JP2011052311A - Electroplating tool and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroplating tool having excellent durability compared to the conventional one. <P>SOLUTION: The electroplating tool has: a wiring member 2 having energizing parts 21, 22 comprising at least one of copper and a copper alloy and electrically connected to a member to be treated and a wiring part 23 for supplying current to the energizing parts 21, 22; a supporting body 1 at least one of which is formed from a metal and which supports the wiring member 2 and a material to be treated and a protective containing film for covering the metal part of the supporting body 1; and the wiring part 2 to have 50-1,000 μm thickness with a tetrafluoroethylene copolymer having 100-220°C melting point. Because the tetrafluoroethylene having excellent stability is used as a coating film, the influence on the electroplating tool due to the plating solution is suppressed. Also, because the tetrafluoroethylene copolymer has 100-220°C melting point, the protective coating film is formed in a melting state to form the excellent protective coating film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electroplating jig excellent in durability and a method for manufacturing the same.

  When applying electroplating such as nickel plating, gold plating, silver plating, copper plating, etc. to the treated member, support / fixing treatment such as sandwiching, placing, hanging, attaching, putting, tightening, entanglement of the treated member A tool (electroplating jig) is required. In general, the electroplating jig not only supports the member to be processed but also supplies current to the member to be processed. In general, the current is supplied to the member to be processed by a wiring member such as an electrode formed of copper or a copper alloy having excellent characteristics. By the way, since the electroplating jig is used by being immersed in a plating bath for performing electroplating, durability becomes a problem.

  Conventionally, an electroplating jig has been aimed at improving durability by forming a film with polyethylene, polyvinyl chloride or the like. However, around the electrodes made of copper and copper alloy, the coating may be damaged and sufficient durability may not be realized due to heat generation or swelling of the coating due to infiltration of the plating solution. It was.

In addition to the metal ions plated by the above plating, the composition of the plating bath includes organic acids such as succinic acid, acetic acid, citric acid and lactic acid as salts, or salts thereof, amine compounds such as ethanolamine and triethanolamine, Boric acid or the like is added, or a salt compound as a conductive agent (halogenated salts (salts such as alkali metals, alkaline earth metals, and aluminum. For example, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, aluminum chloride, etc.) Sulfate, sulfamate, metasulfonate, etc.) are also added, which is a very severe condition. Furthermore, the temperature of the plating bath is as high as 50 to 80 ° C., the current density of 0.1 to 10 A / dm ² and the pH is in the range of 2 to 6, and the heat generation part around the electrode is formed of conventional polyethylene or the like. The coating had a problem with durability. Conventionally known fluororesins such as polytetrafluoroethylene, ETFE, PFA, FEP, etc. are highly durable materials, but these fluororesins are excellent in corrosion resistance, but the processing temperature must be raised to 300 ° C or higher. In other words, copper and copper alloy are oxidized and the adhesion to the coating material is impaired.

International Publication No. 98/58973 Pamphlet

  The present invention has been completed in view of the above circumstances, and provides an electroplating jig having durability superior to that of a conventional electroplating jig coated with polyethylene, polyvinyl chloride, or the like, and a method for manufacturing the same. It is a problem to be solved.

A feature of the electroplating jig according to claim 1 that solves the above-described problem is that the electroplating jig is made of at least one of copper and copper alloy, and supplies current to the energization unit that is electrically connected to the member to be processed. A wiring member having a wiring portion to perform,
A support body that is at least partially formed of metal and supports the wiring member and the member to be processed;
A protective film for covering the metal part of the support and the wiring part so as to have a thickness of 50 μm to 1000 μm with a tetrafluoroethylene copolymer having a melting point in the range of 100 ° C. to 220 ° C .;
It is in having.

  A feature of the electroplating jig according to claim 2 that solves the above-mentioned problem is that, in claim 1, the protective coating is integrated.

