JP2010059532A - Method for plating polymer fiber material, and method for producing polymer fiber material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for plating a polymer fiber material by which adhesion can be enhanced. <P>SOLUTION: The method for plating a polymer fiber material includes: a plasma treatment stage (1) where the surface of a polymer fiber material is hydrophilized or activated; a cation treatment stage (2) where the surface of the polymer fiber material is made into a cation; a first Sn-Pd catalyst immersion stage (3) where the polymer fiber material is immersed into a colloidal solution of Pd and Sn; a first accelerator treatment stage (4) where only Pd is adsorbed and coupled to the polymer fiber material; a heat treatment stage (5) where the polymer fiber material is held to 120 to 180°C for a prescribed time; a second Sn-Pd catalyst immersion stage (6) where the polymer fiber material is immersed into a colloidal solution of Pd and Sn; and a second accelerator treatment stage (7) where only Pd is adsorbed into the polymer fiber material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for plating a polymer fiber material and a method for producing a polymer fiber material, and more particularly to an environment-friendly plating technique that improves the adhesion of a plating film and does not use carbon dioxide.

As this type of plating technology, the method for producing metal-plated organic polymer fibers disclosed in Patent Document 1 includes etching aramid fibers and then fixing Pd metal particles to the surface of the aramid fibers via a silane coupling agent. In addition, a technique for plating a metal such as Cu, Ni, Co, etc. is disclosed.
In addition, the method for producing a low thermal expansion linear body disclosed in Patent Document 2 includes a method of plating a polymer fiber material through a process of degreasing treatment → catalip treatment → cataposit treatment → accelerator treatment → chemical copper plating. It is disclosed.

Further, the polymer material plated with a non-patent document 1 disclosed supercritical fluid, metal complexes in the supercritical CO ₂ fluid (e.g., Pt complexes, Ni complexes, Pd complexes) objects to be plated in a state of dissolved By treating (polymer plate) and diffusing the metal complex into the polymer, the metal complex is adsorbed and fixed to the object to be plated, and further, the metal is deposited by heating, and this is plated as the core of plating. Technology is disclosed.

JP2003-171869 JP 2006-85915 Teruo Hori; Plating of polymer materials using supercritical fluid, Surface technology, Vol. 56, p.79 (2005)

However, in the plating technique using the silane coupling agent described in Patent Document 1, there is a problem that the adhesion with the plating object is poor.
Moreover, in the fiber material plating method described in Patent Document 2, the surface of the fiber material is neutralized by degreasing, and the surface of the neutralized fiber material is covered with the Sn—Pd alloy core. However, since the surface of the transition material in the neutralized state and the Sn—Pd alloy core are in a state of attracting each other by van der Waals force, even if chemical copper plating is performed through the subsequent accelerator treatment, There is a problem of poor adhesion to the object to be plated.
Moreover, the plating technique using the supercritical CO ₂ fluid described in Non-Patent Document 1 has a problem of using a large amount of CO ₂ that is a cause of global warming. In addition, there is a problem that the equipment cost for handling the supercritical CO ₂ fluid and the palladium salt to be used are very expensive.

This invention is made | formed in view of the said situation, The objective of this invention is providing the plating method of the polymeric fiber material which can improve adhesiveness, and the manufacturing method of a polymeric fiber material. .
Another object of the present invention is to provide a method for plating an environmentally friendly polymer fiber material and a method for producing the polymer fiber material without using CO ₂ .
A further object of the present invention is to provide a method for plating a polymer fiber material and a method for producing a polymer fiber material, which can be carried out inexpensively.

