JP2017179604A - Method for regenerating metal plating solution, method for regenerating washing water used in metal plating, plating apparatus and regenerating material for metal plating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for regenerating a plating solution and a washing water simply at a low cost while carrying out plating treatment.SOLUTION: In the method for regenerating a plating solution, a plating apparatus 10 is provided with a withdrawing means 14 for compulsorily withdrawing a plating solution from a plating tank. As a withdrawing means 14, a pump or the like is used. The plating solution compulsorily withdrawn from a plating tank 11 is brought into contact with a polyolefin-based fiber and/or fiber structure 13 disposed in a container 12 for the removal of organic impurities and organic impurities in the plating solution are adsorbed on the polyolefin-based fiber and removed. The plating solution from which organic impurities are removed in the container 12 for the removal of organic impurities is returned to the plating tank 11 after solid matter is removed from the plating solution in a foreign matter removing means 15. As the plating solution from which organic impurities are removed by a polyolefin-based fiber and/or fiber structure passes through the foreign matter removing means 15, the polyolefin-based fiber and/or fiber structure which have dropped out are prevented from flowing out to the plating tank.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for regenerating a metal plating solution, a method for regenerating washing water used for metal plating, a plating apparatus, and a recycled material for metal plating.

  In metal plating, plating solutions such as copper sulfate plating baths tend to decompose or deteriorate organic components such as organic additives in the plating solution over time, and organic impurities tend to accumulate in the plating solution. It is in. This organic impurity adversely affects the physical properties such as hardness and spreadability of the plating film obtained by plating and the deposition state of the plating, and as a result, the plating film breaks and causes abnormal precipitation.

  In order to solve these problems, for example, Patent Document 1 discloses that a total amount of organic substances are removed from a defective plating bath by adsorption with an aromatic amine-based resin, and then a predetermined amount of fresh organic additive is plated. A method of adding to the bath is described. Patent Document 2 describes a method in which an organic solvent is added to a plating solution, and organic substances in the plating solution are extracted and removed with the organic solvent. In the case of the methods described in Patent Documents 1 and 2, since the plating solution is exchanged, there are concerns about a decrease in productivity, an increase in cost, and an environmental impact caused by a large amount of waste.

  In addition, measures have been taken to continue use by removing organic impurities that have deteriorated and decomposed from the plating solution without replacing the plating solution. For example, Patent Documents 3 and 4 propose that an organic compound is decomposed by adding an oxidizing agent to a plating bath. Patent Document 5 proposes a method for regenerating a waste plating solution in a large-scale apparatus using an oxidizing agent. Patent Document 6 proposes that a decomposition / modified organic product generated by decomposition or modification of an organic additive is subjected to oxidative decomposition by nonelectrolytic oxidation. Patent Document 7 proposes a method using a rotatable barrel device and a spherical adsorbent. Patent Documents 8 and 9 propose a method using a plating recycling apparatus. In the methods described in Patent Documents 3 and 4, there is a concern about the influence on plating when the plating operation is started in a state where the oxidant is not completely removed or when components in the middle of decomposition remain. In the methods described in Patent Documents 5 to 9, there is a problem that new equipment needs to be introduced in order to remove deteriorated and decomposed organic impurities from the plating solution.

  As another countermeasure, an activated carbon treatment method in which organic impurities are adsorbed and removed by activated carbon is used as a countermeasure to remove and use organic impurities that have deteriorated and decomposed from the plating liquid without replacing the plating liquid.

  On the other hand, in metal plating, washing with water before plating is performed in order to clean an object to be plated. In addition, washing with water after plating is performed to remove the adhering plating solution and organic impurities and to clean them. The washed intermediate product is dried each time for delivery to the next step. Usually, it is put into 2-3 washing tanks in order and washed. At that time, the amount of water supplied is generally 5 to 10 L / min, supplied to the third tank, sent from the third tank to the second tank, and then from the second tank to the first tank. Drained from one tank. The washing tank contains a certain amount of organic impurities contained in the plating solution and the raw water of the washing water. These organic impurities appear in the form of discoloration (corrosion, oxidation) on the substrate surface after drying, causing non-uniformity due to reaction delay in the next processing (such as pre-processing soft etching in the image process), resulting in poor adhesion of the film laminating process. May occur.

  Although the concentration of organic impurities in the washing water due to bringing in the plating solution can be lowered by increasing the amount of supplied water, it is necessary to suppress the discharge amount of organic impurities during washing.

  The concentration of organic impurities in the water washing tank can be reduced by using pure water or passing activated carbon, but it costs equipment costs and replacement filter costs.

JP-A-52-62136 JP-A-4-272200 Patent No. 4224552 Japanese Patent No. 4753197 Special table 2003-535223 Japanese Patent No. 4957906 JP 2003-24933 A Japanese Patent No. 3568460 Japanese Patent No. 3568461

  Since the activated carbon treatment is performed with the production line suspended, there is a problem that the operating rate of the production apparatus is lowered and the processing unit price is increased. Activated carbon also adsorbs organic additives necessary for plating treatment in addition to organic impurities, so it is necessary to add a large amount of organic additive to the plating solution after activated carbon treatment, but organic additives are expensive. Therefore, there is a problem that the cost becomes high.

  In order to solve the above problems, the present invention provides a metal plating that can regenerate the washing solution used for the plating solution and / or the metal plating at low cost and easily while performing the plating treatment without adversely affecting the plating treatment. A method for regenerating liquid, a method for regenerating washing water used for metal plating, a plating apparatus, and a recycled material for metal plating are provided.

  In one embodiment of the present invention, there is provided a metal plating solution comprising contacting a metal plating solution with a polyolefin fiber and / or a fiber structure containing a polyolefin fiber to remove organic impurities from the metal plating solution. It relates to a playback method.

  In the metal plating solution regeneration method, the polyolefin fiber and / or the fiber structure containing the polyolefin fiber is forced from an overflow tank and a plating tank containing the metal plating solution overflowed from a plating tank containing the metal plating solution. It may be arranged in at least one selected from the group consisting of organic impurity removal containers that contain the metal plating solution drawn out automatically. In the overflow tank and / or the container for removing organic impurities, the metal plating solution from which organic impurities have been removed by contact with the fiber structure containing polyolefin fibers and / or polyolefin fibers may be returned to the plating tank. preferable.

  In one embodiment, the present invention is characterized in that the washing water used for metal plating is brought into contact with a polyolefin fiber and / or a fiber structure containing polyolefin fibers to remove organic impurities from the washing water used for metal plating. The present invention relates to a method for regenerating flush water used for metal plating.

  In the method of reclaiming washing water used for the metal plating, the polyolefin fiber and / or the fiber structure containing the polyolefin fiber is installed to remove a foreign matter contained in the washing tank and / or the washing water containing the washing water. It may be arranged in at least a part of the arranged circulation path.

