is placed in a treatment liquid 201 in which a metal compound has been added to an organic solvent, and ultrasonic waves are applied. The temperature of the treatment liquid 201 can be heated to near the boiling point of the organic solvent to replace the ions in the glass substrate 101. For example, the boiling point of propylene carbonate is 240°C, so the reaction can be carried out by heating the treatment liquid to near this temperature.

[0057] The treatment liquid 201 may be a deep eutectic solvent. The general formula of deep eutectic solvents (DESs) is Cat + X - It is composed of zY. Cat + is an ammonium, phosphonium or sulfonium cation, X is a Lewis base and a halide anion, Y is a Lewis or Bronsted acid, and z is the number of Y molecules. The most commonly used Cat + X - is ChCl (ChCl=HOC2H4N + (CH3)3Cl - Deep eutectic solvents are broadly divided into the following four types: Type 1 Cat + X - zMCl x M=Zn, Sn, Fe, Al, Ga, In Type 2 Cat + X - zMCl x ·yH2O M=Cr(II), Co, Cu, Ni, Fe Type 3 Cat + X - zRZ Z=CONH2, COOH, OH Type 4 MCl x +RZ=MCl x-1 +RZ+MCl x+1 M=Al, Zn, Z=CONH2, OH Type 3 Cat + X -When ChCl is used, the temperature (℃) at which the deep eutectic solvent becomes liquid is as follows:

[0058] Urea (12°C), thiourea (69°C), 1-methylurea (29°C), 1,3-dimethylurea (70), 1,1-dimethylurea (149°C), acetamide (51°C), benzamide (92°C), adipic acid (85°C), benzoic acid (95°C), citric acid (69°C), malonic acid (10°C), oxalic acid (34°C), phenylacetic acid (25°C), phenylphosphonic acid (20°C), succinic acid (71°C), tricarballylic acid (90°C). Glass exchange reactions are possible at temperatures higher than the melting points of these acids.

[0059] In the case of Type 4, the melting points (℃) of ZnCl2 + organic matter are: organic matter = urea (9℃), acetamide (-16℃), ethylene glycol (-30℃), hexanediol (-23℃). Glass exchange reactions are possible at temperatures higher than these melting points.

[0060] The plating metal to be mixed in the treatment liquid 201 is a plating metal RO (R is at least one selected from Mg, Ca, Sr, Ba, Zn, Cu, and Ni). p O q (M is at least one selected from Fe, Ti, V, Cr, Pr, Ce, Bi, Eu, Mn, Er, Nd, W, Rb, K, Zr, B, Na, Li, Au, S, Cr, and Ag), and p and q are the atomic ratios of M and O. Also, KNO3, NaNO3, CoSO4, Na2SO4, Li2SO4, LiCl, and NaCl. The above plating metals may be dissolved in the treatment liquid 201, which may be water, an organic solvent, an ionic liquid, or a deep eutectic solvent, or may be dissolved in a mixture of these solvents.

[0061] In the plating method of the glass substrate 101 of the present invention, the substitution of metal ions is carried out by replacing various monovalent cations contained in the treatment liquid 201 with K + , Na +This is a technique for introducing ions contained in the processing liquid 201 into the glass substrate 101 by replacing them with alkali metal ions such as ions of argon, argon, and the like.

[0062] In glass, etc., at room temperature, alkali metal ions form strong ionic bonds with oxygen shared by Si or Al in the glass. By applying ultrasonic waves 801 to the glass substrate 101, the bond between the oxygen and the alkali metal ions is weakened by the thermal energy obtained, and the alkali metal ions become mobile.

[0063] 3, when glass in which alkali metal ions are mobile is immersed in a treatment liquid 201 such as a molten salt containing any cation, a concentration gradient is generated between the ions in the glass and the ions contained in the treatment liquid. The generated concentration gradient acts as a driving force to cause mutual diffusion between the ions in the glass substrate 101 and the ions contained in the treatment liquid 201, resulting in ion exchange.

[0064] For the ion exchange reaction of glass, it is important to weaken the ionic bonds contained in the glass substrate 101. In the present invention, by introducing an ultrasonic device 301, ion exchange becomes possible even in a general aqueous solution or organic solvent.

[0065] By applying ultrasonic waves 801 to the glass substrate 101, the Si-O - M + The electrostatic bond between oxygen and ions, represented by M=Li, Na, etc., is weakened. Therefore, the same effect as in the case of molten salt appears, and the metal ions contained in the treatment liquid 201 and the M in the glass + The ions undergo an exchange reaction.

[0066] In the case of molten salt, by introducing ultrasonic waves 801, the above-mentioned Si-O - M + The electrostatic bond between oxygen and ions (M=Li, Na, etc.) becomes weaker, and ion exchange becomes more active. The exchange rate of metal ions becomes faster, so it is expected to reduce processing time and material costs. As shown in FIG. 1, Na and K are removed (leached) from the top surface of the glass substrate 101, and metal ions (Cu + ) is inserted (replaced).

[0067] Metal ions (Cu + ) is substituted in a range of 5 nm or more from the surface of the glass substrate 101. Preferably, it is 20 nm or more. The depth of substitution can be controlled by the concentration of the treatment liquid 201, the sodium concentration, the temperature, the time, etc.

[0068] The present invention relates to Na + (Glass)<--> Cu + , Cu 2+ , Ag + , Ni 2+ By ion exchange treatment of Cu + etc. are introduced into the glass substrate 101. + , Ni 2+ By introducing the above into the glass substrate 101 , an electroless plating film 116 of Cu or the like can be attached to the surface of the glass substrate 101 .

[0069] 1 is an explanatory diagram of an embodiment in which Cu substitution is performed on the surface of a glass substrate 101 to form an electroless plating film 116 on the surface of the glass substrate 101. Hereinafter, an embodiment as one aspect of the present invention will be described. (Example 1-1)

[0070] 100 g of CaCl2·6H2O and 0.5 g of CuCl were mixed in a container 107 and kept at a temperature of 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×1 mm was immersed in the liquid and irradiated with ultrasonic waves 801 by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0071] Next, the dried glass substrate 101 was immersed for 1 hour in 100 ml of an aqueous solution of 0.3 g of formaldehyde, 0.8 g of NaOH, and 3 g of ethylenediaminetetraacetic acid, while keeping the temperature at 50° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0072] 0.2 g of CuSO4·5H2O was dissolved in the formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. After that, the glass substrate 101 was washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101.

[0073] In the above embodiment, it has been described that while glass substrate 101 is immersed in treatment liquid 201 containing metal ions, ultrasonic waves 801 are applied, glass substrate 101 is removed, washed with pure water, dried at room temperature, and then immersed in an alkaline solution or the like, and then in an electroless plating solution to form electroless plating film 116, but the present invention is not limited to this. It goes without saying that the step of drying glass substrate 101 after application of ultrasonic waves 801 may be omitted and the step of electroless plating film 116 may be performed consecutively.

[0074] It goes without saying that ultrasonic waves 801 may be applied to glass substrate 101, and then electroless plating solution may be injected into treatment liquid 201, so that the process of electroless plating film 116 may be carried out continuously. The above points also apply to other embodiments of the present invention. (Example 1-2)

[0075] After pouring 100 ml of pure water into the container 107, 5 g of CuSO4·5H2O was dissolved in it and the temperature was kept at 80°C to prepare the treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid and irradiated with ultrasonic waves 801 by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0076] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 0.3 g of formaldehyde, 0.8 g of NaOH, and 3 g of ethylenediaminetetraacetic acid, while maintaining the temperature at 50° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0077] 0.2 g of CuSO4·5H2O was dissolved in the formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. After that, the glass substrate 101 was washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 1-3)

[0078] 100 ml of pure water was placed in the container 107, and 50 g of Cu(NO3)2·3H2O was dissolved in it. The temperature was kept at 80°C to prepare the treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm x 70 mm x 2 mm was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0079] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 0.3 g of formaldehyde, 0.8 g of NaOH, and 3 g of ethylenediaminetetraacetic acid, while maintaining the temperature at 50° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0080] 0.2 g of CuSO4·5H2O was dissolved in the formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. After that, the glass substrate 101 was washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 1 to 4)

[0081] 100 ml of pure water was placed in a container 107, and 50 g of CuCl2 was dissolved in it. The temperature was kept at 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 20 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0082] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 0.3 g of formaldehyde, 0.8 g of NaOH, and 3 g of ethylenediaminetetraacetic acid, while maintaining the temperature at 50° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0083] 0.2 g of CuSO4·5H2O was dissolved in the formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. After that, the glass substrate 101 was washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101.