The method for producing an electroplating jig according to claim 3 for solving the above-mentioned problem is a method for producing the electroplating jig according to claim 1 or 2,
A fluidizing step of floating the tetrafluoroethylene copolymer powder to form a fluid;
The support member supporting the wiring member, the surface temperature of which is adjusted to be equal to or higher than the melting point of the tetrafluoroethylene copolymer, is immersed in the fluid to form the protective film on the surfaces of the wiring member and the support member. A coating process to
It is in having.

  According to the invention according to claim 1, since this electroplating jig uses a tetrafluoroethylene copolymer excellent in chemical and physical stability as a film, the influence of the plating solution on the electroplating jig. Can be suppressed. Moreover, since this tetrafluoroethylene copolymer has a melting point in the range of 100 ° C. to 220 ° C., it is possible to form a protective coating in a molten state, and an excellent protective coating can be formed. Since especially melting | fusing point is 100 degreeC or more, there exists no possibility of fuse | melting in the plating bath which performs electroplating. Moreover, since melting | fusing point is 220 degrees C or less, it is not necessary to select high temperature conditions when forming a protective film, and there exists no possibility that an oxide film may be formed on the surface of copper or a copper alloy. When copper or a copper alloy is exposed to a high temperature (for example, 250 ° C. or more) in an oxidizing atmosphere such as the air, an oxide film of an insulator that impairs adhesion to the protective film is formed on the surface. In order to suppress the formation of the oxide film, there is a method in which heating is performed in an inert atmosphere such as an oxygen-free state.

  According to the second aspect of the present invention, since the protective coating is integrated, the formation of a gap through which the plating solution enters between the wiring member and the support and the protective coating is reduced, and the durability of the protective coating is improved. There is an advantage of higher.

  According to the invention of claim 3, by forming the fluid, there is an advantage that the surface of the wiring member and the support can be evenly distributed, and the protective film can be uniformly formed. .

It is the schematic of the electroplating jig | tool A used in the Example. It is the schematic of the electroplating jig | tool B used in the Example.

  The electroplating jig and its manufacturing method of the present invention will be described in detail below based on the embodiments. The electroplating jig in the present embodiment is a jig that supplies a current to the member to be processed and supports the member to be processed when electroplating the member to be processed.

(Electroplating jig)
The electroplating jig of this embodiment has a wiring member and a support. A protective film is formed on a part of the surfaces of these members. It does not specifically limit as a formation method of a protective film, Methods, such as the method of this invention mentioned later and general electrostatic powder coating, are mentioned. The wiring member has an energization part and a wiring part. The energization unit is a member that is electrically connected to the member to be processed, and the wiring unit is a member that supplies current to the energization unit. The wiring member is made of at least one of copper and copper alloy. The energization part and the wiring part may be integrated.

  The support is a member that supports the wiring member and the member to be processed. The shape of the support is not particularly limited. The shape of the support can be appropriately formed according to the form of the member to be processed. Examples of the shape of the support include a ladder shape, a rod shape, a plate shape, a net shape, and a shape obtained by combining these shapes. The support is at least partially formed from metal. In addition to forming the support entirely from metal, a part of the support can be formed of metal and the other part can be formed of an appropriate material. For example, a part can be formed from engineering plastics such as PEEK, PEI, and PI.

  A protective film is a film which coat | covers at least one part of the surface of a wiring member and a support body. By covering with a protective film, the surface coated with the wiring member and the support can be blocked from the plating solution, and the influence of the plating solution can be suppressed. The thickness of the protective coating is 50 μm to 1000 μm, preferably 100 μm to 800 μm. By setting it in this range, the formed protective film has no defects such as pinholes and can exhibit a sufficient effect. It is desirable that the protective coating is integrated as a whole.

