CN101532157A - Method for applying conducting polymer to nonmetallic surface electroplating - Google Patents
Method for applying conducting polymer to nonmetallic surface electroplating Download PDFInfo
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- CN101532157A CN101532157A CN200810217457A CN200810217457A CN101532157A CN 101532157 A CN101532157 A CN 101532157A CN 200810217457 A CN200810217457 A CN 200810217457A CN 200810217457 A CN200810217457 A CN 200810217457A CN 101532157 A CN101532157 A CN 101532157A
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Abstract
The invention discloses a method for applying conducting polymer to nonmetallic surface electroplating, which comprises the following steps: firstly, coating sizing adhesive on the surface of a product, soaking the product in a mixture of a monomer and a solvent after the sizing adhesive is dry, drying the product soaked in the mixture of the monomer and the solvent, soaking the dried product in a mixture of an initiating agent and the solvent, drying the product soaked in the mixture of the initiating agent and the solvent to generate the conducting polymer, and finally, electroplating metal on the conducting polymer. After the surface of the product is coated with the sizing adhesive, the product can also be directly soaked in a mixture of the monomer, the initiating agent and the solvent, then the soaked product is dried to generate the conducting polymer, and finally the metal is electroplated on the conducting polymer. After the surface of the product is coated with the sizing adhesive, the product can also be directly soaked in a mixture of the conducting polymer and the solvent, then the soaked product is dried to generate the conducting polymer, and finally the metal is electroplated on the conducting polymer. The sizing adhesive is a mixture of ABS paint and solvents. Because the paint has strong adhesion force with various nonmetallic surfaces, good plating layers can be formed on all nonmetallic surfaces after electroplating. The method is simple to operate and suitable for large-scale production; and the nonmetallic surface electroplating is electroplating on various nonmetallic products such as printed circuit substrates, plastics, ceramics, plaster, clay pottery, cement, tiles, stones, artificial stones, animals, plants and the like.
Description
Technical field
The present invention relates to the electroplating technology field of nonmetallic surface, specifically be meant conductive polymers is used for the nonmetallic surface electric plating method.
Background technology
Nonmetallic surface electroplating technique complexity such as present plastics, pottery, printed circuit board base board, generally need steps such as cleaning, degreasing, alligatoring, sensitization, activation, electroless plating, preplating, plating, because the factor of the final electroplating effect of influence is more, thereby technique controlling difficulty is big, is difficult to guarantee the homogeneity and the stability of product.Japan has introduced in the clear 55-79871 patent with carbon granule or silver, copper, nickel powder and has mixed the mobile suspension of formation afterwards with organic binder bond, organic solvent, is coated in and forms conductive layer on the non-metallic material, carries out electric plating method then.Japan has introduced in the flat 1-301882 patent and has a kind ofly applied waterproof paint and electrically conducting coating at nonmetallic surface, carries out electric plating method after the drying again.Introduced precoating waterproof glue against corrosion on nonmetallic surface in the Chinese patent (patent No. 92105061.5), be coated with the mixture of styrenic polymer, solvent and fine copper powder again, electric plating method is carried out at last with the diluted acid activation in dry back.The problem that the above technology exists is: the conductive layer that (1) applies is difficult to various nonmetallic surfaces very strong sticking power is arranged all, thereby can not all form good coating at all nonmetallic surfaces; (2) can not satisfy the requirement of special application field, as require that conductive layer thickness is thin, the conductive layer width is narrower, conductive layer is transparent, conductive layer surface resistance is controlled etc.Therefore the applicant has invented following new departure finally after studying assiduously, and just conductive polymers is used for the nonmetallic surface electric plating method.
Summary of the invention
The objective of the invention is at the deficiency in the above-mentioned technology; provide a kind of can powering on to plate out the method for controlled coating at most nonmetallic surfaces; and this method is simple to operate; be suitable for large-scale production, nonmetallic surface is electroplated to electroplate on various on-metallic articles such as tellite, plastics, pottery, gypsum, mud pottery, cement, brick and tile, stone, rostone, animal, plant.