  In one embodiment, the present invention is a plating apparatus used for metal plating, wherein the plating apparatus includes a plating tank for storing a metal plating solution, a foreign matter removing unit for removing solids from the plating solution, and a plating tank. An overflow tank for storing the metal plating solution overflowed from the metal and / or an organic impurity removing container for storing the metal plating solution forcibly drawn out from the plating tank, and comprising the overflow tank and the organic impurity removing container. At least one selected from the group relates to a plating apparatus in which a polyolefin fiber and / or a fiber structure containing a polyolefin fiber is disposed.

  In one embodiment, the plating apparatus removes organic impurities by contact with a polyolefin fiber and / or a fiber structure including the polyolefin fiber disposed in the overflow tank and / or the organic impurity removing container. It is preferable to have a return means for returning the plated metal plating solution to the plating tank.

  The plating apparatus used for the metal plating may further include a rinsing tank for storing rinsing water and a circulation path installed for removing foreign substances contained in the rinsing water.

  The present invention, in one embodiment, is a recycled material for metal plating used for metal plating, wherein the recycled material for metal plating is composed of a fiber structure including polyolefin fibers and / or polyolefin fibers, Washing water used for metal plating solution and / or metal plating by removing metal impurities by bringing metal plating solution and / or washing water used for metal plating into contact with the polyolefin fiber and / or fiber structure containing polyolefin fiber. The present invention relates to a recycled material for metal plating characterized by regenerating water.

The fiber structure containing the polyolefin fiber preferably contains 50% by mass or more of the polyolefin fiber. The apparent specific gravity of the polyolefin fiber or the fiber structure containing the polyolefin fiber is preferably 0.03 g / cm ³ or more and less than 0.3 g / cm ³ . The polyolefin fiber or the fiber structure containing the polyolefin fiber preferably has an oil agent adhesion amount of 0.1% by mass or less.

  The present invention provides a method for regenerating a metal plating solution that can regenerate the plating solution and / or the washing water used for metal plating while performing the plating treatment without adversely affecting the plating treatment, and metal plating. A method for regenerating flush water, a plating apparatus, and a recycled material for metal plating are provided. By using the recycle material for metal plating or the recycle method of the metal plating solution of the present invention in combination with the activated carbon treatment method, the frequency of activated carbon treatment and disposal of the plating solution can be lowered, and thus the operating rate of the production apparatus is improved, Cost can be reduced. Activated carbon also adsorbs organic additives in addition to organic impurities, but the combined use of the reclaimed material for metal plating or the method for regenerating metal plating solution of the present invention reduces the frequency of activated carbon treatment of the plating solution, and adds organic additives. A sudden change in the agent concentration can be prevented.

FIG. 1 is a schematic explanatory view of a plating apparatus according to an embodiment of the present invention. FIG. 2 is a schematic explanatory view of a plating apparatus according to an embodiment of the present invention. FIG. 3 is a graph showing the change over time in the concentration of organic impurities in the plating solution.

  The inventors of the present invention diligently studied to regenerate the metal plating solution and washing water used for metal plating, and as a recycle material for metal plating, a fiber structure containing polyolefin fiber and / or polyolefin fiber is used. , Found that metal plating solution and / or washing water used for metal plating can be regenerated by contacting the metal plating solution and washing water used for metal plating with a polyolefin fiber and / or a fiber structure containing polyolefin fiber. The present invention has been reached. Specifically, it is found that the polyolefin fiber has a property of easily adsorbing organic impurities in the washing water used for the metal plating solution and / or metal plating, and the washing water used for the metal plating solution or metal plating is treated with the polyolefin fiber and Contact with a fiber structure containing polyolefin fibers to remove organic impurities from the metal plating solution and / or washing water used for metal plating, and regenerate the washing water used for metal plating solution and / or metal plating It came to. In addition, although the polyolefin fiber has a lower degree of adsorptivity to the organic additive than that by the activated carbon treatment, it does not cause a sudden change in the organic additive concentration.

  In the present invention, the metal in the metal plating includes metals such as copper, nickel, gold, and silver.

  In the present invention, the metal plating reclaimed material is composed of a polyolefin fiber and / or a fiber structure containing a polyolefin fiber. The polyolefin constituting the polyolefin fiber is not particularly limited. For example, a homopolymer of an α-olefin having about 2 to 20 carbon atoms, a copolymer composed of two or more α-olefins having about 2 to 20 carbon atoms. Copolymer of α-olefin having about 2 to 20 carbon atoms and vinyl acetate, copolymer of α-olefin having about 2 to 20 carbon atoms and (meth) acrylic acid, α-olefin having about 2 to 20 carbon atoms And a (meth) acrylic acid ester copolymer. Examples of the α-olefin having about 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, Examples include octene and 1-decene. Among these, the polyolefin is preferably polypropylene. When polypropylene is used, polyolefin fibers having a large organic impurity removal effect can be obtained at low cost. The polypropylene may be a homopolymer of propylene or a copolymer of propylene and another α-olefin having about 2 to 20 carbon atoms. In this specification, “(meth) acrylic acid” means methacrylic acid and acrylic acid.

  The polyolefin-based fiber may be a single component fiber or a composite fiber containing two or more components. The polyolefin fiber may be a composite fiber including a low melting point component and a high melting point component, and the low melting point component occupies at least a part of the fiber surface. The polyolefin fiber may be a core-sheath type composite fiber in which the core component is a high melting point component and the sheath component is a low melting point component, the core component is polypropylene, and the sheath component is polyethylene. It may be a composite fiber. When the polyolefin fiber is a core-sheath composite fiber, the core / sheath composite ratio (volume ratio) is preferably 9/1 to 4/6, more preferably 8/2 to 5/5. More preferably, it is 7/3 to 6/4.

  The fineness of the polyolefin-based fiber is not particularly limited, but for example, it is preferable that the single yarn fineness is 0.1 dtex or more and 50 dtex or less. If the fiber is less than 0.1 dtex, the plating solution may be deteriorated, and if it is 50 dtex or more, the surface area relative to the weight is decreased, and the performance of removing organic impurities may be deteriorated. More preferably, it is 0.5 dtex or more and 24 dtex or less, and further preferably 0.9 dtex or more and 10 dtex or less.

  The fiber length of the polyolefin-based fiber is not particularly limited. For example, the fiber length is preferably 5 mm or more and 102 mm or less from the viewpoint of handleability. More preferably, the fiber length is from 38 mm to 76 mm, and more preferably from 38 mm to 64 mm.

  As said polyolefin fiber, what was manufactured with the well-known manufacturing method may be used, and a commercially available thing may be used. The polyolefin fiber is preferably washed. By removing the oil agent (also referred to as a fiber treatment agent) by the cleaning treatment, the removal performance of the organic impurities of the polyolefin fiber is enhanced. Although the method of a washing process is not specifically limited, For example, it can carry out using an anionic surfactant. Specifically, it can be performed as follows. First, after washing the polyolefin fiber with water for 5 minutes, the polyolefin fiber is immersed in a solution of 1 g / L of an anionic surfactant (manufactured by Yushi Kogyo Co., Ltd., product name “Tripon BX-11”) and treated at 70 ° C. for 10 minutes. Then, it is good to dry through hot water washing with 70 degreeC or more hot water, water washing. The adhesion amount of the oil agent in the polyolefin fibers is preferably 1.0% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less. In the present invention, the “adhesion amount of the oil agent on the fiber” is measured and calculated as described later.