In order to solve the above problems, a method for plating a polymeric fiber material according to the present invention includes:
A plasma treatment step of hydrophilizing or activating the surface of the polymer fiber material by plasma-treating the polymer fiber material;
A cation treatment step of cationizing the surface of the polymer fiber material A by immersing the polymer fiber material A having undergone the plasma treatment step in a cationic surfactant solution;
A first Sn—Pd catalyst dipping step for adsorbing and binding Pd and Sn to the surface of the polymer fiber material B by immersing the polymer fiber material B that has undergone the cation treatment step in a colloidal solution of Pd and Sn; ,
By immersing the polymer fiber material C that has undergone the first Sn-Pd catalyst immersion step in an acid solution, Sn is dissolved out of Pd and Sn adsorbed and bound in the first Sn-Pd catalyst immersion step, A first accelerator treatment step for adsorbing and binding only Pd to the polymer fiber material C;
A heat treatment step of opening a molecule of the polymer fiber material D and incorporating Pd into the molecule by holding the polymer fiber material D having undergone the first accelerator treatment step at 120 ° C. to 180 ° C. for a predetermined time; ,
By immersing the polymer fiber material E that has undergone the heat treatment step in a colloidal solution of Pd and Sn, the Pd deactivated by the heat treatment step is reactivated, and the Pd and Sn in the colloidal solution are A second Sn—Pd catalyst immersion step for adsorbing to the surface of the polymeric fiber material E;
By immersing the polymer fiber material F that has undergone the second Sn—Pd catalyst immersion step in an acid solution, Sn is dissolved out of Pd and Sn adsorbed in the second Sn—Pd catalyst immersion step, and the polymer And a second accelerator treatment step for adsorbing only Pd on the fiber material F.

The plating method of the polymer fiber material according to the present invention is as follows.
Instead of the second accelerator treatment step, a conductive film is formed on the polymer fiber material F by immersing the polymer fiber material F that has undergone the second Sn-Pd catalyst immersion step in a conductor treatment solution. You may provide the conductor-ized process process to make.

  The plating method of the polymer fiber material according to the present invention may further include a plating step of electroless plating or electroplating the polymer fiber material G that has undergone the second accelerator treatment step or the conductorization treatment step.

  The gist of the method for producing a polymer fiber material according to the present invention is to use the polymer fiber material plating method according to the present invention.

  According to the polymer fiber material plating method of the present invention, the surface of the polymer fiber material (to-be-plated) is hydrophilized or activated in the plasma treatment step. The surface can be cationized. Then, when the first Sn—Pd catalyst immersion step is performed in a state where the surface of the polymer fiber material is cationized, the anion of the Sn—Pd colloid is applied to the surface of the polymer fiber material by van der Waals force and Coulomb force. Firmly adsorbs and binds. The adsorptive power / binding force due to the van der Waals force and Coulomb force is maintained in the subsequent first accelerator treatment. Therefore, when the first accelerator treatment step is performed, Sn melts and only Pd is adsorbed and bonded to the surface of the polymer fiber material by van der Waals force and Coulomb force.

  In the heat treatment step, the molecules of the polymer fiber material are opened and Pd is taken into the molecules in a state in which the adsorption force and the binding force due to the van der Waals force and the Coulomb force are maintained. However, the catalytic activity on the surface of Pd is lost. Next, when the second Sn—Pd catalyst immersion step is performed, the deactivated Pd is reactivated, and the anion of the Sn—Pd colloid is adsorbed on the surface of the polymer fiber material by van der Waals force. . In the subsequent second accelerator treatment or conductorization treatment, the reactivated Pd is strongly adsorbed and bonded to the polymer fiber material by van der Waals force and Coulomb force, and newly adsorbed Sn- Of the Pd colloid, Sn dissolves and only Pd is adsorbed on the surface of the polymeric fiber material.

  Thus, according to the polymer fiber material plating method of the present invention, the strong adsorption force between Pd taken into the molecule of the polymer fiber material by heat treatment and the polymer fiber material (to-be-plated object). -Since it becomes possible to perform electroless plating or electroplating in a state where the bonding force is maintained, there is an effect of improving the adhesion of the plating to the object to be plated. That is, the method for plating a polymeric fiber material according to the present invention includes a plasma treatment step, a cation treatment step, and a heat treatment step, and thus has an effect of improving the adhesion with a plating object.

Since the method for producing a polymer fiber material according to the present invention uses the method for plating a polymer fiber material according to the present invention, the same effect can be obtained.
Furthermore, since the polymer fiber material plating method and manufacturing method according to the present invention does not use carbon dioxide gas, it is environmentally friendly and can be implemented inexpensively without using expensive equipment or raw materials.

Hereinafter, a method for plating a polymeric fiber material according to a first embodiment of the present invention will be described with reference to the drawings.
The plating method of the polymer fiber material according to the first embodiment of the present invention includes (1) a scouring step, (2) a water washing step, (3) a drying step, (4) a plasma treatment step, and (5) in the order of steps. Alkali treatment step, (6) Water washing step, (7) Cation treatment step, (8) Water washing step, (9) First Sn-Pd catalyst immersion step, (10) Water washing step, (11) First accelerator treatment step (12) Washing step, (13) Drying step, (14) Heat treatment step, (15) Second Sn-Pd catalyst immersion step, (16) Washing step, (17) Second accelerator treatment step, (18) It comprises a washing step, (19) a plating step (electroless plating or electroplating), (20) a washing step, and (21) a drying step.
Hereinafter, each step will be described.