For achieving the above object, technical solution of the present invention is:
A kind of conductive polymers is used for the nonmetallic surface electric plating method, at first apply shaping glue at product surface, shaping glue parches the mixture of back goods dipping monomer and solvent, goods carry out drying after having flooded the mixture of monomer and solvent, the mixture of dry back goods dipping initiator and solvent, dry conductive polymers, the plated metal on conductive polymers at last of generating after the mixture of goods dipping initiator and solvent.
After product surface applies shaping glue, but direct impregnation monomer, initiator, solvent three's mixture also, dry then conductive polymers, the plated metal on conductive polymers at last of generating.
After product surface applies shaping glue, but the mixture of direct impregnation conductive polymers and solvent also, dry then generation conductive polymers, plated metal on conductive polymers afterwards.
Described shaping glue is the mixture of ABS coating and solvent.
Described monomer is for generating the elementary cell of πDian Zi conjugated type conducting polymer, is in acetylene, pyrroles, thiophene, furans, benzene, vinylbenzene, the aniline one or more, or their derivative.
Described solvent is a volatile solvent, be in methyl alcohol, ethanol, propyl carbinol, acetone, the second cyanogen one or more, described initiator is the material with oxidation activity, be in ammonium persulphate, Potassium Iodate, Iron triperchlorate, iron(ic) chloride, the tosic acid iron one or more, the mass percent of initiator and solvent is 10%-90%, dipping time is 1 second-1 hour, and impregnation method is the decompression dipping.
The volume ratio of described monomer and solvent is 1:1-1:50, dipping time is 1 second-1 hour, impregnation method is the normal pressure dipping, described goods have flooded behind the monomer dry under 0-230 ℃ of condition, be 5 minutes-4 hours time of drying, goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying.
The mol ratio of described monomer and initiator is 1:1-1:10, and described goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying.
Described conductive polymers is a πDian Zi conjugated type conducting polymer, polymkeric substance for polyacetylene, polypyrrole, Polythiophene, poly-furans, poly-one or more and their derivatives in benzene, polystyrene, the polyaniline, and described conductive polymers comprises the negatively charged ion of charge balance with it, as negatively charged ion such as polystyrolsulfon acid radical ion, tosic acid ion, Witco 1298 Soft Acid ion, perchlorate, arsenic hexafluoride ion, phosphorus hexafluoride ion, tetrafluoride boron ions.
Described solvent is a volatile solvent, be in methyl alcohol, ethanol, propyl carbinol, acetone, the second cyanogen one or more, the volume ratio of described conductive polymers and solvent is 1:1-1:30, dipping time is 1 second-1 hour, described goods have flooded behind the conductive polymers dry under 0-150 ℃ of condition, and be 5 minutes-5 hours time of drying.
After adopting such scheme, the present invention adopts behind the shaping glue of the mixture of product surface coating ABS coating and solvent and uses above-mentioned different methods to make the generation conductive polymers, plated metal on conductive polymers at last, because the conductive polymers and the various nonmetallic surface that generate all have very strong sticking power, can all form good coating at all nonmetallic surfaces, and can accomplish that conductive layer thickness is thin, the conductive layer width is narrower, conductive layer is transparent, conductive layer surface resistance is controlled.The inventive method is simple to operate, is suitable for large-scale production, and nonmetallic surface is electroplated to electroplate on various on-metallic articles such as tellite, plastics, pottery, gypsum, mud pottery, cement, brick and tile, stone, rostone, animal, plant.
