CN102373446B - Preparation method of composite conductive shielding materials - Google Patents
Preparation method of composite conductive shielding materials Download PDFInfo
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- CN102373446B CN102373446B CN 201110322871 CN201110322871A CN102373446B CN 102373446 B CN102373446 B CN 102373446B CN 201110322871 CN201110322871 CN 201110322871 CN 201110322871 A CN201110322871 A CN 201110322871A CN 102373446 B CN102373446 B CN 102373446B
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Abstract
The invention provides a preparation method of composite conductive shielding materials, which completely adopts a chemical deposition method for preparation. The method has the obvious advantages that the flow process is short, the cost is low, and the environment is protected. The method adopts the following technical scheme that the preparation method of the composite conductive shielding materials is characterized in that a copper layer and a silver layer are coated and plated on the surface of polyester or polyamide nonconductive materials by the chemical deposition method. The method has the process flow that the surface chemical pretreatment, the chemical copper plating, the water cleaning, the chemical silver plating and the color degradation prevention treatment are carried out on the surfaces of the polyester or polyamide nonconductive materials, the chemical pretreatment process is carried out in chemical solution containing 8 to 15ml/l of hydrochloric acid, 0.1 to 0.6g/l of palladium chloride and 10 to 16g/l of stannous chloride, the treatment time is 10 to 15min, and the treatment temperature is 20 to 35 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of composite conducting shielding material, belong to the non-metal material surface processing technology field.
Background technology
Shielding material is a transmission path of utilizing shielding (material with specified property) prevention or decay interfering energy, thereby suppresses electromagnetic interference.Shielding has two purposes: restricted internal radiating electromagnetic energy leaks; Prevent that external radiation interference from entering.Play and absorb energy (eddy-current loss), reflected energy (hertzian wave is at the boundary reflection of interface body) and counteracting energy (electromagnetic induction produces reversed electric field on shielding because of shielding material involves the internal electromagnetic ripple to the electromagnetic interference from the outside, can offset the part hertzian wave) effect, so it has the interferential of weakening function.
Every have the material of electric energy all can discharge hertzian wave, may cause interference to communication equipment, communication information, nerve system of human body, blood circulation, reproductive system etc. are damaged, cause symptoms such as people's giddy, weak, neurasthenia, hypertension, autonomic nervous dysfunction, pregnant woman's miscarriage, fetal anomaly, alopecia and white hair.Progress along with human modern civilization, electronic product such as computer, mobile phone has become people's life, work necessary part, various household electrical appliance such as microwave oven, suction cleaner, televisor, washing machine, refrigerator have spread all over each family, therefore, we can say each corner that we live, work, radiation is ubiquitous, has caused people's great attention.
For reducing the infringement that radiation causes equipment, human body to greatest extent, to shielding material especially software, carry out metalized as cloth, sponge, chemical fibre etc., formation has excellent electrical index and effectiveness of shielding, keeping the conductive shield material of good surface appearance and texture again, is succinct, the most feasible approach.
Popular software conductive shield material has various kinds such as copper facing, copper facing/nickel, silver-plated, copper facing/silver in the market, preparation technology electroplates thickening processing and two kinds of technologies of the direct chemical plating various different metal coating of acquisition after mainly comprising the pre-treatment of software conductionization, the former mainly contains approach such as magnetron sputtering copper, sputter nickel and electroless copper, and thickening is handled and mainly comprised electro-coppering, nickel technology; After the latter comprised that mainly soft material is through alligatoring, sensitization, activation, direct chemical copper facing or chemical silvering reached certain thickness, satisfied requirements such as conduction, shielding.
Copper facing, nickel plating product is because cost is low, widespread use.In recent years, silver-plated product was because its unique static resistance, mildew-resistant deodorization functions, performance such as powerful antibiotic gained great popularity, and market demand sharply increases.At present preparation technology mainly contain that direct chemical is silver-plated, magnetron sputtering copper-electro-coppering-electrosilvering, electroless copper-electrosilvering etc.The direct chemical silver plating process is simple relatively, but desires to reach conduction and effectiveness of shielding, must increase the deposition of silver on silvered film thickness and the unit surface, and the chemical silvering plating bath is disposable plating bath at present, and silver-plated cost is significantly improved; Magnetron sputtering copper-electro-coppering-electrosilvering operational path is long, and facility investment is big, and the electrosilvering technology that adopts at present extensively is still cyaniding plant of silver, does not meet current cleaner production requirement; Electroless copper-electrosilvering cost is low, but electroless copper mainly adopts the formaldehyde reduction method, to environment, very big to human body harm, is subjected to the restriction of electrosilvering technology equally.