  The protective coating is formed from a tetrafluoroethylene copolymer. The tetrafluoroethylene copolymer is a copolymer of tetrafluoroethylene and other monomers, and has a melting point of 100 ° C. or higher and 220 ° C. or lower. Among the polymers listed in Patent Document 1, one having a melting point of 100 ° C. or higher and 220 ° C. or lower can be cited as an example. Examples include those sold by Daikin Industries, Ltd. as NEOFRON EFEP (as grades, RP-4020 (melting point 155 to 170 ° C.), RP-4040, RP-5000 (melting point 190 to 200 ° C.)). In particular, when a protective coating is produced by the production method of the method invention described later or by the electrostatic coating method, it is desirable to adopt what is sold as a powder coating. As the powder coating material, any of these grades of NEOFRON EFEP (RP-4020, RP-4040, RP-5000) may be powdered.

From the viewpoint of improving adhesion to the surfaces of the wiring member and the support, it is preferable that carbonate ends are introduced into the ends of the copolymer. The carbonate terminal can be introduced by using peroxycarbonate as a polymerization initiator used when a copolymer is synthesized. As the content of the carbonate terminal, in the infrared absorption spectrum, the height of the absorption peak at 1808 cm ⁻¹ due to the carbonate terminal (1808 cm) with respect to the height of the absorption peak at 2881 cm ⁻¹ due to the CH group of the main chain. ^-1 / it is desirable 2881Cm ^-1) is expressed by 0.7 or more. The height of the absorption peak is obtained by correcting the baseline. A preferable range of this ratio is 0.7 to 5.0, and more preferably 1.0 to 3.0. Specific monomer ratios in the copolymer include 40 to 81 mol% tetrafluoroethylene (TFE), 6 to 43 mol% ethylene (Et), and 10 to 30 mol% hexafluoropropylene (HFP). It is done.

In addition to (or in place of) these monomers, a monomer represented by the formula (1): CH ₂ = CFRf may be used. Here, Rf is a C2-C10 fluoroalkyl group. From the viewpoint of heat resistance of the resulting copolymer, the Rf group is preferably a perfluoroalkyl group, a ω-hydroperfluoroalkyl group, or a ω-chloroperfluoroalkyl group. Among the fluorovinyl compounds represented by the formula (1), from the copolymerizability, the economical efficiency during production of the monomer, and the physical properties of the obtained copolymer, the formula (2): CH ₂ = CF (CF ₂ ) _n A fluorovinyl compound represented by H (wherein n is a number of 2 to 10) is preferable, and a fluorovinyl compound in which n is a number of 3 to 5 is particularly preferable.

  When the fluorovinyl compound of the formula (1) is used as the modifying monomer, the molar ratio of TFE to Et is 40:60 to 90:10, and the content of the fluorovinyl compound is (with respect to the entire copolymer) And 10 to 30 mol% of the HPP content (relative to the whole copolymer). These tetrafluoroethylene copolymers can be produced by a polymerization method employed for the polymerization of ETFE.

  The peroxycarbonate used for introducing the carbonate terminal is represented by formula (a): ROCOOOCOOR ', formula (b): ROCOOOOR', formula (c):

It is desirable to use a compound represented by the formula (d): ROR "OCOOOCOOR" OR '. Here, R and R ′ in the formula are a linear or branched monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a linear or branched chain having 1 to 15 carbon atoms containing an alkoxy group at the end, or A branched monovalent saturated hydrocarbon group, R ″ is a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a straight chain having 1 to 15 carbon atoms containing an alkoxy group at the terminal. Represents a branched or branched divalent saturated hydrocarbon group.

  Among these, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate preferable.

  As the polymerization method, suspension polymerization in an aqueous medium using a fluorinated solvent industrially and using peroxycarbonate as a polymerization initiator is preferable, but other polymerization methods such as solution polymerization, bulk polymerization, etc. Can also be adopted.