  The polyolefin fiber may be used as raw cotton or may be used as a fiber structure containing 50 mass% or more of polyolefin fiber (hereinafter, also simply referred to as “fiber structure”). The fiber structure may be a fiber structure composed of 100% by mass of polyolefin fibers, or may be a fiber structure containing 50% by mass or more of polyolefin fibers and 50% by mass or less of other fibers. The fiber structure preferably contains 60% by mass or more of polyolefin fibers and 40% by mass or less of other fibers, more preferably 70% by mass or more of polyolefin fibers and 30% by mass or less of other fibers. As other fibers, for example, acrylic fibers or polyester fibers can be used from the viewpoint of chemical resistance. You may use another fiber individually or in combination of 2 or more types.

  As the fiber structure, yarns, woven fabrics, knitted fabrics, and nonwoven fabrics can be used. In addition, as the fiber structure, a cartridge filter using a thread or a nonwoven fabric may be used.

When the polyolefin fiber and other fibers are used in combination, for example, the following method can be employed.
(1) Blending: Blending is when two or more fibers are mixed in the cotton stage. For example, blending with mixed cotton, card, strips, sliver and the like. Used mainly in the case of uniform mixing of spun yarn and nonwoven fabric.
(2) Combined yarn: Two or more types of yarn are twisted together. For example, in the case of twin yarn, a polyolefin fiber yarn and another fiber yarn are twisted together. Used for twisting spun yarns, spun yarns and filament yarns, and filament yarns.
(3) Mixed fiber: Mixed fiber mixes single fibers of filament yarns.
(4) Interweaving: Interwoven is a woven fabric using a plurality of yarns constituting the woven fabric. For example, the warp and the weft may be different types, or a plurality of warps and wefts may be used.
(5) Knitting: Knitting uses a plurality of types of yarn when manufacturing a knitted fabric.
(6) In the production of nonwoven fabric, a plurality of laminated fiber layers are mixed by needle punching or hydroentanglement.

  When the fiber structure is a spun yarn, it can be produced by any method such as a ring method, an open end method, a bundling method, an alternating twist method, a wrapping method, a vortex method, or a non-twist method. The preferred count in this case is an English cotton count in the range of 5 to 100S. A single yarn may be used or a plurality of yarns may be twisted together. The spun yarn preferably contains 60% by mass or more of polyolefin fiber, more preferably 70% by mass or more of polyolefin fiber. It is particularly preferable that the fiber consists of 100% by mass of polyolefin fibers. In the spun yarn, the other fiber can be selected from the viewpoint of chemical resistance as described above, and is preferably included in the range of 40% by mass or less, and more preferably in the range of 30% by mass or less. The spun yarn may be a spun yarn or a worsted yarn.

  When the fiber structure is a knitted fabric, the structure, basis weight, and the like are not particularly limited, and may be any of flat knitting, rubber knitting, double-sided knitting, and the like. Also, when the fiber structure is a woven fabric, the structure, basis weight, etc. are not particularly limited.

The polyolefin fiber or fiber structure is not particularly limited, but for example, the apparent specific gravity is preferably 0.03 g / cm ³ or more and less than 0.3 g / cm ³ . If it is less than 0.03 g / cm ³ , the volume may be larger than the required amount and the economy may be inferior. If it is 0.3 g / cm ³ or more, the liquid permeability is deteriorated and the processing amount may be insufficient. More preferably, it is 0.04 g / cm ³ or more and 0.2 g / cm ³ or less, and further preferably 0.04 g / cm ³ or more and 0.12 g / cm ³ or less. In the present invention, the apparent specific gravity is calculated by the following equation after measuring an object in a cylindrical container having an inner diameter of 16 cm and a height of 16 cm under conditions of 20 ± 5 ° C. and a relative humidity of 60%. .
Apparent specific gravity (g / cm ³ ) = mass of object (g) / volume of cylindrical container (cm ³ )

It is desirable that the polyolefin fiber or fiber structure has a portion that is not uniform but has a different apparent specific gravity. For example an apparent specific gravity of 0.06 g / cm ³ or more 0.6 g / cm ³ less dense portion and an apparent specific gravity of preferably has a low density portion of 0.05 g / cm ³ or less.

  As the polyolefin fiber, staple fiber is preferably used. Usually, an oil agent is applied to the staple fiber, but it is preferable that the applied oil agent is washed as described above to reduce the adhesion amount of the oil agent to the fiber to 1.0% by mass or less. More preferably, the content is reduced to 3% by mass or less, and further preferably 0.1% by mass or less. The fiber structure such as a spun yarn also has an oil agent adhesion amount of preferably 1.0% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less. preferable. Although the reason is unknown, the organic impurity adsorption performance is improved when a small amount of oil is present on the fiber surface within a range that does not elute into the plating solution.

  In this invention, the adhesion amount of the oil agent in polyolefin-type fiber or fiber structure is measured by a rapid extraction method using the Tokai Keiki Co., Ltd. R-II type rapid residue extraction apparatus. First, when the object is a fiber, 4 g of the fiber is put on a card machine to form a web, the mass of the obtained web is measured, and the web whose mass is measured is used as a sample. When the object is a fiber structure such as a spun yarn, 4 g of the fiber structure is measured and used as a sample. Let the mass of the sample be Wf. The sample is filled in a metal tube (inner diameter 16 mm, length 130 mm, bottom is in a mortar shape and the bottom is 1 mm), and 10 ml of methanol is added from the top. Methanol, which is dripped from the bottom hole and dissolved in the oil attached to the sample, is received while heating the aluminum dish (mass: Wtray), and the methanol is evaporated. The mass (Wtray) of the aluminum pan is measured after the aluminum pan is sufficiently dried with a dryer and before receiving methanol. After the methanol has completely evaporated, the mass (Wfat) of the aluminum pan in which the oil remains is measured. After said measurement, the adhesion amount of the oil agent in a fiber or a fiber structure is calculated from the following formula.

  Adhering amount of oil (mass%) = [(Wfat−Wtray) / Wf] × 100

  For example, there are roughly three types of organic additives (also referred to as organic additives) used in copper sulfate plating, and they are generally called P component, S component, and J component. As the P component, PEG (polyethylene glycol, molecular weight of about 2,000), PEGNPE (polyoxyethylene polyoxypropylene glycol, weight average molecular weight Mw of about 3,300) and the like are used. As the S component, 2-methylcaptobenzothiazole S propanesulfonic acid (molecular weight 288), SPS (3,3′-dithiobis (1-propanesulfonic acid) 2 sodium) or the like is used. As the J component, JGB (Yarnus Green B, molecular weight 511) or the like is used.

  Organic additives are also used in other metal plating, for example, saccharin, sodium naphthalene sulfonate, butynediol, propargyl alcohol, and coumarin are used in nickel plating, and dimercaptothiadiazole monomer and dimer are used in copper pyrophosphate plating. Used. In acid tin plating, cresol sulfonic acid, β-naphthol, dihydroxydiphenyl sulfone, ethoxylated α-naphthol sulfonic acid, methoxybenzaldehyde, and the like are used.