In sum, the short flow process of exploitation, low cost, environment-friendly type technique, preparation high-performance copper/silver-colored composite conducting shielding material is the technical barrier that present urgent need solves, the large scale application of elecscreen being covered material plays decisive role.
Summary of the invention
Technical assignment of the present invention is the deficiency at present silver-plated shielding material technology of preparing, and a kind of preparation method of composite conducting shielding material is provided, and adopts chemical deposition preparation, this method to have that flow process is short, cost is low, the outstanding advantage of environmental protection fully.
The technical solution used in the present invention is as follows:
A kind of preparation method of composite conducting shielding material, it is characterized in that: utilization chemical bath deposition method plated copper layer and silver layer on polyester or polyamide-based non-conducting material surface, technical process is: polyester or the pre-treatment of polyamide-based non-conducting material surface chemistry, electroless copper, washing, chemical silvering, anti-variable color are handled, the Chemical Pretreatment process is at hydrochloric acid 8-15ml/l, Palladous chloride 0.1-0.6g/l, carry out in the chemical solution of tin protochloride 10-16g/l, treatment time is 10-15min, and treatment temp is at 20-35 ℃.
In the embodiment of the invention, the solution composition that electroless copper adopts is: CuSO
4.5H
2O 5-12 g/L, Seignette salt 18-33 g/L, Trisodium Citrate 15-28g/L, 2-mercaptobenzothiazole 0.1-0.6 g/L, inferior sodium phosphate 15-30 g/L, bath temperature are 60 ℃, and solution is PH=7-10, and the electroless plating time is 20-40min.
In the embodiment of the invention, the solution composition that chemical silvering adopts is: Silver Nitrate 10-18g/L, potassium pyrosulfite 15-25g/L, Sulfothiorine 80-120g/L, glycolylurea 2-5g/L, solution are pH=3.0-5.5, bath temperature is a normal temperature, electroless plating time 5min.
In the embodiment of the invention, anti-variable color is handled the treatment solution composition that adopts and is: NaCl2-6g/L, and benzotriazole 1-8g/L, solution are PH=4-6, normal temperature is placed 4-5min down.
In the embodiment of the invention, polyester or polyamide-based non-conducting material are polyamide fibre, terylene, sponge or PET plastics.
Preparation method of the present invention compares with prior art, has the following advantages:
Adopt chemical deposition to prepare copper/silver-colored composite conducting shielding material fully; the non-metallic material pre-treatment adopts alligatoring, sensitization, one step of activation to handle; electroless copper, chemical silvering adopt formaldehydeless, cyanide-free technology; technology is lacked flow process, facility investment is little, running cost is low, environmental protection, is easy to realize the mass-producing continuous production.
Embodiment
Below in conjunction with several specific embodiments technical scheme of the present invention is described in further detail, the embodiment of the invention is intended to illustrate the present invention rather than the restriction to inventing.
Embodiment 1
Adopting polyamide fibre in the present embodiment is base material, and base material length is 100-500m, and width is 0.6m-1.5m, heavily is 40-60g/m
2, preparation process is as follows:
1, Chemical Pretreatment: with base material at hydrochloric acid 8ml/l, carry out Chemical Pretreatment in the chemical solution of Palladous chloride 0.3g/l and tin protochloride 10g/l, treatment time is 10-15min, treatment temp is at 20-35 ℃, effect in acid in this process is used, substrate surface is corroded alligatoring, utilize palladium salt formation active points simultaneously, for electroless copper forms nucleus, utilize continuous, fine and close copper coating to form, this process has adopted alligatoring, sensitization, the disposable processing of activation, has shortened technical process, has improved production efficiency.
2, electroless copper: the solution composition of employing is: CuSO
4.5H
2O 5 g/L, Seignette salt 25 g/L, Trisodium Citrate 22g/L, 2-mercaptobenzothiazole 0.1g/L, inferior sodium phosphate 20 g/L are 60 ℃ with above-mentioned base material at bath temperature, and solution is PH=7-10, the electroless plating time is 20-40min, and replacement(metathesis)reaction is finished, and obtains the copper layer that plating has 0.2-1um.
3, the method for copper-plated base material utilization routine is washed.
4, chemical silvering: the solution composition of employing is: Silver Nitrate 15g/L, potassium pyrosulfite 20g/L, Sulfothiorine 100g/L, glycolylurea 2g/L, solution are pH=4.5-5.5, and bath temperature is a normal temperature, electroless plating time 5min, replacement(metathesis)reaction is finished, and obtains the silver layer that plating has 0.1-0.5um.
5, anti-variable color is handled: the treatment solution composition of employing is: NaCl3g/L, and benzotriazole 5g/L, solution are PH=4-6, normal temperature is placed 4-5min down.Can prevent silver variable color in air, and the treatment solution that utilizes organism and inorganics to form, environmental protection.
