JPS60258494A - Electrically conductive high-molecular material - Google Patents

Abstract

PURPOSE:To obtain a high molecular material having high electric conductivity by bonding copper sulfide to the surface of a high molecular material and depositing an electrically conductive metal through the copper sulfide. CONSTITUTION:About 1-5wt% (expressed in terms of metallic copper) copper sulfide is bonded to the surface of a high molecular material having at least one kind of active group bonding to a copper ion such as cyano, mercapto or thiocarboxy, and an electrically conductive metal is deposited by electroplating through the copper sulfide. Ni, Cu, Co, Pb, Zn, Sn or the like are used as the electrically conductive metal and deposited by about 10-80wt% of the amount of the high molecular material. The specific resistance of the high molecular material having bonded copper sulfide is reduced from 1-0.1OMEGA.cm to about 10<-3>-10<-5>OMEGA.cm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a polymeric material having a conductive layer on its surface.

[Prior art]

Conventionally, conductive materials in which copper sulfide is bonded to a polymeric material are known. In this case, copper sulfide is formed on the polymer material by first bonding monovalent copper ions through active groups such as cyano groups contained in the polymer material, and then reacting the copper ion (1) with a sulfurizing agent. This is done by methods such as In the case of such conductive materials bonded with copper sulfide, unlike those in which a metal film is formed on the surface by ordinary chemical plating, the copper sulfide is bonded through active groups, so its There is a limit to the conductivity of a polymer material, and in general, the conductivity of the obtained conductive material is limited to about 10-1 to 10-2 Ω·cm in terms of specific resistance.

〔the purpose〕

An object of the present invention is to improve the conductivity of a conductive polymer material bonded with copper sulfide.

〔composition〕

According to the present invention, there is provided a conductive polymer material in which a conductive metal is adhered to a polymer material having sulfide steel bonded to its surface by electrolytic plating via the copper sulfide. provided.

The present invention is characterized in that, in order to increase the conductivity of a polymeric material having copper sulfide bonded to its surface, a conductive metal is attached to the surface of the polymeric material through the copper sulfide by electrolytic plating. do. In this case, the sulfide steel acts as a base for attaching a conductive metal during electrolytic plating, and the attached metal is formed as a highly continuous film on the surface of the polymer containing copper sulfide. The result is a polymeric material with increased electrical conductivity. In the case of the present invention, the amount of sulfide steel to be bonded to the polymeric material is typically 1 to 5% by weight based on the polymeric material, and even the presence of such a small amount of copper sulfide is sufficient as a base for electrolytic plating. It is possible to attach a conductive metal to the surface of the polymer material by electrolytic plating. Of course, in the absence of copper sulfide, metal deposition by electrolytic plating is not possible.

The polymer material used as the base material for bonding sulfurized steel in the present invention includes cyan group (-CN), mercapto group (-5
H), a thiocarbonyl group CC=S), and at least one active group capable of binding copper ions, such as a quaternary organic ammonium base represented by the following formula.

Silence (In the formula, R1, R2, and R3 are alkyl and aryl.

The polymeric material having such an active group can be obtained as follows.

(1) Cyano group-containing polymer material: Manufactured by polymerizing or copolymerizing acrylonitrile.

(2) Polymer materials with mercapto groups: (a) Use vinyl chloride resin or fiber as a base material, heat it in the presence of chlorosulfuric acid to introduce sulfonyl groups, and then perform hydrogen reduction treatment to convert mercapto groups into How to convert to base. In this case, examples of the vinyl chloride resin or fiber base material include polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/maleic acid copolymer, and vinyl chloride/vinyl acetate copolymer. Ethylene copolymer.

Examples include vinyl chloride/acrylic acid (or acrylic ester) copolymer.

(b) A method in which a polymeric material having a hydroxyl group (-on) or an amino group (NO3) is used as a base material, and a compound having a mercapto group and a reactive group capable of reacting with a hydroxyl group or an amino group is reacted with the polymer material. . Examples of mercapto group-containing reactive compounds include mercaptoacetic acid, mercaptopropionic acid, thiosalicylic acid, thiomalic acid, and dimercaptoadipic acid, as well as bromopropyl mercaptan, bromothiophenol, iodothiophenol, mercaptoacetaldehyde, mercaptopropionaldehyde, Examples include methoxyethyl mercaptan, hydroxypropyl mercaptan, and mercaptoacetone. Further, in place of the mercapto group, the above compound may contain a group that forms mercapto by reacting with water or the like, such as a thioester group, a disulfide group, an episulfide group, etc.