[0084] 4 is an explanatory diagram of an embodiment in which Ni substitution is performed on the surface of glass substrate 101 to form electroless plating film 116 on the surface of glass substrate 101. Hereinafter, an embodiment as one aspect of the present invention will be described. (Example 2-1)

[0085] 100 g of CaCl2·6H2O and 0.5 g of NiCl2 were mixed in a container 107 and kept at a temperature of 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid and irradiated with ultrasonic waves 801 by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0086] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0087] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Example 2-2)

[0088] After pouring 100 ml of pure water into the container 107, 50 g of NiSO4·6H2O was dissolved in it and the temperature was kept at 80° C. to prepare the treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid and irradiated with ultrasonic waves 801 by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0089] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0090] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Example 2-3)

[0091] 100 ml of 1 mol / L sulfuric acid solution was placed in the container 107, and 50 g of NiSO4·6H2O was dissolved in it. The temperature was kept at 80°C to prepare the treatment solution 201 for ion exchange. A soda glass substrate 101 measuring 30 mm x 70 mm x 2 mmt was immersed in the solution, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 20 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0092] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0093] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 2-4)

[0094] 100 ml of 1 mol / L nitric acid solution was placed in container 107, and 50 g of Ni(NO3)2·6H2O was dissolved in it. The temperature was kept at 50°C to prepare treatment solution 201 for ion exchange. A soda glass substrate 101 measuring 30 mm x 70 mm x 2 mmt was immersed in the solution, and ultrasonic waves 801 were irradiated using ultrasonic device 301. The ultrasonic waves 801 were irradiated for one hour with a frequency of 20 kHz and an output of 2 W / cm2. After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0095] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0096] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 2-5)

[0097] Container 107 contains 5 g of choline chloride (ChCl, ChCl = HOC2H4N + (CH3)3Cl - ) was mixed with 40 g of urea and 1.3 g of NiCl2, and the temperature was kept at 80°C to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm x 70 mm x 2 mmt was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0098] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0099] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 2-6)

[0100] 100 ml of dimethyl sulfoxide was placed in the container 107, and 5 g of NiSO4 was dissolved in it. The temperature was kept at 80° C. to prepare the treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0101] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0102] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Examples 2-7)

[0103] 100 ml of 1-allyl-3-butylimidazolium bis(trifluoromethanesulfonylimide) was placed in a container 107, and 1 g of NiSO4 was dissolved in it. The temperature was kept at 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0104] Next, the dried glass substrate 101 was immersed for 1 hour in 100 mL of an aqueous solution of 3 g of hypophosphorous acid and 5 g of succinic acid, which was kept at 90° C. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0105] 5 g of NiSO4·6H2O was dissolved in the hypophosphorous acid aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101.

[0106] 5 is an explanatory diagram of an embodiment in which Ag substitution is performed on the surface of glass substrate 101 to form electroless plating film 116 on the surface of glass substrate 101. Hereinafter, an embodiment as one aspect of the present invention will be described. (Example 3-1)

[0107] 100 g of CaCl2·6H2O and 0.03 g of AgCl were mixed in a container 107 and kept at a temperature of 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid and irradiated with ultrasonic waves 801 by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0108] Next, the dried glass substrate 101 was immersed for 10 hours in a solution prepared by adding ammonia water to 100 mL of a 0.4 mol / L aqueous formaldehyde solution to adjust the pH to 11. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0109] 1 g of AgNO3 was dissolved in the 0.4 mol / L formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Example 3-2)

[0110] 100 ml of dimethyl sulfoxide was placed in a container 107, and 5 g of AgNO3 was dissolved in it. The temperature was kept at 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mmt was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0111] Next, the dried glass substrate 101 was immersed for 10 hours in a solution prepared by adding ammonia water to 100 mL of a 0.4 mol / L aqueous formaldehyde solution to adjust the pH to 11. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0112] 1 g of AgNO3 was dissolved in the 0.4 mol / L formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101. (Example 3-3)

[0113] Container 107 contains 5 g of choline chloride (ChCl, ChCl=HOC2H4N + (CH3)3Cl - ) was mixed with 40 g of urea and 0.5 g of AgCl, and the temperature was kept at 80° C. to prepare a treatment liquid 201 for ion exchange. A soda glass substrate 101 measuring 30 mm×70 mm×2 mm was immersed in the liquid, and ultrasonic waves 801 were irradiated by an ultrasonic device 301. The ultrasonic waves 801 had a frequency of 40 kHz and an output of 2 W / cm. 2 After that, the glass substrate 101 was taken out, washed with pure water, and then dried at room temperature.

[0114] Next, the dried glass substrate 101 was immersed for 10 hours in a solution prepared by adding ammonia water to 100 mL of a 0.4 mol / L aqueous formaldehyde solution to adjust the pH to 11. Thereafter, the glass substrate 101 was washed with pure water and dried at room temperature, and then the surface was observed to confirm that the ions contained in the glass substrate 101 had been exchanged.

[0115] 1 g of AgNO3 was dissolved in the 0.4 mol / L formaldehyde aqueous solution prepared above. The ion-exchanged glass substrate 101 was immersed in the solution for 1 hour. The glass substrate 101 was then washed with pure water and dried at room temperature. When the surface was observed, it was found that an electroless plating film 116 had been formed on the surface of the glass substrate 101.

[0116] In the above-mentioned Cu ion exchange Examples 1-1, 1-2, 1-3, 1-4, Ni ion exchange Examples 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, and Ag ion exchange Examples 3-1, 3-2, 3-3, the exchange rates of Na ions and metal ions in the glass were compared, and the results showed that the ion exchange rate was faster in the case of Ag and Cu than in the case of Ni.

[0117] The results showed that the exchange rate of water coordinated to metal ions in aqueous solution was 10 8 ~10 9 s -1 So Ni is 10 5 s-1 This is thought to be related to the fact that the faster the water exchange rate, the easier it is for water coordinated to the metal to leave. In this patent, the easier it is for ligands such as water coordinated to metal ions to leave the metal ions, the more favorable the ion exchange becomes, so it is thought that the exchange rate between Na ions and metal ions in glass is faster for Ag and Cu than for Ni.

[0118] In addition, among the Cu ion-exchange Examples 1-1, 1-2, 1-3, and 1-4, Example 1-1 showed the fastest ion exchange. The reason for this is that the coordination of a ligand such as water around a metal ion has the effect of increasing the radius of the metal ion, which works against the ion exchange with the Na ion in the glass.

[0119] In Example 1-1, in the system in which CaCl2·6H2O and CuCl were mixed, there was almost no water available to coordinate around the Cu ions. Therefore, when the Cu ions exchanged with the Na ions in the glass, the inhibiting effect of the coordinated water was small, and it is thought that the exchange rate was relatively fast.

[0120] Among the Ni ion exchange Examples 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, and 2-7, the non-aqueous Examples 2-5, 2-6, and 2-7 showed fast ion exchange.

[0121] This result is believed to be due to the fact that choline chloride, dimethyl sulfoxide, and ionic liquid have a smaller ability to coordinate with Ni than water. Among them, the ion exchange rate was the fastest in the case of Example 2-6.

[0122] The reason for this is that 2-6, which used a dimethyl sulfoxide treatment solution, had the lowest viscosity compared to 2-5, which used choline chloride, and 2-7, which used an ionic liquid. In the Ag ion exchange examples 3-1, 3-2, and 3-3, 3-2, which used dimethyl sulfoxide, showed the fastest ion exchange, as in the above.

[0123] 6, 7 and 9 are explanatory views and configuration diagrams of the glass substrate processing apparatus of the present invention. The glass substrate 101 is transported on transport rollers 302. The glass substrate 101 is immersed in a processing liquid 201.

[0124] The temperature regulator 304 heats the processing liquid 201. An example of the temperature regulator 304 is a liquid heating heater. Examples of the liquid heating heater include a liquid in-line heater, a liquid flange heater, a liquid plug heater, an immersion heater, a sheath heater element, and a submersible heater. The diffusion fan (agitation fan) 305 agitates the processing liquid 201 so that the processing liquid 201 has a uniform temperature distribution.

[0125] The ultrasonic device 301 is attached to an XYZ moving stage 401, and is moved and positioned in the Z direction (up and down), X direction (long side direction of the glass substrate 101), and Y direction (short side direction of the glass substrate 101). Positioning is performed by a linear motor.

[0126] A horn 303 is attached to the ultrasonic device 301, and the ultrasonic device 301 is configured to be able to apply directional ultrasonic waves 801 to the glass substrate 101. The ultrasonic device 301 moves in the Z-axis direction and is positioned so as to be close to the glass substrate 101.

[0127] In the configuration diagram of the present invention in FIG. 7, horn 303 is illustrated as a square (cube), but this is not limited thereto. It may be a circle, an ellipse, or a rectangle. Horn 303 may also be in a line shape. For example, the length of the line shape may be the same as the length of the short side of glass substrate 101.

[0128] The ultrasonic device 301 is changed in the Z direction (up and down direction) and positioned close to the glass substrate 101. It also moves in the X direction (long side direction of the glass substrate 101) and the Y direction (short side direction of the glass substrate 101) and irradiates the glass substrate 101 with ultrasonic waves 801 to replace metal ions.

[0129] The glass substrate 101 is immersed in the processing liquid 201 set at a predetermined temperature, and ultrasonic waves 801 are applied to the glass substrate 101. By introducing the ultrasonic device 301, ion exchange can be performed in a general aqueous solution or an organic solvent.

[0130] By applying ultrasonic waves 801 to the glass substrate 101, the Si-O - M + The electrostatic bond (ionic bond) between oxygen and ions, such as those represented by (M: Li, Na, etc.), is weakened. + The ions undergo an exchange reaction.

[0131] When the glass substrate 101 is a soda glass substrate, Na + The above Si-O - ···The electrostatic bond (electrostatic bond) between the oxygen and ions of Na becomes weaker, making ion exchange more active and increasing the exchange rate of metal ions. As shown in FIG. 6, the method for processing a glass substrate 101 of the present invention includes the steps of: + ions are replaced with other metal ions.

[0132] In the present invention, ultrasonic waves are applied to the glass substrate 101 to form a Si-O - and Na + At this time, the ionic bonds of the metal ions (Cu + , Ag + , Ni 2+ ) and Na + The surface of the glass substrate 101 is replaced or placed with metal ions.

[0133] Next, the glass substrate 101 is put into a cleaning process, where the glass substrate is cleaned. Next, the processing liquid 201 is changed to an alkaline cleaning liquid and an electroless plating liquid, and an electroless plating film forming process is carried out.

[0134] 8 is a configuration diagram and an explanatory diagram of the processing apparatus of the present invention. The glass substrate 101 is transported by transport rollers 302, positioned, and immersed in the processing liquid 201. As an example, when forming a copper plating film on the glass substrate 101 as described in the embodiment, a mixture of CaCl2·6H2O and 0.5 g of CuCl is used as the processing liquid 201. The temperature of the processing liquid 201 is maintained at a predetermined temperature (for example, 80° C.).