Test-results is as follows: weight: 55-70 g/m behind the electroless copper
2, 65-85 g/m behind the chemical silvering
2The composite deposite volume resistance is less than 0.1 Ω .cm; Bonding force adopts the test of adhesive tape method, obscission do not occur; The product effectiveness of shielding reaches 55dB-85dB, and hertzian wave stops rate 99.99%.
Embodiment 2
Adopting terylene in the present embodiment is base material, and preparation process is as follows: other steps are constant, change into prescription for the treatment of liquid in the Chemical Pretreatment as follows: hydrochloric acid 15ml/l, Palladous chloride 0.4g/l and tin protochloride 16g/l; The electroless copper prescription changes into as follows: CuSO
4.5H
2O 12 g/L, Seignette salt 18 g/L, Trisodium Citrate 20g/L, 2-mercaptobenzothiazole 0.6 g/L, inferior sodium phosphate 30 g/L, bath temperature are 60 ℃, and solution is PH=7-10, and the electroless plating time is 20-40min; The chemical silvering prescription changes into as follows: Silver Nitrate 10g/L, and potassium pyrosulfite 25g/L, Sulfothiorine 80g/L, glycolylurea 2g/L, solution are pH=3.0-5.5, bath temperature is a normal temperature, electroless plating time 5min; Anti-variable color is handled the treatment solution composition that adopts and is changed into as follows:: NaCl2-6g/L, benzotriazole 1-8g/L, solution are PH=4-6, normal temperature is placed 4-5min down.
Test-results is as follows: weight: 55-70 g/m behind the electroless copper
2, 65-85 g/m behind the chemical silvering
2The composite deposite volume resistance is less than 0.1 Ω .cm; Bonding force adopts the test of adhesive tape method, obscission do not occur; The product effectiveness of shielding reaches 55dB-85dB, and hertzian wave stops rate 99.99%.
Embodiment 3
Adopting sponge in the present embodiment is base material, and preparation process is as follows: other steps are constant, change into prescription for the treatment of liquid in the Chemical Pretreatment as follows: hydrochloric acid 12ml/l, Palladous chloride 0.1g/l and tin protochloride 12g/l; The electroless copper prescription changes into as follows: CuSO
4.5H
2O 10g/L, Seignette salt 33 g/L, Trisodium Citrate 28g/L, 2-mercaptobenzothiazole 0.5 g/L, inferior sodium phosphate 15-30 g/L, bath temperature are 60 ℃, and solution is PH=7-10, and the electroless plating time is 20-40min; The chemical silvering prescription changes into as follows: Silver Nitrate 18g/L, and potassium pyrosulfite 25g/L, Sulfothiorine 120g/L, glycolylurea 5g/L, solution are pH=3.0-5.5, bath temperature is a normal temperature, electroless plating time 5min; Anti-variable color is handled the treatment solution composition that adopts and is changed into as follows:: NaCl2g/L, benzotriazole 8g/L, solution are PH=4-6, normal temperature is placed 4-5min down.
Test-results is as follows: weight: 55-75 g/m behind the electroless copper
2, 65-100 g/m behind the chemical silvering
2The composite deposite volume resistance is less than 0.1 Ω .cm; Bonding force adopts the test of adhesive tape method, obscission do not occur; The product effectiveness of shielding reaches 45dB-80dB, and hertzian wave stops rate 99%.
Embodiment 4
Adopting the PET plastics in the present embodiment is base material, and preparation process is as follows: other steps are constant, change into prescription for the treatment of liquid in the Chemical Pretreatment as follows: hydrochloric acid 10ml/l, Palladous chloride 0.6g/l and tin protochloride 15g/l; The electroless copper prescription changes into as follows: CuSO
4.5H
2O 8 g/L, Seignette salt 28 g/L, Trisodium Citrate 15g/L, 2-mercaptobenzothiazole 0.2 g/L, inferior sodium phosphate 15 g/L, bath temperature are 60 ℃, and solution is PH=7-10, and the electroless plating time is 20-40min; The chemical silvering prescription changes into as follows: Silver Nitrate 15g/L, and potassium pyrosulfite 20g/L, Sulfothiorine 80g/L, glycolylurea 3g/L, solution are pH=3.0-5.5, bath temperature is a normal temperature, electroless plating time 5min; Anti-variable color is handled the treatment solution composition that adopts and is changed into as follows:: NaCl6g/L, benzotriazole 1g/L, solution are PH=4-6, normal temperature is placed 4-5min down.