On the other hand, polymeric materials having hydroxyl groups include various celluloses, polyvinyl alcohol resins and fibers, as well as voriclar fibers, and polymeric materials having amino groups include polyamide resins and fibers.

(c) A method of introducing a mercapto group by using a polymeric material having a cystine bond (-S-S-) as a base material and subjecting it to a heating reaction with mercaptocarboxylic acid.

In this case, examples of the polymeric material include those containing proteins such as wool.

(3) Polymer material with thiocarbonyl groups = (a) A polymer material containing amino groups and hydroxyl groups, such as animal fiber, is used as a base material, and thioisocyanate is reacted with it to remove the amino groups contained therein. A method of introducing a thiocarbonyl group via a hydroxyl group.

(b) A polymer material containing amino groups and hydroxyl groups such as animal fiber is used as a base material, and carbon disulfide is reacted with this material in the presence of methanol to form a thiophyl group through the amino groups and hydroxyl groups contained therein. A method of introducing a carbonyl group.

(4) Polymer material having a quaternary organic ammonium base: (a) A polymer material having a hydroxyl group or an amino group is reacted with a reactive group that can react with a hydroxyl group or an amino group with a compound having a quaternary organic ammonium base. How to do it.

In this case, examples of reactive groups that can react with hydroxyl groups and amino groups include the following.

(dichloropyrimidine-containing residue) Q CΩ (dichlorotriazine-containing residue) (TV), SO2CHz CH20S○3H (sulfate ethyl sulfone-containing residue) (difluoromonochloropyrimidine-containing residue) (monochloromethoxytriazine-containing residue) ( ■) -8o 2NH-CH2-CH
2-OSO3H (sulfate ethylene sulfonamide-containing residue) (monochlorotriazine-containing residue) (4,5-dichlorotriazine-containing residue) (X) -N
HC○-CH=CHZ (acrylamide-containing residue) αI) S i (OR) 3 (R=alkyl group) (
trialkoxysilicon-containing residue) The polymeric material used as the base material in the present invention may have a quaternary organic ammonium base, a mercapto group, a thiocarbonyl group, a cyanide group, or other copper ion-binding active group. It should be noted that the invention is not limited to those obtained as described above, but can be produced by various conventionally known methods. In the case of the present invention, active groups such as quaternary organic ammonium bases, cyan groups, mercapto groups, and thiocarbonyl groups contained in the polymeric material are sulfur atoms (S) in the polymeric material.
Alternatively, it is preferable to set the proportion to at least 0.3% by weight or more, preferably 0.5 to 10% by weight in terms of nitrogen atoms (N). Further, the polymeric material of the present invention can be applied in various forms such as powder, fiber, film, pellet, plate-like material, etc.

In the present invention, sulfide steel is bonded to the polymeric material having the above-mentioned active groups via the active groups. In this case, the amount of copper sulfide to be bonded to the polymeric material is
There are no particular restrictions, but in general, it is usually 0.
The amount is about 5 to 20% by weight, but in the case of the present invention, when considered as a base in the subsequent plating process, a small amount of about 1 to 5% by weight is sufficient.

There are various methods for bonding copper sulfide to the polymer material, but the first method is to first bond monovalent copper ions to the polymer material, and then bond the copper sulfide to the polymer material. There is a method of reacting copper ions (1) with a sulfiding agent to form copper sulfide. In this case, the monovalent copper ions can be bonded by bringing the polymer material into contact with a solution containing monovalent copper ions or a solution containing divalent copper ions and a reducing agent. Examples of copper compounds that give monovalent copper ions include cuprous salts such as cuprous chloride and cuprous bromide, and examples of copper compounds that give divalent ions include cupric chloride and cupric bromide. There are cupric salts such as copper, cupric sulfate, and cupric acetate.

Further, the reducing agent used in combination with divalent copper ions may be any one that can convert divalent copper ions into monovalent copper ions, such as metallic copper, ferrous sulfate, sodium hypophosphite, hydroxyl Amines and the like are used in sufficient amounts to convert divalent ions to monovalent ions. Various sulfur compounds capable of releasing sulfur atoms and sulfur ions are used as the sulfurizing agent, such as sodium sulfide, dithionite, sodium dithionite, mono-lithium thiosulfate, sulfite, sodium bisulfite, and pyrochloride. Examples include sodium sulfite, Rongalit C, Rongalit Z, hydrogen sulfide, thiourea, and thioacetamide. The amount of the sulfurizing agent to be used is not particularly limited, as long as it is sufficient to convert copper ions bonded to the polymeric material into copper sulfide. In addition, in the step (first step) of bonding the monovalent copper ions, the temperature is at room temperature or heated, preferably 80 to 10°C.
Reaction conditions of about 30 minutes to 120 minutes were adopted, and on the other hand,
In the monovalent copper ion sulfurization step, the treated product obtained in the first step is sufficiently washed and then heated to room temperature or heated, preferably at 80℃.
Reaction conditions of about 30 minutes to 120 minutes at ~110°C are employed.