  The P component and the J component form a film on the surface of the convex portion and function as a plating inhibitor, and the S component enters the concave portion, and the concentration becomes higher than the portion other than the concave portion and functions as an accelerator for proceeding with filling of the hole. In addition, when the concave portion is small, the P component has a large molecular weight, so that it cannot enter the concave portion, and the suppression effect is low. As a result, the plating deposition proceeds more than the other portions due to the synergistic effect with the S component.

  Reduction in molecular weight due to degradation of PEG as the P component has been reported (“Effect of pre-electrolysis time of polyethylene glycol on copper plating film”, Kyoto City Industrial Technology Research Institute, Research Report No. 4 (2014), 57-63). As for the S component, it has been reported that the S—S bond may be broken depending on the SPS conditions (“Mechanism of plating additive and surface shape control”, Osaka Prefectural Industrial Technology Research Institute report No. 1). 5, 2011, pages 13-21).

  Most organic additives are pre-mixed by additive manufacturers.

  In metal plating, as organic impurities other than those derived from organic additives, dissolution from a printed wiring board is considered, and the dissolution is a pattern plating photoresist.

  A metal plating solution (hereinafter also simply referred to as “plating solution”) is brought into contact with a polyolefin fiber and / or a fiber structure containing polyolefin fiber, and the polyolefin fiber absorbs and removes organic impurities in the plating solution. By doing so, it is possible to regenerate the plating solution. The method for bringing the metal plating solution into contact with the polyolefin fiber and / or the fiber structure is not particularly limited. For example, at least one selected from the group consisting of an overflow tank containing a metal plating solution overflowed from a plating tank containing a metal plating solution and an organic impurity removing container containing a metal plating solution forcibly drawn out from the plating tank. Polyolefin fibers or fiber structures may be disposed on one, and the plating solution may be brought into contact with the polyolefin fibers and / or fiber structures. The plating solution from which the organic impurities are removed by contacting with the polyolefin fibers and / or the fiber structure is returned to the plating solution.

  The container for removing organic impurities is not particularly limited as long as it can be used for a metal plating line. For example, a column, a housing, etc. can be used. As the column, for example, a material such as polypropylene (PP) or polymethyl methacrylate (PMMA) can be used. As the housing, a material such as polypropylene (PP) or polymethyl methacrylate (PMMA) can be used.

  Washing water used for metal plating (hereinafter, also simply referred to as “washing water”) is brought into contact with polyolefin fibers and / or fiber structures, and the polyolefin fibers absorb and remove organic impurities in the washing water. The water can be regenerated. By regenerating the washing water, it is possible to reduce the organic impurities contained in the washing water and reduce the occurrence of discoloration (corrosion, oxidation) or the like in a product such as a substrate after plating. The method for bringing the washing water into contact with the polyolefin fibers and / or the fiber structure is not particularly limited. For example, a polyolefin fiber or a fiber structure is disposed in at least a part of a circulation tank installed to remove foreign matters contained in a washing tank and / or washing water for containing washing water, and the washing water is used as polyolefin fiber. And / or contact with the fiber structure. As a circulation path installed in order to remove the foreign substance contained in the washing water which arrange | positions a polyolefin-type fiber or a fiber structure, a storage tank (washing tank of a circulation path) is mentioned, for example. The flush water in the storage tank is regenerated and then returned to the flush tank that contains the flush water.

  Z-axis connection (conduction) is indispensable for manufacturing a multilayer substrate. Connections such as through vias, blind vias, filled vias, and stacked vias are used for Z-axis connection. Although it is necessary to perform plating on the surface with holes in the insulator, it is impossible to deposit on the surface of the insulator with electroplating, so there is a method of forming a thin plating layer by electroless plating and increasing the plating thickness by electroplating. Used.

  Electroless plating is usually performed in the following order: cleaner conditioner, water washing, pickling, water washing, micro etch, water washing, acid washing, water washing, pre-dip, catalyst, water washing, accelerator, water washing, electroless plating, water washing, and drying. Is called.

  Electroplating is usually performed in the order of degreasing, washing with water, pickling, electroplating, drag-out, washing with water, rust prevention, and drying.

  In order to create a circuit pattern, a pattern forming process using a resist is required either before or after plating. The pattern forming process is usually performed in the order of attaching or applying a photosensitive agent, attaching a photo tool, exposing, and developing. In the print etching method in which pattern formation is performed after plating, etching, etching resist peeling, water washing, and drying are performed thereafter. In the metal resist method for forming a pattern before plating, washing with water, drying, plating with a resist metal, washing with water, peeling of a plating resist, etching, peeling of an etching resist metal, washing with water and drying are performed.

  Solder resist (covering the surface with a resist on a portion where solder is not required) for performing HASL (molten solder immersion) after circuit pattern formation is usually performed by applying or applying a photosensitizer or applying a photo tool. , Exposure, development, washing with water, etching, washing with water, peeling of the etching resist, washing with water, and drying.

  The preflux (protecting the exposed copper surface) step for protecting the exposed copper surface is usually performed in the order of soft etching, water washing, acid washing, water washing, chelating agent immersion, water washing, and drying.

  The polyolefin fiber and / or fiber structure is preferably filled in a mesh-like storage bag. For example, polypropylene (PP) or polyethylene terephthalate (PET) can be used as the material of the storage bag. The size of the mesh is preferably such that the fibers do not flow out without hindering the passage of the plating solution.

  The amount of the polyolefin-based fiber to be brought into contact with the metal plating solution is not particularly limited as long as the organic impurities in the metal plating solution can be removed. For example, at least one selected from the group consisting of an overflow tank containing a metal plating solution overflowed from a plating tank containing a metal plating solution and an organic impurity removing container containing a metal plating solution forcibly drawn out from the plating tank. When the polyolefin fiber and / or fiber structure is arranged in one, the amount of the polyolefin fiber and / or fiber structure used is 0.05 g / L to 1.0 g / L with respect to the capacity of the metal plating solution. It is preferable that it is 0.15 g / L to 0.6 g / L. When the mass of the olefin fiber or fiber structure with respect to the capacity of the metal plating solution is within the above range, the effect of removing organic impurities in the plating solution is high, and the cost can be further reduced.

  The amount of the polyolefin-based fiber to be brought into contact with the washing water is not particularly limited as long as the organic impurities in the washing water can be removed. For example, the amount of polyolefin fiber and / or fiber structure used is preferably 0.05 g / L to 4.0 g / L, and preferably 0.2 g / L to 2.0 g / L with respect to the washing water capacity. More preferably, it is L. When the mass of the olefin fiber or fiber structure with respect to the capacity of the washing water is within the above range, the effect of removing organic impurities in the washing water is high and the cost can be further reduced.

  In a plating apparatus used for metal plating, the plating solution can be regenerated by using the method for regenerating a metal plating solution using the polyolefin fibers and / or fiber structures described above.

