US3864148A - Process for production of metal-plated fibers - Google Patents

Process for production of metal-plated fibers Download PDF

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US3864148A
US3864148A US296021A US29602172A US3864148A US 3864148 A US3864148 A US 3864148A US 296021 A US296021 A US 296021A US 29602172 A US29602172 A US 29602172A US 3864148 A US3864148 A US 3864148A
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fibers
plating
plating solution
plated
hank
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Minoru Maeawa
Hiroka Morioka
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Kuraray Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1619—Apparatus for electroless plating
    • C23C18/1628—Specific elements or parts of the apparatus
    • C23C18/163—Supporting devices for articles to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • D06B3/08—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments as hanks
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/04—Decorating textiles by metallising
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/14—Reflecting surfaces; Equivalent structures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • PROCESS FUR PRODUCTION OF METAL-PLATED FIBERS This invention relates to a process for the production of metal-plated fibers by the electroless plating method.
  • fibers which have been subjected to such pretreatments as deoiling, etching, activation and the like are generally dipped in electroless plating solutions containing metallic ions, reducing agents, complexing agents, hydrogen ion-adjusting agents, stabilizers and other additives.
  • electroless plating solutions containing metallic ions, reducing agents, complexing agents, hydrogen ion-adjusting agents, stabilizers and other additives.
  • the surface area is much greater than in the case of molded articles of plastics having the same weight, and in threads the distances between individual fibers are very short and they are very close to one another.
  • fine bubbles of hydrogen and other gases are generated from the fiber surfaces as the plating reaction advances.
  • a process for the production of metal-plated fibers by electrolessly plating pre-treated fibers which comprises reeling the fibers into hanks, hanging the fibers in the hank form on a rotary cylinder having projection holes to suspend the fibers in the air, allowing the fibers to move rotatively around the cylinder by rotation of the cylinder, projecting a plating solution from said projection holes at a rate of to 50 cm/sec against the rotatively moving fibers and thereby effecting the electroless plating of the fibers.
  • FIG. 1 is a diagram illustrating one embodiment of apparatus for use in the practice of the electroless plating according to this invention
  • FIG. 2 is a sectional view illustrating the state in the fibers of the hank form being hung on the rotary cylinder of the apparatus illustrated in FIG. 1;
  • FIG. 3 is a diagram illustrating the state where the fibers in the hank form to be subjected to the electroless plating treatment are tied by lea threads and divided into several portions.
  • any chemical fibers such as polyamide fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, acetate fibers and rayon fibers and natural fibers such as cotton and wool fibers may be electrolessly plated according to this invention.
  • polyvinyl alcohol fibers are most preferably treated according to the process of this invention, because polyvinyl alcohol fibers have the property that metal-plated fibers excellent in durability of adherence between the plating layer and fibers can be obtained, even if the etching pre-treatment is not effected.
  • the etching pretreatment is indispensable because without the etching pre-treatment the adherence durability is much lowered and it is impossible to obtain metal-plated fibers of practical value.
  • the surprising result is obtained that the adherence durability of metal-plated fibers derived from polyvinyl alcohol fibers which have not been subjected to the etching pre-treatment is superior to the adherence durability of metal-plated fibers derived from other fibers which have been subjected to the etching pretreatment.
  • Polyacrylonitrile fibers are most preferred among fibers other than polyvinyl alcohol fibers, but omission of the etching pre-treatment is not permissible in polyacrylonitrile fibers.
  • the fibers to be metal-plated according to the process of this invention may take any form. For instance, they may be a monofilament, multi-filament yarn, spun yarn, split yarn, tape yarn, cord, tape, etc.
  • fiber or fibers is used to mean all of these fibrous articles inclusively.
  • polyester and polyacrylonitrile fibers are treated with etching agents such as alkali metal hydroxides and polyolefin and polyamide fibers are treated with such etching agents as solutions of the chromic acid-sulfuric acid type.
  • Other fibers are subjected to the etching treatment with use of appropriate etching agents such as alkaline substances, chromic acid, etc.
  • this etching treatment can be omitted in the case of polyvinyl alcohol fibers, which results in an industrial advantage of reduction of the manufacturing cost.
  • the activation treatment is conducted. This activation treatment is also accomplished according to customary procedures.