Examples of the fluorine-based solvent include hydrochlorofluoroalkanes (for example, CH ₃ CClF ₂ , CH ₃ CCl ₂ FCF ₃ CF ₂ CCl ₂ H, CF ₂ ClCF ₂ CFHCl), chlorofluoroalkanes (for example, CF ₂ ClCFClCF ₂ CF ₃ , CF ₃ CFClCFClCF ₃ ), perfluoroalkanes (eg, perfluorocyclobutane, CF ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ) can be used, and perfluoroalkanes are particularly preferable.

  The amount of the solvent used is preferably 10 to 100% by mass with respect to water from the viewpoint of suspendability and economy.

  The polymerization temperature is not particularly limited, but may be 0 to 100 ° C. In order to avoid a decrease in heat resistance due to ethylene-ethylene chain formation in the copolymer, a low temperature is generally preferred.

The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, polymerization temperature, etc., but the gauge pressure is 0 to 4.9 MPa (0 to 50 kgf / cm ² ). it can.

  In the production of the tetrafluoroethylene copolymer, in order to adjust the molecular weight, conventional chain transfer agents such as hydrocarbons such as isopentane, n-pentane, n-hexane and cyclohexane; alcohols such as methanol and ethanol; Halogenated hydrocarbons such as carbon chloride, chloroform, methylene chloride, and methyl chloride can be used.

(Method for manufacturing electroplating jig)
The manufacturing method of the electroplating jig of this embodiment is a method of manufacturing the electroplating jig of this embodiment described above.

  This manufacturing method has a fluidizing step and a coating step. The wiring member is supported by the support before being subjected to these manufacturing methods. Of the surfaces of the wiring member and the support, it is desirable to roughen the portion where the protective coating is formed in anticipation of the anchor effect. Examples of the roughening method include sandblasting and grid shot processing. Further, masking is performed so that the protective film does not adhere to portions of the surface of the wiring member and the support that do not form the protective film. The masking method is not particularly limited. For example, in forming the protective film, a masking member is attached to the surfaces of the wiring member and the support and peeled off after the protective film is formed. The masking member is made of a material that can exist stably even under the conditions for forming a protective film made of a tetrafluoroethylene copolymer. For example, the masking tape with high heat resistance is masked, and the masking tape is peeled off after the protective film is formed. As a part which does not form a protective film, the part which supplies an electric current to a wiring part other than the electricity supply part which contacts a to-be-processed member directly and energizes is mentioned. Further, it is not always necessary to form a protective film on the surface of a member formed of a material resistant to the plating solution even if it is a support (even if it is formed of a material resistant to the plating solution). A protective film may be formed).

  The fluidizing step is a step of floating the powder of tetrafluoroethylene copolymer to form a fluid. The particle size of the tetrafluoroethylene copolymer powder is not particularly limited, but is preferably 15 μm to 200 μm, and more preferably 20 μm to 80 μm. The powder preferably has an apparent density of 0.3 g / mL to 1.0 g / mL, more preferably 0.4 g / mL to 0.8 g / mL. A fluid can be obtained by supplying a fluid (preferably a gas such as air) to the powder. The degree of fluidization is preferably about 2 to 4 times based on the apparent volume of the powder. During fluidization, in addition to (or instead of) introducing the fluid, the powder can be vibrated. By applying vibration, the fluid can be smoothly formed. As a method for applying vibration, a vibration motor, ultrasonic waves, sound waves, or the like can be used.

  The covering step is a step of immersing the support supporting the wiring member in the fluid. Of the surfaces of the wiring member and the support, at least the portion where the protective film is formed is heated to a temperature equal to or higher than the melting point of the tetrafluoroethylene copolymer. The heating temperature is desirably 250 ° C. or lower. It is because an oxide film will be formed on the surface of copper and a copper alloy if it heats exceeding 250 degreeC. The heating method is not particularly limited. When the wiring member and the support heated to a temperature equal to or higher than the melting point are immersed in the fluid, at least a part of the adhered powder is melted to form a coating. The adhering powder can be melted by heating above its melting point. The formed film is integrated by cooling and solidifying to become a protective film. Of the adhering powder, it is desirable to remove the extra adhering powder or the one not melted and integrated by a method such as blowing off.