The concentration of copper ions in the solution used in the first step is usually 1 to 30 g/Q, preferably 2 to 10 g in terms of metal.
It is IQ.

Further, as a second method, there is a method in which a solution containing monovalent copper ions and a sulfurizing agent or a solution containing divalent copper ions, a reducing agent, and a sulfurizing agent is brought into contact with the polymer material. In this case, specific examples of the compound that generates monovalent copper ions, the compound that generates divalent copper ions, the reducing agent, and the sulfurizing agent include those mentioned above.

The copper ion concentration in the solution is usually 1 to 30 g/Q.
Preferably it is 2 to 10 g/Q, and the concentration of the sulfurizing agent is
1 to 40, IQ, preferably 2 to 20 g/II. The reaction temperature is room temperature to elevated temperature, preferably 30 to 80°C.
It is.

Furthermore, as another method, the sulfurizing agent, preferably hydrogen sulfide, is adsorbed on the polymeric material in advance, and monovalent copper ions are bonded to this in the same manner as in the first method to form copper sulfide. Bye.

In the present invention, a metal component selected from silver, gold, and platinum metals is used together with copper sulfide in order to stabilize the binding of copper sulfide to the polymer material and improve the wash resistance and moisture resistance of the product. Preferably, they are combined. In this case, platinum metals include ruthenium, rhodium, palladium, osmium, iridium and platinum. Such an auxiliary metal component used as an auxiliary component for copper sulfide may be used in a very small amount compared to the bond amount of copper sulfide, and is usually 0.0005 to 10 in terms of metal amount to the polymer material. % by weight, preferably 0.005 to 5% by weight, and the proportion to copper sulfide is usually 0.0001 to 0.5, preferably 0.0001 to 0.5, expressed as the atomic molar ratio M/Cu (M: auxiliary metal). , approximately 0.001 to 0.3.

The auxiliary metal component may be added to the polymeric material by contacting the polymeric material to which the copper sulfide obtained above is bonded using a solution containing auxiliary metal ions. In this case, examples of compounds that provide auxiliary metal ions include inorganic acid salts such as sulfates and nitrates, organic acid salts such as acetates and benzoates, and various complex salts such as rhodan salts and thiosulfate complexes. can be mentioned. The concentration of the auxiliary metal compound in the solution is not particularly limited, but is usually 0.005 to 10
g/Q, preferably 0.01 to 6 g/μ. When processing a copper sulfide-containing polymer material by immersing it in a solution,
The bath ratio for the polymer material is 5 to 50 parts by weight of the solution to 1 part by weight of the polymer material, preferably JO ~ 300 to 30 parts by weight.
Weight part treatment temperature is room temperature to 110°C, preferably 30 to 8°C
The temperature is 0°C, and the treatment time is 0.5 to 20 hours, preferably 1 to 10 hours.

As described above, simply by bringing a solution containing auxiliary metal ions into contact with a polymer material bonded to sulfide steel, the stability of the sulfide bond to the polymer can be increased, resulting in improved wash resistance, moisture resistance, etc. A product can be obtained, and during this treatment, a reducing sulfur compound can be used in combination, if necessary, thereby further increasing the bonding stability of copper sulfide. The sulfur compound in this case may be one that has a reducing effect, such as sodium sulfide (Na2S), hydrogen sulfide (H2S), sulfur dioxide (
SO2), sodium bisulfite (NaH303), sodium thiosulfate (Na2S205), sulfite (H2S
O3) Sodium dihedral sulfate (Na2S205), sodium dihionite (Na2SzO4), diphthionite (
H2S204), Rongalite (an adduct of dithionite and formalin), or a mixture of the above. When using a gaseous sulfur compound such as hydrogen sulfide or sulfur dioxide, it is preferable to carry out the process under pressure or to continuously blow the gaseous sulfur compound into the solution in order to increase the solubility in the solution. The amount of the sulfur compound added is usually 0.2 to 5 mol per mol of the auxiliary metal compound in the solution.
mol, preferably in the range of 0.4 to 3 mol. The use of this sulfur compound promotes and stabilizes the bonding of the auxiliary metal component onto the copper sulfide bonded polymeric material, and also exhibits the effect of improving electrical conductivity. When the reducing sulfur compound is used in combination, treatment with a solution containing auxiliary metal ions can be performed in the presence of the sulfur compound, and treatment with the sulfur compound can be performed after the treatment with the solution.