(1) Scouring process Scouring process consists of polymer fiber materials (aromatic polyamide (polyparaphenylene terephthalamide), polyester, para-aramid fiber (copolyparaphenylene 3,4'oxydiphenylene terephthalamide), glass fiber, In the process of preventing fibrillation, re-adhesion of oils, dirt, etc. by treating alumina fibers, carbon fibers, and other organic and inorganic polymer fiber materials) with a scouring agent (surfactant for scouring) is there. Examples of the surfactant for scouring include, but are not limited to, NaOH, nonionic surfactants, organic solvents, and the like. The scouring step does not have to be performed when the polymer fiber material does not have an oil agent. Moreover, the glass fiber and the alumina fiber can be used because the wettability is improved by the surface modification effect when the plasma treatment described later is applied to the glass fiber. Furthermore, carbon fiber can be used because, when the plasma treatment described later is applied to the carbon fiber, Ar ions and O ions that are excited and turned into a plasma state strike the surface of the carbon fiber, and the surface of the carbon fiber is cleaned. In addition, the effect of being activated is obtained. Therefore, it contributes to improving the adhesion of the plated object to the object to be plated.

(2) Washing process The washing process is a process of washing the polymer fiber material with water. Thereby, it is the process of removing the excess deposit | attachment to polymer fiber material. Although the washing method is not particularly limited, a method of passing through the flowing water tank can be employed. In addition, this water washing process does not need to be performed when not performing said (1) scouring process.

(3) Drying process A drying process is a process of drying the polymeric fiber material which passed through the said (2) water washing process. The drying method may be hot air drying (60 ° C. to 100 ° C.), but is not limited thereto. For example, warm air drying may be used for skein winding, and drum drying may be used for reel-to-reel. In addition, a drying process does not need to be performed when not performing said (1) scouring process and said (2) water washing process.
According to the scouring process, the water washing process and the drying process, as shown in the surface state diagram of the object to be plated after the scouring / water washing / drying process in FIG. Has been removed. Note that the polymer fiber material free from oil, dust, static electricity, etc. is in the surface state shown in FIG.

(4) Plasma treatment step The plasma treatment step is a step of hydrophilizing or activating the surface of the polymer fiber material by subjecting the polymer fiber material to plasma treatment. That is, in the plasma treatment, a gas (O ₂ , air, Ar, etc.) is excited in a vacuum or at atmospheric pressure using a high frequency power source to form a highly reactive plasma state, and the plasma state gas is converted into an object to be plated. This is a step of hydrophilizing or activating the surface of the polymer fiber material by bringing it into contact with (polymer fiber material).
According to the plasma treatment step, the surface of the polymer fiber material is hydrophilized as shown in the surface state diagram of the object to be plated after the plasma treatment in FIG. In the case of carbon fibers, it is considered that the surface carbon is knocked out and the surface is activated.

In the plasma treatment, for example, a squeezed polymer fiber material is put in a vacuum chamber, the inside of the chamber is evacuated to about 0.001 Torr, and then an O ₂ gas (flow rate: 100 ml / L) is supplied while a high frequency power source (output: 100 W) is used. ) As a trigger, and the polymer fiber material is exposed to an O ₂ plasma atmosphere for a predetermined time. Since the plasma has directionality, the same thing may be repeated by replacing the upper and lower sides. A vacuum chamber or vacuum pump having an optimum size and shape may be used according to the amount of the polymer fiber material to be subjected to plasma treatment.
In the case of performing atmospheric plasma treatment as the plasma treatment, Ar gas and / or O ₂ gas or the like is allowed to flow in the atmosphere (flow rate 15 L / min for Ar gas, 1.5 L / min for O ₂ gas). ), Ar gas and / or O ₂ gas is converted into plasma using a high frequency power source (output: 100 W) as a trigger, and the polymer fiber material is exposed to the atmospheric plasma atmosphere for a predetermined time. Specifically, the skeined fiber having an outer shape of 1 m may be exposed to a plasma atmosphere for about 5 minutes while rotating (6 m / min).