[0135] The processing liquid 201 circulates in the container 107. The processing liquid 201 is injected into the container 107 through the injection / discharge hole 121a, and the processing liquid 201 is discharged out of the container 107 through the injection / discharge hole 121b.

[0136] The processing liquid 201 is filled in a refill container 403. The filled processing liquid 201 is pumped out by an electric pump 404, impurities are removed by a filter 405, and the processing liquid 201 is poured into the container 107 through the injection / discharge hole 121a.

[0137] The processing liquid 201b is discharged from the container 107 through the inlet / outlet hole 121b, and alkali metals such as Na are adsorbed by an ion exchange device (activated carbon or the like) 406. The processing liquid 201b with the alkali metals adsorbed thereto is returned to the replenishment container 403. Whether or not the processing liquid 201b is returned to the replenishment container 403 is controlled by an electromagnetic valve 402.

[0138] The ultrasonic device 301 moves in the X-axis direction by a moving stage 401X and in the Y-axis direction by a moving stage 401Y. By applying ultrasonic waves 801 to the glass substrate 101, alkali metals (such as Na) in the glass substrate 101 are dissolved into the processing liquid 201. The intensity of the ultrasonic waves 801 is 1 to 200 W / cm 2 and is set to a predetermined value depending on the material of the glass substrate 101, the strength per unit time, the temperature of the processing liquid 201, etc.

[0139] By introducing an ultrasonic device 301 and applying ultrasonic waves 801 to the processing liquid 201 and the glass substrate 101, metal ions contained in the processing liquid 201 and alkali metal Na in the glass are oxidized. +The ions undergo an exchange reaction. The alkali metals dissolved in the treatment liquid 201 are adsorbed by the ion exchange resin of the ion exchange device 406. The treatment liquid 201 from which the alkali metals have been removed is injected into the container 107 through the injection / discharge hole 121a and reused. Through the above steps, metal ions (Cu, Ag, Ni, etc.) in the processing liquid 201 penetrate into the surface of the glass substrate 101 and are replaced. In the next step, the processing liquid 201 is changed to pure water or ion-exchanged water, and the front and back surfaces of the glass substrate 101 are cleaned with these. In the next step, an aqueous formaldehyde solution as a treatment liquid 201 made of formaldehyde, NaOH, and ethylenediaminetetraacetic acid is poured into the container 107 .

[0140] In the next step, CuSO4·5H2O is dissolved in the formaldehyde aqueous solution from the previous step to form a treatment liquid 201, which is poured into the container 107 and circulated to form an electroless plating film 116 on the surface of the glass substrate 101.

[0141] By applying ultrasonic waves, metal ions are arranged on the surface layer of glass substrate 101. After washing glass substrate 101 with pure water or ion-exchanged water, it is placed in an electroless plating solution and electroless plating is performed. Since metal ions are present on the surface layer of glass substrate 101, these metal ions and the metal ions in the electroless plating solution are reduced by a reducing agent to form metallic bonds, and a metal film 116 (electroless plating film 116) is formed or configured on the surface layer of glass substrate 101.

[0142] As described above, by changing the treatment liquid filled in container 107, it is possible to consistently perform metal ion substitution on glass substrate 101 and formation of electroless plating film 116.

[0143] The above embodiment is for forming a copper plating film as the electroless plating film 116. The same can be said for forming a Ni plating film or a silver plating film, and the procedure and treatment liquids of the previously described embodiment can be used. 9 is an explanatory diagram of a plating method for a glass substrate 101 in another embodiment of the present invention. The present invention is characterized in that a DC electric field is applied to the glass substrate 101.

[0144] The front surface (surface to be processed) of the glass substrate 101 is in contact with the processing liquid 201a. The back surface (opposite surface) of the glass substrate 101 is in contact with the processing liquid 201b. The processing liquids 201a and 201b are insulated from each other so that no current path is generated. Therefore, the electric field from the anode electrode (+) 106a to the cathode electrode (-) 106b passes through the glass substrate 101.

[0145] In the present invention, ultrasonic waves 801 are applied to the glass substrate 101 while applying an electric field so that the surface to be treated becomes an anode electrode (+) 106a and the opposite surface becomes a cathode electrode (-) 106b, as shown in FIG. + ) ions.

[0146] In the embodiment of the present invention, the copper plating film 116 is formed, but the present invention is not limited to this. It goes without saying that the present invention can also be applied to the case of silver (Ag) plating or nickel (Ni). The processing solution 201 in the above case has been described in the embodiment, so the description will be omitted.

[0147] Although the present invention will be described mainly by taking a metal-plated glass substrate as an example, the present invention is not limited thereto. For example, a glass substrate in which a metal such as silver is substituted, constituted, or formed on the surface or surface layer of the glass, such as the glass on the rear of a car, for the purpose of blocking infrared rays, is also within the technical scope of the present invention. The Coulomb field produced by the application of an electric field acts as a driving force to move alkali metal ions, which are cations, in the glass substrate 101 toward the cathode electrode (-) 106b.

[0148] The components in the glass substrate 101 that are moved by the electric field are mainly alkali metal ions. The alkali metal ions tend to be more easily moved in the order Li>Na>K, depending on the ion radius. Ultrasonic wave 801 is applied to glass substrate 101 from ultrasonic device 301. Ultrasonic wave 801 is converted by horn 303 into ultrasonic wave 801 with narrow directionality.

[0149] The alkali metal ions that reach the rear surface of the glass substrate 101 on the side of the cathode electrode (-) 106b migrate to the processing liquid 201b on the side of the glass cathode electrode (-) 106b. The cations (Cu + ) migrates from the surface of the glass substrate 101 into the glass substrate. These reactions occur simultaneously.

[0150] Ultrasonic waves 801 are applied to the processing surface (front surface) of the glass substrate 101. At the same time, laser light 105 is irradiated, whereby the surface of the glass substrate 101 is heated and activated.

[0151] The cations (Cu) are ionized from the processing solution 201a on the anode electrode (+) 106a side, replacing the alkali metal ions on the surface of the glass substrate 101. + ) penetrates into the surface of the glass substrate 101.

[0152] The laser light 105 is preferably one having a wavelength that is absorbed by, and not transmitted through, the glass substrate 101. For example, a carbon dioxide laser (CO2 laser) is exemplified. Other examples include a YAG laser and a YVO laser.

[0153] A laser beam 105 from a laser device 104 is irradiated onto the surface of a glass substrate 101 or a glass sheet 101. The surface of the glass substrate 101 is heated by the laser beam 105, and ultrasonic waves 801 are simultaneously applied to the surface. The action of the ultrasonic waves 801 and the laser beam 105 causes the migration of alkali metal ions and the release of cations (Cu, + ) penetration is accelerated and the process is completed in a short time.

[0154] When a protective film or protective sheet (not shown) for protecting the surface of the glass substrate 101 from the processing liquid 201 is formed, and the protective film or protective sheet is irradiated with laser light to remove the protective film or protective sheet so that the removed area comes into contact with the processing liquid 201, thereby forming a plating pattern or the like, it goes without saying that a DUV device (deep ultraviolet) laser device (wavelength 266 nm), a blue diode laser device (semiconductor) (wavelength 445 nm to 450 nm), a green laser device (wavelength 532 nm), or the like may be used as the laser device 104.

[0155] In the processing method of the present invention, the alkali metal ions in the glass substrate 101 are successively transferred to the cathode electrode (-) 106b side by the DC electric field, and ion exchange occurs, so that a uniform ion-exchanged layer is formed.

[0156] To compensate for the electric charge of the alkali metal ions that have escaped from the cathode electrode (-) 106b to the outside of the glass substrate 101, monovalent ions enter the glass substrate 101 from the molten salt on the anode electrode (+) 106a side. Therefore, a current flows between the electrodes 106a and 106b. The present invention is configured so that the processing liquid 201 a and the processing liquid 201 b are insulated from each other so that no leak current flows between them, and a DC electric field passes through the glass substrate 101 .

[0157] The amount of charge flowing between the anode electrode (+) 106a and the cathode electrode (-) 106b can be measured or monitored by the ammeter 102. The measurement value of the ammeter 102 makes it possible to grasp the replacement state of the metal ions.

[0158] The processing thickness and processing state of the glass substrate 101 can be grasped from the laser light 105, its irradiation intensity, position, the irradiation area (processing area) of the ultrasonic wave 801, and the current value or current change of the ammeter 102.

[0159] The processing time can be shortened by increasing the intensity of the ultrasonic waves 801. However, when increasing the intensity of the ultrasonic waves 801, care must be taken to prevent the glass substrate 101 from being damaged or the surface of the glass substrate 101 from cracking. By irradiating the laser light 105 and by the synergistic effect of applying an electric field and applying ultrasonic waves, the processing time can be shortened.

[0160] The present invention has combinations of ultrasonic wave 801 application, ultrasonic wave 801 application + laser light 105 irradiation, ultrasonic wave 801 application + DC voltage application, ultrasonic wave 801 application + DC voltage application + laser light 105 irradiation, and DC voltage application + laser light 105 irradiation. The more combined devices and combined energies there are, the more the processing time can be shortened.

[0161] The treatment progresses as ions diffuse from the treatment liquid 201 to the glass substrate 101. The treatment temperature has a large effect on the treatment time, and the lower the treatment temperature, the longer the treatment time. By increasing the temperature of the treatment liquid 201, the treatment time can be shortened. In addition, by irradiating the surface of the glass substrate 101 with laser light 105, the surface of the glass substrate 101 is heated, and the treatment time can be shortened.