  For example, it was forcibly pulled out from a plating tank containing a metal plating solution, a foreign matter removing means for removing solids from the plating solution, and an overflow tank and / or a plating tank containing a metal plating solution overflowed from the plating tank. In a plating apparatus including an organic impurity removing container that contains a metal plating solution, a polyolefin fiber and / or a fiber structure is disposed in at least one selected from the group consisting of the overflow tank and the organic impurity removing container. . In at least one selected from the group consisting of the overflow tank and the organic impurity removing container, the plating solution comes into contact with the polyolefin-based fiber and / or the fiber structure to remove the organic impurities in the plating solution. Further, the plating solution from which the organic impurities are removed in the overflow tank and / or the organic impurity removing container is returned to the plating solution, and the plating solution is regenerated.

  In the plating apparatus used for metal plating, the washing water can be regenerated by using the above-described washing water recycling method using the polyolefin fibers and / or fiber structures.

  For example, in a plating apparatus provided with a washing tank for containing washing water and a circulation path installed to remove solid foreign substances contained in the washing water, a solid contained in the washing tank and / or washing water for containing washing water Polyolefin fibers and / or fiber structures are arranged in at least a part of a circulation path installed to remove foreign substances. The washing water comes into contact with the polyolefin fiber and / or the fiber structure in at least a part of the washing tank containing the washing water and a circulation path installed to remove solid foreign matters contained in the washing water. Organic impurities in the water are removed. In addition, at least part of the circulation path installed to remove solid foreign substances contained in the washing water, for example, the washing water from which organic impurities have been removed in the storage tank is returned to the washing tank containing the washing water. In addition, the washing water is regenerated.

  Examples of the simple plating apparatus include a plating tank that contains a metal plating solution, an overflow tank that contains a metal plating solution that has overflowed from the plating tank, and a foreign matter removing unit that removes solid matter from the plating solution. By placing polyolefin fiber and / or fiber structure in the overflow tank and bringing the plating solution into contact with the polyolefin fiber and / or fiber structure, organic impurities in the plating solution are adsorbed and removed by the polyolefin fiber. Is done. The plating solution from which organic impurities have been removed in the overflow tank is returned to the plating solution by a return means such as a pump after the solid matter is removed by the foreign matter removing means, and the plating solution is regenerated. The polyolefin-based fiber disposed in the overflow tank may be in the form of the fiber, or may be in the form of the fiber structure described above. From the viewpoint of handling properties and cost, it is preferable to use a spun yarn as the fiber structure. The polyolefin fiber and / or fiber structure is preferably arranged after filling a mesh-like storage bag. This is because the use of a storage bag facilitates replacement and saves labor for maintenance.

  Usually, a filter is used as the foreign matter removing means. In general, a filter using a cartridge filter is used. Examples of the cartridge filter include a pincushion type, a melt blow type, and a membrane filter paper.

  The plating apparatus includes a plating tank for storing a metal plating solution, an organic impurity removing container for storing a metal plating solution forcibly pulled out from the plating tank, and a foreign matter removing means for removing solids from the plating solution. It may be a device. The organic impurity removing container may be a column or a housing. As the housing, a back filter or a cartridge filter type can be used. When the housing is a back filter type, the filter is filled with polyolefin fibers and / or fiber structures. When the housing is of a cartridge filter type, a polyolefin fiber and / or a fiber structure is filled instead of the cartridge filter. The housing may be one stage or two or more stages. For example, when the housing has two stages, a cartridge filter for removing foreign matter that removes solid matter in the plating solution is arranged in one housing and used for removing foreign matter, and the other housing is made of organic material in the plating solution. It can be used for removing organic impurities by filling with polyolefin fibers and / or fiber structures for removing impurities. The apparatus forcibly pulls the metal plating solution from the plating tank by a drawing means such as a pump, and sends it into a container for removing organic impurities filled with polyolefin fibers and / or fiber structures. By contacting with the system fiber and / or the fiber structure, the organic impurities in the plating solution are adsorbed and removed by the polyolefin system fiber. In this case, organic impurity removal efficiency can be further improved by connecting in parallel the plating tank and the housing filled with two or more stages of polyolefin fibers and / or fiber structures. Thereafter, the plating solution from which the organic impurities have been removed is returned to the plating solution by a returning means such as a pump after the solid matter is removed by the foreign matter removing means, and the plating solution is regenerated.

  The organic impurity removing container may be incorporated in a line for removing foreign substances. In this case, the pump and piping can be shared, which is economical. In addition, if an organic impurity removing container in which polyolefin fibers and / or fiber structures are arranged in front of the foreign matter removing means is incorporated, the foreign matter removing means captures the dropped fibers, thus preventing foreign matter from being mixed into the plating solution. be able to.

  The plating apparatus may further include a rinsing tank for storing rinsing water and a circulation path installed for removing solid foreign substances contained in the rinsing water. In metal plating, washing with water before plating is performed in order to clean an object to be plated. In addition, washing with water after plating is performed in order to remove the adhering plating solution and clean it. From the viewpoint of cost and water washing efficiency, the number of water washing tanks is preferably 2 to 3 tanks. The circulation path installed to remove solid foreign substances contained in the washing water is, for example, a storage tank (a washing tank of the circulation circuit), an outflow means for flowing the washing water from the washing tank to the storage tank, and a washing tank from the storage tank. Returning means for returning the washed water regenerated to the water may be included.

  Hereinafter, the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to what is shown in the following drawings.

  FIG. 1 is a schematic explanatory diagram of a plating apparatus according to an embodiment of the present invention. The plating apparatus 1 of this embodiment includes a plating tank 2, an overflow tank 3, and foreign matter removing means 6. A plating solution is accommodated in the plating tank 2. The overflow tank 3 stores the plating solution overflowed from the plating tank. In the overflow tank 3, polyolefin fibers and / or fiber structures 4 are arranged. The polyolefin-based fiber and / or the fiber structure 4 is filled in a mesh storage bag 5. The foreign matter removing means 6 includes a cartridge filter 8. The plating solution overflowed from the plating tank 2 to the overflow tank 3 comes into contact with the polyolefin fibers and / or the fiber structure 4 disposed in the overflow tank 3, so that the organic impurities in the plating solution become polyolefin fibers and / or Or it is adsorbed and removed by the fiber structure. The plating solution from which the organic impurities in the overflow tank 3 are removed is returned to the plating tank 2 by the return means 7 after the solid matter is removed by the foreign matter removing means 6. A pump or the like is used as the return means 7. Since the plating solution from which organic impurities have been removed from the polyolefin fibers and / or fiber structure passes through the foreign matter removing means 6, it is possible to prevent the dropped polyolefin fibers and / or fiber structures from flowing into the plating tank. The