(5) Alkali treatment step The alkali treatment step is a step of removing and washing the polymer fiber material by immersing the polymer fiber material in an alkaline solution. As the alkaline solution, for example, NaOH or KOH can be used.
In the case of carbon fiber, the alkali treatment step may not be performed. This is because argon in the plasma atmosphere also serves as a cleaning function, so that alkali treatment is not necessary, and if the alkaline cleaning solution becomes dirty, the dirt may adhere to the carbon fibers.

(6) Water washing process Although it is the water washing process similar to said (2), detailed water washing conditions do not need to be the same and can be changed suitably. The water washing step may not be performed when the (5) alkali treatment step is not performed.

(7) Cation treatment step The cation treatment step is a step of cationizing the surface of the polymer fiber material by immersing the polymer fiber material in a cationic surfactant solution. Here, the surface of the polymer fiber material can be cationized on the premise that the surface of the polymer fiber material is hydrophilized or activated in the (4) plasma treatment step.
Examples of the cationic surfactant solution include monoalkyl ammonium chloride (45 ° C., 5 minutes, 0.01 to 10%), tetramethyl ammonium chloride (55 ° C., 5 minutes, 0.01 to 10%), and tetrabutyl ammonium. Chloride (50 ° C., 10 minutes, 0.01 to 10%) and polyamide polyamine / epichlorohydrin polymer can be used (see Tables 4 and 5).
According to the cation treatment, the surface of the polymer fiber material is cationized as shown in the surface state diagram of the object to be plated after the cation treatment in FIG.

(8) Washing step Although it is a washing step similar to said (2), detailed washing conditions do not need to be the same and can be changed suitably.

(9) First Sn-Pd catalyst dipping step The first Sn-Pd catalyst dipping step is to immerse the polymer fiber material in a colloidal solution of Pd and Sn, thereby bringing Pd and Sn onto the surface of the polymer fiber material. This is a process of adsorption and bonding. As the colloidal solution of Pd and Sn, those prepared by dissolving tin (II) chloride and palladium (II) with a hydrochloric acid solution, mixing them with stirring, and aging them while heating can be used. .

  According to the first Sn—Pd catalyst immersion step, as shown in the surface state diagram of the object to be plated after the first Sn—Pd catalyst immersion treatment in FIG. 1 (d), the surface of the cationized polymer fiber material In addition, an anion composed of Pd and Sn is adsorbed and bound by van der Waals force (attraction by interaction between molecules) and Coulomb force (interaction of positive and negative charges). The bonding (ionic bonding) is also caused by the Coulomb force because the surface of the polymer fiber material is cationized by cation treatment. And this improves the adhesiveness of the plating performed in the plating process described later. In the heat treatment described later, Pd is taken in between the molecules of the polymer fiber material opened by the heat treatment, but the adsorbing force by the van der Waals force and the binding force by the Coulomb force are maintained. It is because it is taken in.

(10) Rinsing step Although it is a rinsing step similar to (2) above, the detailed rinsing conditions do not have to be the same and can be changed as appropriate.

(11) First accelerator treatment step The first accelerator treatment step dissolves Sn out of Pd and Sn adsorbed in the Sn-Pd catalyst immersion step by immersing the polymer fiber material in an acid solution. This is a step of adsorbing and bonding only Pd to the polymer fiber material. The acid solution is not particularly limited as long as it is an acid that dissolves Sn but does not dissolve Pd, and the concentration, temperature, and treatment time are not particularly limited. Examples of suitable acid solutions include, for example, hydrochloric acid (10%, room temperature, 5 minutes), sulfuric acid (10%, 45 ° C., 5 minutes), hydrofluoric acid (5%, room temperature, 5 minutes), borofluoride Acid (5-10%, room temperature, 5 minutes).

  According to the first accelerator treatment step, van der Waals force on the surface of the polymeric fiber material that has undergone the cationization treatment step, as shown in the surface state diagram of the object to be plated after the accelerator treatment in FIG. In a state where the Coulomb force is maintained, Pd is firmly adsorbed and bonded to the surface of the polymer fiber material by Van der Waals force and Coulomb force. The reason why Pd is bonded (ionic bond) by Coulomb force is that the surface of the polymer fiber material is cationized by cation treatment. And this improves the adhesiveness of the plating performed in the plating process described later. In the heat treatment described later, the adhesion is improved by the fact that Pd is taken in between the molecules of the polymer fiber material opened by the heat treatment, but the adsorption force by the van der Waals force and the ion binding force by the Coulomb force are maintained. It is because it is taken in.