[0162] In applying a DC voltage, the higher the applied voltage, the more the ion exchange is accelerated. Therefore, the shorter the distance between electrode 106a and electrode 106b, the higher the electric field strength applied to glass substrate 101. Therefore, when the voltage generated by DC voltage device 103 is a predetermined value, the thinner the glass substrate 101 to be processed, the higher the electric field strength applied to glass substrate 101. Also, the shorter the distance (gap) between glass substrate 101 and electrode 106, the higher the electric field strength applied to glass substrate 101.

[0163] The closer the distance between electrodes 106a and 106b, the stronger the electric field strength between electrodes 106a and 106b. By forming and configuring electrodes 106a and 106b in a triangular shape so that they have acute angles, for example, and aligning the acute angles of the triangle, the distance between the acute angles becomes shorter, and the electric field strength can be strengthened.

[0164] After the above steps, the processing liquid 201 is changed to an electroless plating liquid, whereby an electroless plating film 116 is formed on the surface of the glass substrate 101, as shown in FIG. 9(b). For example, a copper plating solution can be prepared by dissolving 0.2 g of CuSO4·5H2O in an aqueous formaldehyde solution. FIG. 10 shows an embodiment in which a nickel (Ni) plating film 116 is formed as the electroless plating film 116. In FIG.

[0165] The basic process is the same as for the copper plating film 116, so a description thereof will be omitted. The processing solution 201 for replacing metal ions and the processing solution 201 for forming the nickel plating film are different from those in the case of the copper plating film 116.

[0166] For example, a mixture of CaCl2·6H2O and NiCl2 is used as the treatment solution 201 used to replace alkali metals such as Na with metal ions such as Ni. The treatment solution 201 used to form the nickel plating film 116 is prepared by immersing the glass substrate 101 in an aqueous solution of hypophosphorous acid, which is made of hypophosphorous acid and succinic acid, and dissolving NiSO4·6H2O in the aqueous solution of hypophosphorous acid. The above-mentioned embodiment of the formation of the nickel plating film 116 has been described in (Example), so the description will be omitted.

[0167] The above matters are also described in the method for forming the silver (Ag) plating film 116 (Example), and are similar to the manufacturing or processing method of the copper (Cu) plating film 116 or the nickel (Ni) plating film 116, so the explanation will be omitted. 11, 12, 13 and 14 are explanatory and structural diagrams of an apparatus for forming a plating film on a glass substrate 101 or the like according to the present invention, mainly using a DC voltage application method.

[0168] 12, an electrode 106a is disposed above and adjacent to the glass substrate 101. An electrode 106b is disposed below and adjacent to the glass substrate 101. The electrodes 106a and 106b are disposed so as to sandwich the glass substrate 101. However, a processing liquid 201 is disposed between the electrode 106 and the glass substrate 101. The processing liquid 201 is configured to circulate between the electrode 106 and the glass substrate 101 so that alkali metals and the like are eluted into the processing liquid 201 .

[0169] The temperature regulator 304a heats the processing liquid 201a. An example of the temperature regulator 304 is a liquid heating heater. Examples of the liquid heating heater include a liquid in-line heater, a liquid flange heater, a liquid plug heater, an immersion heater, a sheath heater element, and a submersible heater. The diffusion fan (agitation fan) 305a agitates the processing liquid 201a so that the processing liquid 201a has a uniform temperature distribution.

[0170] The temperature regulator 304b heats the processing liquid 201b. The diffusion fan (agitation fan) 305b agitates the processing liquid 201b so that the processing liquid 201b has a uniform temperature distribution.

[0171] The processing liquid 201a circulates through the injection and discharge holes 121a arranged at diagonal positions of the container 107. The circulation is performed by controlling the electric pump 404 and the solenoid valve 402 as described in FIG. 8. The processing liquid 201b circulates in the same manner through the injection and discharge holes 121b arranged at diagonal positions of the container 107. The circulation is performed by controlling the electric pump 404 and the solenoid valve 402 as described in FIG. 8. The processing liquid 201a and the processing liquid 201b are prevented from coming into contact with each other. The electric field from the electrode 106a passes through the glass substrate 101 and reaches the electrode 106b.

[0172] As shown in Fig. 12, glass substrate 101 is sandwiched between sealing portion 108 and sealing portion 109. Sealing portion 109 seals the periphery of glass substrate 101 from below. Sealing portion 108 seals the periphery of glass substrate 101 from above. An example of the material of the sealing portion is a plastic raw material containing fluorine atoms. An example of a plastic raw material containing fluorine atoms is polytetrafluoroethylene. Polytetrafluoroethylene is a polymer of tetrafluoroethylene, and is a fluororesin consisting only of fluorine atoms and carbon atoms. The processing liquid 201b above the glass substrate 101 and the processing liquid 201a below the glass substrate 101 are separated by the sealing portion 108 and the sealing portion 109.

[0173] The electrode 106 is a conductor such as a plate or rod that generates an electric field and passes a current, and may have any configuration. It is preferably arranged parallel to the glass substrate 101, and has a structure in which the electrodes 106a and 106b can be arranged parallel to each other. In the present invention, the electrode 106 is referred to as an electrode, but it may be a positive electrode or a negative electrode. It may also be an anode or a cathode.

[0174] The DC voltage generated by the DC voltage device 103 is preferably 300 V or more and 3000 V or less. An electric field strength (V / m) is applied to the glass substrate 101, and the electric field strength (V / m) is configured so as to be set or adjustable to 100 (V / m) or more and 1000 (V / m) or less.

[0175] The generated DC voltage is configured so that the polarity can be reversed. For example, the DC voltage device 103 of the present invention can change the state from a state in which a negative (-) voltage is applied to the electrode 106a and a positive (+) voltage is applied to the electrode 106b as shown in Fig. 21(a) to a state in which a positive (+) voltage is applied to the electrode 106a and a negative (-) voltage is applied to the electrode 106b as shown in Fig. 21(b).

[0176] The ammeter 102 has a function of measuring or monitoring the current flowing between the electrodes 106a and 106b. The measured current value is transmitted to the controller 407, which controls the output of the laser device 104 and the ultrasonic device 301, etc.

[0177] The switch (switch) 120 has a function of applying and cutting off a voltage or current to be applied to the electrode 106. This applies to electrical switches such as a mechanical switch and an analog switch.

[0178] 11, the electrode 106 is mounted on a moving stage (not shown) and moves in the direction of the longer side of the glass substrate 101 to sequentially apply an electric field to the glass substrate 101. Note that, as shown in FIG. 7, the electrodes 106a and 106b may be attached to a moving stage that moves in the X and Y directions.

[0179] 13 is a configuration diagram and an explanatory diagram of a plating apparatus for a glass substrate according to the present invention. In the following examples, (1) ultrasonic waves 801 are applied to a glass substrate 101, (2) an electric field (voltage) is applied by an electrode 106, and (3) laser light 105 is irradiated to the glass substrate 101, but the present invention is not limited to this. It goes without saying that a combination of at least two of (1), (2), and (3) is sufficient.

[0180] For example, (1) applying ultrasonic waves 801 and (2) applying an electric field (voltage) by the electrode 106 are exemplified. (1) applying ultrasonic waves 801 and (3) irradiating with laser light 105 are exemplified.

[0181] As shown in FIGS. 12 and 13, ultrasonic waves 801 are applied to the glass substrate 101, and a DC electric field is applied to the glass substrate 101 by applying a voltage between the electrodes 106a and 106b. In the present invention, by introducing the ultrasonic device 301, metal ion exchange can be easily performed even in an aqueous solution or an organic solvent.

[0182] By applying ultrasonic waves 801 to the glass substrate 101, the Si-O - M + The electrostatic bond between oxygen and ions (electrostatic bond) represented by (M: Li, Na, etc.) is weakened. In addition, the metal ions (Cu, + , Ag + , Ni 2+ , Cu 2+ etc.) and M in glass n+ The ions undergo an exchange reaction.

[0183] The front surface (surface to be processed) of the glass substrate 101 is in contact with the processing liquid 201a. The back surface (opposite surface) of the glass substrate 101 is in contact with the processing liquid 201b. An electric field from the anode electrode (+) 106a to the cathode electrode (-) 106b passes through the glass substrate 101. When an electric field is applied between the electrodes 106, alkali metal ions, which are cations, in the glass substrate 101 move toward the cathode electrode (-) 106b.

[0184] The alkali metal ions that reach the rear surface of the glass substrate 101 on the side of the cathode electrode (-) 106b migrate to the processing liquid 201b on the side of the glass cathode electrode (-) 106b. The cations (Cu + , Ag + , Ni 2+ , Cu 2+ etc.) migrate from the surface of the glass substrate 101 into the glass substrate.

[0185] The cations (Cu) are ionized from the processing solution 201a on the anode electrode (+) 106a side, replacing the alkali metal ions on the surface of the glass substrate 101. + ) penetrates into the surface of the glass substrate 101.

[0186] By applying ultrasonic waves 801 to the glass substrate 101 and by applying an electric field by a direct current voltage between the front and rear surfaces of the glass substrate 101, the replacement of metal ions is promoted.

[0187] When an electric field is applied by a DC voltage, the movement or the amount of movement of the metal ions changes. This change or movement is measured and monitored by a DC ammeter 102, thereby monitoring the state of movement of the metal ions and controlling the substitution state.

[0188] As shown in FIG. 11, the above operation is repeated by moving the electrode 106 in the direction of the arrow and by moving the irradiation position of the ultrasonic wave 801, whereby metal ion replacement can be sequentially performed on the surface of the glass substrate 101.

[0189] 11, 12, and 13, the metal ion replacement is performed while the position of the electrode 106 is moved in sequence, but the present invention is not limited to this. For example, the left half of the glass substrate 101 may be replaced with metal ions, and then the right half of the glass substrate 101 may be replaced with metal ions.