  FIG. 2 is a schematic explanatory view of a plating apparatus according to another embodiment of the present invention. The plating apparatus 10 according to this embodiment includes a plating tank 11, an organic impurity removing container 12, and foreign matter removing means 15. A plating solution is accommodated in the plating tank 11. The organic impurity removing container 12 contains a plating solution forcibly drawn out from the plating tank. Polyolefin fibers and / or fiber structures 13 are disposed in the organic impurity removing container 12. The polyolefin fiber and / or fiber structure is preferably filled in a storage bag. As the organic impurity removing container 12, a column, a housing, or the like is used. When the housing is a back filter type, the filter is filled with polyolefin fibers and / or fiber structures. When the housing is of a cartridge filter type, a polyolefin fiber and / or a fiber structure is filled instead of the cartridge filter. The foreign matter removing means 15 includes a cartridge filter 16. In addition, the plating apparatus 10 includes a drawing unit 14 that forcibly draws the plating solution from the plating tank. A pump or the like is used as the drawing means 14. The plating solution forcibly withdrawn from the plating tank 11 comes into contact with the polyolefin fibers and / or the fiber structure 13 disposed in the organic impurity removing container 12 so that the organic impurities in the plating solution are polyolefin-based. It is adsorbed and removed by the fiber. The plating solution from which the organic impurities are removed in the organic impurity removing container 12 is returned to the plating tank 11 after the solid matter is removed by the foreign matter removing means 15. Since the plating solution from which organic impurities have been removed by the polyolefin fibers and / or fiber structure passes through the foreign matter removing means 15, it is possible to prevent the dropped polyolefin fibers and / or fiber structures from flowing into the plating tank. The The extraction means 14 also functions as a return means for returning the metal plating solution from which the organic impurities have been removed to the plating tank. In this embodiment, the housing which is a container for removing organic impurities is one stage, but it may be two or more stages.

  The metal plating solution generally contains metal ions of the metal to be plated, an acid such as sulfuric acid or phosphoric acid, and chloride ions. It also contains one or more organic additives. By using the regeneration method and apparatus of the present invention, it is possible to remove organic impurities generated by decomposition and deterioration of the organic additive without causing a large change in the concentration of the organic additive in the plating solution. Further, organic impurities brought into the plating solution and organic impurities eluted into the plating solution can be removed.

  The organic impurities in the washing water and the plating solution may be due to decomposition of organic impurities and organic additives contained in the raw water, and may include organic impurities derived from microorganisms, bacteria, and algae. In addition to electroplating, it is known that organic impurities derived from living organisms are generated in water washing in electroless plating, a preflux process, a resist process, and the like. Can be reproduced.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.

  In Examples and Comparative Examples, the degree of organic impurities in the copper sulfate plating solution is confirmed by increasing or decreasing the absorbance at 200 to 500 nm, and the organic impurity concentration is set. The organic impurity concentration indicated by the degree of organic impurities, the plating physical properties, the plating tensile strength, and the plating ductility elongation correlated as described in Table 1 below. As a guide, it has been found that when the organic impurity concentration exceeds 80, the plating physical properties are adversely affected. The plating physical properties, plating tensile strength and plating ductility elongation were measured and evaluated as follows. Similarly, the degree of organic impurities in the rinsing water is confirmed by an increase / decrease in absorbance at 200 to 500 nm to obtain the organic impurity concentration. The organic impurity concentration indicated by the degree of organic impurities and the occurrence frequency of discoloration had a correlation as described in Table 2 below. As a guide, it has been found that when the organic impurity concentration exceeds 7, discoloration occurs and adverse effects occur. The discoloration was visually inspected. The frequency of occurrence was calculated from the number of manufactured products and the number of products with discoloration.

(Plating properties)
Judgment was made in four stages of “bad”, “slightly bad”, “slightly good”, and “good” based on the test results of plating tensile strength and plating elongation.

(Plating tensile strength)
The tensile strength after the tensile test was divided by the cross-sectional area to obtain the plating tensile strength (N / mm ² ).

(Plating elongation)
It calculated by the following formula from the length before and after the tensile test in the length direction of the plating film.
Plating elongation (%) = (length after tensile test−length before tensile test) / length before tensile test × 100

Example 1
The plating solution was regenerated using the plating apparatus shown in FIG. Copper impurity plating with copper sulfate plating solution (copper 20g / L, sulfuric acid 190g / L, 2 types of organic additives, 11mL / L, 1mL / L respectively), organic impurity concentration after copper plating The plating solution No. 65 was regenerated. A housing was used as the organic impurity removing container 12. The organic impurity removing housing 12 was filled with polypropylene spun yarn (product name “35006-S” manufactured by Daiwabo Progress Co., Ltd., the amount of oil adhered was 0.01% by mass or less, the amount used was 0.16 g / L). The polypropylene spun yarn was stored in a 60 mesh polypropylene mesh bag using polypropylene monofilament. As the foreign matter removing means 15, it was used in a housing equipped with a cartridge filter 16 (PP wool wound type, manufactured by Zet Kogyo Co., Ltd., product name “ZW-PP (washing)”). As the housing, product name “EAGLE” (material reinforced polypropylene) manufactured by Nippon Filter Co., Ltd. was used. The copper sulfate plating solution was circulated at a flow rate of 19,000 L / hour through the organic impurity removing housing 12 for 8 hours / day and through the foreign matter removing means 15 for 24 hours / day. The increase or decrease in absorbance at 200 to 500 nm of the copper sulfate plating solution was confirmed every week, and the circulation was carried out for 28 weeks until the organic impurity concentration exceeded 80. During this time, it was not necessary to remove organic impurities with activated carbon, and there was no need to replace the cartridge filter 16 for the purpose of removing foreign substances. If organic impurities are not removed with the polypropylene spun yarn arranged in the organic impurity removal housing, it is necessary to treat the organic impurities with activated carbon in the middle, and it is necessary to add it to the plating solution after the organic impurities treatment with activated carbon. Compared to the case where the amount of an organic additive is 100, the amount of the organic additive added to the plating solution after removing the organic impurities in this example is 0 for the addition of 11 mL / L and 18 for the addition of 1 mL / L. there were.

(Example 2)
The plating solution was regenerated using the plating apparatus shown in FIG. Copper impurity plating with copper sulfate plating solution (copper 20g / L, sulfuric acid 190g / L, 2 types of organic additives, 14mL / L and 1mL / L, respectively), organic impurity concentration after copper plating Recycled 30 plating solutions. The plating solution was prepared in the same manner as in Example 1 except that the organic impurity removing housing 12 was filled with a 60-mesh polypropylene mesh bag made of polypropylene monofilament and filled with a polypropylene fiber (usage 0.14 g / L). Circulation was performed. As the polypropylene fiber, a washed product obtained by washing a polypropylene fiber having a product name “PN 1.7 × 45 mm” manufactured by Daiwabo Progress Co., Ltd., having an oil agent adhesion amount of 0.02% by mass was used. In the washing treatment, the fiber was washed with water for 5 minutes, and then treated at 70 ° C. for 10 minutes in a solution of 1 g / L of an anionic surfactant (manufactured by Yufu Kogyo Co., Ltd., product name “Tripon BX-11”). It was performed by washing with hot water at a temperature of ℃ or higher, followed by washing with water and drying. The increase / decrease in the absorbance of the copper sulfate plating solution at 200 to 500 nm was confirmed every week, and the circulation was carried out until the 27th week when the organic impurity concentration exceeded 80. During this time, it was not necessary to remove organic impurities with activated carbon, and there was no need to replace the cartridge filter 16 for the purpose of removing foreign substances. When organic impurities are not removed with polypropylene fibers placed in the organic impurity removal housing, it is necessary to treat organic impurities with activated carbon in the middle, and it is necessary to add to the plating solution after treating organic impurities with activated carbon. Compared with the case where the amount of organic additive is 100, the amount of added organic additive in the plating solution after removal of organic impurities in this example was 0 for 14 mL / L addition and 18 for 1 mL / L addition. It was.