(12) Washing step Although the washing step is the same as (2) above, the detailed washing conditions do not have to be the same and can be changed as appropriate.

(13) Drying step The drying step is a step of drying the polymer fiber material that has undergone the water washing step. The drying method may be hot air drying, but is not limited thereto. In the case of skein winding, hot air drying may be used, and in the case of reel-to-reel, drum drying may be used. Furthermore, natural drying can also be employed.

(14) Heat treatment step In the heat treatment step, the polymer fiber material is preferably 120 ° C to 220 ° C (in the case of organic polymer fiber material, 120 ° C to 180 ° C, and in the case of inorganic polymer fiber material, 140 ° C to 220 ° C is preferable. (Which is not particularly limited) is a step of opening the molecules of the polymer fiber material and holding Pd (which becomes the core of the plating) therein by holding for a predetermined time. What is necessary is just to select the temperature to hold | maintain suitably between 120 to 180 degreeC according to the kind of polymer fiber material. For example, in the case of aromatic polyamide (polyparaphenylene terephthalamide), 120 ° C to 170 ° C is particularly preferable, and in the case of polyester, 100 ° C to 140 ° C (30 minutes to 90 minutes in an electric furnace (atmosphere furnace)) is particularly preferable. In the case of para-type aramid fiber (copolyparaphenylene, 3,4'oxydiphenylene terephthalamide), 140 ° C to 170 ° C (30 minutes to 90 minutes in an electric furnace (atmosphere furnace)) is particularly preferable, and in the case of carbon fiber 50 ° C to 300 ° C, particularly preferably 150 ° C to 250 ° C, and the time is preferably 30 minutes to 60 minutes.

  According to the heat treatment step, as shown in the surface state diagram of the object to be plated during and after the heat treatment in FIG. 1 (f), the surface of the polymeric fiber material that has undergone the cationization treatment step and the Pd adsorbed and bonded thereto. While the van der Waals force and Coulomb force are maintained, the surface of the polymeric fiber material is opened and Pd enters there. Therefore, compared to the case where the heat treatment is performed in a state where both van der Waals force and Coulomb force do not exist, Pd which is the core of plating in this embodiment is between the molecules of the polymer fiber material. It enters in the state where adsorption force / bonding force exists. And when heat processing is complete | finished, temperature falls and the open molecule | numerator of polymeric fiber material closes. Then, Pd is a polymer fiber in a state where van der Waals force and Coulomb force between Pd and the polymer fiber material are maintained, that is, in a state where the adhesion of the plating is improved when plating is applied. It is incorporated into the molecule of the material. Therefore, the adhesion of the plating applied by the plating process described later is improved. In addition, since the catalytic activity of Pd is lost when Pd is oxidized in the heat treatment process, the reactivation process (second Sn—Pd catalyst immersion process) described below is performed.

(15) Second Sn—Pd catalyst immersion step The second Sn—Pd catalyst immersion step is the same step as the above (9) first Sn—Pd catalyst immersion step, but the detailed conditions are the first Sn— It is not necessary to make it the same as the conditions of a Pd catalyst immersion process, and can change suitably.
According to the second Sn—Pd catalyst immersion step, as shown in the surface state diagram of the object to be plated after the second Sn—Pd catalyst immersion treatment in FIG. Pd) taken into the molecular fiber material is reactivated, and an anion composed of Pd and Sn is adsorbed on the surface of the polymer fiber material by van der Waals force.

(16) Water washing step Although the water washing step is the same as (2) above, the detailed water washing conditions do not have to be the same and can be changed as appropriate.

(17) Second accelerator processing step The second accelerator processing step is the same step as the above (11) first accelerator processing step, but the detailed conditions are the same as the conditions of the first accelerator processing step. There is no need to change it, and it can be changed appropriately.
According to the second accelerator treatment step, Pd is adsorbed on the surface of the polymer fiber material by van der Waals force as shown in the surface state diagram of the object to be plated after the accelerator treatment in FIG. Further, Pd whose catalytic activity has been lost by the heat treatment process is reactivated. The reactivated Pd is adsorbed and bonded by the polymer fiber material, van der Waals force and coulomb force. Therefore, the adhesion of the plating applied by the plating process described later is improved.