[0190] In the second step of the present invention, the glass substrate 101 obtained in the first step is washed with pure water, and then immersed in an electroless plating solution to perform electroless plating. Since the surface layer of the glass substrate 101 contains metal ions, these metal ions bond with the metal in the electroless plating solution, forming or configuring a metal film 116 (electroless plating film 116) on the surface layer of the glass substrate 101.

[0191] As shown in FIG. 12, the replacement of metal ions is promoted or carried out by applying ultrasonic waves 801 to the glass substrate 101 and by applying an electric field by a DC voltage between the front and rear surfaces of the glass substrate 101.

[0192] The replacement speed of the metal ions can be changed or controlled by changing the strength of the electric field created by the DC voltage. Also, the replacement speed of the metal ions can be changed or controlled by changing the strength of the ultrasonic wave 801 irradiated per unit area of ​​the glass substrate 101.

[0193] The movement of metal ions or the change in the amount of movement can be monitored by ammeter 102. The strength of ultrasonic wave 801 and the electric field are controlled according to the magnitude of the current measured by ammeter 102. The above matters are also explained in Figs. 6 and 8, so the explanation will be omitted.

[0194] 13(a)->13(b), laser light 105 may be emitted from a laser device 104. The glass substrate 101 is irradiated with the laser light 105, ultrasonic waves 801, and an electric field is applied by an electrode .

[0195] The position where an electric field is applied by the electrode 106, the position where the laser light 105 is irradiated, and the position where the ultrasonic wave 801 is irradiated are sequentially moved to substitute metal ions on the surface of the glass substrate 101. The irradiation of the laser light 105, the irradiation of the ultrasonic wave 801, and the application of the electric field exert a synergistic effect, and the substitution of metal ions on the surface of the glass substrate 101 is promoted.

[0196] 14 is an explanatory diagram of an embodiment in which a plurality of circuit boards 110 are formed on a glass substrate 101. A large number of the plurality of circuit boards 110 are obtained from one glass substrate 101.

[0197] When the glass substrate 101 is irradiated with the laser beam 105, the surface of the glass substrate 101 irradiated with the laser beam 105 is heated, and the replacement and progression of the metal ions is accelerated. The laser beam 105 has good directionality and can draw a fine circuit wiring pattern. The replacement of the metal ions can be performed along the circuit wiring pattern 112 drawn by the laser beam 105.

[0198] As shown in FIG. 14, by irradiating ultrasonic wave 801 to activate metal ion substitution, and then irradiating laser light 105, a fine circuit wiring pattern 112 that has been metal ionized or has a large amount of metal ions can be drawn.

[0199] The position where the electric field is applied by the electrode 106 is moved in the direction A, and the position where the laser light 105 is irradiated and the position where the ultrasonic wave 801 is irradiated are also moved in accordance with the moving position of the electrode 106. By applying the electric field from the electrode 106, the metal ions can be fixed to the circuit wiring pattern 112. The movement step of the electrode 106 may be for each circuit board 110, or the circuit board 110 may be divided into a plurality of steps and moved.

[0200] It is also effective to form a protective film or sheet (not shown) on the surface of the circuit board 110 to protect it from the treatment liquid 201. Examples of the protective film or sheet include polyimide resin, polyamide resin, epoxy resin, silicone resin, fluororesin, or sheets made of these resins. Alternatively, a metal mask made of a metal material or the like may be used. Alternatively, a metal pattern made of a vapor-deposited thin film may be used.

[0201] A protective film or sheet is provided to prevent the processing liquid 201 from directly contacting the circuit board 110 , and the circuit board 110 and the glass substrate 101 are permeated, immersed or soaked in the processing liquid 201 .

[0202] The protective film or protective sheet is irradiated with laser light 105 by laser device 104, and the protective film or protective sheet is removed from the area irradiated with laser light 105. The surfaces of circuit board 110 and glass substrate 101 from the area where the protective film or protective sheet has been removed come into direct contact with processing liquid 201, causing replacement of metal ions and migration of metal.

[0203] For example, as shown in FIG. 14, when the protective film or protective sheet is removed from the area of ​​the wiring pattern 112, replacement of metal ions and migration of metal occur in the wiring pattern 112, and a good wiring pattern 112 can be formed and configured.

[0204] It goes without saying that the above items or contents can be applied to other embodiments such as those shown in Figures 1, 4, 5, 10, 19, 22, and 24. It goes without saying that they can also be combined.

[0205] In the embodiment of FIG. 13 and FIG. 14, after irradiation with ultrasonic wave 801 and laser light 105, an electric field is applied to glass substrate 101 by electrode 106, but the present invention is not limited to this.

[0206] As shown in FIG. 15, an electric field may be applied to the glass substrate 101 via the electrode 106, and ultrasonic waves 801 may also be applied to activate the surface of the glass substrate 101, after which laser light 105 may be irradiated to draw the circuit wiring pattern 112.

[0207] Alternatively, the position of electrode 106 may be moved in small increments to the left and right (directions A and B) and laser light 105 may be irradiated to draw circuit wiring pattern 112 in synchronization with the left and right (directions A and B) movement of electrode 106, thereby completing wiring pattern 112 of circuit board 110. It is preferable to perform left and right (directions A and B) movement multiple times so as to include the same position.

[0208] By moving the position of electrode 106 left and right (direction A, direction B) and irradiating ultrasonic wave 801, the position irradiated with laser light 105 is constantly activated, and wiring pattern 112 can be formed efficiently.

[0209] As described above, the present invention is not limited to the order of (1) applying ultrasonic waves 801, (2) applying an electric field (voltage) by electrodes 106, and (3) irradiating laser light 105. (1) applying ultrasonic waves 801, (2) applying an electric field (voltage) by electrodes 106, and (3) irradiating laser light 105 may be performed simultaneously.

[0210] Also, for example, (2) application of an electric field (voltage) by the electrode 106 may precede (1) application of ultrasonic wave 801, and (3) irradiation with laser light 105 may follow.

[0211] 16 is an explanatory diagram of the method of processing a glass substrate 101 of the present invention. Irradiation with laser light 105, irradiation with ultrasonic waves 801, and application of voltage to an electrode 106 cause alkali metal ions and metal ions to move, causing a current to flow in an ammeter 102.

[0212] The magnitude of the current flowing through ammeter 102 changes in response to the irradiation of laser light 105, the irradiation of ultrasonic wave 801, and the application of voltage to electrode 106. The change in the current changes according to the replacement state of metal ions. Therefore, by monitoring the current flowing through ammeter 102, it is possible to know whether metal ions have been injected into the surface of glass substrate 101 and replaced therewith.

[0213] When the circuit wiring pattern 112 is drawn by irradiation with the laser beam 105, the current flowing through the ammeter 102 changes in response to the drawing area of ​​the wiring pattern 112. For example, as shown in Fig. 16(b), the current value changes, and the change in current is repeated at the terminals of the circuit board 110. This is because the amount and position of the wiring pattern 112 formed on the circuit board 110 are fixed.

[0214] The ammeter 102, switch 120, and DC voltage device 103 are stored in a DC electric field control device 202, which sends data from the ammeter 102 to a controller 407. The controller 407 controls the intensity of the ultrasonic wave 801, the intensity of the laser light 105, and the position (movement) of the electrode 106 based on the current data.

[0215] 16, the controller 407 controls the output voltage value and voltage polarity of the DC voltage device 103 of the DC electric field control device 202. It also controls the on / off of the switch 120. It also obtains the value of the current flowing through the ammeter 102.

[0216] The electrode 106 is composed of an electrode 106a arranged on the upper surface of the glass substrate 101 and an electrode 106b arranged on the lower surface of the glass substrate 101. A leakage current flowing between the processing liquid 201a and the processing liquid 201b may occur between the electrode 106a and the electrode 106b. The leakage current is measured by the ammeter 102. The leakage current is treated as a dark current and is subtracted from the current generated by the irradiation of the ultrasonic wave 801, the irradiation of the laser light 105, and the application of a voltage to the electrode 106.

[0217] 16(b), the current flowing through ammeter 102 changes in response to the drawing area of ​​wiring pattern 112. The current value changes, and the change in current is repeated at the terminal of circuit board 110. The irradiation intensity of ultrasonic wave 801, the irradiation intensity of laser light 105, and the voltage application intensity of electrode 106 are controlled, adjusted, or set to match this repeating current pattern.

[0218] 17 is a block diagram and an explanatory diagram of the processing apparatus of the present invention. It comprises an ultrasonic device 301, a laser device 104, and a DC electric field control device 202 for applying a voltage to the electrode 106.

[0219] The glass substrate 101 is transported by transport rollers (not shown), positioned, and immersed in the treatment liquid 201. As an example, when forming a copper plating film on the glass substrate 101 as described in the embodiment, a mixture of CaCl2·6H2O and 0.5 g of CuCl is used as the treatment liquid 201. The treatment liquid 201 and the glass substrate 101 are heated by a temperature regulator 304. The temperature of the treatment liquid 201 is maintained at a predetermined temperature (for example, 80° C.). The temperature is changed and adjusted according to the treatment process.

[0220] The processing liquid 201 (processing liquid 201a, processing liquid 201b) circulates in the container 107. The processing liquid 201 is injected into the container 107 through the injection / discharge hole 121a, and the processing liquid 201 is discharged from the container 107 through the injection / discharge hole 121b. The injection / discharge hole 121a and the injection / discharge hole 121b are arranged corresponding to the processing liquid 201a and the processing liquid 201b.

[0221] The processing liquid 201 is filled into a refill container 403. The filled processing liquid 201 is pumped out by an electric pump 404, impurities are removed by a filter 405, and the processing liquid 201 is poured into the container 107 through the injection / discharge hole 121a. In addition, the pH of the processing liquid 201 is adjusted.