(Example 3)
Copper impurity plating with copper sulfate plating solution (copper 20g / L, sulfuric acid 200g / L, 2 types of organic additives, 12mL / L and 1mL / L, respectively), organic impurity concentration after copper plating The 35 plating solution was regenerated. In the apparatus shown in FIG. 2, polypropylene spun yarn (product name “35006-S” manufactured by Daiwabo Progress Co., Ltd., amount of oil applied is 0.01 mass% or less, amount used is 0.35 g / L) in the organic impurity removing housing 12. The plating solution was circulated in the same manner as in Example 1 except that was filled. Increase / decrease in the absorbance of the copper sulfate plating solution at 200 to 500 nm was confirmed every week, and circulation was carried out by 27 weeks until the organic impurity concentration exceeded 80. During this time, there was no need to remove organic impurities with activated carbon, and there was no cartridge filter replacement for the purpose of removing foreign substances.

(Comparative Example 1)
In Comparative Example 1, in the plating apparatus shown in FIG. 2, the organic impurity removing container in which the polypropylene spun yarn is disposed is omitted. Copper plating was performed with a copper sulfate plating solution (copper 20 g / L, sulfuric acid 190 g / L, two organic additives were used, 11 mL / L and 1 mL / L, respectively). In the copper sulfate plating solution after copper plating, the organic impurity concentration was 67. Next, the copper sulfate plating solution after performing the copper plating is placed in a housing in which a cartridge filter (PP yarn wound type, manufactured by Zet Kogyo Co., Ltd., product name “ZW-PP (washed)”) is placed at 120,000 L / hour. Circulation was carried out at a flow rate of 24 hours / day. The increase / decrease in the absorbance of the copper sulfate plating solution at 200 to 500 nm was confirmed every week, and the circulation was carried out until the 12th week when the organic impurity concentration exceeded 80.

(Comparative Example 2)
In Comparative Example 2, the organic impurity removing container in which the polypropylene spun yarn is disposed in the plating apparatus shown in FIG. 2 is omitted. Copper plating was performed with a copper sulfate plating solution (copper 20 g / L, sulfuric acid 200 g / L, two organic additives were used, 12 mL / L and 1 mL / L, respectively). In the copper sulfate plating solution after copper plating, the organic impurity concentration was 59. Next, the copper sulfate plating solution after performing the copper plating is placed in a housing in which a cartridge filter (PP yarn wound type, manufactured by Zet Kogyo Co., Ltd., product name “ZW-PP (washed)”) is placed at 42,000 L / hour. Circulation was carried out at a flow rate of 24 hours / day. The increase / decrease in the absorbance of the copper sulfate plating solution at 200 to 500 nm was confirmed every week, and the circulation was carried out until the 21st week when the organic impurity concentration exceeded 80.

(Comparative Example 3)
Copper sulfate plating (copper 20g / L, sulfuric acid 200g / L, 2 types of organic additives are used, and copper plating is performed using 13mL / L and 1mL / L, respectively). In the liquid, the organic impurity concentration was 23. The plating solution was regenerated in the same manner as in Comparative Example 1, except that the copper sulfate plating solution after the copper plating was used. The increase / decrease in the absorbance of the copper sulfate plating solution at 200 to 500 nm was confirmed every week, and circulation was performed by 25 weeks until the organic impurity concentration exceeded 80.

Example 4
Copper impurity plating solution (copper 20g / L, sulfuric acid 200g / L, 2 types of organic additives are used, 14mL / L, 1mL / L respectively) No. 58 was regenerated. The plating solution was circulated in the same manner as in Example 2 except that a 60-mesh polypropylene mesh bag using polypropylene monofilament in the organic impurity removing housing 12 was filled with a bag filled with polypropylene fibers (amount used: 0.18 g / L). Went. The filled bags were changed every 8 weeks.

(Comparative Example 4)
Copper impurity plating solution (copper 20g / L, sulfuric acid 200g / L, 2 types of organic additives are used, 14mL / L, 1mL / L respectively) No. 58 was regenerated. The plating solution was circulated in the same manner as in Example 4 except that the organic impurity removing housing 12 was filled with a bag filled with activated carbon (amount used: 1.80 g / L).

(Example 5)
In the copper sulfate plating step of Example 4, polypropylene fibers were placed in a 60-mesh polypropylene mesh bag (20 cm × 30 cm) using polypropylene monofilaments in a storage tank (a washing tank in the circulation circuit) in the washing circuit before and after plating. One bag filled with (use amount 0.85 g / L) was put. As the polypropylene fiber, a washed product obtained by washing a polypropylene fiber having a product name “PN 1.7 × 45 mm” manufactured by Daiwabo Progress Co., Ltd., having an oil agent adhesion amount of 0.02 mass% was used. Water supply was 5 liters per minute and circulation was 10 liters per minute. The organic impurity concentration of the washing water in the washing tank of the plating line was 2.

(Comparative Example 5)
In the copper sulfate plating process of Example 5, washing is performed under the same conditions as in Example 5 except that polypropylene fibers are not used in the storage tank (the washing tank of the circulation line) in the washing water circulation line before and after plating. It was.

  In Examples 1 to 4 and Comparative Examples 1 to 3, the material of the cartridge filter disposed in the foreign matter removal housing, the amount of material used (mass relative to the volume of the plating solution) and the apparent specific gravity, and the polyolefin system disposed in the organic impurity removal housing Table 2 below shows the type of fiber and / or fiber structure, the amount used (mass relative to the volume of the plating solution), the apparent specific gravity, and the activated carbon treatment frequency. The apparent specific gravity was measured and calculated as described above.

  In Examples 1 to 4 and Comparative Examples 1 to 3, the initial value of the organic impurity concentration of the plating solution before regeneration, the rate of increase of the organic impurity concentration per week of the circulation treatment, and the organic impurity concentration exceeded 80. The week is shown in Table 3 below. The number of times the cartridge filter was replaced during the circulation period is also shown in Table 3 below.

  From the results of Examples 1 to 4 and Comparative Examples 1 to 3 in Table 3 and Table 4 above, it was found that an increase in the concentration of organic impurities was suppressed in Examples using polypropylene fibers. In the embodiment, by contacting the plating solution with polypropylene fiber or fiber structure separately from the foreign matter removing filter, the organic impurities can be easily and inexpensively removed from the plating solution without adversely affecting the plating process. did it.

  In Example 4 and Comparative Example 4, the consumption of the organic additive in the plating solution was measured as follows. Moreover, in Example 4 and Comparative Example 4, the consumption amount of the additive by polypropylene fiber or activated carbon was calculated as follows. The results are shown in Table 5 below.