  The thickness of the protective coating formed can be controlled by controlling the temperature at which the wiring member and the support are heated, the degree to which the powder is fluidized, the amount of powder, and the like. Increasing the heating temperature increases the degree of powder adhesion, increasing the degree of powder fluidization (fluid volume) decreases the degree of powder adhesion, and increasing the amount of powder increases the powder adhesion. You can increase the degree. Moreover, the thickness of a protective film becomes large by increasing the frequency | count of immersing in a fluid.

  According to the present method of immersing in a fluid, the coating efficiency can be increased by 3 to 5 times and the coating time is shortened to 1 / 1.5-1 to 比 べ as compared with the conventional electrostatic powder coating.

  The electroplating jig of the present invention will be specifically described below based on examples. In the electroplating jig of this example, as shown in FIG. 1, a protective film (not shown) is formed on the surface of a member in which the support 1 and the wiring member 2 are combined (electroplating jig A). . The support 1 includes vertical frames 11 and 12 and horizontal frames 13 to 15 having both ends fixed to the vertical frames 11 and 12 by welding. The horizontal frames 13 to 15 are fixed at intervals in the length direction of the vertical frames 11 and 12. The wiring member 2 has current-carrying parts 21 and 22 and a wiring part 23. The wiring portion 23 is fixed at both ends near the ends of the vertical frames 11 and 12. The energization parts 21 and 22 are welded and fixed to the wiring part 23 at one end. The other ends of the energization parts 21 and 22 are connected to the member to be processed. The electroplating jig is used by being arranged in an arbitrary direction in consideration of the shape of the member to be processed and the shape of the plating tank. As shown in FIG. 2, the horizontal frames 13-15 can be equipped with PEEK fasteners 16 and 17 (electroplating jig B). Two stoppers 16 are disposed on the horizontal frame 13 with a space therebetween, and two stoppers 17 are disposed on the horizontal frame 15 with a space therebetween.

(Test 1)
An electroplating jig A was manufactured. The size of the vertical frames 11 and 12 is 20 mm × 500 mm × 2 mm, the size of the horizontal frames 13 to 15 is 20 mm × 200 mm × 2 mm, and the vertical frames 11 and 12 and the horizontal frames 13 to 15 are made of SUS304. This was done by welding. The size of the wiring part 23 was 20 mm × 200 mm × 2 mm, and the material was copper. The size of the energization parts 21 and 22 was 5 mmφ × 100 mm.

A method for forming a protective film in the electroplating jig A will be described below.
The wiring member and support of the electroplating jig A were degreased with acetone and roughened with sandblasting # 240. Thereafter, the energized portion was masked with a heat-resistant tape and heated in an electric furnace heated to 250 ° C. for 60 minutes. A SUS304 fluid immersion bath of 200 mm × 300 mm × 1200 mm is used, and Daikin Industries, Ltd. Neoflon EFEP RC-4520 (particle size: 25 μm to 50 μm (laser diffraction method)) as a tetrafluoroethylene copolymer powder; A density of 0.45 to 0.95 g / mL (based on JIS K6891); melting point 155 ° C. to 170 ° C. (DSC)) was added at 15 kg. The powder was suspended to a height of 1000 mm while being vibrated by a vibration plate to form a fluid. The heated jig A was inserted into the fluid from the current-carrying parts 21 and 22 side and immersed for 30 seconds. The excess powder was removed with air and again heated in an electric furnace at 250 ° C. for 20 minutes. After heating to 250 ° C., immersion in the fluid for 30 seconds was repeated a total of 4 times. As a result, a protective film having an average film thickness of 550 μm was formed. The powder used was 82 g. The thickness unevenness was ± 50 μm.