  • fibers are activated by a method comprising treating fibers with a hydrochloric aqueous solution of stannous chloride, washing the fibers with water, treating the fibers with a hydrochloric aqueous solution of palladium chloride, and washing the fibers with water to remove unreacted palladium chloride remaining on fiber surfaces or in voids formed among the fibers.
  • Fibers may be subjected to these pre-treatments in the form of cheese, cone or hank, but it is preferred that these pre-treatments are effected on fibers in the hank form.
  • Fibers which have been subjected to these pretreatments are then the electroless plated.
  • the electroless plating process of this invention is unique and different from electroless plating techniques heretofore adopted in the art. Furthermore, the electroless plating process of this invention can give a plating layer which is superior in its uniformity and evenness over plating layers formed by the. conventional electroless plating techniques.
  • FIGS. 1 and 2 fibers 1 in the hank form ready to be plated, which have passed through the steps of the abovementioned pre-treatments, are hung on a rotary cylinder in a uniform thickness with no overlapping of hanks.
  • This cylinder 5 is driven by a motor 10, and the fibers 1 are moved rotatively around the rotary cylinder 5 by rotation thereof.
  • the rotary cylinder 5 is provided with partition plates 2 for preventing the overlapping of hanks during the operation and with forwarding plates 3 for conducting the rotary movement of the hanks smoothly.
  • Projecting holes 4 are mounted on the rotary cylinder 5 to project a plating solution against the fibers 1.
  • FIG. 1 In FIG.
  • a plating solution 7 contained in a plating solution tank 11 is fed to the cylinder 5 by means of a pump 8 after its temperature has been adjusted to a prescribed level by a heating or cooling device, and the solution 7 is projected against the fibers l of the hank form through projection holes 4.
  • the adjustment in the feed rate of the plating solution and the agitation of the plating solution are accomplished by means of a valve 9.
  • the fibers l in the hank form are contacted with the plating solution projected through the projection holes 4 and the electroless plating is accomplished.
  • the plating solution flows downwardly along the fibers in the hank form suspended in the air, and is returned to the tank 11.
  • the system for circulation (i.e. tank or cylinder) of the plating solution be lined with glass or plastic so as to prevent occurrence of the plating reaction by contact with the plating solution. Occurrence of the undesired plating of the circulation system may also be prevented if the system is constructed of stainless steel.
  • the most important feature of the process of this invention reside, as described above, in that the electroless plating is effected while projecting a plating solution against fibers hung (in the form of hanks) on the rotary cylinder which is provided with plating solutionprojecting holes.
  • this electroless treatment it is important that the fibers in the hank form are hung on the rotary cylinder uniformly in either the lateral direction or the thickness direction, and the overlapping of the hanks of fibers or unequal distribution of the fibers hung on the rotary cylinder must be avoided as much as possible.
  • partition plates 2 are mounted on the rotary cylinder 5.
  • the uniform hanging of the fiber hanks can be effectively attained by tying the hanks with the use of lea threads and dividing each hank into several portions, which feature is illustrated in FIG. 3.
  • the plating solution is then projected through the projection holes against the fibers hung in the form of hanks uniformly on the rotary cylinder.
  • each individual filament has a denier of from 0.l to l5, and especially from I to 6.
  • the flexibility inherent in the fibers is lost when the metal is plated to a thickness of about 1 a, and the surface area per unit weight is increased, resulting in an economic disadvantage.
  • fibers having a filament denier exceeding 15 In the case of fibers having a filament denier exceeding 15, the durability of adherence between the plating layer and the fibers is reduced because of swelling and expansion of the fibers brought about during the plating step or shrinkage of the fibers caused during the drying or cooling step. Furthermore, cracks are readily formed in the metal plating layer by mechanical deformation or the like. Additionally, plated fibers derived from fibers having a filament denier exceeding 15 exhibit low antistatic activity. For these reasons, the use of fibers having a filament denier exceeding 15 is not preferred.
  • the total denier of the fibers to be plated is more than 20.
  • the upper limit of the total denier is not particularly critical and even fibers having a total denier of about l,000 can be conveniently treated according to the electroless plating process of this invention.