Test-results is as follows: weight: 50-70 g/m behind the electroless copper
2, 60-85 g/m behind the chemical silvering
2The composite deposite volume resistance is less than 0.1 Ω .cm; Bonding force adopts the test of adhesive tape method, obscission do not occur; The product effectiveness of shielding reaches 55dB-85dB, and hertzian wave stops rate 99.99%.
Claims (3)
1. the preparation method of a composite conducting shielding material, it is characterized in that: utilization chemical bath deposition method plated copper layer and silver layer on polyester or polyamide-based non-conducting material surface, technical process is: polyester or the pre-treatment of polyamide-based non-conducting material surface chemistry, electroless copper, washing, chemical silvering, anti-variable color are handled, the Chemical Pretreatment process is at hydrochloric acid 8-15ml/l, Palladous chloride 0.1-0.6g/l, carry out in the chemical solution of tin protochloride 10-16g/l, treatment time is 10-15min, and treatment temp is at 20-35 ℃; The solution composition that electroless copper adopts is: CuSO
4.5H
2O 5-12 g/L, Seignette salt 18-33 g/L, Trisodium Citrate 15-28g/L, 2-mercaptobenzothiazole 0.1-0.6 g/L, inferior sodium phosphate 15-30 g/L, bath temperature are 60 ℃, and solution is PH=7-10, and the electroless plating time is 20-40min; The solution composition that chemical silvering adopts is: Silver Nitrate 10-18g/L, and potassium pyrosulfite 15-25g/L, Sulfothiorine 80-120g/L, glycolylurea 2-5g/L, solution are pH=3.0-5.5, bath temperature is a normal temperature, electroless plating time 5min.
2. according to the preparation method of the described composite conducting shielding material of claim 1, it is characterized in that: anti-variable color is handled the treatment solution composition that adopts and is: NaCl2-6g/L, and benzotriazole 1-8g/L, solution are PH=4-6, normal temperature is placed 4-5min down.
3. according to the preparation method of the described composite conducting shielding material of claim 1, it is characterized in that: polyester or polyamide-based non-conducting material are polyamide fibre, terylene, sponge or PET plastics.
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| CN105063705A (en) * | 2015-07-30 | 2015-11-18 | 柳州市旭平首饰有限公司 | Method for preventing color change of copper ornament plated with silver |
| CN105063798A (en) * | 2015-08-25 | 2015-11-18 | 无锡市长安曙光手套厂 | Conductive fabric |
| CN109137011A (en) * | 2018-09-20 | 2019-01-04 | 吕莉 | A kind of preparation method of high voltage isolator contact material |
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| US4645574A (en) * | 1985-05-02 | 1987-02-24 | Material Concepts, Inc. | Continuous process for the sequential coating of polyamide filaments with copper and silver |
| CN1401819A (en) * | 2002-09-23 | 2003-03-12 | 北京工业大学 | Inorganic powder surface metallizing method |
| CN1502720A (en) * | 2002-11-20 | 2004-06-09 | 希普雷公司 | Methyl free copper plating method and used solution thereof |
| CN1793425A (en) * | 2005-12-30 | 2006-06-28 | 东北大学 | Process for compound surface sheilding of metal magnesium and magnesium alloy |
| CN101590778A (en) * | 2009-06-25 | 2009-12-02 | 邱天祥 | The method of manufacturing electric field shielding decoration board by electroless plating |
| CN102121107A (en) * | 2011-01-13 | 2011-07-13 | 福州永通电线电缆有限公司 | Antioxidant cooling liquid composition |
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- 2011-10-21 CN CN 201110322871 patent/CN102373446B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4645574A (en) * | 1985-05-02 | 1987-02-24 | Material Concepts, Inc. | Continuous process for the sequential coating of polyamide filaments with copper and silver |
| CN1401819A (en) * | 2002-09-23 | 2003-03-12 | 北京工业大学 | Inorganic powder surface metallizing method |
| CN1502720A (en) * | 2002-11-20 | 2004-06-09 | 希普雷公司 | Methyl free copper plating method and used solution thereof |
| CN1793425A (en) * | 2005-12-30 | 2006-06-28 | 东北大学 | Process for compound surface sheilding of metal magnesium and magnesium alloy |
| CN101590778A (en) * | 2009-06-25 | 2009-12-02 | 邱天祥 | The method of manufacturing electric field shielding decoration board by electroless plating |
| CN102121107A (en) * | 2011-01-13 | 2011-07-13 | 福州永通电线电缆有限公司 | Antioxidant cooling liquid composition |
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Inventor after: Feng Liming Inventor after: Li Pingsheng Inventor after: Sun Yanming Inventor after: Liu Yanqing Inventor after: Gong Yunxiang Inventor before: Feng Liming Inventor before: Sun Yanming Inventor before: Liu Yanqing Inventor before: Yang Maode |
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