In the second embodiment, the auxiliary metal component is bonded to the polymeric material to which copper sulfide has been bonded in advance. In this case, the auxiliary metal component may coexist with the copper ion.

In the present invention, a conductive metal is attached to the above-described polymeric material to which copper sulfide is bonded via the copper sulfide. In this case, the conductive metal can be deposited by a conventional electrolytic plating method. That is, a polymer material to which copper sulfide is bonded is used as a cathode, and electricity is passed between the cathode and anode in an electrolytic bath containing the required metal ions. The metal for electrolytic plating may be any conductive metal, such as nickel, copper, cobalt, button, zinc, tin, etc.

In the present invention, the conductive metal is deposited in an amount of 10 to 80% by weight, preferably 15 to 50% by weight, based on the polymer material. By this electrolytic plating treatment, the specific resistance is 1 to 0.
1Ω・cm copper sulfide bonded polymer material with a specific resistance of 10-3
It can be improved to 10-SΩ·Cm.

〔effect〕

The present invention has the above configuration, and according to the present invention, by simply bonding about 1 to 5% by weight of copper sulfide to a polymer material, a highly conductive metal is attached to the surface of the polymer material. can be done. In the case of the present invention, high conductivity can be imparted to the polymer material by electrolytic plating simply by incorporating a small amount of sulfurized steel into the polymer material, so its practical value is great.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Acrylic long fiber as a sample (Silparon, Mitsubishi Kasei ■
Copper sulfate 10%, sodium thiosulfate 6.
5%, acidic sodium sulfite 3%, acetic acid 5%, sodium acetate 5
% in a bath at a bath ratio of 1:20 at 60°C for 1 hour. By this treatment, fibers having a specific resistance of 5.2×10 −1 Ω·cm and binding 3% by weight of copper sulfide were obtained.

Next, this copper sulfide bonded fiber was mixed with 200 g of nickel sulfate/
By performing electrolytic plating treatment for 20 minutes at 60°C and a current density of 8A/drrf in a bath containing Q, boric acid 40g/Q, and citric acid 40g/Q, the nickel-plated specific resistance 1. A conductive fiber of 8×10′Ω·cm was obtained.

Example 2 The same copper sulfide bonded fibers as shown in Example 1 were treated in a bath containing 200 g/Q of copper sulfate and 50 g/Q of sulfuric acid at a temperature of 30° C. and a current density of 4 A/d r4 for 20 minutes. Electrolytic plating treatment was performed for 1 minute. The surface of the thus obtained fiber was plated with metallic copper, and the fiber was 6.5X10-Ω・
The specific resistance was expressed in cm.

Example 3 The same copper sulfide bonded fibers as shown in Example 1 were treated with diluted sulfuric acid.
Electrolytic plating was performed in a plating bath containing 40 g/Q of tin, 60 g/Q of sulfuric acid, 40 g/Q of cresolsulfonic acid, and 2 g/fl of gelatin at 20° C., current density of 1, and 5 A/d r&. The fibers thus obtained were plated with metal tin; 2. ], X10-”
The specific resistance is shown in Ω·cm.

Example 4 5 g of an acrylonitrile film (Zekron, manufactured by Mitsui Toatsu Kagaku ■, thickness 0.1 mm) was treated in the same manner as in Example 1 to bond copper sulfide to its surface. This film contained 2.5% by weight of copper sulfide, and the specific resistance of the film was 5.6×10 Ω·cm.

Next, this film was subjected to electrolytic plating treatment for 30 minutes under the same conditions as in Example 2. The film thus obtained was plated with metal steel and was 3.5X10-'
The specific resistance of Ω·Cl11 is shown.

Example 5 5 g of cotton cloth was treated with a silane coupling agent solution containing a quaternary ammonium base (silane coupling agent ratio to sample = 10% by weight) at 40°C for 30 minutes, and then treated under the same conditions as Example 1. 2.8% by weight of sulfurized steel was combined. This product exhibited a specific resistance of 3.6×10 −” Ω·cm.

Next, this cotton cloth was subjected to electrolytic plating treatment under the same conditions as in Example 1. The obtained cotton cloth was plated with metallic nickel and exhibited a resistance of 7.0×10''-'Ω·cm.

Patent applicant: Nippon Silk Hair Dyeing Co., Ltd. Representative Patent Attorney Toshiaki Ikeura

Claims (1)

[Claims] (1) A conductive polymer material, characterized in that a conductive metal is attached to a polymer material having copper sulfide bonded to its surface by electrolytic plating via the copper sulfide.