Further be illustrated below in conjunction with specific embodiment:
Embodiment
Technical scheme of the present invention is conductive polymers to be used for nonmetallic surface electroplate, and it can realize all that by following three kinds of programs visual different nonmetallic surface is selected different programs: as shown in Figure 1:
Program one:
Mixture → the drying that applies shaping glue → dipping monomer and solvent mixture → drying → dipping initiator and solvent generates conductive polymers → plated metal
At first apply shaping glue at product surface, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches the mixture of back goods dipping monomer and solvent, monomer is for generating the elementary cell of πDian Zi conjugated type conducting polymer, as acetylene, pyrroles, thiophene, furans, benzene, vinylbenzene, aniline etc. and their derivative, solvent is a volatile solvent, and as methyl alcohol, ethanol, propyl carbinol, acetone, second cyanogen etc., the volume ratio of monomer and solvent is 1:1-1:50, dipping time is 1 second-1 hour, and impregnation method is the normal pressure dipping; Goods have flooded behind the monomer dry under 0-230 ℃ of condition, and be 5 minutes-4 hours time of drying; The mixture of dry back goods dipping initiator and solvent, initiator is the material with oxidation activity, as ammonium persulphate, Potassium Iodate, Iron triperchlorate, iron(ic) chloride, tosic acid iron etc., the mass percent of initiator and solvent is 10%-90%, dipping time is 1 second-1 hour, and impregnation method is the decompression dipping; Goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying, will generate one deck conductive polymers uniformly after drying is finished on nonmetallic surface, can be on this conductive polymers plated metal.
Program two:
Mixture → the drying that applies shaping glue → dipping monomer, initiator, solvent three generates conductive polymers → plated metal
At first apply shaping glue at product surface, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches back goods dipping monomer, initiator, the mixture of solvent, monomer is for generating the elementary cell of πDian Zi conjugated type conducting polymer, as acetylene, the pyrroles, thiophene, furans, benzene, vinylbenzene, aniline etc. and their derivative, initiator is the material with oxidation activity, as ammonium persulphate, Potassium Iodate, the Iron triperchlorate, iron(ic) chloride, tosic acid iron etc., solvent is a volatile solvent, as methyl alcohol, ethanol, propyl carbinol, acetone, second cyanogen etc., the mol ratio of monomer and initiator is 1:1-1:10, the mass percent of initiator and solvent is 10%-90%, dipping time is 1 second-1 hour, and impregnation method is the decompression dipping; Goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying, will generate one deck conductive polymers uniformly after drying is finished on nonmetallic surface, can be on this conductive polymers plated metal.
Program three:
Apply the mixture → drying → plated metal of shaping glue → dipping conductive polymers and solvent
At first apply shaping glue at product surface, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches the mixture of back goods dipping conductive polymers and solvent, conductive polymers is a πDian Zi conjugated type conducting polymer, as polyacetylene, polypyrrole, Polythiophene, poly-furans, poly-to benzene, polystyrene, the polymkeric substance of polyaniline etc. and their derivatives, and conductive polymers comprises the negatively charged ion of charge balance with it, as the polystyrolsulfon acid radical ion, the tosic acid ion, the Witco 1298 Soft Acid ion, perchlorate, the arsenic hexafluoride ion, the phosphorus hexafluoride ion, negatively charged ion such as tetrafluoride boron ion, solvent is a volatile solvent, as methyl alcohol, ethanol, propyl carbinol, acetone, second cyanogen etc., the volume ratio of conductive polymers and solvent is 1:1-1:30, and dipping time is 1 second-1 hour; Goods have flooded behind the conductive polymers dry under 0-150 ℃ of condition, and be 5 minutes-5 hours time of drying, will generate one deck conductive polymers uniformly after drying is finished on nonmetallic surface, can be on this conductive polymers plated metal.