[0222] The processing liquid 201b is discharged from the container 107 through the inlet / outlet hole 121b, and alkali metals such as Na eluted from the glass substrate 101s are adsorbed by the ion exchange resin of the ion exchange device 406. The processing liquid 201b with the adsorbed alkali metals is returned to the replenishment container 403. Whether or not the processing liquid 201b is returned to the replenishment container 403 is controlled by an electromagnetic valve 402.

[0223] The ultrasonic device 301 moves in the Z-axis direction, and its position is adjusted to a position where ultrasonic waves 801 are applied close to the glass substrate 101. The ultrasonic device 301 moves in the X-axis direction by a moving stage 401X, and moves in the Y-axis direction by a moving stage 401Y. A laser beam 105 generated by a laser device 104 is scanned by a galvanometer mirror to search for a position where a wiring pattern 112 is to be formed.

[0224] In the present invention, the wiring pattern 112 is formed by the laser beam 105, but the present invention is not limited to this. It goes without saying that the laser beam 105 may be configured to irradiate a line or a certain area, and the surface of the glass substrate 101 may be heated and activated.

[0225] It goes without saying that the embodiments of the present invention can be combined with other embodiments, that the whole or part of the configuration of the embodiments can be applied to other embodiments, and that the whole or part of the method of the embodiments can be applied to other embodiments.

[0226] By applying ultrasonic waves 801 to the glass substrate 101, alkali metals (such as Na) in the glass substrate 101 are dissolved into the processing liquid 201. In addition, by applying ultrasonic waves 801 to the glass substrate 101, metal ions are injected into the glass substrate 101 or replaced therewith. The intensity of the ultrasonic 801 is 1 to 200 W / cm 2 and is set to a predetermined value depending on the material of the glass substrate 101, the strength per unit time, the temperature of the processing liquid 201, etc.

[0227] Furthermore, by irradiation with laser light 105 and application of a DC voltage, alkali metals (such as Na) in glass substrate 101 are dissolved into processing liquid 201. Furthermore, by application of ultrasonic waves 801 to glass substrate 101, metal ions are injected into glass substrate 101 or replaced therewith. The above factors have a synergistic effect, accelerating and activating the elution of alkali metal ions and the replacement of metal ions, thereby shortening the process time.

[0228] By applying ultrasonic waves 801 to the processing liquid 201 and the glass substrate 101, metal ions contained in the processing liquid 201 and alkali metal Na in the glass are + The ions undergo an exchange reaction, which is accelerated by irradiation with laser light 105 and application of a DC voltage, resulting in the elution of the alkali metal and the replacement of the metal ions.

[0229] The alkali metals dissolved in the treatment liquid 201 are adsorbed by the ion exchange resin of the ion exchange device 406. The treatment liquid 201 from which the alkali metals have been removed is injected into the container 107 through the injection / discharge hole 121a and is reused. As described with reference to FIGS. 11, 12, 13, 14, 15, and 16, the irradiation position of the laser light 105, the irradiation position of the voltage, and the irradiation position of the ultrasonic wave 801 move in sequence. Through the above steps, metal ions (Cu, Ag, Ni, etc.) in the processing liquid 201 penetrate into the surface of the glass substrate 101 and are replaced. In the next step, the processing liquid 201 is changed to pure water or ion-exchanged water, and the front and back surfaces of the glass substrate 101 are cleaned with these.

[0230] In the next step, an aqueous formaldehyde solution as a treatment liquid 201 made of formaldehyde, NaOH, ethylenediaminetetraacetic acid, and hypophosphorous acid is poured into the container 107 .

[0231] In the next step, CuSO4·5H2O is dissolved in the formaldehyde aqueous solution from the previous step to form a treatment liquid 201, which is poured into the container 107 and circulated to form an electroless plating film 116 on the surface of the glass substrate 101.

[0232] The above examples are for cases where the plating film is electroless copper plating film 116. As explained in the other examples, it goes without saying that the treatment liquid 201 and plating solution can be changed depending on the type and material of electroless plating film 116.

[0233] Metal ions are arranged on the surface layer of glass substrate 101 by applying ultrasonic wave 801, irradiating laser light 105, and applying a DC voltage. After washing glass substrate 101 with pure water or ion-exchanged water, it is placed in an electroless plating solution for electroless plating. Since metal ions are present on the surface layer of glass substrate 101, these metal ions bond with the metal in the electroless plating solution, forming or configuring a metal film 116 (electroless plating film 116) on the surface layer of glass substrate 101.

[0234] As described above, by changing the processing liquid 201 filled in the container 107, it is possible to consistently perform the metal ion substitution on the glass substrate 101 and the formation of the electroless plating film 116.

[0235] The above embodiment is for forming a copper plating film as the electroless plating film 116. The same can be said for forming a Ni plating film or a silver plating film, and the procedure and treatment liquid 201 of the embodiment previously described may be used.

[0236] 18 is an explanatory diagram and a configuration diagram of a manufacturing apparatus for glass substrate 101 of the present invention. Ultrasonic wave 801 is applied to glass substrate 101 via horn 303. A waveguide through which laser light 105 passes is formed in the center of horn 303.

[0237] The injection and discharge hole 121 is attached to the horn 303. The processing liquid 201a is supplied from the injection and discharge hole 121, and the processing liquid 201a is supplied onto the surface of the glass substrate 101 via the horn 303.

[0238] The horn 303 and other components are made of a conductor, and the horn 303 functions as an electrode 106a. An electrode 106b is disposed on the rear surface of the glass substrate 101. A processing liquid 201b is filled between the glass substrate 101 and the electrode 106b and circulated. A DC voltage is applied between the horn 303 (electrode 106a) and the electrode 106b by the DC voltage device 103 of the DC electric field control device 202.

[0239] Laser light 105 passes through laser light passing hole 114 formed in horn 303. Laser light 105 passes through processing liquid 201a and horn 303, and is irradiated onto glass substrate 101. Processing liquid 201a is supplied to replacement portion 115 (e.g., wiring pattern 112) where metal ions of glass substrate 101 are replaced, and ultrasonic wave 801 is applied from horn 303. Laser light 105 is also irradiated, and a DC voltage is applied by electrode 106.

[0240] Horn 303 is positioned and changed in the Z-axis direction by a moving stage (not shown) so as to be close to glass substrate 101. Horn 303 is moved and positioned in the X-axis and Y-axis directions by a moving stage (not shown) until it is positioned at replacement section (metal ion section) 115.

[0241] In the embodiments of Figures 9 and 10, the electrodes 106a and 106b are the same size and arranged in parallel, and a parallel electric field is applied between the electrodes 106a and 106b. The present invention is not limited to this. One of the electrodes 106 may be small in size, and may be configured to generate an electric field other than a parallel electric field between the electrodes 106a and 106b.

[0242] The elution of alkali metals from the glass substrate 101 and the replacement of metal ions are correlated with the electric field strength. In areas where the electric field strength is high, the elution of alkali metals and the replacement of metal ions are promoted. In areas where the electric field strength is weak, the elution of alkali metals and the replacement of metal ions do not proceed.

[0243] 19 is an explanatory diagram of a method for processing a glass substrate 101 according to the present invention. In FIG.

[0244] The electric field lines from electrode 106a to electrode 106b are stronger where electrode 106a and electrode 106b are closer, and weaker as they are farther apart. Therefore, the electric field lines are arc-shaped, as shown in Fig. 19(a). Electric field lines 805a in the center are strong, and electric field lines 805b in the peripheral areas are weak.

[0245] As shown in FIG. 19(a), a DC voltage is applied between an electrode 106a arranged in a partial area on the front surface of a glass substrate 101 and an electrode 106b arranged on the rear surface of the glass substrate 101. A stronger electric field is applied near the electrode 106a than in other areas, so that Ag + , Pb 2+ There is a concentration of substitutions with etc.

[0246] In the area where the electric field lines 805 are strong, the replacement of metal ions and the elution of alkali metals are strong, whereas in the area where the electric field lines 805 are weak, the replacement of metal ions and the elution of alkali metals are weak.

[0247] The density distribution of the electric field lines 805 can generate the distribution of metal ions shown in Fig. 19(b). The refractive index becomes higher in areas of the glass substrate 101 where metal ions are concentrated. Areas with no or few metal ions have a refractive index that is not significantly different from the refractive index of the glass substrate 101. Therefore, by generating the distribution of metal ions (metal) shown in Fig. 19(b), a lens effect can be achieved, or the material can function as a lens.

[0248] As shown in FIG. 19(b), the Na + Ag + , Pb 2+ By replacing the refractive index with the refractive index distribution, a refractive index distribution can be formed in the glass substrate 101. By applying an electric field, Ag + (thin film)->Na +(glass) ion exchange, or Pb 2+ (thin film)->Na + (Glass) ion exchange is performed.

[0249] The above embodiment is a method for generating a distribution of the strength of the electric field lines 805 by changing the position and arrangement of the electrode 106. However, the present invention is not limited to this. For example, when a distribution of high and low temperatures is generated on the glass substrate 101 by irradiation with the laser light 105, a distribution of metal ions and the like that correlates with the temperature is generated.

[0250] Furthermore, when an intensity distribution of ultrasonic waves 801 is generated on glass substrate 101 by irradiation with ultrasonic waves 801 or by the shape of horn 303, a distribution of metal ions etc. is generated that correlates with the intensity of ultrasonic waves 801. Therefore, not only the density distribution of electric field lines but also laser light 105 and ultrasonic waves 801 can form the distribution of metal ions shown in Fig. 19(b), and a lens effect shown and described in Fig. 19(c) can be achieved.