(Test 2)
Electroplating jig B was used. The electroplating jig B has the same configuration except that the stoppers 16 and 17 are provided on the wiring member and the support in the electroplating jig A. The stops 16 and 17 are made of PEEK and have a size of 1.5 mmφ × 20 mm. By performing the same operation as in Test Example 1, an electroplating jig B having an average film thickness of 580 μm was obtained. The powder used was 95 g. The thickness unevenness was ± 40 μm.

(Test 3)
An electroplating jig A was manufactured. Electrostatic coating was adopted as a method for forming the protective coating. Heating was performed in the same manner as in Test 1, and then coating was performed with an electrostatic coating machine. A total of nine heating and coating cycles were performed, and finally heated to form a protective coating. As the protective coating, a plating jig A having an average film thickness of 510 μm was obtained. The powder coating used was 145 g. The thickness unevenness was ± 60 μm.

(Test 4)
An electroplating jig A was produced in the same manner as in Test 1 except that the direction of immersion in the fluid was reversed (intrusion from the direction opposite to the energizing portions 21 and 22). The protective film had an average film thickness of 450 μm, the powder used was 70 g, and the thickness unevenness was ± 150 μm.

(Discussion)
As is clear from Tests 1 to 4, when the method for producing a protective coating using the fluid of the present invention is adopted, the number of coatings is less than the conventional method for producing a protective coating using electrostatic coating, and the thickness is increased. The unevenness has also become smaller. That is, the number of processing steps can be greatly reduced, and the thickness of the unevenness of the thickness can be reduced, so that a highly accurate protective coating can be produced.

(An endurance test)
In a plating tank (600 mm × 400 mm × 1200 mm), 250 L of a plating solution prepared to be 300 g / L of nickel sulfate, 55 g / L of nickel chloride, and 40 g / L of boric acid was put, and the temperature was adjusted to 60 ° C. At electroplating jig B created in Test 2 while supporting the member to be processed of 100 dm ^2, it was supplied for 20 minutes current under the condition of 1A / dm ^2. This step was defined as one cycle, and a plating bath was newly prepared every 40 cycles. The plating operation was performed 60 cycles per day, and the appearance of the electroplating jig B was observed. Since the electroplating jig B of Test 2 did not change significantly after 1200 cycles, the test was stopped there. As a comparative test, durability was also examined for an electroplating jig in which a conventional protective film (polyethylene: film thickness 800 μm, vinyl chloride (vinyl chloride): film thickness 1000 μm) was formed instead of the protective film in the electroplating jig B. .

  As is clear from Table 1, it was found that the use of a protective coating formed from a tetrafluoroethylene copolymer showed excellent durability even though the film thickness was thinner than that of a conventional protective coating. It was.

DESCRIPTION OF SYMBOLS 1 ... Support body 11, 12 ... Vertical frame 13-15 ... Horizontal frame 16, 17 ... Stopper 2 ... Wiring member 21, 22 ... Current supply part 23 ... Wiring part

Claims (3)

A wiring member comprising at least one of copper and a copper alloy, and having a current-carrying part electrically connected to the member to be treated and a wiring part for supplying a current to the current-carrying part;
A support body that is at least partially formed of metal and supports the wiring member and the member to be processed;
A protective film for covering the metal part of the support and the wiring part so as to have a thickness of 50 μm to 1000 μm with a tetrafluoroethylene copolymer having a melting point in the range of 100 ° C. to 220 ° C .;
An electroplating jig characterized by comprising:   The electroplating jig according to claim 1, wherein the protective coating is integrated. A method for producing the electroplating jig according to claim 1 or 2,
A fluidizing step of floating the tetrafluoroethylene copolymer powder to form a fluid;
The support member supporting the wiring member, the surface temperature of which is adjusted to be equal to or higher than the melting point of the tetrafluoroethylene copolymer, is immersed in the fluid to form the protective film on the surfaces of the wiring member and the support member. A coating process to
A method for producing an electroplating jig, comprising:

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