Embodiment one:
With the plastic surface galvanizing gold is the embodiment that example describes program one in detail:
At first apply shaping glue in surface of plastic products, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches back plastics dipping 3,4-enedioxy thiophene monomer and alcoholic acid mixture, and 3,4 enedioxy thiophene monomers and alcoholic acid volume ratio are 1:5, and dipping time is 2 minutes, and impregnation method is the normal pressure dipping; Plastics have flooded behind 3, the 4 enedioxy thiophene monomers dry under 60 ℃ of conditions, and be 60 minutes time of drying; The mixture of goods dipping tosic acid iron and propyl carbinol after the plastics drying, the mass percent of tosic acid iron in propyl carbinol is 50%, and dipping time is 5 minutes, and impregnation method is the decompression dipping; Plastics have flooded behind the tosic acid iron initiator dry under 85 ℃ of conditions, be 4 hours time of drying, after finishing, drying will have in the plastics immersion plating gold plating bath of conductive polymers, and be negative electrode with the frosting that contains conductive polymers, with the titanium plate is that anode is electroplated, and can generate good gold plate on the conductive polymers surface.
Embodiment two:
With the ceramic surface imitation gold plating is the embodiment that example describes program two in detail:
At first at ceramic surface-coated shaping glue, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches back ceramic dipping 3,4-enedioxy thiophene monomer, tosic acid iron initiator, the alcoholic acid mixture, 3, the mol ratio of 4-enedioxy thiophene and tosic acid iron is 1:2.3, and the mass percent of initiator and solvent is 50%, dipping time is 3 minutes, and impregnation method is the decompression dipping; Ceramic has flooded behind the initiator dry under 105 ℃ of conditions, be 5 hours time of drying, after drying is finished the ceramic immersion plating that conductive polymers is arranged is imitated in the golden plating bath, and be negative electrode with the ceramic surface that contains conductive polymers, with the titanium plate is that anode is electroplated, and can generate good imitation gold deposit on the conductive polymers surface.
Embodiment three:
(3) be the embodiment that example describes program three in detail with the copper facing of printed circuit board base board surface electrical:
At first at printed circuit board base board surface-coated shaping glue, shaping glue is the mixture of ABS coating and solvent; Shaping glue parches back printed circuit board base board dipping poly-3,4-enedioxy thiophene: polystyrolsulfon acid root (PEDOT:PSS), alcoholic acid mixture, poly-3,4-enedioxy thiophene: polystyrolsulfon acid root (PEDOT:PSS) is 1:5 with the alcoholic acid volume ratio, and dipping time is 1 minute; Printed circuit board base board has flooded behind the conductive polymers dry under 125 ℃ of conditions, be 45 minutes time of drying, after finishing, drying will have in the tellite immersion plating copper electrolyte of conductive polymers, and be negative electrode with the printed circuit board base board surface that contains conductive polymers, with the titanium plate is that anode is electroplated, and can generate good copper coating on the conductive polymers surface.
Above embodiment is only for the usefulness that the present invention is described, but not the restriction to inventing, person skilled in the relevant technique under the situation that does not break away from the spirit and scope of the present invention, can also be made various conversion or variation.Therefore, all technical schemes that are equal to also should belong to category of the present invention, should be limited by each claim.
Claims (10)
1, a kind of conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: at first apply shaping glue at product surface, shaping glue parches the mixture of back goods dipping monomer and solvent, goods carry out drying after having flooded the mixture of monomer and solvent, the mixture of dry back goods dipping initiator and solvent, dry conductive polymers, the plated metal on conductive polymers at last of generating after the mixture of goods dipping initiator and solvent.
2, as claimed in claim 1 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: after product surface applies shaping glue, but direct impregnation monomer, initiator, solvent three's mixture also, dry then conductive polymers, the plated metal on conductive polymers at last of generating.
3, as claimed in claim 1 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: after product surface applies shaping glue, but the mixture of direct impregnation conductive polymers and solvent also, dry then conductive polymers, the plated metal on conductive polymers afterwards of generating.
4, described conductive polymers is used for the nonmetallic surface electric plating method as claim 1 or 2 or 3, it is characterized in that: described shaping glue is the mixture of ABS coating and solvent.