[0251] 19(c), a high refractive index portion 802 and a low refractive index portion 803 (portion lower than the high refractive index portion 802 ≒ refractive index of the glass substrate 101) are generated, and a light ray 804 is condensed. Therefore, a microlens can be formed or fabricated on the glass substrate 101.

[0252] In order to effectively focus the light beam 804, an electroless plating film 116b is formed on the light emission side of the glass substrate 101. The electroless plating film 116b forms a pinhole-like hole at the focal point of the lens. Electroless plating 116a is formed on the periphery of the adjacent lens (high refractive index portion 802). In the embodiments shown in Figs. 1, 4, 5, 9, 10, 12, 19, etc., the electrode 106a is an anode (+) and the electrode 106b is a cathode (-). FIG. 22 is an explanatory diagram of a manufacturing method of the present invention in which the potential polarities of the electrodes 106a and 106b are changed.

[0253] 22(a), the electrode 106a is a cathode (-) and the electrode 106b is an anode (+). The glass substrate 101 is immersed in the processing liquid 201. While the glass substrate 101 is immersed, ultrasonic waves 801 are applied.

[0254] In the embodiment of the present invention, the metal ions of the glass substrate 101 are replaced, but the present invention is not limited to this. The substrate may be a substrate other than an inorganic material such as a metal substrate, on whose surface an inorganic material such as a glass material is deposited, coated or formed.

[0255] When irradiating the glass substrate 101 using the horn 303, it is preferable to use high-frequency ultrasonic waves 801 when placing the horn 303 close to the glass substrate 101 and irradiating ultrasonic waves 801 to a small area. Also, when irradiating ultrasonic waves 801 to the entire glass substrate 101, it is preferable to irradiate ultrasonic waves 801 to a relatively low frequency.

[0256] In the embodiment of Fig. 22, it is preferable to make the frequency of ultrasonic wave 801a irradiated in Fig. 22(a) different from the frequency of ultrasonic wave 801b irradiated in Fig. 22(b). By making the frequencies different, it is possible to change the film quality and film thickness of electroless plated film 116a and electroless plated film 116b.

[0257] It is preferable to make the intensity of ultrasonic wave 801a irradiated in Fig. 22(a) different from the intensity of ultrasonic wave 801b irradiated in Fig. 22(b). By making the intensity different, it is possible to change the film quality and film thickness of electroless plated film 116a and electroless plated film 116b.

[0258] As described above, in the method for plating glass substrate 101, the method for processing a glass substrate, or the method for manufacturing a glass substrate of the present invention, the frequency of the ultrasonic waves is changed or altered in accordance with the unit area to which the ultrasonic waves are irradiated and the processing strength.

[0259] It is preferable that the intensity of the ultrasonic waves 801 applied to the glass substrate 101 is weaker than the average value at the beginning of the application to the relevant portion, and the intensity is increased as the metal replacement progresses. This is presumably because the energy of the ultrasonic waves 801 required for the metal replacement increases the deeper into the glass substrate 101.

[0260] In the present invention, a processing liquid 201a is brought into contact with the front surface of the glass substrate 101, and a processing liquid 201b is brought into contact with the rear surface of the glass substrate 101. A DC voltage is applied between the electrodes 106a and 106b. The processing liquid 201a and the processing liquid 201b are configured not to come into contact with the glass substrate 101, etc.

[0261] 22(a), the electrode 106a is at a negative (-) potential, and the electrode 106b is at a positive (+) potential. When the DC voltage is increased, alkali ions near the surface of the glass substrate 101 move toward the surface of the glass substrate 101.

[0262] When the glass in which the alkali metal ions are mobile is immersed in a treatment liquid 201 such as a molten salt containing any cation, a concentration gradient occurs between the ions in the glass and the ions in the treatment liquid. The concentration gradient acts as a driving force to cause mutual diffusion between the ions in the glass substrate 101 and the ions in the treatment liquid 201, resulting in ion exchange.

[0263] For the ion exchange reaction of glass, it is important to weaken the ionic bonds contained in the glass substrate 101. As shown in Fig. 22(a), ion exchange is facilitated by applying ultrasonic waves 801a from an ultrasonic device 301. As shown in Fig. 22(a), Na and K are removed (leached) from the outermost surface of the glass substrate 101.

[0264] 22(b), the electrode 106a is changed to a positive (+) potential, and the electrode 106b is changed to a negative (-) potential. The glass substrate 101 is immersed in the processing liquid 201. While the glass substrate 101 is immersed, ultrasonic waves 801b are applied. Furthermore, laser light 105 is irradiated as necessary.

[0265] Metal ions are dissolved in the treatment liquid 201a and the treatment liquid 201b. Metal ions (Cu, + ) enters (is replaced by) metal ions (Cu + ) is substituted in a range of 5 nm or more from the surface of the glass substrate 101. Preferably, it is 20 nm or more. The depth of substitution can be controlled by the concentration of the treatment liquid 201, the sodium concentration, the temperature, the time, etc.

[0266] As shown in FIG. + (Glass)<-->Cu + By metal ion exchange treatment, Cu + is introduced into the glass substrate 101. + By introducing the above into the glass substrate 101 , an electroless plating film 116 of Cu or the like can be attached to the surface of the glass substrate 101 .

[0267] 22(c), electroless plating film 116a is formed on the front surface of glass substrate 101, and electroless plating film 116b is formed on the back surface of glass substrate 101. Electroless plating film 116a is formed with high adhesion strength by the action of laser light 105. Electroless plating film 116b is formed with high uniformity and high adhesion strength. Electroless plating film 116a is effective as a wiring pattern for electric circuits, and electroless plating film 116b is effective as a ground layer and a shield layer.

[0268] In the embodiment of FIG. 22, the Cu electroless plating film 116 is formed. However, it goes without saying that Ni or Ag can also be used by simply changing the treatment liquid 201.

[0269] Fig. 22 shows an embodiment in which one surface of glass substrate 101 is irradiated with laser beam 105. Fig. 24 shows an embodiment in which both surfaces of glass substrate 101 are irradiated with laser beam 105. Fig. 24 is an explanatory diagram of the manufacturing method of the present invention in which the potential polarities of electrodes 106a and 106b are changed.

[0270] 24(a), the electrode 106a is a cathode (-) and the electrode 106b is an anode (+). The glass substrate 101 is immersed in the treatment liquid 201. While the glass substrate 101 is immersed, ultrasonic waves 801a are applied to the rear surface of the glass substrate 101.

[0271] In the embodiment of Fig. 24, it is preferable to make at least one of the frequency of ultrasonic wave 801a and the intensity of laser light 105a irradiated in Fig. 24(a) different from the frequency of ultrasonic wave 801b and the intensity of laser light 105b irradiated in Fig. 24(b). By making them different, the film quality and film thickness of electroless plated film 116a and electroless plated film 116b can be changed.

[0272] As described above, in the plating method for glass substrate 101, the processing method for a glass substrate, or the manufacturing method for a glass substrate of the present invention, the frequency of the ultrasonic waves, the intensity of laser light 105, and the wavelength of the laser light are changed or altered in accordance with the unit area to which the ultrasonic waves are irradiated and the processing strength.

[0273] In the present invention, a processing liquid 201a is brought into contact with the front surface of the glass substrate 101, and a processing liquid 201b is brought into contact with the rear surface of the glass substrate 101. A DC voltage is applied between the electrodes 106a and 106b. The processing liquid 201a and the processing liquid 201b are configured not to come into contact with the glass substrate 101, etc.

[0274] 24(a), the electrode 106a is set to a negative (-) potential, and the electrode 106b is set to a positive (+) potential. Alkaline ions near the surface of the glass substrate 101 move to the processing liquid 201a. Copper (Cu) metal ions move from the rear surface of the glass substrate 101 to the rear surface of the glass substrate 101.

[0275] In the ion exchange reaction of glass, it is important to weaken the ionic bonds contained in the glass substrate 101. As shown in FIG. 24(a), ion exchange is facilitated by irradiating ultrasonic waves 801a by an ultrasonic device 301. As shown in FIG. 24(a), Na is introduced into the processing liquid 201a from the surface of the glass substrate 101. + Or K +comes out.

[0276] 24(b), the electrode 106a is changed to a positive (+) potential, and the electrode 106b is changed to a negative (-) potential. The glass substrate 101 is immersed in the processing liquid 201. While the glass substrate 101 is immersed, ultrasonic waves 801b are applied to the surface of the glass substrate 101. Furthermore, laser light 105b is irradiated as necessary.

[0277] Metal ions are dissolved in the processing liquid 201a and the processing liquid 201b. Metal ions (Cu, + ) enters (is replaced by) metal ions (Cu + ) is substituted in a range of 5 nm or more from the surface of the glass substrate 101. Preferably, it is 20 nm or more. The depth of substitution can be controlled by the concentration of the treatment liquid 201, the sodium concentration, the temperature, the time, etc.

[0278] As shown in FIG. + (Glass)<->Cu + By metal ion exchange treatment, Cu + is introduced into the glass substrate 101. + By introducing the above into the glass substrate 101 , an electroless plating film 116 of Cu or the like can be attached to the surface of the glass substrate 101 .

[0279] 24(c), electroless plating film 116a is formed on the front surface of glass substrate 101, and electroless plating film 116b is formed on the back surface of glass substrate 101. Electroless plating film 116a and electroless plating film 116b are formed with high adhesion strength by the action of laser light 105.

[0280] In the embodiment of FIG. 24, the Cu electroless plating film 116 is formed. However, it goes without saying that Ni or Ag can also be used by simply changing the treatment liquid 201. Fig. 20 is an explanatory diagram of the method for producing an electronic circuit board of the present invention, and Fig. 21 is a flow chart of the method for producing an electronic circuit board of the present invention.