(18) Washing step Although the washing step is the same as the above (2), the detailed washing conditions do not have to be the same and can be appropriately changed.

(19) Plating process (electroless plating or electroplating)
The plating step is a step of forming a metal film on the polymer fiber material by electroless plating or electroplating the polymer fiber material.
According to the plating process, as shown in the surface state diagram of the object to be plated after electroless or electroplating treatment in FIG. 1 (i), the intermolecular molecules of the polymer fiber material are made by van der Waals force and / or coulomb force. A plating film is formed on Pd adsorbed and bonded to the surface. In particular, Pd that has entered between molecules of the polymer fiber material is firmly fixed to the polymer fiber material by van der Waals force and Coulomb force. Therefore, when a plating film is formed with this Pd as a nucleus, Improves plating adhesion. Therefore, compared with the thing which is not made | formed by the said (7) cation treatment process and the said (14) heat processing process, a plating film with favorable adhesiveness is obtained.

Here, in electroless plating, metal ions contained in the plating solution are reduced by electrons released when the reducing agent contained in the plating solution is oxidized on the Pd surface having high catalytic activity, and the metal is converted into a metal. This is a method of depositing on the object to be plated as a film. A film with a uniform thickness can be obtained regardless of the shape and type of the material.
Examples of electroless plating that can be used in the present embodiment include electroless copper plating, electroless nickel plating, and electroless silver plating, but are not particularly limited (see Tables 4 and 5).

Electroplating is a method in which a metal ion contained in a plating solution is reduced on a Pd surface having a high catalytic activity by using an object to be plated as an electrode, and the metal is deposited on the object as a metal film. is there.
Examples of the electroplating that can be used in the present embodiment include, but are not particularly limited to, electrocopper plating, electronickel plating, electrosilver plating, electrogold plating, and electroplating Sn (see Tables 4 and 5). .

(20) Rinsing step Although it is a rinsing step similar to (2) above, the detailed rinsing conditions do not have to be the same and can be changed as appropriate.

(21) Drying step The drying step is a step of drying the polymer fiber material that has undergone the water washing step. The drying method may be hot air drying, but is not limited thereto. In the case of skein winding, hot air drying may be used, and in the case of reel-to-reel, drum drying may be used. Furthermore, centrifugal drying and vacuum drying may be employed.

  By performing the steps (1) to (21) according to the first embodiment described above, a plated polymer fiber material can be obtained.

Next, a method for plating a polymeric fiber material according to the second embodiment of the present invention will be described.
The plating method of the polymer fiber material according to the second embodiment of the present invention includes (1) a scouring step, (2) a water washing step, (3) a drying step, (4) a plasma treatment step, and (5) in the order of steps. Alkali treatment step, (6) Water washing step, (7) Cation treatment step, (8) Water washing step, (9) First Sn-Pd catalyst immersion step, (10) Water washing step, (11) First accelerator treatment step (12) Washing step, (13) Drying step, (14) Heat treatment step, (15) Second Sn-Pd catalyst immersion step, (16) Washing step, (17) Conducting treatment step, (18) Washing step (19) A plating step (electroless plating or electroplating), (20) a washing step, and (21) a drying step. That is, the method for plating a polymer fiber material according to the second embodiment of the present invention is to perform a conductor treatment process instead of the second accelerator treatment process of the first embodiment. Except for this, since it is the same as that of the first embodiment (however, only electroplating is used as the plating method), the following describes the conductorization process.

(17) The conductor treatment step is a step of making the polymer fiber material a conductor by immersing the polymer fiber material in a conductor treatment solution to form a conductive film on the polymer fiber material. is there.
Examples of the conductive film formed in the present embodiment include a copper film (see the left side of FIG. 2 (h)) and a palladium sulfide film (see the right side of FIG. 2 (h)), but are not particularly limited.
According to the conductor treatment process, as shown in the surface state diagram of the object to be plated after the conductor treatment in FIG. 2 (h), Pd is adsorbed and bonded between the molecules of the polymer fiber material and on the surface. A conductive film (copper film or palladium sulfide film) is formed thereon. The conductive film is formed in a state where Pd reactivated by the (15) second Sn—Pd catalyst immersion step is adsorbed and bonded by the polymer fiber material, van der Waals force and Coulomb force. Therefore, the adhesion of the plating applied by the plating process described later is not impaired.