  • the size of the hank to be used in this invention is determined appropriately depending on the amount of the fiber treated, of the fiber, the form of the fiber, the size of the electroless plating apparatus and other factors, but it is generallypreferred that a hank has a weight of from 30 to 500 g per 1.5 m circle. In case the hank has a weight of less than 30 g per 1.5 m circle, it takes a long time to effect the reeling and the use of such hank is not economical. Use of a hank having a weight of greater than 500 g per 1.5 m circle is also undesired because the penetration of the plating solution into the hank fibers is insufficient.
  • the lea thread to be used for tying the hanks exhibits a shrinkage not exceeding 5 percent during the plating step, When the lea thread shrinks by more than 5 percent during the plating step, the part tied by the lea thread undergoes contraction and penetration of the plating solution into the fibers of this part is insufficient, with the result that unevenness is brought about in the resulting plating layer.
  • the hank be divided into 3 to 6 portions per 1.5 m with the lea thread.
  • the number of leas is less than 3 per l.5 m. the hanks become disor dered during the plating step and consequently. the hanks are difficult to reel. Penetration of the plating solution is insufficient when the number of leas exceeds 6 per 1.5 m.
  • one bank of fibers is hung on each section of the rotary cylinder such section being partitioned by two partition plates.
  • the distance between two adjoining partition plates is varied depending on the size of the hank, but it is generally preferable that the distance be within a range of from 5 to 10 cm.
  • a preferable amount of fibers hung on one section partitioned by the two adjoining partition plates is within a range of from 30 to 500 g, especially 50 to 200 g.
  • the rate of rotation of the fibers hung in the hank form on the rotary cylinder is not critical but a rotation rate of about 9 to about 18 m/min is usually adopted.
  • the rotation direction may be reversed at suitable intervals, for instance, every two minutes.
  • the projection holes for projecting a plating solution have a diameter of from 2 to 5 mm and that such projection holes are distributed on the rotary cylinder to such an extent that to 150 projection holes are present per 100 cm of the surface of the rotary cylinder
  • the number of projection holes is less than 25 per 100 cm the thickness of the plating layer differs in the outer and interior portions of the plated thread and it is difficult to obtain metal-plated fibers having a uniform plating layer.
  • the number of projection holes is more than l50 per 100 em it is difficult to maintain the constant flow rate of the plating solution at a prescribed level.
  • the plating reaction is carried out at a temperature ranging from 40 to 100C.
  • the reaction time varies depending on the amount of fibers to be treated and the intended amount of the metal to be plated on the fibers, but generally, the reaction is conducted for from 5 to minutes.
  • a conventional solution for electroless plating which contains, in addition to ions of a metal to be plated on the fibers, a reducing agent, a complexing agent, a hydrogen ionadjusting agent and other additives.
  • the plating solution may further contain a stabilizer according to need.
  • the metal to be plated on fibers there may be mentioned nickel, copper, cobalt, chromuim, tin, etc.
  • the metals be used singly or in the form of mixtures of two or more (for instance, a mixture of nickel and cobalt).
  • an electrolytic plating may be formed on the resulting electroless plating layer, if desired.
  • the plating reaction is conducted by employing a plating solution containing at least one stabilizer selected from: guanidines such as diphenyl guanidine and diortho-tolyl guanidine; thiourea derivatives such as thioearbanilide; imidazoline derivatives such as 2- mercaptoimidazoline; dithiocarbamic acid salts such as sodium dimethyldithiocarbamate and sodium dibutyldithiocarbamate; thiurams such as tetramethyl thiuram disulfide; thiazoles such as mercaptobenzthiazole; and imidazoles such as mercaptobenzimidazole. It is possible to conduct the electroless plating process of this invention by employing a plating solution free of such stabilizer, but that causes the undesired phenomenon of blacking ofthe plating solution in a short time from initiation of the plating reaction.
  • guanidines such as diphenyl guanidine and di
  • a plating solution containing a stabilizer such as mentioned above. It is considered that this undesired phenomenon of blacking is due to the selfdecomposition of the plating solution, and it has been known to avoid occurrence of this phenomenon by incorporation of a stabilizer such as sodium thiosulfate.
  • a stabilizer such as sodium thiosulfate.
  • known stabilizers lose their stabilizing activity in a relatively short time when incorporated in a plating solution maintained at high temperatures, and they cannot be used for a long time or continuously.