[0281] 20(a) shows a glass substrate 101 produced by the processing method or manufacturing apparatus of the present invention for glass substrate 101. Metal ion portions 115 are formed on glass substrate 101 by ion exchange of alkali metal ions and metal ions (S01). Metal ion portions (metal ion replacement portions) that will become wiring pattern 112 are formed on the surface of glass substrate 101. Next, the glass substrate 101 is washed with ion-exchanged water or pure water, and then dried (S2). As shown in FIG. 20(b), electroless Cu plating is performed on the surface of the glass substrate 101 to form an electroless plating film 116 (S03).

[0282] A reduction precipitation type electroless Cu plating solution in a strong alkaline region using formalin as a reducing agent can be used as the electroless Cu plating solution serving as the treatment solution 201. EDTA or Rochelle salt can be used as the chelating agent.

[0283] Prior to electroless plating, Pd is added as a catalyst so that the reducing agent in the electroless Cu plating solution will release electrons on the glass substrate 101. Cu ions in the electroless Cu plating solution are reduced by electrons released by the oxidation reaction of the reducing agent and are precipitated on the surface of the glass substrate 101, forming an electroless plated film 116.

[0284] Next, unnecessary electroless plating film 116 is removed. Next, as shown in Fig. 20(c), an electrolytic Cu plating formation step is performed to form electrolytic plating film 117 on electroless plating film 116 (S04). An example of the electrolytic Cu plating solution composition and plating conditions are shown below. <Composition of electrolytic Cu plating solution> Copper sulfate pentahydrate: 100g / L Sulfuric acid: 190g / L Chlorine: 50mg / L Gloss agent: appropriate amount <Electrolytic Cu plating conditions> Liquid temperature: Room temperature Current density: 2A / dm 2

[0285] Next, a baking step is performed. For example, baking is performed at 80 to 200° C. for 30 minutes to 1 hour (S04). Furthermore, as shown in FIG. 20(d), electronic components 119 are mounted by solder 118 using electrolytic plating film 118 as terminals to complete the product. In the embodiment of FIG. 22 and FIG. 24, the metal ion substituted portions 115 can be formed on both the front and back surfaces of the glass substrate 101 . FIG. 23 is an explanatory diagram of a manufacturing method for forming a plating film on the glass substrate 101 manufactured in the manner shown in FIG. 22 and FIG.

[0286] Fig. 23(a) shows a glass substrate 101 produced by the processing method or manufacturing apparatus for glass substrate 101 of the present invention explained in Fig. 22 and Fig. 23. In the embodiment of Fig. 22 and Fig. 24, metal ion substituted parts 115 can be formed on both the front and back surfaces of glass substrate 101.

[0287] Alkaline metal ions and metal ions are exchanged on glass substrate 101 to form metal ion portions 115. Metal ion portions (metal ion substituted portions) that become wiring pattern 112 are formed on the surface of glass substrate 101.

[0288] The glass substrate 101 is washed with ion-exchanged water or pure water and dried. Next, as shown in FIG. 23(b), electroless Cu plating is performed on the surface of the glass substrate 101 to form an electroless plating film 116.

[0289] A reduction precipitation type electroless Cu plating solution in a strong alkaline region using formalin as a reducing agent can be used as the electroless Cu plating solution serving as the treatment solution 201. EDTA or Rochelle salt can be used as the chelating agent.

[0290] Prior to electroless plating, Pd is added as a catalyst so that the reducing agent in the electroless Cu plating solution will release electrons on the glass substrate 101. Cu ions in the electroless Cu plating solution are reduced by electrons released by the oxidation reaction of the reducing agent and are precipitated on the surface of the glass substrate 101, forming an electroless plated film 116.

[0291] Next, unnecessary electroless plating film 116 is removed. Next, as shown in Fig. 23(c), an electrolytic Cu plating formation step is performed to form electrolytic plating film 117 on electroless plating film 116. An example of the composition of the electrolytic Cu plating solution and plating conditions are shown below. <Composition of electrolytic Cu plating solution> Copper sulfate pentahydrate: 100g / L Sulfuric acid: 190g / L Chlorine: 50mg / L Gloss agent: appropriate amount <Electrolytic Cu plating conditions> Liquid temperature: Room temperature Current density: 2A / dm 2

[0292] Next, a baking step is performed, for example, at 80 to 200° C. for 30 minutes to 1 hour. Furthermore, as shown in FIG. 23(d), electronic components 119 are mounted with solder 118 using the electrolytic plating film 118 as terminals to complete the product.

[0293] For example, a film made of silver or the like is formed on car glass for the purpose of blocking infrared rays, and it goes without saying that the present invention can be applied to the formation and manufacturing method of this car glass, or to the car glass itself.

[0294] Needless to say, the present invention can also be applied to circuit boards for smartphones. Furthermore, the circuit board is not limited to a single-layer or double-sided board with wiring formed on the surface, but can also be applied to a multi-layer board. For example, a wiring pattern 112 may be formed on a glass substrate, and a glass layer may be formed on the wiring by using a technique such as deposition, and the wiring pattern 112 may be formed. Furthermore, interlayer connection of wiring may be achieved by irradiating a portion where a through hole is to be formed with laser light 105 to generate metal replacement, forming a through hole, and connecting the wiring patterns 112 between two layers.

[0295] The embodiments disclosed herein are illustrative in all respects and are not restrictive. The scope of the present invention is indicated by the claims, not by the above meaning, and is intended to include all modifications within the meaning and scope of the claims. It goes without saying that the matters or contents described in this specification and drawings can be mutually combined. [Explanation of symbols]

[0296] 101 Glass (ceramic) substrate (sheet) 102 Ammeter 103 DC voltage device 104 Laser device 105 Laser light 106 Electrode 107 Container 108 Sealed part 109 Sealed part 110 Circuit Board 112 Wiring Pattern 114 Laser light passage hole 115 Metal ion part (substitution part) 116 Electroless plating film 117 Electrolytic plating film 118 Solder 119 Electronic Components 120 Switch (switch) 121 Injection and discharge hole 201 Processing liquid 202 DC electric field control device 301 Ultrasonic device 302 Conveyor roller 303 Horn 304 Temperature regulator 305 Diffusion fan (agitating fan) 401 Moving Stage 402 Solenoid valve 403 Refill container 404 Electric Pump 405 Filter 406 Ion exchange device (alkali metal adsorbent) 407 Controller 801 Ultrasound 802 High refractive index part 803 Low refractive index section 804 Ray of light 805 Electric Field Lines

Claims

1. A treatment solution containing at least one cation selected from Cu, Ag, Ni, Fe, Au, and Pb is contacted with a treatment position of a substrate having alkali metal ions, applying ultrasonic waves to the treatment position to replace the alkali metal ions with the cations; A method for manufacturing a substrate, comprising forming a plating film at the location where the alkali metal ions have been replaced with the cations.

2. A treatment solution containing at least one cation selected from Cu, Ag, Ni, Fe, Au, and Pb is contacted with a treatment position of a substrate having alkali metal ions; applying a DC electric field and ultrasonic waves to the treatment position to replace the alkali metal ions with the cations; A method for manufacturing a substrate, comprising forming a plating film at the location where the alkali metal ions have been replaced with the cations.

3. A treatment solution containing at least one cation selected from Cu, Ag, Ni, Fe, Au, and Pb is contacted with a treatment position of a substrate having alkali metal ions; irradiating the processing position with laser light and applying ultrasonic waves to replace the alkali metal ions with the cations; A method for manufacturing a substrate, comprising forming a plating film at the location where the alkali metal ions have been replaced with the cations.

4. A protective film or protective sheet is formed at the treatment position, peeling or removing the protective film or protective sheet at the position where the alkali metal ions are to be substituted with the cations; 4. The method for manufacturing a substrate according to claim 1, 2 or 3, wherein the treatment liquid is brought into contact with the area from which the protective film or protective sheet has been peeled or removed.

5. A first electrode is disposed on a first surface of the substrate; a second electrode disposed on a second surface opposite the substrate; 4. The method for manufacturing a substrate according to claim 1, 2 or 3, wherein a voltage is applied between the first electrode and the second electrode, and a DC electric field is applied to the substrate.

6. A contact part that contacts a treatment liquid containing at least one cation of Cu, Ag, Ni, Fe, Au, and Pb with a treatment position of a substrate having alkali metal ions; an ultrasonic device that applies ultrasonic waves to the treatment position to replace the alkali metal ions with the cations; A substrate manufacturing apparatus comprising a temperature regulator for adjusting the temperature of the treatment liquid.

7. A contact part that contacts a treatment liquid containing at least one cation of Cu, Ag, Ni, Fe, Au, and Pb with a treatment position of a substrate having alkali metal ions; an ultrasonic device that applies ultrasonic waves to the treatment position to replace the alkali metal ions with the cations; a first electrode disposed on a first surface of the substrate; a second electrode disposed on a second surface opposite the substrate; A substrate manufacturing apparatus comprising: a DC voltage device that generates a voltage to be applied between the first electrode and the second electrode.

8. A contact part that contacts a treatment liquid containing at least one cation of Cu, Ag, Ni, Fe, Au, and Pb with a treatment position of a substrate having alkali metal ions; an ultrasonic device that applies ultrasonic waves to the treatment position to replace the alkali metal ions with the cations; A substrate manufacturing apparatus comprising: a laser device that irradiates the processing position with laser light.

9. Further comprising a laser device, the laser device is a carbon dioxide gas laser device, 8. The substrate manufacturing apparatus according to claim 6, wherein the laser device draws a circuit wiring pattern.

10. A first electrode disposed on a first surface of the substrate; a second electrode disposed on a second surface opposite the substrate; a DC voltage device that generates a voltage to be applied between the first electrode and the second electrode; a current measuring device for measuring a current flowing between the first electrode and the second electrode; 9. The substrate manufacturing apparatus according to claim 6, wherein:

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