  In addition, when attaching copper or palladium sulfide thinly as an electroconductive film, the conductor treatment liquid of Table 4 or Table 5 can be used. A thin copper film or palladium sulfide film is formed on the polymer fiber material by immersing the polymer fiber material (to-be-plated object) in these conductor treatment solutions (conductor treatment).

Hereinafter, since the plating method according to the present embodiment was performed using various polymer fibers, it will be described.
(Plating treatment)
Tables 1 to 4 collectively show the polymer fibers used in the examples and comparative examples, the steps performed, and the results of the tape test. Moreover, the processing liquid used by each process shown in Table 1-Table 4 is put together in Table 5 and Table 6, and is shown.

Examples 1 to 5 shown in Table 1 and Table 3 use the polymer fibers described in each table as an object to be plated, and about Examples 1 to 4, Steps 1 to 21 and Example 5 shown in Table 1 Steps 4 to 21 shown in Table 3, that is, a scouring step → a water washing step → a drying step (for Example 5, a scouring step → a water washing step → no drying step) → a plasma treatment step → an alkali treatment step → a water washing step → a cation Treatment step → Washing step → First Sn—Pd catalyst soaking step → Washing step → First accelerator treatment step → Water washing step → Drying step → Heat treatment step → Second Sn—Pd catalyst soaking step → Water washing step → Second accelerator The treatment process (Examples 3 to 4 are conductorization treatment instead of the second accelerator treatment) → water washing step → plating step → water washing step → drying step.
Comparative Examples 1 to 5 shown in Tables 2 and 3 are the same as those of Examples 1 to 5 except that the plasma process or the heat treatment process was not performed (Comparative Examples 1-a to 1-a). 5-a is without the plasma treatment step, and Comparative Examples 1-b to 5-b are those without the heat treatment step). In the plasma treatments in Tables 1 to 3, 5 minutes × 2 means that the same thing was repeated twice with the up and down directions of the polymer fibers reversed.
Examples 6 to 7 shown in Table 4 use the carbon fiber described in the same table as an object to be plated, and are Step 4, Step 7 to 21, ie, plasma treatment step → cation treatment step → water washing step → first Sn— Pd catalyst soaking process → water washing process → first accelerator treatment process → water washing process → drying process → heat treatment process → second Sn—Pd catalyst soaking process → water washing process → second accelerator treatment process (Example 7 is the second Conductor treatment instead of accelerator treatment) → water washing step → plating step → water washing step → drying step.
Comparative Examples 6-a to 7-b shown in Table 4 are the same as those of Examples 6 to 7 except that the plasma process or the heat treatment process was not performed (Comparative Example 6-a). ˜7-a is without the plasma treatment step, and Comparative Examples 6-b to 7-b are those without the heat treatment step).

  In Examples and Comparative Examples, the pretreatment (step 1 to step 20) and electroless plating (step 21) of the object to be plated are made of PVC using the pretreatment tank 1 or the electroless plating tank 2 shown in FIG. The object 5 is wound around the rollers 3 and 4 and the object 5 is immersed for a predetermined time at a predetermined temperature while winding the object 5 as necessary (the entire PVC rollers 3 and 4 are all in the liquid. Dipped in). Conditions in each step are as shown in Tables 1 to 3. The slit 6 is a slit for moving the PVC rollers 3 and 4 up and down.

  On the other hand, the electroplating (step 21) of the object to be plated was performed using the electroplating tank 7 shown in FIG. In the electroplating tank 7, anode plates 8 and 9 (copper plate in the case of copper plating, silver plate in the case of silver plating) are provided so as to be immersed in the plating solution, and the anode plates 8 and 9 are rectifiers (not shown). ) To the positive terminal with a lead wire (copper wire). The SUS (made of SUS304) power supply roller 10 has a gear head 11 and a motor 12 attached thereto, and the SUS power supply roller 10 is connected to a negative terminal of a rectifier (not shown) by a lead wire (copper wire). And the to-be-plated object 5 is wound around the PVC roller 4 and the SUS power supply roller 10, and the to-be-plated object 5 is immersed at a predetermined temperature for a predetermined time while winding the to-be-plated object (PVC roller 4). Electroplating was performed by immersing only in the solution) and energizing. Conditions in each step are as shown in Tables 1 to 3.