  • the specific stabilizers exemplified above are advantageous over known stabilizers in that their stabilizing activity undergoes no change even if they are used at high temperatures for a long time.
  • the specific stabilizer to be used in this invention is incorporated preferably in an amount of 0.5 to 20 mg per liter of the plating solution.
  • mercapto group-containing stabilizers such as mercaptobenzimidazole, mercaptobenzthiazole and 2- mercaptoimidazoline exhibit particularly great stabilizing effects.
  • these stabilizers are difficultly soluble in the plating solution when it is necessary to incorporate them in great quantities, it is preferred that these stabilizers are used in the form of an aqueous solution of caustic alkali, e.g., an aqueous solution of sodium hydroxide of 0.05 l N.
  • the metal-plated fibers obtained according to the process of this invention usually have a metal plating layer with a thickness ranging from 0.01 to 15 microns, and preferably from 0.05 to 2.0 microns.
  • the metal-plated fibers obtained according to the process of this invention are superior to metal-plated fibers formed by conventional methods where fibers to be plated are dipped in plating solutions in that the thickness of the plating layer is highly uniform and hence, the deviation of the electric resistance in the longitudinal direction is very small.
  • the metal-plated fibers as they are or after incorporation with unplated fibers, are used in the form of knitted fabrics, woven fabrics, non-woven fabrics, cords or tapes, and as electric heaters, protective suits for high voltage linemen, electromagnetic shieldings, and the like. Further, when they are incorporated in fibrous and plastic products in which static charges are readily generated and accumulated, an antistatic effect is attained in these products.
  • Values of the thickness of the plating layer of the metal plated fibers are those calculated by the weight method or microscope method. The values measured by the two methods agree with each other quite well.
  • EXAMPLE 1 A hank of a circle of 1.5 m was prepared from g of filaments of 250 denier/36 filaments (which will be abbreviated as 250 dr/36 f below) having a twist number of turns per meter and composed of a polyvinyl alcohol having a degree of formalization of 20 mole percent (sold under the trademark "Vinylon”), and the hank was tied with a lea thread and divided into lution consisting of l [of water, l6 g of stannous chloride and 20 m1 of 36 percent by weight hydrochloric acid at room temperature for 3 minutes, and washed Table 1-c0miHIIJ Amount of plating solution 200 l p 5.0 Plating time 20 minutes Plating temperature 80C.
  • Vinylon filaments were activated under the same conditions as described above and the plating was conducted at 80C. for minutes by dip- 'Tiieictrbi's's plating was th en conducteti according to the process of this invention in the same manner as described above except that mercaptoimidazole was not incorporated in the plating solution (the rate of projection of the plating solution being 40 cm/sec). In about 3 minutes from the initiation of the plating reaction, the plating solution was blackened, and the plating ratio was only 12 percent.
  • each hank was dipped in gog um citrate 0.10 mole/l an aqueous solution of sodium hydroxide having a conf g iggf centration of 100 g/l at 60C. for 30 minutes and then solution (in 0.2-N NaOH) 0.! g/l washed with water to remove the alkali therefrom, follec Plating Conditions lowing which the activation treatment was carried out in the same manner as in Example 1.
  • the hanks were hung on a cylinder having a total length of l m and a diameter of cm and being provided with forwarding plates having 120 per 100 cm of holes for projection of a plating solution having a diameter of 2 mm and partition plates, one hank being hung on one section formed between the two adjoining partition plates.
  • the cylinder was rotated at a rate of 60 rotations per minute and the rotation direction was reversed every two minutes.
  • the plating was carried out at 80C. for 20 minutes while projecting a plating solution having the same composition as illustrated in Table l of Example 1 at a flow rate of 30 cm/sec.
  • the thickness of the plating layer was 0.23-0.25 p. in the outer portion of the hank and 0.24 0.26 p. in the interior portion.
  • EXAMPLE 3 Five hanks of Vinylon spun yarn (count No. 20; monofilament denier l; degree of formalization 30 mole percent), each having a weight of 100 g, were reeled and activated in the same manner as in Example 1. Then. the hanks were plated under the same conditions as shown in Table l of Example I. Namely, the hanks were hung on a cylinder having a total length of 0.5 m and a diameter of 5 cm and being provided with forwarding plates having 76 per 100 cm of projection holes of a diameter of 4 mm, one hank being hung on one section formed between the two adjoining partition plates. The electroless plating was effected at 87C.