(Organic additive concentration)
The organic additive concentration in the plating solution was measured using a CVS analyzer (cyclic voltammetry stripping analyzer).

(Consumer consumption by polypropylene fiber or activated carbon)
The amount of organic additive consumed by the polypropylene or activated carbon (mL / L) was calculated by dividing the amount of organic additive replenished by the calculated amount of organic additive consumed in the plating treatment.

  As can be seen from the results in Table 5 above, in Comparative Example 4 in which the organic impurity removal treatment was performed using activated carbon that was stopped in production, the organic additive was 4 in the amount of the organic additive added at 14 mL / L before and after the treatment. 0.0 mL / L was consumed, and 0.7 mL / L was consumed at the addition of 1 mL / L. On the other hand, in Example 4, it was hardly consumed by the addition amount of organic additive 14mL / L. In the case of 1 mL / L addition, 0.12 mL / L after 1 week and 0.06 mL / L organic additive was consumed after 2 weeks, but much less than Comparative Example 4 and decreased after 3 weeks. I couldn't see it.

  In Example 4, organic impurities were removed with activated carbon as needed without regeneration with polypropylene fibers until the 20th week. FIG. 3 shows the transition of the concentration of organic impurities in the plating solution when regeneration with polypropylene fibers was performed from the 20th week. As can be seen from FIG. 3, the regeneration with polypropylene fibers was able to be removed to the extent that the increase in organic impurity concentration was suppressed.

  In Example 5 and Comparative Example 5, the organic impurity concentration in the washing water after plating was confirmed as described above, and the results are shown in Table 6 below.

  As can be seen from the results of Table 6 above, in Comparative Example 5, the fluctuation was large and the concentration of organic impurities was high, whereas in Example 5, the organic impurities concentration was reduced by removing the organic impurities during the water washing.

DESCRIPTION OF SYMBOLS 1, 10 Plating apparatus 2, 11 Plating tank 3 Overflow tank 4, 13 Polyolefin fiber and / or fiber structure 5 Storage bag 6, 15 Foreign matter removing means 7 Return means 8, 16 Cartridge filter 12 Organic impurity removing container (housing )
14 Withdrawal means

Claims (20)

  A method for regenerating a metal plating solution, comprising bringing a metal plating solution into contact with a polyolefin fiber and / or a fiber structure containing a polyolefin fiber to remove organic impurities from the metal plating solution.   The polyolefin-based fiber and / or the fiber structure containing the polyolefin-based fiber includes an overflow tank that contains a metal plating solution overflowed from a plating tank that contains a metal plating solution, and a metal plating solution that is forcibly drawn from the plating tank. The method for regenerating a metal plating solution according to claim 1, wherein the metal plating solution is disposed in at least one selected from the group consisting of organic impurity removal containers containing slag.   The metal plating solution from which organic impurities have been removed by contact with the fiber structure containing polyolefin fibers and / or polyolefin fibers in the overflow tank and / or the organic impurity removal container is returned to the plating tank. A method for regenerating a metal plating solution as described.   The method for regenerating a metal plating solution according to any one of claims 1 to 3, wherein the fiber structure including the polyolefin-based fiber includes 50% by mass or more of the polyolefin-based fiber. The metal plating solution according to any one of claims 1 to 4, wherein an apparent specific gravity of the polyolefin fiber or a fiber structure including the polyolefin fiber is 0.03 g / cm ³ or more and less than 0.3 g / cm ^3. How to play.   The method for regenerating a metal plating solution according to any one of claims 1 to 5, wherein the polyolefin fiber or the fiber structure containing the polyolefin fiber has an adhesion amount of oil of 0.1% by mass or less.   A method for regenerating flush water, wherein the flush water used for metal plating is brought into contact with a polyolefin fiber and / or a fiber structure containing polyolefin fiber to remove organic impurities from the wash water used for metal plating.   The polyolefin-based fiber and / or the fiber structure containing the polyolefin-based fiber is provided in at least a part of a circulation tank installed to remove foreign substances contained in the washing water and / or washing water that contains the washing water. The method for regenerating flush water according to claim 7 arranged.   The method for regenerating flush water according to claim 7 or 8, wherein the fiber structure containing the polyolefin fibers contains 50 mass% or more of the polyolefin fibers. The apparent specific gravity of the polyolefin fiber or a fiber structure containing the polyolefin fiber is 0.03 g / cm ³ or more and less than 0.3 g / cm ³ , and the flush water according to any one of claims 7 to 9. Playback method.   The method for regenerating flush water according to any one of claims 7 to 10, wherein the polyolefin fiber or the fiber structure containing the polyolefin fiber has an adhesion amount of oil of 0.1% by mass or less. A plating apparatus used for metal plating,
The plating apparatus is forced from a plating tank for storing a metal plating solution, a foreign matter removing means for removing solids from the metal plating solution, an overflow tank and / or a plating tank for storing a metal plating solution overflowed from the plating tank. And a container for removing organic impurities containing the metal plating solution drawn into
A plating apparatus, wherein at least one selected from the group consisting of the overflow tank and the organic impurity removing container is arranged with a polyolefin fiber and / or a fiber structure containing a polyolefin fiber.   The plating apparatus is configured to apply a metal plating solution from which organic impurities are removed by contact with a polyolefin fiber and / or a fiber structure including a polyolefin fiber disposed in the overflow tank and / or the organic impurity removing container. The plating apparatus of Claim 12 which has a return means to return to a plating tank.   The said plating apparatus is a plating apparatus of Claim 12 or 13 further provided with the washing | cleaning tank which accommodates washing water, and the circulation path installed in order to remove the foreign material contained in washing water.   The plating apparatus according to any one of claims 12 to 14, wherein the fiber structure including the polyolefin-based fiber includes 50% by mass or more of the polyolefin-based fiber. The plating apparatus according to any one of claims 12 to 15, wherein an apparent specific gravity of the polyolefin fiber or a fiber structure including the polyolefin fiber is 0.03 g / cm ³ or more and less than 0.3 g / cm ³ . Recycled material for metal plating used for metal plating,
The recycled material for metal plating is composed of a polyolefin structure and / or a fiber structure containing a polyolefin fiber,
Washing water used for metal plating solution and / or metal plating by removing metal impurities by bringing metal plating solution and / or washing water used for metal plating into contact with the polyolefin fiber and / or fiber structure containing polyolefin fiber. Recycled material for metal plating, characterized by regenerating water.   The recycled material for metal plating according to claim 17, wherein the fiber structure including the polyolefin-based fiber includes 50% by mass or more of the polyolefin-based fiber. The recycled material for metal plating according to claim 17 or 18, wherein an apparent specific gravity of the polyolefin fiber or a fiber structure containing the polyolefin fiber is 0.03 g / cm ³ or more and less than 0.3 g / cm ³ .   The recycled material for metal plating according to any one of claims 17 to 19, wherein the polyolefin fiber or the fiber structure containing the polyolefin fiber has an adhesion amount of oil of 0.1% by mass or less.