5, as claimed in claim 1 or 2 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: described monomer is for generating the elementary cell of πDian Zi conjugated type conducting polymer, be in acetylene, pyrroles, thiophene, furans, benzene, vinylbenzene, the aniline one or more, or their derivative.
6, as claimed in claim 1 or 2 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: described solvent is a volatile solvent, be in methyl alcohol, ethanol, propyl carbinol, acetone, the second cyanogen one or more, described initiator is the material with oxidation activity, be in ammonium persulphate, Potassium Iodate, Iron triperchlorate, iron(ic) chloride, the tosic acid iron one or more, the mass percent of initiator and solvent is 10%-90%, dipping time is 1 second-1 hour, and impregnation method is the decompression dipping.
7, as claimed in claim 1 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: the volume ratio of described monomer and solvent is 1:1-1:50, dipping time is 1 second-1 hour, impregnation method is the normal pressure dipping, described goods have flooded behind the monomer dry under 0-230 ℃ of condition, be 5 minutes-4 hours time of drying, and goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying.
8, as claimed in claim 2 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: the mol ratio of described monomer and initiator is 1:1-1:10, described goods have flooded behind the initiator dry under 30-180 ℃ of condition, and be 10 minutes-50 hours time of drying.
9, as claimed in claim 3 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: described conductive polymers is a πDian Zi conjugated type conducting polymer, be polyacetylene, polypyrrole, Polythiophene, poly-furans, poly-to benzene, polystyrene, the polymkeric substance of one or more in the polyaniline and their derivatives, and described conductive polymers comprises the negatively charged ion of charge balance with it, as the polystyrolsulfon acid radical ion, the tosic acid ion, the Witco 1298 Soft Acid ion, perchlorate, the arsenic hexafluoride ion, the phosphorus hexafluoride ion, negatively charged ion such as tetrafluoride boron ion.
10, as claimed in claim 3 conductive polymers is used for the nonmetallic surface electric plating method, it is characterized in that: described solvent is a volatile solvent, be in methyl alcohol, ethanol, propyl carbinol, acetone, the second cyanogen one or more, the volume ratio of described conductive polymers and solvent is 1:1-1:30, dipping time is 1 second-1 hour, described goods have flooded behind the conductive polymers dry under 0-150 ℃ of condition, and be 5 minutes-5 hours time of drying.
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| CN200810217457A CN101532157A (en) | 2008-11-14 | 2008-11-14 | Method for applying conducting polymer to nonmetallic surface electroplating |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911389A (en) * | 2012-11-01 | 2013-02-06 | 喻小琦 | Polythiophene composite material and preparation method thereof |
| CN103806034A (en) * | 2014-03-11 | 2014-05-21 | 东华大学 | Method for electrodepositing metal copper on surface of textile by using constant current |
| CN107917939A (en) * | 2017-11-27 | 2018-04-17 | 电子科技大学 | Electromagnetism chemical sensor based on conducting polymer and preparation method thereof |
-
2008
- 2008-11-14 CN CN200810217457A patent/CN101532157A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911389A (en) * | 2012-11-01 | 2013-02-06 | 喻小琦 | Polythiophene composite material and preparation method thereof |
| CN102911389B (en) * | 2012-11-01 | 2014-08-06 | 喻小琦 | Polythiophene composite material and preparation method thereof |
| CN103806034A (en) * | 2014-03-11 | 2014-05-21 | 东华大学 | Method for electrodepositing metal copper on surface of textile by using constant current |
| CN103806034B (en) * | 2014-03-11 | 2016-05-04 | 东华大学 | A kind of method of textile surface constant current electrodeposit metals copper |
| CN107917939A (en) * | 2017-11-27 | 2018-04-17 | 电子科技大学 | Electromagnetism chemical sensor based on conducting polymer and preparation method thereof |
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Open date: 20090916 |