  • the thickness of the resulting plating layer was 0.40 0.43 p. in the outer portion of the hank and 0.42 0.43 p. in the interior portion of the hank.
  • a nickel-plated Vinylon spun yarn having a uniform plating layer was obtained.
  • a nickel-plated Vinylon spun yarn was prepared according to the conventional dipping plating method. in this comparative yarn. the thickness ofthe plating layer was 0.15 0.50 a in the interior portion of the hank and 0.32 0.47 t in the outer portion thereof.
  • EXAMPLE 4 Ten hanks, each having a weight of 50 g, were reeled from 210 dr/24 nylon filaments having a twist number of 100 turns per meter and deoiled according to customary procedures. Then, the hanks were etched with a solution consisting of l [of water, 30 g of chromic anhydride, 150 g of concentrated sulfuric acid and 100 g of phosphoric acid at 40C. for 3 minutes, and washed with water. Then the activation treatment was carried out in the same manner as described in Example 1, and the activated hanks were electrolessly plated by employing the same plating solution and plating apparatus as in Example 1, at 80C.
  • nickel-plated nylon filaments with a uniform plating having a thickness of 0.35 0.37 ,u. in the outer portion of the hank and 0.36 0.38 p. in the interior portion of the hank were obtained.
  • Comparative nickel-plated nylon filaments prepared by the conventional dipping plating method had a plating layer with a thickness of 0.25 0.39 p. in the outer portion of the hank and 0.19 0.32 ,u in the interior portion of the bank.
  • EXAMPLE 5 Ten hanks of the same Vinylon filaments as used in Example 1, each hank having a weight of g, were subjected to the deoiling and activation treatments in the same manner as in Example 1. The activated hanks were then subjected to the electroless copper-plating using the same plating apparatus as used in Example 1.
  • the composition of the plating solution used and the plating conditions adopted are shown below:
  • EXAMPLE 7 This Example illustrates that metal-plated filaments having a very excellent adherence durability can be obtained from polyvinyl alcohol filaments without conducting the etching treatment.
  • Polyvinyl alcohol filaments as used in Example 1 were subjected to the deoiling and activation treatments conducted in the same manner as in Example 1 without performing the etching treatment as in Example l.
  • the electroless plating was effected on the thus treated polyvinyl alcohol filaments under the same conditions as shown in Table l of Example 1 by employing the plating solution shown in Table l of Example 1.
  • Each sample of the three kinds of the plated filaments was subjected to the bending test using a custom bending tester, and the electrical resistance was measured after the bending was conducted a prescribed number of times. The measured value was compared with the value of the electrical resistance of the sample before the bending test. Further, each sample was subjected to the washing test.
  • One cycle of washing treatment comprised washing the sample with a rinsing liquor containing 1 g/l of a surface active agent (sold under the trademark Monogen Uni at 40C. for 12.5 minutes by employing an ordinary electric washing machine.
  • a process for the production of metal-plated fibers by electrolessly plating pre-treated fibers which comprises reeling the fibers into hanks, hanging the fibers in the hank form on a rotary cylinder having projection holes to suspend the fibers in the air, wherein the projection holes are from about 2 to about 5 mm in diameter and present in from about 25 to about holes per 100 cm of the cylinder surface, and wherein the fibers have a denier of from about 0.1 to about 15, allowing the fibers to move rotatively around the cylinder by rotation of the cylinder, projecting an electroless metal plating solution at a rate of 5 to 50 cm/sec from said projection holes against the rotatively moving fibers and thereby effecting the electroless plating of the fibers.
  • the plating solution contains as a stabilizer at least one member selected from the group consisting of guanidines, thiourea derivatives, imidazolines, dithiocarbamic acid salts, thiurams, thiazoles and imidazoles.