(Tape test)
A commercially available cellophane tape was affixed to the polymer fiber with plating obtained in Examples and Comparative Examples, and the cellophane tape was peeled off. In Examples 1 to 5, no metal adhered to the cellophane tape, but in Comparative Examples 1-a to 5-b, all or part of the plating was peeled off, and the metal was adhered to the cellophane tape. In particular, Examples 1 to 5 and Comparative Examples 1-a to 5-b differ only in the presence or absence of the plasma treatment step or the heat treatment step, but such a result is obtained by the presence or absence of any of these steps. It was. Therefore, it has been found that performing both the plasma treatment step and the heat treatment step has a great effect in improving the adhesion to the plating object.
In Examples 6 to 7 and Comparative Examples 6-a to 6-b and 7-b, no metal adhered to the cellophane tape, but in Comparative Example 7-a, the plating partially peeled off, and the cellophane tape. There was metal adhesion. From these, in the case of carbon fiber, in the comparison between Example 6 and Comparative Examples 6-a to 6-b, the clear effect by performing both the plasma treatment step and the heat treatment step was not remarkable, From the comparison between Example 7 and Comparative Examples 7-a to 7-b, it was confirmed that the plasma treatment in particular has the effect of improving the adhesion to the plating object.

(Other)
When plasma treatment was performed using alumina fibers, it was confirmed that water wettability was remarkably improved. Thus, when plating was performed in the same procedure as in each example using alumina fibers as the object to be plated, it was found that a plating film having excellent adhesion could be obtained.
From the above, it was confirmed that the present invention can be applied to a polymer fiber material.

  Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. In the said embodiment, although the example which does not perform a cation treatment before performing a 2nd Sn-Pd catalyst immersion process was shown, you may perform a cation treatment before performing a 2nd Sn-Pd catalyst immersion process. Thereby, the adhesiveness with the to-be-plated thing of plating can be improved further.

  The polymer fiber material plating method and the polymer fiber material manufacturing method according to the present invention improve the adhesion of the plating and are environmentally friendly because carbon dioxide is not used, and are inexpensive because expensive equipment and raw materials are not used. Can be implemented. Therefore, the polymer fiber material plating method and the polymer fiber material production method according to the present invention have high industrial utility value in manufacturers of polymer fiber materials and other various industries.

It is the figure which showed typically the surface state of the to-be-plated object at the time of implementing the plating method of the polymeric fiber material which concerns on 1st embodiment of this invention. It is the figure (figure which showed the part different from FIG. 1) which showed typically the surface state of the to-be-plated object at the time of implementing the plating method of the polymeric fiber material which concerns on 2nd embodiment of this invention. In an Example and a comparative example, it is the schematic for demonstrating the condition which processes a to-be-plated object by a pre-processing tank or an electroless-plating tank (the left side is a schematic side view, the right side is a schematic front view). In an Example and a comparative example, it is the schematic for demonstrating the condition which processes a to-be-plated object with an electroplating tank (the left side is a schematic side view, the right side is a schematic front view).

Claims (4)

A plasma processing step of plasma processing a polymer fiber material;
A cation treatment step of immersing the polymer fiber material A that has undergone the plasma treatment step in a cationic surfactant solution;
A first Sn—Pd catalyst immersion step of immersing the polymer fiber material B that has undergone the cation treatment step in a colloidal solution of Pd and Sn;
A first accelerator treatment step of immersing the polymer fiber material C that has undergone the first Sn-Pd catalyst immersion step in an acid solution;
A heat treatment step of maintaining the polymer fiber material D that has undergone the first accelerator treatment step at 120 ° C. to 180 ° C. for a predetermined time;
A second Sn—Pd catalyst immersion step of immersing the polymer fiber material E that has undergone the heat treatment step in a colloidal solution of Pd and Sn;
And a second accelerator treatment step of immersing the polymer fiber material F that has undergone the second Sn—Pd catalyst immersion step in an acid solution.   2. A conductorization treatment step of immersing the polymer fiber material F that has undergone the second Sn—Pd catalyst immersion step in a conductorization treatment liquid, instead of the second accelerator treatment step. The plating method of polymeric fiber material as described in 2.   The polymer according to claim 1, further comprising a plating step of electroless plating or electroplating the polymer fiber material G that has undergone the second accelerator treatment step or the conductorization treatment step. Method for plating fiber material.   A method for producing a polymer fiber material, wherein the method for plating a polymer fiber material according to any one of claims 1 to 3 is used.

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