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Cited By (19)

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US3986530A (en) * 1974-07-02 1976-10-19 Kuraray Co., Ltd. Cloth having antistatic properties
EP0141507A3 (en) * 1983-09-08 1985-07-10 Brent Chemicals International Plc Method and apparatus for electroless plating
US4614684A (en) * 1981-10-02 1986-09-30 Bayer Aktiengesellschaft Reinforced composite comprising resin impregnated metallized polyaramide fabric and method of making same
US4636998A (en) * 1984-04-18 1987-01-13 Allied Corporation Elongated retaining and electromagnetic shielding member for a towed underwater acoustic array
US4680100A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Electrochemical cells and electrodes therefor
US4925706A (en) * 1986-10-31 1990-05-15 Deutsche Automobilgesellschaft Mbh Process for the chemical metallizing of textile material
US5017410A (en) * 1988-05-23 1991-05-21 United Technologies Corporation Wear resistant electroless nickel-boron coating compositions
DE4316607A1 (de) * 1993-05-18 1994-11-24 Wilhelm Endlich Metallisierte Kunststoff-Faserabschnitte als Füllstoff in Kleb-, Dicht-, Beschichtungs- und Schmierstoffen
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
EP1130154A3 (en) * 2000-02-18 2001-09-12 Mitsubishi Materials Corporation Conductive fiber, manufacturing method therefor, apparatus, and application
US20080318483A1 (en) * 2007-06-07 2008-12-25 Joseph Salitsky Conductive Monofilament and Fabric
WO2009149365A1 (en) * 2008-06-06 2009-12-10 Carolina Silver, Llc Metal plating
US20120104331A1 (en) * 2010-10-29 2012-05-03 Artur Kolics Solutions and methods for metal deposition
CN102586766A (zh) * 2012-04-01 2012-07-18 惠州建邦精密塑胶有限公司 一种尼龙电镀化学镍电镀液
US20140178572A1 (en) * 2012-12-26 2014-06-26 Rohm And Haas Electronic Materials Llc Formaldehyde free electroless copper plating compositions and methods
CN106626167A (zh) * 2015-10-30 2017-05-10 中山联合光电科技股份有限公司 一种长效环保型脱模剂及其制备方法
US20170307454A1 (en) * 2014-10-20 2017-10-26 Bae Systems Plc Strain sensing in composite materials
US20220033973A1 (en) * 2020-07-28 2022-02-03 C. Uyemura & Co., Ltd. Electroless palladium plating bath
CN119306515A (zh) * 2024-10-23 2025-01-14 娄底市安地亚斯电子陶瓷有限公司 一种用于储能系统的陶瓷二次金属化旋转镀镍工艺

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DE2658234C3 (de) * 1976-12-22 1983-03-03 Siemens AG, 1000 Berlin und 8000 München Verfahren zur Beschichtung von Einzelfasern eines Faserbündels sowie Vorrichtung zur Durchführung des Verfahrens
US4733228A (en) * 1985-07-31 1988-03-22 Planar Systems, Inc. Transformer-coupled drive network for a TFEL panel
DE3710895C1 (de) * 1987-04-01 1987-09-17 Deutsche Automobilgesellsch Verfahren zum stromlosen Metallisieren flaechiger textiler Substrate
JP2010037623A (ja) * 2008-08-07 2010-02-18 Surface Giken Kk カーボン素材のめっき方法及びカーボン素材の製造方法
JP5362534B2 (ja) * 2009-12-15 2013-12-11 株式会社サンライン 金属メッキが施された釣糸及びその製造方法
JP5576682B2 (ja) * 2010-03-11 2014-08-20 名古屋メッキ工業株式会社 繊維めっき治具、及び、これを用いた繊維めっき方法
JP7561485B2 (ja) * 2019-01-15 2024-10-04 株式会社プロテリアル 導電性繊維、ケーブル及び導電性繊維の製造方法

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US2410626A (en) * 1942-02-16 1946-11-05 Joseph M Boudreau Means and method of treating surfaces
US2425214A (en) * 1942-10-10 1947-08-05 Goodrich Co B F Apparatus for spraying beamed yarns
US3663242A (en) * 1970-09-25 1972-05-16 Shipley Co Stabilized electroless plating solutions

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Publication number Priority date Publication date Assignee Title
US2410626A (en) * 1942-02-16 1946-11-05 Joseph M Boudreau Means and method of treating surfaces
US2425214A (en) * 1942-10-10 1947-08-05 Goodrich Co B F Apparatus for spraying beamed yarns
US3663242A (en) * 1970-09-25 1972-05-16 Shipley Co Stabilized electroless plating solutions

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3986530A (en) * 1974-07-02 1976-10-19 Kuraray Co., Ltd. Cloth having antistatic properties
US4614684A (en) * 1981-10-02 1986-09-30 Bayer Aktiengesellschaft Reinforced composite comprising resin impregnated metallized polyaramide fabric and method of making same
US4680100A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Electrochemical cells and electrodes therefor
EP0141507A3 (en) * 1983-09-08 1985-07-10 Brent Chemicals International Plc Method and apparatus for electroless plating
US4636998A (en) * 1984-04-18 1987-01-13 Allied Corporation Elongated retaining and electromagnetic shielding member for a towed underwater acoustic array
US4925706A (en) * 1986-10-31 1990-05-15 Deutsche Automobilgesellschaft Mbh Process for the chemical metallizing of textile material
US5017410A (en) * 1988-05-23 1991-05-21 United Technologies Corporation Wear resistant electroless nickel-boron coating compositions
DE4316607A1 (de) * 1993-05-18 1994-11-24 Wilhelm Endlich Metallisierte Kunststoff-Faserabschnitte als Füllstoff in Kleb-, Dicht-, Beschichtungs- und Schmierstoffen
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
EP1130154A3 (en) * 2000-02-18 2001-09-12 Mitsubishi Materials Corporation Conductive fiber, manufacturing method therefor, apparatus, and application
EP1312711A3 (en) * 2000-02-18 2003-06-18 Mitsubishi Materials Corporation Conductive fiber, manufacturing method therefor, apparatus, and application
US6703123B1 (en) 2000-02-18 2004-03-09 Mitsubishi Materials Corporation Conductive fiber, manufacturing method therefor, apparatus, and application
KR100639093B1 (ko) * 2000-02-18 2006-10-27 미쓰비시 마테리알 가부시키가이샤 도전성 섬유와 그 제조 방법과 장치 및 용도
US20080318483A1 (en) * 2007-06-07 2008-12-25 Joseph Salitsky Conductive Monofilament and Fabric
US10227714B2 (en) * 2007-06-07 2019-03-12 Albany International Corp. Conductive monofilament and fabric
WO2009149365A1 (en) * 2008-06-06 2009-12-10 Carolina Silver, Llc Metal plating
US20090304934A1 (en) * 2008-06-06 2009-12-10 Carolina Silver, Llc Metal plating
US20120104331A1 (en) * 2010-10-29 2012-05-03 Artur Kolics Solutions and methods for metal deposition
US8632628B2 (en) * 2010-10-29 2014-01-21 Lam Research Corporation Solutions and methods for metal deposition
CN102586766A (zh) * 2012-04-01 2012-07-18 惠州建邦精密塑胶有限公司 一种尼龙电镀化学镍电镀液
US20140178572A1 (en) * 2012-12-26 2014-06-26 Rohm And Haas Electronic Materials Llc Formaldehyde free electroless copper plating compositions and methods
US9611550B2 (en) * 2012-12-26 2017-04-04 Rohm And Haas Electronic Materials Llc Formaldehyde free electroless copper plating compositions and methods
US9809883B2 (en) 2012-12-26 2017-11-07 Rohm And Haas Electronic Materials Llc Formaldehyde free electroless copper plating compositions and methods
US20170307454A1 (en) * 2014-10-20 2017-10-26 Bae Systems Plc Strain sensing in composite materials
US10444089B2 (en) * 2014-10-20 2019-10-15 Bae Systems Plc Strain sensing in composite materials
CN106626167A (zh) * 2015-10-30 2017-05-10 中山联合光电科技股份有限公司 一种长效环保型脱模剂及其制备方法
US20220033973A1 (en) * 2020-07-28 2022-02-03 C. Uyemura & Co., Ltd. Electroless palladium plating bath
CN119306515A (zh) * 2024-10-23 2025-01-14 娄底市安地亚斯电子陶瓷有限公司 一种用于储能系统的陶瓷二次金属化旋转镀镍工艺

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DE2250309C3 (de) 1978-06-29
JPS4844599A (enExample) 1973-06-26
JPS4943518B2 (enExample) 1974-11-21
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GB1406102A (en) 1975-09-17
NL7213967A (enExample) 1973-04-17
DE2250309A1 (de) 1973-04-19

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